Biodegradable resin composition, and biodegradable molded article including the same

Abstract

To provide: a biodegradable resin composition that has excellent biodegradability, is improved in spinning ability, injection moldability and foamability, and has excellent mechanical properties, and a biodegradable molded article including the same; and a biodegradable resin composition that can have soft texture, has excellent elasticity, and is eco-friendly, and a biodegradable nonwoven fabric including the same.SOLUTION: A biodegradable resin composition is provided which includes a first biodegradable resin and a crystallization accelerator. The first biodegradable resin includes a first repeating unit derived from a diol, a second repeating unit derived from aromatic dicarboxylic acid, and a third repeating unit derived from aliphatic dicarboxylic acid. The crystallization accelerator is included in a content of 100 ppm to 50,000 ppm. An isothermal crystallization time at 90°C according to a specific measurement method is 10 to 900 seconds.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a biodegradable resin composition and a biodegradable molded article containing the same.

Background Art

[0002] Conventionally, polyethylene, polypropylene, and polyethylene terephthalate have been used as materials for clothing fibers, non-woven fabrics, etc. In recent years, as concerns about environmental problems have increased, solutions to the problems of clothing fibers with a short service life and the treatment of non-woven fabrics used as disposable items have been demanded.

[0003] As solutions to these problems, active research has been conducted on biodegradable resins. As biodegradable resins, poly lactic acid (PLA), polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), etc. have been introduced as alternatives.

[0004] However, biodegradable resins are not superior in spinnability compared to the materials, and there are limitations in manufacturing them as fibers or non-woven fabrics.

[0005] In addition, various biodegradable resins have been combined to improve the spinnability of biodegradable resins, but the kneadability between biodegradable resins with different physical properties has decreased, and problems such as fusion occurring between fibers or the thread breaking after spinning have occurred.

Summary of the Invention

Problems to be Solved by the Invention

[0006] The present invention provides a biodegradable resin composition excellent in biodegradability, improved in spinnability, injectability, and foamability, and excellent in mechanical properties, and a biodegradable molded article containing the same.

[0007] The present invention also provides a biodegradable resin composition that can have a soft touch feeling, has excellent stretchability, and is environmentally friendly, and a biodegradable nonwoven fabric containing the same.

Means for Solving the Problems

[0008] The biodegradable resin composition according to the present invention includes a first biodegradable resin containing a first repeating unit derived from a diol, a second repeating unit derived from an aromatic dicarboxylic acid, and a third repeating unit derived from an aliphatic dicarboxylic acid, and a crystallization accelerator. The crystallization accelerator is contained in an amount of 100 ppm to 50,000 ppm, and the isothermal crystallization time at 90 °C according to the following measurement method 1 is 10 seconds to 900 seconds.

[0009] [Measurement Method 1] 1) After heating the biodegradable resin composition to 220 °C at a heating rate of 10 °C / min, it is maintained for 5 minutes.

[0010] 2) Then, after cooling the biodegradable resin composition to 90 °C at a cooling rate of 100 °C / min, it is maintained in an isothermal state for 100 minutes.

[0011] 3) Using a differential scanning calorimeter, the time that becomes half of the total area of the crystallization peak of the biodegradable resin composition is measured with respect to the total area of the crystallization peak of the biodegradable resin composition.

[0012] In one embodiment of the present invention, the biodegradable resin composition may further include one or more second biodegradable resins selected from the group consisting of polybutylene succinate, polylactic acid, polybutylene adipate, polybutylene succinate-adipate, polybutylene succinate-terephthalate, polyhydroxybutyrate-valerate, polycaprolactone, polybutylene adipate-co-butylene succinate terephthalate, and polybutylene succinate adipate terephthalate.

[0013] In one embodiment of the present invention, the crystallization accelerator may include at least one of an organic nucleating agent and an inorganic nucleating agent.

[0014] In one embodiment of the present invention, the biodegradable resin composition may contain the organic nucleating agent in a content of 10 ppm to 5,000 ppm.

[0015] In one embodiment of the present invention, the biodegradable resin composition may contain the inorganic nucleating agent in a content of 100 ppm to 10,000 ppm.

[0016] In one embodiment of the present invention, the inorganic nucleating agent may include at least one of rutile type titanium dioxide and anatase type titanium dioxide.

[0017] In one embodiment of the present invention, the average diameter (D 50 ) of the inorganic nucleating agent may be 0.1 μm to 0.5 μm.

[0018] In one embodiment of the present invention, the biodegradable resin composition may further contain an external lubricant.

[0019] In one embodiment of the present invention, the biodegradable resin composition may contain the external lubricant in a content of 100 ppm to 5,000 ppm.

[0020] In one embodiment of the present invention, the crystallization temperature (Tc) measured using the differential scanning calorimeter of the biodegradable resin composition may be 35°C to 90°C.

[0021] In one embodiment of the present invention, the value of the melt flow index measured under the conditions of 190°C and 2.16 kg of the biodegradable resin composition may be 2 g / 10 min to 60 g / 10 min.

[0022] In one embodiment of the present invention, the biodegradable resin composition may have a tensile strength of 25 MPa or more according to the following measuring method 2.

[0023] [Measuring method 2] 1) The biodegradable resin composition is made into a specimen with a thickness of 300 μm.

[0024] 2) For the specimen, the tensile strength is measured at a speed of 100 mm / min using a universal testing machine.

[0025] In one embodiment of the present invention, the elongation at break of the specimen measured using the universal testing machine may be 800% to 1,200%.

[0026] In one embodiment of the present invention, the isothermal crystallization time may be 40 seconds to 800 seconds.

[0027] The biodegradable molded article according to the present invention includes a first biodegradable resin containing a first repeating unit derived from a diol, a second repeating unit derived from an aromatic dicarboxylic acid, and a third repeating unit derived from an aliphatic dicarboxylic acid, and a crystallization accelerator. Based on the total weight of the biodegradable resin composition, the crystallization accelerator is contained in an amount of 100 ppm to 50,000 ppm, and the isothermal crystallization time at 90°C according to the following measuring method 3 is 10 seconds to 900 seconds.

[0028] [Measuring method 1] 1) After heating the biodegradable resin composition to 220°C at a heating rate of 10°C / min, it is maintained for 5 minutes.

[0029] 2) Then, after cooling the biodegradable resin composition to 90°C at a cooling rate of 100°C / min, it is maintained in an isothermal state for 100 minutes.

[0030] 3) Using a differential scanning calorimeter, measure the time that becomes half of the total area of the crystallization peak of the biodegradable resin composition with respect to the total area of the crystallization peak of the biodegradable resin composition.

[0031] In one embodiment of the present invention, the biodegradable molded article may be a nonwoven fabric, an injection molded product, or a foamed molded product.

[0032] The biodegradable nonwoven fabric according to the present invention includes a biodegradable resin composition containing a first biodegradable resin containing a diol, an aromatic dicarboxylic acid, and an aliphatic dicarboxylic acid, and the biodegradable resin composition has a first irreversible deformation rate measured by the following measurement method 3 of less than 30%.

[0033] [Measurement method 3] 1) With the biodegradable resin composition placed between a pair of flat stainless steel molds, compress it at a temperature of 200 °C and a pressure of 20 Mpa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0034] 2) Cut the sheet of the biodegradable resin composition to produce a sample including a test portion having a width of 3.18 mm and a length of 25 mm.

[0035] 3) The test portion is pulled at a speed of 10 mm / min in the length direction at room temperature. At this time, it is further pulled by 40% with respect to the total length of the test portion.

[0036] 4) The test portion recovers at room temperature for 5 minutes in a state without an external force.

[0037] 5) The first irreversible deformation rate is derived by the following formula 1.

[0038] [Formula 1] First irreversible deformation rate = (length of the test portion after recovery - 25 mm) / 25 mm

[0039] In one embodiment of the present invention, the biodegradable resin composition may have a second irreversible deformation rate measured by the following Measuring Method 4 of less than 20%.

[0040] [Measuring Method 4] 1) With the biodegradable resin composition placed between a pair of flat stainless steel molds, it is compressed at a temperature of 200 °C and a pressure of 20 Mpa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0041] 2) The sheet of the biodegradable resin composition is cut to produce a sample including a test portion having a width of 3.18 mm and a length of 25 mm.

[0042] 3) The test portion is pulled at a speed of 10 mm / min in the longitudinal direction at room temperature. At this time, it is further pulled by 30% with respect to the total length of the test portion.

[0043] 4) The test portion recovers at room temperature for 5 minutes in the absence of an external force.

[0044] 5) The second irreversible deformation rate is derived by the following formula 2.

[0045] [Formula 2] Second irreversible deformation rate = (length of the test portion after recovery - 25 mm) / 25 mm

[0046] In one embodiment of the present invention, the biodegradable resin composition may have a third irreversible deformation rate measured by the following Measuring Method 5 of less than 10%.

[0047] [Measuring Method 5] 1) With the biodegradable resin composition placed between a pair of flat stainless steel molds, it is compressed at a temperature of 200 °C and a pressure of 20 Mpa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0048] 2) The sheet of the biodegradable resin composition is cut to produce a sample including a test portion having a width of 3.18 mm and a length of 25 mm.

[0049] 3) The test portion is pulled at a speed of 10 mm / min in the length direction at normal temperature. At this time, it is further pulled by 20% with respect to the total length of the test portion.

[0050] 4) The test portion recovers at normal temperature for 5 minutes in the state without external force.

[0051] 5) The third irreversible deformation rate is derived by the following formula 3.

[0052] [Formula 3] Third irreversible deformation rate = (length of the test portion after recovery - 25 mm) / 25 mm

[0053] In one embodiment of the present invention, the biodegradable resin composition may have a fourth irreversible deformation rate measured by the following measuring method 6 of less than 5%.

[0054] [Measuring method 6] 1) With the biodegradable resin composition placed between a pair of flat stainless steel molds, it is compressed at a temperature of 200 °C and a pressure of 20 Mpa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0055] 2) The sheet of the biodegradable resin composition is cut to produce a sample including a test portion having a width of 3.18 mm and a length of 25 mm.

[0056] 3) The test portion is pulled at a speed of 10 mm / min in the length direction at normal temperature. At this time, it is further pulled by 10% with respect to the total length of the test portion.

[0057] 4) The test portion recovers at normal temperature for 5 minutes in the state without external force.

[0058] 5) The fourth non-reversible deformation rate is derived by the following formula 4.

[0059] [Formula 4] Fourth non-reversible deformation rate = (length of the test part after recovery - 25 mm) / 25 mm

[0060] In one embodiment of the present invention, the biodegradable resin composition further includes a second biodegradable resin, and the second biodegradable resin may include one or more selected from the group consisting of polybutylene succinate, polylactic acid, polybutylene adipate, polybutylene succinate-adipate, polybutylene succinate-terephthalate, polyhydroxybutyrate-valerate, polycaprolactone, and polybutylene succinate adipate terephthalate.

[0061] The biodegradable nonwoven fabric according to the present invention includes a biodegradable resin composition containing a first biodegradable resin including a diol, an aromatic dicarboxylic acid, and an aliphatic dicarboxylic acid. The biodegradable resin composition has a maximum loss tangent temperature by dynamic mechanical analysis of -40°C to 0°C, a minimum temperature of the rubber plateau region of less than 30°C, the rubber plateau region is further greater than the maximum loss tangent temperature, and a temperature range where the change rate of the loss tangent is less than 0.025 / 10°C.

[0062] The biodegradable resin composition according to the present invention includes a first biodegradable resin including a diol, an aromatic dicarboxylic acid, and an aliphatic dicarboxylic acid, and the first non-reversible deformation rate measured by the following measurement method 3 is less than 30%.

[0063] [Measurement method 3] 1) With the biodegradable resin composition placed between a pair of flat stainless steel molds, it is compressed at a temperature of 200°C and a pressure of 20 Mpa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0064] 2) The sheet of the biodegradable resin composition is cut to produce a sample including a test part having a width of 3.18 mm and a length of 25 mm.

[0065] 3) The test part is pulled at a speed of 10 mm / min in the length direction at room temperature. At this time, it is further pulled by 40% of the total length of the test part.

[0066] 4) The test part recovers at room temperature for 5 minutes in a state without external force.

[0067] 5) The first irreversible deformation rate is derived by the following formula 1.

[0068] [Formula 1] First irreversible deformation rate = (length of the test part after recovery - 25 mm) / 25 mm

[0069] The biodegradable resin composition according to the present invention contains a first biodegradable resin containing a diol, an aromatic dicarboxylic acid, and an aliphatic dicarboxylic acid, the temperature of the maximum loss tangent by dynamic mechanical analysis is -40°C to 0°C, the minimum temperature of the rubber plateau region is less than 30°C, the rubber plateau region is further larger than the temperature of the maximum loss tangent, and it is a temperature range where the change rate of the loss tangent is less than 0.025 / 10°C.

[0070] The biodegradable nonwoven fabric according to the present invention contains a biodegradable resin composition containing a first biodegradable resin containing a diol, an aromatic dicarboxylic acid, and an aliphatic dicarboxylic acid, the temperature of the maximum loss tangent measured by the following measurement method 7 is -40°C to 0°C, and the minimum temperature of the rubber plateau region is less than 30°C.

[0071] [Measurement method 7] 1) With the biodegradable resin composition placed between a pair of flat stainless steel molds, it is compressed at a temperature of 200°C and a pressure of 20 Mpa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0072] 2) The sheet of the biodegradable resin composition is cut to produce a sample including a test part having a width of 5 mm and a length of 12 mm.

[0073] 3) The test section measures the loss tangent due to temperature while rising from -40°C to 80°C by dynamic mechanical analysis.

[0074] 4) The temperature having the maximum value among the loss tangents is derived as the temperature of the maximum loss tangent.

[0075] 5) The temperature range where the change rate of the loss tangent is less than 0.025 / 10°C is derived as the rubber plateau region.

Advantages of the Invention

[0076] The biodegradable resin composition according to the present invention may be such that the type of biodegradable resin is selected, the content of the crystallization accelerator is adjusted, and it has an isothermal crystallization time that can be manufactured into a nonwoven fabric by a spinning process. Thereby, the biodegradable resin composition is excellent in spinnability and can suppress the phenomenon of fiber breakage in the spinning process. Further, the biodegradable resin composition may be excellent in injectability, excellent in mold release property in the injection process, and maintain the shape of the injection molded product. Further, the biodegradable resin composition is excellent in foamability, and when manufacturing a molded product, the foam expansion ratio can be increased, and a uniform foam cell size and the thickness of the molded product can be realized. Further, the biodegradable molded product manufactured from the biodegradable resin composition is excellent in mechanical properties, is naturally biodegradable, and has the effect of not requiring incineration or discharging harmful substances.

[0077] The biodegradable resin composition according to the present invention, and the biodegradable nonwoven fabric containing the same, by containing a biodegradable resin, when the life of the biodegradable nonwoven fabric ends, it is naturally biodegradable and has the effect of not requiring incineration or discharging harmful substances. The biodegradable resin composition according to the present invention can be manufactured from ultrafine fibers, and the biodegradable nonwoven fabric containing the ultrafine fibers may have a soft touch feeling. Further, the biodegradable nonwoven fabric has an irreversible deformation rate below a specific range and has a rubber plateau region in the temperature range where nonwoven fabrics are generally used, so that it can exhibit excellent stretchability.

Brief Description of the Drawings

[0078]

Figure 1

Figure 2

Figure 3

Mode for Carrying Out the Invention

[0079] The structural or functional description regarding the examples disclosed in this specification or the application is merely exemplified for the purpose of explaining the examples according to the technical idea of the present invention. The examples according to the technical idea of the present invention can be implemented in various forms in addition to the examples disclosed in this specification or the application, and the technical idea of the present invention is not to be construed as being limited to the examples described in this specification or the application.

[0080] Also, when a component in this specification or the application is described as "including", this means that, unless otherwise stated, it does not exclude other components and may further include other components. Also, any numerical range indicating physical property values, dimensions, etc. of the components described in this specification or the application must be understood to be modified by the term "about" in all cases unless otherwise specified. Also, "ppm" in this specification or the application means a weight basis. Also, the description of "A and / or B" in this specification or the application means "A, B, or A and B".

[0081] The biodegradable resin composition according to the present invention includes a first biodegradable resin including a first repeating unit derived from a diol, a second repeating unit derived from an aromatic dicarboxylic acid, and a third repeating unit derived from an aliphatic dicarboxylic acid.

[0082] The diol may be an aliphatic diol. The diol may be a bio-derived diol. The diol may be at least one selected from the group consisting of ethanediol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2,4-dimethyl-2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-octadecanediol, or derivatives thereof.

[0083] The diol may be at least one selected from the group consisting of 1,4-butanediol, 1,2-ethanediol, 1,3-propanediol, diethylene glycol, neopentyl glycol, or derivatives thereof.

[0084] The diol may be at least one selected from the group consisting of 1,4-butanediol, 1,2-ethanediol, 1,3-propanediol, or derivatives thereof.

[0085] The diol may contain 1,4-butanediol or a derivative thereof.

[0086] The aromatic dicarboxylic acid may be at least one selected from the group consisting of phthalic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, anthracenedicarboxylic acid, phenanthrenedicarboxylic acid, or derivatives thereof.

[0087] The aromatic dicarboxylic acid may be at least one selected from the group consisting of terephthalic acid, dimethyl terephthalate, 2,6-naphthalenedicarboxylic acid, isophthalic acid, or derivatives thereof.

[0088] The aromatic dicarboxylic acid may contain terephthalic acid, dimethyl terephthalate, or derivatives thereof.

[0089] The aliphatic dicarboxylic acid may be at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, or derivatives thereof.

[0090] The aliphatic dicarboxylic acid may be at least one selected from the group consisting of adipic acid, succinic acid, sebacic acid, or derivatives thereof.

[0091] The aliphatic dicarboxylic acid may contain adipic acid or a derivative thereof.

[0092] The molar ratio of the first repeating unit: the second repeating unit and the third repeating unit may be 1:0.9 to 1:1.1. The molar ratio of the first repeating unit: the second repeating unit and the third repeating unit may be 1:0.95 to 1:1.05. The molar ratio of the first repeating unit: the second repeating unit and the third repeating unit may be 1:0.98 to 1:1.03.

[0093] The molar ratio of the second repeating unit: the third repeating unit may be 3:7 to 7:3. The molar ratio of the second repeating unit: the third repeating unit may be 3.3:6.7 to 6.7:3.3. The molar ratio of the second repeating unit: the third repeating unit may be 4:6 to 6:4. The molar ratio of the second repeating unit: the third repeating unit may be 4.2:5.8 to 5:5.

[0094] When the above ranges are satisfied, the spinning ability of the biodegradable resin composition can be improved.

[0095] The first biodegradable resin may contain a first repeating unit derived from 1,4-butanediol in a content of about 90 mol% or more based on the total diol. The first biodegradable resin may contain a first repeating unit derived from 1,4-butanediol in a content of about 95 mol% or more based on the total diol. The first biodegradable resin may contain a first repeating unit derived from 1,4-butanediol in a content of about 98 mol% or more based on the total diol.

[0096] The first biodegradable resin may contain a second repeating unit derived from terephthalic acid or dimethyl terephthalate in a content of about 30 mol% to about 70 mol% based on the total dicarboxylic acid. The first biodegradable resin may contain a second repeating unit derived from terephthalic acid or dimethyl terephthalate in a content of about 35 mol% to about 65 mol% based on the total dicarboxylic acid. The first biodegradable resin may contain a second repeating unit derived from terephthalic acid or dimethyl terephthalate in a content of about 40 mol% to about 60 mol% based on the total dicarboxylic acid. The first biodegradable resin may contain a second repeating unit derived from terephthalic acid or dimethyl terephthalate in a content of about 43 mol% to about 53 mol% based on the total dicarboxylic acid.

[0097] The first biodegradable resin may contain a third repeating unit derived from adipic acid in a content of about 30 mol% to about 70 mol% based on the total dicarboxylic acid. The first biodegradable resin may contain a third repeating unit derived from adipic acid in a content of about 35 mol% to about 65 mol% based on the total dicarboxylic acid. The first biodegradable resin may contain a third repeating unit derived from adipic acid in a content of about 40 mol% to about 60 mol% based on the total dicarboxylic acid. The first biodegradable resin may contain a third repeating unit derived from adipic acid in a content of about 47 mol% to about 57 mol% based on the total dicarboxylic acid.

[0098] The biodegradable resin composition may further contain one or more second biodegradable resins selected from the group consisting of polybutylene succinate, polylactic acid, polybutylene adipate, polybutylene succinate - adipate, polybutylene succinate - terephthalate, polyhydroxybutyrate - valerate, polycaprolactone, polybutylene adipate - co - butylene succinate terephthalate, and polybutylene succinate adipate terephthalate.

[0099] The weight ratio of the first biodegradable resin to the second biodegradable resin may be 1:99 to 30:70, 2:98 to 30:70, 3:97 to 30:70, 4:96 to 30:70, or 5:95 to 30:70. When the above range is satisfied, the biodegradable resin composition may have excellent spinning ability during the spinning process, and the tensile strength and elongation rate of the produced biodegradable nonwoven fabric can be improved.

[0100] Preferably, the second biodegradable resin may contain polylactic acid.

[0101] The polylactic acid may be a high melting point polylactic acid having stereocomplex crystals. Also, the polylactic acid may be formed by solution mixing or melt mixing of poly-L-lactic acid and poly-D-lactic acid.

[0102] The polylactic acid may contain units represented by Chemical Formula 1 below.

[0103] JPEG2025089271000002.jpg5058

[0104] The polylactic acid may be a polymer containing L-lactic acid units and / or D-lactic acid units. The polylactic acid may contain poly-L-lactic acid and / or poly-D-lactic acid.

[0105] The poly-L-lactic acid may be a polymer mainly containing L-lactic acid units. The poly-L-lactic acid may contain L-lactic acid units in a content of about 90 mol% to about 100 mol%, about 95 mol% to about 100 mol%, or about 97 mol% to about 100 mol%. The poly-L-lactic acid may contain D-lactic acid units and / or units other than lactic acid. The poly-L-lactic acid may contain the D-lactic acid units and / or units other than lactic acid in a content of about 0 mol% to about 10 mol%, about 0 mol% to about 5 mol%, or about 0 mol% to about 3 mol%.

[0106] The poly-D-lactic acid may be a polymer mainly containing D-lactic acid units. The poly-D-lactic acid may contain the D-lactic acid units in a content of about 90 mol% to about 100 mol%, about 95 mol% to about 100 mol%, or about 97 mol% to about 100 mol%. The poly-D-lactic acid may contain the L-lactic acid units and / or units other than lactic acid. The poly-D-lactic acid may contain the L-lactic acid units and / or units other than lactic acid in a content of about 0 mol% to about 10 mol%, about 0 mol% to about 5 mol%, or about 0 mol% to about 3 mol%.

[0107] The units other than lactic acid may be units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, etc. having functional groups capable of forming two or more ester bonds, and units derived from various polyesters, various polyethers, various polycarbonates, etc. composed of these various components.

[0108] Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, etc. Examples of the polyhydric alcohol include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, etc., or aromatic polyhydric alcohols such as those obtained by adding ethylene oxide to bisphenol.

[0109] Examples of the hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid, etc. Examples of the lactone include glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, δ-valerolactone, etc.

[0110] The polylactic acid may be commercially available under the name BIOMER L9000 from Biomer, Inc. Also, the polylactic acid may be commercially available from Natureworks LLC (Natureworks (R)) or Mitsui Chemical (LACEA). TM Further, the polylactic acid may be one described in U.S. Patent Nos. 4,797,468, 5,470,944, 5,770,682, 5,821,327, 5,880,254, and 6,326,458, the entire texts of which are incorporated herein by reference for all purposes. TM The melting temperature (Tm) of the polylactic acid may be about 100°C to about 240°C. The melting temperature of the polylactic acid may be about 120°C to about 220°C. The melting temperature of the polylactic acid may be about 140°C to about 200°C. The melting temperature of the polylactic acid may be about 140°C to about 180°C.

[0111] The crystallization temperature (Tc) of the polylactic acid may be about 50°C to about 80°C. The crystallization temperature of the polylactic acid may be about 55°C to about 75°C.

[0112] The glass transition temperature (Tg) of the polylactic acid may be about 20°C to about 80°C. The glass transition temperature of the polylactic acid may be about 30°C to about 70°C. The glass transition temperature of the polylactic acid may be about 40°C to about 65°C. The melting temperature and the glass transition temperature can be measured by a differential scanning calorimeter (DSC) in accordance with ASTM D-3417.

[0113]

[0114] ​The polylactic acid can be easily extruded by having a melting temperature and a glass transition temperature within the above ranges. Further, the polylactic acid may have improved mechanical properties of the biodegradable nonwoven fabric produced by having a melting temperature and a glass transition temperature within the above ranges.

[0115] The biodegradable resin composition according to the present invention contains a crystallization accelerator, and the crystallization accelerator is contained in an amount of 100 ppm to 50,000 ppm based on the total weight of the biodegradable resin composition. The crystallization accelerator may be contained in an amount of 100 ppm to 50,000 ppm, 100 ppm to 40,000 ppm, 100 ppm to 30,000 ppm, 100 ppm to 10,000 ppm, or 100 ppm to 6,000 ppm based on the total weight of the biodegradable resin composition.

[0116] The crystallization accelerator may be mixed in the polymerization reaction of the first biodegradable resin and / or the compounding step with the first biodegradable resin.

[0117] Further, the biodegradable resin composition containing a crystallization accelerator having the above content range may have an appropriate isothermal crystallization time that can be produced into a nonwoven fabric by a spinning process.

[0118] Thereby, the biodegradable resin composition is excellent in spinnability and can suppress the phenomenon of fiber breakage in the spinning process.

[0119] Further, the biodegradable resin composition may be excellent in injectability, excellent in mold release property in the injection process, and maintain the shape of the injection molded product.

[0120] Further, the biodegradable resin composition is excellent in foamability, and when producing a biodegradable molded product, the foaming ratio can be increased, and the size of uniform foam cells and the thickness of the molded product can be realized.

[0121] The crystallization accelerator may contain at least one of an organic nucleating agent and an inorganic nucleating agent.

[0122] The organic nucleating agent may mean a nucleating agent composed of an organic compound.

[0123] The biodegradable resin composition may contain the organic nucleating agent in a content of 10 ppm to 5,000 ppm, 10 ppm to 3,000 ppm, 10 ppm to 1,000 ppm, or 100 ppm to 500 ppm.

[0124] The organic nucleating agent may contain nanocellulose having an average length of 10 nm to 300 nm, 10 nm to 200 nm, 20 nm to 200 nm, or 30 nm to 200 nm.

[0125] The content of the nanocellulose may be 10 ppm to 500 ppm, 50 ppm to 500 ppm, 50 ppm to 300 ppm, or 50 ppm to 200 ppm with respect to the total weight of the biodegradable resin composition. When the above range is satisfied, the crystallization rate can be improved, the fusion between fibers can be suppressed during the spinning process, and the denier can be adjusted. Also, the mold release property in the injection process is excellent, and the shape of the injection molded product can be maintained. Further, the foaming ratio in the foaming process can be increased, and the size of uniform foam cells and the thickness of the molded product can be realized.

[0126] The nanocellulose may be pretreated with a bead mill or ultrasonic waves. The nanocellulose may be pretreated with both a bead mill and ultrasonic waves. The nanocellulose is preferably pretreated with ultrasonic waves after bead mill pretreatment to prevent re-aggregation and improve dispersibility.

[0127] The bead mill pretreatment can be carried out using a vertical mill or a horizontal mill as a wet milling device. Although the horizontal mill can hold a larger amount of beads inside the chamber, which is preferable in terms of reducing mechanical eccentric wear, reducing bead wear, and facilitating maintenance, it is not limited thereto.

[0128] The bead mill pretreatment can be carried out using one or more beads selected from the group consisting of zirconium, zircon, zirconia, quartz, and aluminum oxide.

[0129] The bead mill pretreatment can be carried out using beads having a diameter of about 0.3 mm to about 1 mm. For example, the diameter of the beads may be about 0.3 mm to about 0.9 mm, about 0.4 mm to about 0.8 mm, about 0.45 mm to about 0.7 mm, or about 0.45 mm to about 0.6 mm. When the above range is satisfied, the dispersibility of the nanocellulose can be improved.

[0130] The ultrasonic pretreatment means a method of physically closing or pulverizing nanoparticles by waves generated by emitting ultrasonic waves of 20 kHz into a solution.

[0131] The ultrasonic pretreatment can be carried out with an output of 30,000 J / s or less for a time of less than 30 minutes. For example, the ultrasonic pretreatment can be carried out with an output of 25,000 J / s or less or 22,000 J / s or less for a time of 25 minutes or less, 20 minutes or less, or 18 minutes or less. When the above range is satisfied, the effect of the ultrasonic pretreatment, that is, the improvement of dispersibility, can be maximized.

[0132] The inorganic nucleating agent may mean a nucleating agent composed of an inorganic compound.

[0133] The biodegradable resin composition may contain the inorganic nucleating agent in a content of 100 ppm to 10,000 ppm, 100 ppm to 8,000 ppm, 300 ppm to 8,000 ppm, 500 ppm to 8,000 ppm, or 500 ppm to 6,000 ppm. When the above range is satisfied, the phenomenon of yarn breakage of the fiber in the spinning process can be suppressed, and the spinning process can be carried out smoothly. Also, the mold release property in the injection process is excellent, and the shape of the injection molded product can be maintained. Further, the foaming ratio in the foaming process can be increased, and a uniform cell size and the thickness of the molded product can be realized.

[0134] The inorganic nucleating agent may contain one or more selected from the group consisting of titanium dioxide, talc, kaolinite, montmorillonite, mica, clay, zeolite, silica, graphite, carbon black, mica, barium sulfate, calcium silicate, calcium carbonate, calcium sulfide, calcium titanate, zinc oxide, aluminum oxide, magnesium oxide, neodymium oxide, and boron nitride.

[0135] The inorganic nucleating agent may contain at least one or more of rutile type titanium dioxide and anatase type titanium dioxide.

[0136] Preferably, the inorganic nucleating agent may contain anatase type titanium dioxide. The anatase type titanium dioxide exhibits high photoactivity and can further improve biodegradability.

[0137] The average diameter (D 50 ) of the inorganic nucleating agent may be 0.1 μm to 0.5 μm, 0.1 μm to 0.4 μm, 0.15 μm to 0.4 μm, 0.15 μm to 0.3 μm, or 0.15 μm to 0.25 μm. When the above range is satisfied, the kneadability with the first biodegradable resin and the mechanical strength of the biodegradable resin composition can be improved.

[0138] The biodegradable resin composition may further contain an external lubricant.

[0139] When mixing, melting, and processing the raw materials, the external lubricant can reduce the generation of heat due to friction, has excellent dispersion effect on the first biodegradable resin, excellent lubrication effect, and can improve the manufacturing efficiency.

[0140] The external lubricant may be selected from the group consisting of carbodiimide lubricants, ester lubricants, amide lubricants, paraffin lubricants, and stearate lubricants.

[0141] The external lubricant may contain a stearate lubricant.

[0142] Calcium stearate and / or stearyl stearate can be used as the external lubricant.

[0143] The biodegradable resin composition may contain the external lubricant in an amount of 100 ppm to 5,000 ppm, 200 ppm to 5,000 ppm, 200 ppm to 4,000 ppm, 200 ppm to 3,000 ppm, 200 ppm to 2,000 ppm, 300 ppm to 2,000 ppm, 400 ppm to 2,000 ppm, or 500 ppm to 2,000 ppm. When the above range is satisfied, the mechanical properties of the biodegradable resin composition can be improved without decreasing, and the manufacturing efficiency can be enhanced.

[0144] The biodegradable resin composition may contain a branching agent containing at least one of a trihydric or higher alcohol and a trihydric or higher carboxylic acid. The branching agent can react with the diol, the aliphatic dicarboxylic acid, and / or the aromatic dicarboxylic acid. The branching agent may be included as a part of the molecular structure of the first biodegradable resin.

[0145] The trihydric or higher alcohol may be at least one selected from the group consisting of glycerol, pentaerythritol, and trimethylolpropane.

[0146] The trivalent or higher carboxylic acid may be at least one selected from the group consisting of methane tricarboxylic acid, ethanetricarboxylic acid, citric acid, benzene-1,3,5-tricarboxylic acid, 5-sulfo-1,2,4-benzenetricarboxylic acid, ethane-1,1,2,2-tetracarboxylic acid, propane-1,1,2,3-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, and benzene-1,2,4,5-tetracarboxylic acid.

[0147] The branching agent may contain glycerol.

[0148] The content of the branching agent may be 500 ppm to 3,000 ppm, 700 ppm to 3,000 ppm, 700 ppm to 2,500 ppm, or 1,000 ppm to 2,000 ppm with respect to the total weight of the biodegradable resin composition. When the above range is satisfied, the nonwoven fabric produced from the biodegradable resin composition may have appropriate biodegradability and the mechanical properties can be improved.

[0149] The biodegradable resin composition may contain a heat stabilizer. The heat stabilizer may be at least one selected from the group consisting of amine-based high-temperature heat stabilizers such as tetraethylenepentamine, triethyl phosphonoacetate, phosphoric acid, phosphorous acid, polyphosphric acid, trimethyl phosphate (TMP), triethyl phosphate, trimethyl phosphine, and triphenyl phosphine.

[0150] The heat stabilizer may contain triethyl phosphonoacetate.

[0151] The content of the heat stabilizer may be 10 ppm to 3,000 ppm, 20 ppm to 2,000 ppm, 20 ppm to 1,500 ppm, or 20 ppm to 1,000 ppm based on the total weight of the biodegradable resin composition. When the above range is satisfied, the deterioration of the polymer due to high temperature during the reaction process can be controlled, the end groups of the polymer can be reduced, and the color can be improved.

[0152] The biodegradable resin composition has an isothermal crystallization time of 10 seconds to 900 seconds at 90 °C according to the following Measuring Method 1.

[0153] [Measuring Method 1] 1) After heating the biodegradable resin composition to 220 °C at a heating rate of 10 °C / min, maintain it for 5 minutes.

[0154] 2) Then, after cooling the biodegradable resin composition to 90 °C at a cooling rate of 100 °C / min, maintain the isothermal state for 100 minutes.

[0155] 3) Using a differential scanning calorimeter, measure the time that is half of the total area of the crystallization peak of the biodegradable resin composition with respect to the total area of the crystallization peak of the biodegradable resin composition.

[0156] The isothermal crystallization time is to rapidly cool the biodegradable resin composition in a molten state and evaluate the time until crystallization.

[0157] A short isothermal crystallization time indicates that crystallization occurs rapidly. The fact that crystallization occurs rapidly may mean that the movement of molecules is suppressed at an early stage after cooling and a crystalline part is formed.

[0158] The isothermal crystallization time can be adjusted by whether or not the above-mentioned crystallization accelerator is included and its content.

[0159] The biodegradable resin composition having the isothermal crystallization time according to the measurement method 1 means the crystallization rate at which the biodegradable resin composition can be manufactured into a non-woven fabric by a spinning process, and may also have a meaning as an index for suppressing the occurrence of fusion between fibers and the phenomenon of thread breakage of fibers in the spinning process.

[0160] Also, the biodegradable resin composition having the isothermal crystallization time according to the measurement method 1 means the crystallization rate at which the biodegradable resin composition can be manufactured into an injection molded product by an injection process, and may also have a meaning as an index for excellent mold release properties in the injection process and maintaining the shape of the injection molded product.

[0161] Also, the biodegradable resin composition having the isothermal crystallization time according to the measurement method 1 means the crystallization rate at which the biodegradable resin composition can be manufactured into a foamed molded product by a foaming process, and may also have a meaning as an index for increasing the foaming ratio and realizing a uniform cell size and the thickness of the molded product.

[0162] Also, the fact that the biodegradable resin composition has an isothermal crystallization time by the measurement method 1 may have a meaning as an index indicating that the mechanical properties of the nonwoven fabric, injection molded product, and foam molded product produced from the biodegradable resin composition can be improved.

[0163] The biodegradable resin composition may have an isothermal crystallization time at 90°C by the measurement method 1 of 40 seconds to 800 seconds. Preferably, the biodegradable resin composition may have an isothermal crystallization time at 90°C by the measurement method 1 of 41 seconds to 795 seconds, 40 seconds to 790 seconds, 40 seconds to 785 seconds, or 41 seconds to 784 seconds. When the above range is satisfied, the biodegradable resin composition is excellent in spinnability and can suppress the phenomenon of yarn breakage of fibers in the spinning process. Also, the biodegradable resin composition is excellent in injectability, has excellent mold release properties in the injection process, and the form of the injection molded product may be maintained. Further, the biodegradable resin composition is excellent in foamability, and when producing a biodegradable molded product, the foam expansion ratio can increase, and a uniform cell size and the thickness of the molded product can be realized. Also, the mechanical properties of the biodegradable molded product produced from the biodegradable resin composition can be improved.

[0164] In the measurement method 1, the biodegradable resin composition may have an isothermal crystallization time of 240 seconds or less, 200 seconds or less, 180 seconds or less, or 130 seconds or less when the temperature is decreased to 70°C instead of decreasing to 90°C.

[0165] In the measurement method 1, the biodegradable resin composition may have an isothermal crystallization time of 120 seconds or less, 100 seconds or less, 80 seconds or less, or 60 seconds or less when the temperature is decreased to 50°C instead of decreasing to 90°C.

[0166] When the above range is satisfied, a nonwoven fabric, an injection molded product, and a foam molded product may be produced from the biodegradable resin composition, and the mechanical properties can be improved.

[0167] The biodegradable resin composition may have a crystallization temperature (Tc) measured using the differential scanning calorimeter of 35°C to 90°C, 40°C to 90°C, 45°C to 90°C, 45°C to 85°C, or 50°C to 83°C.

[0168] The biodegradable resin composition may have a melting temperature (Tm). The melting temperature can be measured by the differential scanning calorimeter. The biodegradable resin composition may have a melting temperature of 100°C to 180°C, 100°C to 150°C, 110°C to 130°C, or 119°C to 124°C.

[0169] The biodegradable resin composition may have a glass transition temperature (Tg). The glass transition temperature can be measured by the differential scanning calorimeter. The biodegradable resin composition may have a glass transition temperature of -50°C to 0°C, -40°C to 0°C, -40°C to -20°C, or -33°C to -28°C.

[0170] The biodegradable resin composition may have a melt flow rate value measured under the conditions of 190°C and 2.16 kg of 2 g / 10 min to 60 g / 10 min, 2 g / 10 min to 50 g / 10 min, 3 g / 10 min to 50 g / 10 min, or 4 g / 10 min to 45 g / 10 min.

[0171] When the ranges of the crystallization temperature, melting temperature, and glass transition temperature are satisfied, the discharge amount of the biodegradable resin composition is uniform during the spinning process, it has excellent spinning ability, excellent mold release property during the injection process, and has a uniform cell size in the foaming process.

[0172] The biodegradable resin composition may have a tensile strength according to the following Measuring Method 2 of 25 MPa or more, 27 MPa or more, 29 MPa or more, 31 MPa or more, or 31 MPa or more to 50 MPa or less.

[0173] [Measuring Method 2] 1) Manufacture the biodegradable resin composition into a specimen with a thickness of 300 μm.

[0174] 2) For the test piece, use a universal testing machine to measure the tensile strength at a speed of 100 mm / min.

[0175] The elongation at break of the test piece measured using the universal testing machine may be 800% - 1,200%, 800% - 1,100%, 800% - 1,000%, 800% - 950%, or 805% - 940%.

[0176] The tensile strength and elongation at break of the biodegradable resin composition may be indicators showing the mechanical properties of the biodegradable resin composition. The tensile strength and elongation at break of the biodegradable resin composition may vary depending on whether or not it contains the above-described crystallization accelerator and its content. When the above range is satisfied, formation of beads of the biodegradable molded article can be suppressed, and it may have mechanical strength that can be used as a biodegradable molded article.

[0177] Figure 1 schematically shows an apparatus for manufacturing a biodegradable resin composition according to an example. Referring to Figure 1, the apparatus may include a slurry stirrer 100, an esterification reaction section 200, a polycondensation reaction section 300, a post-treatment section 400, a first recovery section 510, and a second recovery section 520.

[0178] The step of manufacturing the biodegradable resin composition may include the step of manufacturing a slurry containing the diol and the aromatic dicarboxylic acid.

[0179] The step may include the step of mixing and treating the diol and the aromatic dicarboxylic acid.

[0180] The step is a pre-treatment step before the esterification reaction, and may be a step of mixing the diol and the aromatic dicarboxylic acid and slurrying them. At this time, the diol may contain a diol component based on biomass.

[0181] The diol and the aromatic dicarboxylic acid may be put into the slurry stirrer 100 and stirred to produce the slurry. By mixing and pre-treating the diol and the aromatic dicarboxylic acid to form a slurry, not only can the diol and the aromatic dicarboxylic acid react uniformly, but it is also effective for quickly carrying out the esterification reaction rate, so the reaction efficiency can be enhanced. In particular, when the aromatic dicarboxylic acid such as terephthalic acid has complete crystallinity and is in powder form, its solubility in the diol is very low, and a homogeneous reaction may not easily occur. Therefore, the pre-treatment process of forming the slurry can play a very important role in realizing the excellent physical properties of the biodegradable nonwoven fabric according to the present invention.

[0182] When the aromatic dicarboxylic acid is terephthalic acid, the terephthalic acid has complete crystallinity and is a white crystal that sublimes at nearly 300 °C at normal pressure without a melting point, and its solubility in the diol is very low, and a homogeneous reaction may not easily occur. Therefore, when a pre-treatment process is carried out before the esterification reaction, since it reacts with the diol within the solid matrix of terephthalic acid, the surface area can be increased to induce a uniform reaction.

[0183] When the aromatic dicarboxylic acid is dimethyl terephthalic acid, due to the pre-treatment process, the dimethyl terephthalic acid can be made into a molten state at about 142 °C to 170 °C and reacted with the diol, so that the esterification reaction rate can be made faster and more efficiently.

[0184] On the other hand, in the pre-treatment stage of manufacturing the slurry, the structure and physical properties of the biodegradable resin composition may change depending on the particle size, particle size distribution, pre-treatment reaction conditions, etc. of the aromatic dicarboxylic acid.

[0185] The aromatic dicarboxylic acid may contain terephthalic acid. The average particle diameter (D) of the terephthalic acid is measured by a particle size analyzer Microtrac S3500 in the particle size distribution (PSD).50 ) may be 10 μm to 400 μm, and the standard deviation with respect to the average particle size (D 50 ) may be 100 or less. The standard deviation means the square root of the variance. The average particle size (D 50 ) of the terephthalic acid may be 20 μm to 200 μm, 30 μm to 180 μm, or 50 μm to 150 μm. When the average particle size (D 50 ) of the terephthalic acid satisfies the above range, it may be more advantageous in terms of improving the solubility in the diol and the reaction rate.

[0186] In the pretreatment step, the diol and the aromatic dicarboxylic acid can be mixed and charged into the slurry stirrer 100 (tank).

[0187] The slurry stirrer 100 may have an anchor type at the lowermost part, and the height to the agitator may be 20 mm or more. Also, a stirrer having two or more rotating blades may be more advantageous for achieving an efficient stirring effect.

[0188] The slurry stirrer 100 may have a height to the agitator of 20 mm or more, that is, the space between the reactor and the lowermost part of the agitator is almost attached. In this case, a slurry can be obtained without precipitation. If the pattern, form, and rotating blades of the agitator do not satisfy the above conditions, when the diol and the aromatic dicarboxylic acid are initially mixed, the aromatic dicarboxylic acid may settle to the bottom, and in this case, phase separation may occur.

[0189] The pretreatment step of manufacturing the slurry may include a step of mixing the diol and the aromatic dicarboxylic acid and stirring at about 30 °C to about 100 °C, at about 50 rpm to about 200 rpm, for 10 minutes or more or for 10 minutes to 200 minutes.

[0190] The diol may have the same characteristics as described above.

[0191] The diol may be introduced all at once or in portions.

[0192] The diol may be introduced separately when mixing with the aromatic dicarboxylic acid and when mixing with the aliphatic dicarboxylic acid. The aromatic dicarboxylic acid may have the same characteristics as described above. In the pretreatment stage of manufacturing the slurry, the molar ratio of the diol to the aromatic dicarboxylic acid may be about 0.8:1 to about 1.2:1. In the pretreatment stage of manufacturing the slurry, the molar ratio of the diol to the aromatic dicarboxylic acid may be about 0.9:1 to about 1.1:1. When the diol is introduced in an amount even more than the aromatic dicarboxylic acid, the aromatic dicarboxylic acid can be easily dispersed.

[0193] The stage may include a stage of subjecting the slurry and the aliphatic dicarboxylic acid to an esterification reaction to produce a prepolymer. The slurry and the aliphatic dicarboxylic acid can react in the ester reaction unit 200. By using the slurry in the esterification reaction, the reaction time can be shortened.

[0194] The slurry obtained in the pretreatment stage can shorten the reaction time of the ester reaction by 1.5 times or more. The esterification reaction can be carried out at least twice or more. A prepolymer to be introduced into the polycondensation step can be formed by the esterification reaction.

[0195] For example, the esterification reaction can be carried out all at once after the aliphatic dicarboxylic acid, or the diol and the aliphatic dicarboxylic acid are introduced into the slurry. That is, the slurry is introduced into the esterification reactor, and the aliphatic dicarboxylic acid alone, or the aliphatic dicarboxylic acid and the diol are introduced into the esterification reaction unit 200 to carry out the esterification reaction.

[0196] The esterification reaction can be carried out at about 250 °C or lower for about 0.5 hours to about 5 hours. Specifically, the esterification reaction can be carried out at about 180 °C to about 250 °C, about 185 °C to about 240 °C, or about 200 °C to about 240 °C under normal pressure or reduced pressure until the by-product water theoretically reaches 95%. For example, the esterification reaction can be carried out for 0.5 hours to 5.5 hours, 0.5 hours to 4.5 hours, or 1 hour to 4 hours, but is not limited thereto.

[0197] At least one of the polycarbonate diol and the polyether polyol can be mixed with the slurry to carry out the first esterification reaction. Differently, at least one of the polycarbonate diol and the polyether polyol may be introduced into the second esterification reaction.

[0198] Further, after the first ester reaction, a mixture of the aliphatic dicarboxylic acid and the diol can be introduced into the esterification reaction section 200 to carry out the second ester reaction together with the first ester reaction product. Also, at least one of the polycarbonate diol and the polyether polyol may be introduced into the second esterification reaction.

[0199] The first ester reaction can be carried out at 250 °C or lower for 1.25 hours to 4 hours. Specifically, the first esterification reaction can be carried out at 180 °C to 250 °C, 185 °C to 240 °C, or 200 °C to 240 °C under normal pressure or reduced pressure until the by-product water theoretically reaches 95%. For example, the first esterification reaction can be carried out for 1.25 hours to 4 hours, 1.25 hours to 3.5 hours, or 2.5 hours to 3 hours, but is not limited thereto.

[0200] The second ester reaction can be carried out at about 250 °C or lower for 0.25 hours to 3.5 hours. Specifically, the second esterification reaction can be carried out at 180 °C to 250 °C, 185 °C to 240 °C, or 200 °C to 240 °C under normal pressure or reduced pressure until the by-product water theoretically reaches 95%. For example, the second esterification reaction can be carried out for 0.5 hours to 3 hours, 1 hour to 2.5 hours, or 1.5 hours to 2.5 hours, but is not limited thereto.

[0201] When the ester reaction is carried out separately as the first ester reaction and the second ester reaction, the overall ester reaction can be precisely controlled. Thereby, when the ester reaction is carried out separately, the reaction stability and reaction uniformity of the ester reaction can be improved.

[0202] A prepolymer can be formed by the esterification reaction.

[0203] The number average molecular weight of the prepolymer may be about 500 g / mol to about 10,000 g / mol. For example, the number average molecular weight of the prepolymer may be about 500 g / mol to about 8,500 g / mol, about 500 g / mol to about 8,000 g / mol, about 500 g / mol to about 7,000 g / mol, about 500 g / mol to about 5,000 g / mol, or about 800 g / mol to about 3,000 g / mol. By satisfying the above range of the number average molecular weight of the prepolymer, the molecular weight of the polymer in the polycondensation reaction can be efficiently increased.

[0204] The number average molecular weight can be measured using gel permeation chromatography (GPC). Specifically, the data calculated by gel permeation chromatography has various items such as Mn, Mw, Mp, etc., among which the molecular weight can be measured based on the number average molecular weight (Mn).

[0205] The crystallization accelerator may be added together with the slurry before the esterification reaction.

[0206] The crystallization accelerator may be introduced into the esterification reaction section 200 during the esterification reaction.

[0207] The crystallization accelerator may be introduced into the ester reaction product after the esterification reaction.

[0208] The crystallization accelerator may be introduced together with the aliphatic dicarboxylic acid.

[0209] The crystallization accelerator may be introduced into the esterification reaction section 200 after the first esterification reaction and before the second esterification reaction. Since the crystallization accelerator is introduced into the esterification reaction, the crystallization accelerator may be uniformly dispersed in the first biodegradable resin. The crystallization accelerator may have the characteristics described above.

[0210] A titanium-based catalyst and / or a germanium-based catalyst can be used in the esterification reaction. Specifically, the titanium-based catalyst and / or the germanium-based catalyst can be added to the slurry to carry out the esterification reaction.

[0211] Before the first esterification reaction, the titanium-based catalyst and / or the germanium-based catalyst may be added to the slurry, and the titanium-based catalyst and / or the germanium-based catalyst may be further added to the product of the first esterification reaction.

[0212] The content of the catalyst may be about 100 ppm to 2,000 ppm based on the total weight of the diol, aromatic dicarboxylic acid, and aliphatic dicarboxylic acid. For example, it may contain a titanium-based catalyst or a germanium-based catalyst that is about 100 ppm to about 1,600 ppm, about 150 ppm to about 1,400 ppm, about 200 ppm to about 1,200 ppm, or about 250 ppm to about 1,100 ppm. By making the content of the catalyst satisfy the above range, the physical properties can be further improved.

[0213] The heat stabilizer may be introduced together with the slurry before the esterification reaction. The heat stabilizer may be introduced into the esterification reaction unit 200 during the esterification reaction. The heat stabilizer may be introduced into the ester reaction product after the esterification reaction. Further, the heat stabilizer may be introduced together with the aliphatic dicarboxylic acid. Further, the heat stabilizer may be introduced into the esterification reaction unit 200 after the first ester reaction and before the second ester reaction.

[0214] The characteristics of the heat stabilizer are as described above.

[0215] The content of the heat stabilizer may be 3,000 ppm or less based on the total weight of the diol, aromatic dicarboxylic acid, and aliphatic dicarboxylic acid. Specifically, the content of the heat stabilizer may be 10 ppm to 3,000 ppm, 20 ppm to 2,000 ppm, 20 ppm to 1,500 ppm, or 20 ppm to 1,000 ppm based on the total weight of the diol, aromatic dicarboxylic acid, and aliphatic dicarboxylic acid. By the content of the heat stabilizer satisfying the above range, the deterioration of the polymer due to high temperature during the reaction process can be controlled, the end groups of the polymer can be reduced, and the color can be improved.

[0216] After the esterification reaction is completed, one or more selected from the group consisting of additives such as silica, potassium, or magnesium, and color correctors such as cobalt acetate may be further added to the esterification reaction product. That is, after the esterification reaction is completed, after the additive and / or color corrector is introduced and stabilized, a polycondensation reaction can be carried out. The additive and / or the color corrector may be added after the esterification reaction is completed and introduced into the polycondensation reaction unit 300 together with the prepolymer.

[0217] After the esterification reaction is completed, the crystallization accelerator may be added to the esterification reaction product. After the esterification reaction is completed, the crystallization accelerator may be introduced and stabilized, and then the polycondensation reaction can be carried out. The crystallization accelerator may be introduced into the polycondensation reaction section 300 together with the prepolymer, and the polycondensation step may be carried out. Thereby, the crystallization accelerator may be uniformly dispersed in the first biodegradable resin.

[0218] The first recovery section 510 can recover reaction by-products such as water from the esterification reaction section 200. The first recovery section 510 can recover the by-products generated in the esterification reaction by applying a vacuum pressure to the esterification reaction section 200 or performing reflux.

[0219] The step may include a step of subjecting the prepolymer to a polycondensation reaction. The polycondensation reaction can be carried out as follows. The prepolymer may be introduced into the polycondensation reaction section 300. Further, the crystallization accelerator may be introduced into the polycondensation reaction section 300 together with the prepolymer.

[0220] Thereafter, the polycondensation reaction can be carried out at about 180°C to about 280°C and about 10 torr or less for about 1 hour to about 5 hours. For example, the polycondensation reaction can be carried out at about 190°C to about 270°C, about 210°C to about 260°C, or about 230°C to about 255°C, and at about 0.9 torr or less, about 0.7 torr or less, about 0.2 torr to about 10 torr, about 0.3 torr to about 0.9 torr, or about 0.4 torr to about 0.6 torr, and for about 1.5 hours to about 5 hours, about 2 hours to about 4.5 hours, or about 2 hours to about 4 hours.

[0221] The polycondensation reaction may include a primary polycondensation and a secondary polycondensation.

[0222] For example, the first polycondensation can be carried out at about 260 °C or lower, about 250 °C or lower, about 215 °C to about 250 °C, about 215 °C to about 245 °C, or about 230 °C to about 245 °C, at about 1 torr to about 200 torr, about 2 torr to about 100 torr, about 4 torr to about 50 torr, about 5 torr to about 45 torr, or about 8 torr to about 32 torr, for about 0.5 hours to about 3.5 hours, about 0.5 hours to about 3.0 hours, or about 0.5 hours to about 2.8 hours.

[0223] The second polycondensation can be carried out at about 220 °C to about 265 °C, about 230 °C to about 260 °C, or about 235 °C to about 255 °C, at about 1 torr or lower, about 0.8 torr or lower, about 0.6 torr or lower, about 0.1 torr to about 1 torr, about 0.3 torr to about 0.8 torr, or about 0.4 torr to about 0.6 torr, for about 0.5 hours to about 4 hours, about 1 hour to about 3.5 hours, or about 1.5 hours to about 3.5 hours.

[0224] Before the polycondensation reaction, a titanium-based catalyst or a germanium-based catalyst may be further added to the prepolymer. Also, before the polycondensation reaction, one or more selected from the group consisting of additives such as silica, potassium, or magnesium; amine-based stabilizers such as trimethyl phosphate, triphenyl phosphate, trimethylphosphine, phosphoric acid, phosphorous acid, or tetraethylenepentamine; and polymerization catalysts such as antimony trioxide, antimony trioxide, or tetrabutyl titanate can be further added to the prepolymer.

[0225] The number average molecular weight of the polymer may be about 20,000 g / mol or more. For example, the number average molecular weight of the polymer may be about 20,000 g / mol or more, about 30,000 g / mol or more, about 40,000 g / mol or more, about 43,000 g / mol or more, about 45,000 g / mol or more, or about 50,000 g / mol to about 70,000 g / mol. By the number average molecular weight of the polymer satisfying the above range, the physical properties, impact resistance, durability, and moldability can be further improved.

[0226] The second recovery unit 520 can recover reaction by-products such as water from the polycondensation reaction unit 300. The second recovery unit 520 can apply a vacuum pressure to the polycondensation reaction unit 300 to recover the by-products generated in the polycondensation reaction.

[0227] The second recovery unit 520 can apply a vacuum pressure of about 0.1 torr to about 1 torr inside the polycondensation reaction unit 300. The second recovery unit 520 can apply a vacuum pressure of about 0.1 torr to about 0.9 torr inside the polycondensation reaction unit 300.

[0228] The chain extender may be added to the polymer. The polymer and the chain extender may be uniformly mixed and maintained at a temperature of about 200°C to about 260°C for about 1 minute to about 15 minutes.

[0229] The above stage may include the stage of manufacturing pellets from the polymer. Specifically, after cooling the polymer to about 15 °C or lower, about 10 °C or lower, or about 6 °C or lower, the cooled polymer can be cut into pellets. The cutting stage can be carried out without limitation using a pellet cutting machine used in the industry, and the pellets may have various forms. In the method of cutting the pellets, an underwater cutting method or a strand cutting method can be used. The pellets can undergo further post-treatment processes. The pellets may be put into the post-treatment unit 400 and the post-treatment process may be carried out. The post-treatment process can be carried out within the post-treatment unit 400. The pellets may be put into the post-treatment unit 400. Thereafter, the post-treatment unit 400 can melt the input pellets by frictional heat and re-extrude them. That is, the post-treatment unit 400 may include an extruder such as a twin-screw extruder. The temperature of the post-treatment process may be about 230 °C to about 270 °C. The temperature of the post-treatment process may be about 230 °C to about 260 °C. The temperature of the post-treatment process may be about 240 °C to about 265 °C. The temperature of the post-treatment process may be about 240 °C to about 260 °C. The time of the post-treatment process may be about 30 seconds to about 3 minutes. The time of the post-treatment process may be about 50 seconds to about 2 minutes. The time of the post-treatment process may be about 1 minute to about 2 minutes. Thereafter, the resin extruded by the extruder may be cooled, cut, and processed into post-treated pellets. That is, the resin extruded from the extruder may be reprocessed into pellets by the above-described cutting stage. The crystallinity of the pellets can be improved in the post-treatment process. Also, the content of the residues contained in the pellets can be adjusted in the post-treatment process. In particular, the content of the oligomers contained in the pellets can be adjusted by the post-treatment process. The content of the residual solvent contained in the pellets can be adjusted by the post-treatment process.

[0230] The post-treatment process can appropriately adjust the crystallinity and mechanical properties of the biodegradable resin composition.

[0231] After the pellets are manufactured, the first biodegradable resin can be compounded with the aforementioned second biodegradable resin. Further, the crystallization accelerator can be compounded with the first biodegradable resin together with the second biodegradable resin.

[0232] The biodegradable molded article according to the present invention includes a first biodegradable resin containing a first repeating unit derived from a diol, a second repeating unit derived from an aromatic dicarboxylic acid, and a third repeating unit derived from an aliphatic dicarboxylic acid, and a crystallization accelerator. Based on the total weight of the biodegradable resin composition, the crystallization accelerator is contained in an amount of 100 ppm to 50,000 ppm, and the isothermal crystallization time at 90 °C by the following measurement method 1 is 10 seconds to 900 seconds.

[0233] [Measurement method 1] 1) After heating the biodegradable resin composition to 220 °C at a heating rate of 10 °C / min, it is maintained for 5 minutes.

[0234] 2) Then, after cooling the biodegradable resin composition to 90 °C at a cooling rate of 100 °C / min, an isothermal state is maintained for 100 minutes.

[0235] 3) Using a differential scanning calorimeter, the time that becomes half of the total area of the crystallization peak of the biodegradable resin composition is measured with respect to the total area of the crystallization peak of the biodegradable resin composition.

[0236] The biodegradable molded article may be a non-woven fabric, an injection molded product, or a foamed molded product.

[0237] The non-woven fabric may include a step of manufacturing biodegradable raw yarn from the biodegradable resin composition by a spinning process, a step of cooling the biodegradable raw yarn, a step of stretching the biodegradable raw yarn, and a step of bonding the cooled biodegradable raw yarns to form a biodegradable raw yarn web.

[0238] The spinning process may include a step of melting the biodegradable resin composition and feeding it into a spinning block. In the spinning block, the melted biodegradable resin composition from an extruder can be spun from a nozzle. The biodegradable resin composition may form filaments by the spinning block. The filaments may be solidified and crystallized by cooling to produce undrawn biodegradable raw yarns.

[0239] There may be a plurality of the nozzles. The number of the nozzles may be 2fila to 30fila, 10fila to 30fila, or 18fila to 30fila. A plurality of the filaments can be produced from the biodegradable resin composition by the plurality of nozzles. The pressure of the nozzle at about 220 °C is 80 kg / cm 2 ~120 kg / cm 2 、90 kg / cm 2 ~120 kg / cm 2 、90 kg / cm 2 ~110 kg / cm 2 、or 95 kg / cm 2 ~105 kg / cm 2 and may be. The spinning temperature in the spinning block may be 180 °C to 250 °C, 190 °C to 250 °C, 190 °C to 240 °C, or 190 °C to 230 °C.

[0240] The biodegradable resin composition in the spinning process may have a melt flow index within a specific range.

[0241] The biodegradable resin composition may have a melt flow rate value measured under the conditions of 190°C and 2.16 kg of 2 g / 10 min to 60 g / 10 min, 2 g / 10 min to 50 g / 10 min, 3 g / 10 min to 50 g / 10 min, or 4 g / 10 min to 45 g / 10 min.

[0242] When the above range is satisfied, the discharge amount of the biodegradable resin composition during the spinning process is uniform, and it can have excellent spinning ability. The raw yarn of the biodegradable nonwoven fabric produced from the biodegradable resin composition can be uncut, and the tensile strength and elongation rate can be improved.

[0243] The step may include a step of cooling the biodegradable raw yarn.

[0244] The biodegradable raw yarn may be an undrawn biodegradable raw yarn produced from the biodegradable resin composition.

[0245] The cooling can be carried out at about 1°C to 15°C, 1°C to 13°C, 2°C to 13°C, or 5°C to 13°C. The cooling can be carried out in a quench chamber. The length of the quench chamber may be about 1 m to 5 m, about 1 m to 4 m, about 1 m to 3 m, or about 1 m to 2 m.

[0246] When the above range is satisfied, the phenomenon of mutual fusion between adjacent undrawn biodegradable raw yarns can be suppressed.

[0247] The step may include a step of stretching the cooled biodegradable raw yarn.

[0248] By the stretching step, a biodegradable raw yarn stretched 1.1 times to 3 times, 1.2 times to 3 times, 1.2 times to 2.7 times, 1.2 times to 2.6 times, or 1.2 times to 2.5 times compared to the undrawn biodegradable raw yarn can be produced.

[0249] The stretched biodegradable raw yarn may be heat-treated at an appropriate temperature.

[0250] The extended biodegradable raw yarn may be wound. The extended biodegradable raw yarn may be wound by a winding machine. The winding speed of the winding machine may be 300 m / min to 3,000 m / min, 300 m / min to 2,500 m / min, 400 m / min to 2,500 m / min, 500 m / min to 2,500 m / min, or 250 m / min to 2,000 m / min. When the above range is satisfied, the phenomenon that the biodegradable raw yarns fuse or cut each other can be suppressed.

[0251] The biodegradable raw yarn may have a tensile strength of 0.5 g / de to 5.0 g / de, 0.5 g / de to 5.0 g / de, 0.5 g / de to 5.0 g / de, 0.5 g / de to 5.0 g / de, or 1.0 g / de to 3.0 g / de. The biodegradable raw yarn may have an elongation at break of 20% to 400%, 20% to 300%, 25% to 300%, 25% to 250%, 30% to 250%, or 35% to 200%. The biodegradable raw yarn may have a tensile strength of 1.0 g / de to 3.0 g / de and an elongation at break of 35% to 200%. When the above range is satisfied, the biodegradable raw yarns can be easily crimped to each other and can be easily applied to a biodegradable nonwoven fabric, and the mechanical strength of the biodegradable nonwoven fabric can be improved.

[0252] The biodegradable raw yarn may have an average diameter of 1 μm to 500 μm, 1 μm to 400 μm, 1 μm to 300 μm, 1 μm to 200 μm, or 10 μm to 100 μm. When the above range is satisfied, the biodegradable nonwoven fabric containing the biodegradable raw yarn has lightness, excellent strength, a high surface area and porosity, and can also be applied to products that require hygroscopicity.

[0253] The step may include a step of combining the cooled biodegradable raw yarns to form a biodegradable raw yarn web.

[0254] The method of binding the biodegradable raw fibers may be by means of a carding, air laid, water suspension, or spun bond process.

[0255] The carding process may mean a process in which the biodegradable raw fibers are laminated on a collector by a device including a plurality of gears to form a biodegradable raw fiber web.

[0256] The air laid process may mean a process in which the biodegradable raw fibers are arranged on a collector by a device moved by an air flow to form a biodegradable raw fiber web.

[0257] The water suspension process may mean a process in which the biodegradable raw fibers are dispersed in water, transferred onto a wire screen or a perforated drum, and then the residual moisture of the transferred biodegradable raw fibers is sucked, pressurized, and dried to form a biodegradable raw fiber web.

[0258] The spun bond process may mean a process in which the biodegradable raw fibers are formed into a Venturi web on a collector and then into a biodegradable raw fiber web.

[0259] The stage may further include a stage of binding the biodegradable raw fiber web by at least one or more processes of needle punching, spun lacing, stitch bonding, calendaring, and air through bonding.

[0260] By the above process, the bonding force between the biodegradable raw fiber webs can be strengthened, the tensile strength and elongation rate can be improved, and the generation of fluff on the biodegradable non-woven fabric can be prevented.

[0261] The needle punch process may mean a process of passing the biodegradable raw yarn web through needles so that the biodegradable raw yarns are entangled with each other by the barbs of the needles.

[0262] The spun lace process may mean a process of causing the biodegradable raw yarn web to bond by, on the one hand, injecting a high-pressure water stream and, on the other hand, absorbing the high-pressure water stream.

[0263] The stitch bond process may mean a process of causing the biodegradable raw yarn web to bond by a sewing thread and needles.

[0264] The calendaring process may mean a process of heat-sealing the biodegradable raw yarn web after applying pressure to it.

[0265] The air through bonding process may mean a process of causing the biodegradable raw yarn web to bond by hot air at a high temperature.

[0266] By the above process, the biodegradable nonwoven fabric according to the present invention can be manufactured.

[0267] The biodegradable nonwoven fabric has lightness, excellent strength, a high surface area and porosity, and can also be applied to products that require moisture absorption.

[0268] The biodegradable nonwoven fabric may contain yarns having an average diameter of 1 μm to 500 μm, 1 μm to 400 μm, 1 μm to 300 μm, 1 μm to 200 μm, or 10 μm to 100 μm.

[0269] The biodegradable nonwoven fabric may be processed. The biodegradable nonwoven fabric may be antistatically treated with an antistatic agent. The biodegradable nonwoven fabric may be water-repellent treated with a hydrophobic substance. The biodegradable nonwoven fabric may be water-repellent treated with an antibacterial substance.

[0270] The biodegradable nonwoven fabric may be embossed. The biodegradable nonwoven fabric may be printed. The biodegradable nonwoven fabric may be embossed or printed to a thickness and size suitable for the article to which it is applied.

[0271] The biodegradable resin composition may be manufactured into an injection molded product by an injection process.

[0272] The biodegradable resin composition may be a pelletized biodegradable resin composition.

[0273] The pelletized biodegradable resin composition may be manufactured into an injection molded product using an injection molding machine at an injection barrel temperature of 150°C to 250°C, 160°C to 250°C, 160°C to 240°C, or 160°C to 230°C.

[0274] The injection process may be by an injection molding method such as injection compression molding, injection press molding, gas assist injection molding, foam molding, insert molding, in-mold coating molding, adiabatic mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding.

[0275] The biodegradable resin composition may be excellent in injectability, excellent in mold release property in the injection process, and maintain the shape of the injection molded product.

[0276] The biodegradable resin composition may be manufactured into a foam molded product by a foaming process.

[0277] The biodegradable resin composition may contain a foaming agent.

[0278] The foaming agent is mixed with the biodegradable resin composition in a molten state, or injected under pressure, and may be one that undergoes a phase change from solid to gas or from liquid to gas, or may be a gas itself, and may be used to control the foaming ratio (foaming density) of the foamed sheet.

[0279] The foaming agent may contain one or more selected from the group consisting of aliphatic hydrocarbons, cycloaliphatic hydrocarbons, halogenated hydrocarbons, inorganic gases, and water.

[0280] The biodegradable resin composition is excellent in foamability, and when manufacturing a molded article, the foaming ratio can increase, and the size of uniform foam cells and the thickness of the molded article can be realized.

[0281] The biodegradable nonwoven fabric according to the present invention contains a biodegradable resin composition. The biodegradable resin composition contains a first biodegradable resin. The first biodegradable resin may be the same as the first biodegradable resin described above.

[0282] The biodegradable resin composition may further contain a second biodegradable resin. The second biodegradable resin may be the same as the second biodegradable resin described above.

[0283] The second biodegradable resin may be contained in an amount of less than 95%, 90% or less, 85% or less, 80% or less, more than 0% by weight to 80% or less based on the total weight of the biodegradable resin composition. When the above range is satisfied, the biodegradable nonwoven fabric produced from the biodegradable resin composition has a soft touch feeling, does not have a decrease in stretchability, and can improve mechanical properties.

[0284] The second biodegradable resin may contain polylactic acid. The polylactic acid may be the same as the polylactic acid described above.

[0285] The biodegradable resin composition may contain an inorganic filler.

[0286] The inorganic filler may be at least one selected from the group consisting of calcium sulfate, barium sulfate, talc, talcum powder, bentonite, kaolin, chalk powder, calcium carbonate, graphite, gypsum, electrically conductive carbon black, calcium chloride, iron oxide, aluminum oxide, potassium oxide, dolomite, silicon dioxide, wollastonite, titanium dioxide, silicate, mica, glass fiber, or mineral fiber.

[0287] Preferably, the inorganic filler may contain titanium dioxide (TiO 2 ). The titanium dioxide can act as a nucleating agent for the first biodegradable resin and / or the second biodegradable resin, and the crystallization rate can be improved. In addition, the phenomenon of adhesion of the biodegradable raw yarn produced from the biodegradable resin composition can be suppressed.

[0288] The cumulative D in the particle size distribution of the inorganic filler obtained by the laser diffraction method 50 may be about 100 μm or less, about 85 μm or less, about 70 μm or less, about 50 μm or less, about 25 μm or less, about 10 μm or less, about 5 μm or less, about 3 μm or less, or about 1 μm or less.

[0289] The specific surface area of the inorganic filler may be about 100 m 2 / g or more. For example, the specific surface area of the inorganic filler may be about 100 m 2 / g or more, about 105 m 2 / g or more, or about 110 m 2 / g or more.

[0290] The inorganic filler may be contained in an amount of 0.01% by weight to 5% by weight, 0.01% by weight to 4% by weight, 0.01% by weight to 3% by weight, 0.01% by weight to 2% by weight, 0.05% by weight to 2% by weight, or 0.05% by weight to 1% by weight based on the total weight of the biodegradable resin composition. When the above range is satisfied, it may minimize the increase in the weight of the biodegradable nonwoven fabric and have an appropriate biodegradation rate.

[0291] The biodegradable resin composition may contain an elongation improver.

[0292] The elongation improver may be an oil such as paraffin oil, naphthene oil, or aromatic oil, or may have an adipate such as dibutyl adipate, diethylhexyl adipate, dioctyl adipate, or diisopropyl adipate.

[0293] The elongation improver may be contained in an amount of 0.001% by weight to 1% by weight, 0.005% by weight to 1% by weight, 0.01% by weight to 1% by weight, 0.01% by weight to 0.8% by weight, or 0.01% by weight to 0.5% by weight based on the total weight of the biodegradable resin composition. When the above range is satisfied, the mechanical properties of the biodegradable nonwoven fabric can be improved.

[0294] The biodegradable resin composition may contain a metal salt.

[0295] The metal salt may be contained in an amount of about 0.1 ppm to about 1,000 ppm based on the total weight of the biodegradable resin composition. The metal salt may be contained in an amount of about 1 ppm to about 500 ppm based on the total weight of the biodegradable resin composition. The metal salt may be contained in an amount of about 1 ppm to about 100 ppm based on the total weight of the biodegradable resin composition. The metal salt may be contained in an amount of about 1 ppm to about 50 ppm based on the total weight of the biodegradable resin composition. When the above range is satisfied, the biodegradation rate of the biodegradable nonwoven fabric can be adjusted as appropriate. The metal salt may be at least one selected from the group consisting of nitrates, sulfates, hydrochlorides, carboxylates, etc. The metal salt may be at least one selected from the group consisting of sodium salts, calcium salts, potassium salts, magnesium salts, copper salts, iron salts, aluminum salts, silver salts, etc. The metal salt may be at least one selected from the group consisting of magnesium acetate, calcium acetate, potassium acetate, copper nitrate, silver nitrate, sodium nitrate, etc.

[0296] The biodegradable resin composition may contain a chain extender.

[0297] The chain extender may contain isocyanate. The chain extender may be at least one selected from the group consisting of monofunctional isocyanate and polyfunctional isocyanate. The chain extender may be at least one selected from the group consisting of tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, diphenylmethane 4,4'-diisocyanate, 2,4'-diisocyanate, naphthalene 1,5-diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate, and methylene bis(4-isocyanatocyclohexane). The chain extender may contain triisocyanate. The chain extender may contain tris(4-isocyanatophenyl)methane. The chain extender may be chemically bonded to the first biodegradable resin and / or the second biodegradable resin. The chain extender may be chemically bonded to the polymer contained in the first biodegradable resin and / or the second biodegradable resin. The chain extender may be bonded to the end of the polymer contained in the first biodegradable resin and / or the second biodegradable resin. Further, the chain extender may be bonded to the ends of three polymers contained in the first biodegradable resin and / or the second biodegradable resin.

[0298] The chain extender may be contained in an amount of 0.1% by weight to 10% by weight, 0.1% by weight to 5% by weight, 0.1% by weight to 3% by weight, 0.1% by weight to 1% by weight, or 0.1% by weight to 0.5% by weight based on the total weight of the biodegradable resin composition. When the above range is satisfied, the mechanical properties of the biodegradable nonwoven fabric can be improved. When the above range is satisfied, the biodegradable nonwoven fabric may have appropriate biodegradability. The chain extender can also react with the terminal carboxyl groups or unreacted carboxyl groups contained in the biodegradable resin composition. As a result, the biodegradable resin composition may have a low acid value. In addition, the chain extender can couple the polymers contained in the first biodegradable resin and / or the second biodegradable resin to increase the proportion of high molecular weight polymers contained in the biodegradable resin composition. As a result, the mechanical properties of the biodegradable nonwoven fabric can be improved.

[0299] The biodegradable resin composition may contain a heat stabilizer. The heat stabilizer may be the same as the heat stabilizer described above.

[0300] The biodegradable resin composition may contain a reinforcing material.

[0301] The reinforcing material can improve the mechanical properties of the biodegradable resin composition and the biodegradable nonwoven fabric produced thereby. In addition, the reinforcing material can adjust the deformation characteristics of the biodegradable nonwoven fabric due to ultraviolet rays. Also, the reinforcing material can adjust the biodegradability of the biodegradable nonwoven fabric.

[0302] The reinforcing material may be a fiber derived from biomass. The reinforcing material may be a fiber made of an organic substance. The reinforcing material may be nanocellulose.

[0303] The nano-cellulose may be one or more selected from the group consisting of nano-crystalline cellulose, cellulose nanofibers, microfibrillated cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, pentyl cellulose, hexyl cellulose, or cyclohexyl cellulose.

[0304] The nano-cellulose may contain a metal bonded by an ionic bond. The nano-crystalline cellulose may contain a sodium element, a carboxylate sodium salt, etc. Further, the nano-crystalline cellulose may contain a sulphate. The nano-crystalline cellulose may be cellulose hydrogen sulphate sodium salt.

[0305] The nano-cellulose may be represented by Chemical Formula 2 below.

[0306] JPEG2025089271000003.jpg2568

[0307] In Chemical Formula 2 above, x may be 15 to 35, and y may be 1 to 10. The nano-cellulose may have a specific surface area of about 200 m 2 / g to about 600 m 2 / g. The nano-cellulose may have a specific surface area of about 300 m 2 / g to about 500 m 2 / g. The weight average molecular weight of the nano-cellulose may be about 10,000 g / mol to about 40,000 g / mol. The weight average molecular weight of the nano-crystalline cellulose may be about 11,000 g / mol to about 35,000 g / mol.

[0308] The average diameter of the nanocellulose may be about 0.5 nm to about 10 nm. The average diameter of the nanocellulose may be about 1 nm to about 8 nm. The average diameter of the nanocellulose may be about 1.5 nm to about 7 nm.

[0309] The average length of the nanocellulose may be about 20 nm to about 200 nm. The average length of the nanocellulose may be about 30 nm to about 180 nm. The average length of the nanocellulose may be about 35 nm to about 150 nm. By the diameter and length of the nanocellulose satisfying the above ranges, the physical properties of the biodegradable resin composition and the biodegradable nonwoven fabric obtained using the same can be further improved. The diameter and length of the nanocellulose can be measured by atomic force microscopy in a state dispersed in water.

[0310] The content of the sulfate of the nanocellulose may be about 0.6 wt% to about 1.2 wt% based on the whole of the nanocrystalline cellulose. The content of the sulfate of the nanocrystalline cellulose may be about 0.75 wt% to about 1.1 wt% based on the whole of the nanocellulose.

[0311] The pH of the nanocellulose may be 5 to 7. The pH of the nanocellulose may be 6 to 7.

[0312] The zeta potential of the nanocellulose may be about -25 mV to about -50 mV. The zeta potential of the nanocellulose may be about -30 mV to about -45 mV.

[0313] The nanocellulose may be contained in an amount of about 0.1 parts by weight to about 2 parts by weight based on 100 parts by weight of the biodegradable resin composition. The nanocellulose may be contained in an amount of about 0.3 parts by weight to about 1.5 parts by weight based on 100 parts by weight of the biodegradable resin composition. The nanocellulose may be contained in an amount of about 0.5 parts by weight to about 1.2 parts by weight based on 100 parts by weight of the biodegradable resin composition. The nanocellulose may be contained in an amount of about 0.6 parts by weight to about 1 part by weight based on 100 parts by weight of the biodegradable resin composition.

[0314] Since the nanocellulose has the above characteristics, it may be uniformly dispersed in the biodegradable resin composition. Since the nanocellulose has the above characteristics, the mechanical properties of the biodegradable nonwoven fabric produced from the biodegradable resin composition can be improved. Since the nanocellulose has the above characteristics, the biodegradable nonwoven fabric produced from the biodegradable resin composition may have appropriate UV resistance characteristics. Since the nanocellulose has the above characteristics, the biodegradable nonwoven fabric produced from the biodegradable resin composition may have an appropriate biodegradation rate.

[0315] The biodegradable resin composition may contain a plasticizer.

[0316] The plasticizer can impart processability or flexibility to the biodegradable nonwoven fabric to be produced. The plasticizer may be glycerol, acrylate, glycerin, glycerol monostearate (GMS), sorbitol, or a mixture thereof. The content of the plasticizer may be 0.1% by weight to 2% by weight or less, 0.1% by weight to 1.5% by weight or less, 0.1% by weight to 1.2% by weight or less, or 0.1% by weight to 1% by weight or less based on the total weight of the biodegradable resin composition. When the above range is satisfied, flexibility can be imparted to the biodegradable nonwoven fabric produced from the biodegradable resin composition, and the user can maintain a certain degree of water resistance during the normal use period.

[0317] The biodegradable resin composition may contain a different biodegradable resin other than the first biodegradable resin and the second biodegradable resin.

[0318] At least one of the different biodegradable resins may be selected from the group consisting of polybutylene azelate terephthalate (PBAzT), polyhydroxybutyrate (PHB), polybutylene succinate (PBS), polybutylene sebacate terephthalate (PBSeT), polybutylene succinate terephthalate (PBST), and polyhydroxyalkanoate (PHA).

[0319] The different biodegradable resin may be contained in an amount of about 10 parts by weight to about 100 parts by weight based on 100 parts by weight of the first and second biodegradable resins. The different biodegradable resin may be contained in an amount of about 10 parts by weight to about 60 parts by weight based on 100 parts by weight of the first and second biodegradable resins. The different biodegradable resin may be contained in an amount of about 20 parts by weight to about 50 parts by weight based on 100 parts by weight of the first and second biodegradable resins. When the above range is satisfied, the mechanical, optical, and chemical physical properties of the biodegradable resin are complemented, and the biodegradable nonwoven fabric produced from the biodegradable resin composition may have appropriate UV resistance characteristics and an appropriate biodegradation rate.

[0320] The biodegradable nonwoven fabric contains the biodegradable resin composition, and the biodegradable resin composition has a first irreversible deformation rate measured by the following measurement method 3 of less than 30%.

[0321] [Measurement Method 3] 1) With the biodegradable resin composition placed between a pair of flat stainless steel molds, it is compressed at a temperature of 200°C and a pressure of 20 Mpa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0322] 2) The sheet of the biodegradable resin composition is cut to produce a sample including a test portion having a width of 3.18 mm and a length of 25 mm.

[0323] 3) The test portion is pulled at a speed of 10 mm / min in the length direction at room temperature. At this time, it is further pulled by 40% of the total length of the test portion.

[0324] 4) The test portion recovers at room temperature for 5 minutes in the absence of an external force.

[0325] 5) The first irreversible deformation rate is derived by the following formula 1.

[0326] [Formula 1] First irreversible deformation rate = (length of the test portion after recovery - 25 mm) / 25 mm

[0327] The length of the test portion in Formula 1 means the length of the test portion after recovery after being pulled by 40% of the total length of the test portion.

[0328] The biodegradable resin composition may have a second irreversible deformation rate measured by the following Measuring Method 4 of less than 20%.

[0329] [Measuring Method 4] 1) With the biodegradable resin composition placed between a pair of flat stainless steel molds, it is compressed at a temperature of 200 °C and a pressure of 20 Mpa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0330] 2) The sheet of the biodegradable resin composition is cut to produce a sample including a test portion having a width of 3.18 mm and a length of 25 mm.

[0331] 3) The test portion is pulled at a speed of 10 mm / min in the length direction at room temperature. At this time, it is further pulled by 30% of the total length of the test portion.

[0332] 4) The test part recovers at room temperature for 5 minutes in the absence of an external force.

[0333] 5) The second non-reversible deformation rate is derived by the following formula 2.

[0334] [Formula 2] Second non-reversible deformation rate = (length of the test part after recovery - 25 mm) / 25 mm

[0335] The length of the test part in Formula 2 means the length of the recovered test part after being stretched by 30% of the total length of the test part.

[0336] The biodegradable resin composition may have a third non-reversible deformation rate measured by the following Measuring Method 5 of less than 10%.

[0337] [Measuring Method 5] 1) With the biodegradable resin composition placed between a pair of flat stainless steel molds, it is compressed at a temperature of 200 °C and a pressure of 20 Mpa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0338] 2) The sheet of the biodegradable resin composition is cut to produce a sample including a test part having a width of 3.18 mm and a length of 25 mm.

[0339] 3) The test part is pulled at a speed of 10 mm / min in the longitudinal direction at room temperature. At this time, it is further pulled by 20% of the total length of the test part.

[0340] 4) The test part recovers at room temperature for 5 minutes in the absence of an external force.

[0341] 5) The third non-reversible deformation rate is derived by the following formula 3.

[0342] [Formula 3] Third non-reversible deformation rate = (length of the test part after recovery - 25 mm) / 25 mm

[0343] The length of the test part in the above formula 3 means the length of the recovered test part after being stretched by 20% with respect to the total length of the test part.

[0344] The biodegradable resin composition may have a fourth irreversible deformation rate of less than 5% as measured by the following measuring method 6.

[0345] [Measuring method 6] 1) With the biodegradable resin composition placed between a pair of flat stainless steel molds, it is compressed at a temperature of 200 °C and a pressure of 20 Mpa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0346] 2) The sheet of the biodegradable resin composition is cut to produce a sample including a test part having a width of 3.18 mm and a length of 25 mm.

[0347] 3) The test part is pulled at a rate of 10 mm / min in the longitudinal direction at room temperature. At this time, it is further pulled by 10% with respect to the total length of the test part.

[0348] 4) The test part recovers at room temperature for 5 minutes in the absence of an external force.

[0349] 5) The fourth irreversible deformation rate is derived by the following formula 4.

[0350] [Formula 4] Fourth irreversible deformation rate = (length of the test part after recovery - 25 mm) / 25 mm

[0351] The length of the test part in the above formula 4 means the length of the recovered test part after being stretched by 10% with respect to the total length of the test part.

[0352] The irreversible deformation rate may be an index indicating the elastic recovery and stretchability of the biodegradable nonwoven fabric in the absence of external force. Further, having a value of the irreversible deformation rate less than a specific range may be an index indicating that the biodegradable resin composition is manufactured into ultrafine fibers with a diameter of less than 3 μm by a melt blowing process, and the manufactured biodegradable nonwoven fabric has a soft touch. Further, having a value of the irreversible deformation rate less than a specific range may be an index indicating that even if the biodegradable resin composition is manufactured into short fibers with a diameter of 10 μm to 15 μm by a spinning process, the manufactured biodegradable nonwoven fabric has a soft touch. Further, having a value of the irreversible deformation rate less than a specific range may be an index indicating that the soft touch of the manufactured biodegradable nonwoven fabric is exhibited and stretchability is imparted in a temperature range of about 15°C to 40°C where nonwoven fabrics are generally used.

[0353] Specifically, the irreversible deformation rate may be derived with reference to FIGS. 2 and 3. FIG. 2 is a diagram schematically showing the manufacturing process of a sheet of the biodegradable resin composition according to an example. FIG. 3 is a diagram schematically showing the method for measuring the irreversible deformation rate of a test part according to an example.

[0354] Referring to FIGS. 2 and 3, the biodegradable resin composition may be disposed between a pair of flat stainless steel molds 100 and 200. Thereafter, a temperature of 200°C and a pressure of 20 Mpa can be applied to the pair of flat stainless steel molds 100 and 200. Due to the pressure, the biodegradable resin composition may be compressed to produce a sheet 300 of the biodegradable resin composition having a thickness of 300 μm.

[0355] The sheet 300 of the biodegradable resin composition may be manufactured into a sample 400 including a test part 500 having a width of 3.18 mm and a length of 25 mm based on the ASTM318 standard.

[0356] Under normal temperature conditions, both ends 600 of the sample 400 excluding the test part 500 are pulled in the length direction at a speed of 10 mm / min by a fixing member (not shown), whereby the test part 500 may be further pulled by 40%, 30%, 20%, or 10% with respect to the total length (L) of the test part 500.

[0357] Thereafter, after the test part 500 is recovered at normal temperature for 5 minutes without an external force, the deformation rate of the total length (L) of the test part 500 in the irreversible state may be derived by the above formulas 1 to 4.

[0358] The biodegradable nonwoven fabric contains the biodegradable resin composition, and the biodegradable resin composition has a temperature of the maximum loss tangent by dynamic mechanical analysis of -40°C to 0°C, a minimum temperature of the rubber plateau region of less than 30°C, and the rubber plateau region is larger than the temperature of the maximum loss tangent and is a temperature range where the change rate of the loss tangent is less than 0.025 / 10°C.

[0359] Specifically, the temperature of the maximum loss tangent and the minimum temperature of the rubber plateau region may be derived by dynamic mechanical analysis under the following conditions.

[0360] - Measuring instrument: Dynamic Mechanical Analyzer (DMA) TA2980 / Q800 - Heating temperature: from -40°C to 80°C - Heating rate: 10°C / min

[0361] The loss tangent (tanδ) may be calculated by the formula tanδ = (G") / (G') after the storage modulus (G') and the loss modulus (G") at a frequency of 1 Hz are measured by the dynamic mechanical analysis.

[0362] The temperature of the maximum loss tangent may mean the peak temperature confirmed by the loss tangent spectrum for the heating temperature range of -40°C to 80°C in the dynamic mechanical analysis.

[0363] The rubbery plateau region is defined as the plateau modulus, and may mean a region where the storage modulus and loss modulus in the glass transition region decrease rapidly and then the storage modulus and loss modulus are maintained substantially constant. Specifically, it may mean a temperature range in which the change rate of the loss tangent is less than 0.025 / 10 °C. The minimum temperature of the rubbery plateau region may mean the minimum temperature value in the temperature range of the rubbery plateau region.

[0364] Having the values of the temperature range of the maximum loss tangent and the minimum temperature range of the rubbery plateau region may mean that the nonwoven fabric has elastic recovery in the temperature range where it can be used. Thus, even when the nonwoven fabric is stretched by an external force, it does not break and may be an index for imparting elasticity that can be restored to the original length.

[0365] The biodegradable resin composition has a temperature of the maximum loss tangent by dynamic mechanical analysis in the range of -40 °C to 0 °C, a minimum temperature of the rubbery plateau region less than 30 °C, and the rubbery plateau region is at a temperature higher than the temperature of the maximum loss tangent and is a temperature range where the change rate of the loss tangent is less than 0.025 / 10 °C.

[0366] Further, the biodegradable resin composition has a temperature of the maximum loss tangent measured by the following measuring method 7 in the range of -40 °C to 0 °C, and a minimum temperature of the rubbery plateau region less than 30 °C.

[0367] [Measuring method 7] 1) With the biodegradable resin composition placed between a pair of flat stainless steel molds, it is compressed at a temperature of 200 °C and a pressure of 20 Mpa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0368] 2) The sheet of the biodegradable resin composition is cut to produce a sample including a test portion having a width of 5 mm and a length of 12 mm.

[0369] 3) The test section measures the loss tangent due to temperature while rising from -40°C to 80°C by dynamic mechanical analysis.

[0370] 4) The temperature having the maximum value among the loss tangents is derived as the temperature of the maximum loss tangent.

[0371] 5) A temperature range where the change rate of the loss tangent is less than 0.025 / 10°C is derived as the rubber plateau region.

[0372] For the biodegradable resin composition, the temperature of the maximum loss tangent measured by the measurement method 5 may be -40°C to -5°C, and the minimum temperature of the rubber plateau region may be less than 28°C. For the biodegradable resin composition, the temperature of the maximum loss tangent measured by the measurement method 5 may be -40°C to -10°C, and the minimum temperature of the rubber plateau region may be less than 26°C. For the biodegradable resin composition, the temperature of the maximum loss tangent measured by the measurement method 5 may be -40°C to -15°C, and the minimum temperature of the rubber plateau region may be 15°C or more and 25°C or less. When the above ranges are satisfied, the biodegradable nonwoven fabric produced from the biodegradable resin composition may be excellent in stretchability and have a soft touch feeling.

[0373] The crystallization temperature of the biodegradable resin composition may be 20°C to 130°C, 30°C to 130°C, 30°C to 100°C, 30°C to 90°C, 30°C to 80°C, or 30°C to 70°C. When the biodegradable resin composition has a crystallization temperature within the above range, when manufacturing the biodegradable nonwoven fabric, the biodegradable resin composition may be extruded and may crystallize promptly. Thereby, it may have the meaning as an index that can prevent the short circuit of the produced biodegradable raw yarn and suppress the yarn joining between the biodegradable raw yarns at an appropriate crystallization rate, and can improve the tensile strength and elongation rate.

[0374] The crystallization temperature may be measured based on ASTM D3417. Specifically, the crystallization temperature may be measured using a Differential Scanning Calorimeter (DSC). After heating from 40°C to 200°C at a rate of 10°C / min, isothermal for 5 minutes to perform a primary heat history removal process, then cooling from 200°C to -50°C at a rate of 10°C / min, isothermal for 5 minutes, and performing a secondary cooling process.

[0375] The biodegradable resin composition may have a Melt Index.

[0376] Based on ASTM D1238, for the biodegradable resin composition, the discharge amount after being pressed with a weight of about 2.16 kg at a temperature of about 190°C for 10 minutes may be 5 g / 10 min to 50 g / 10 min, 10 g / 10 min to 50 g / 10 min, 15 g / 10 min to 50 g / 10 min, 20 g / 10 min to 50 g / 10 min, or 22 g / 10 min to 50 g / 10 min.

[0377] Based on ASTM D1238, for the biodegradable resin composition, the discharge amount after being pressed with a weight of about 2.16 kg at a temperature of about 230°C for 10 minutes may be 50 g / 10 min to 130 g / 10 min, 55 g / 10 min to 130 g / 10 min, 60 g / 10 min to 130 g / 10 min, 60 g / 10 min to 125 g / 10 min, or 60 g / 10 min to 120 g / 10 min.

[0378] Based on ASTM D1238, for the biodegradable resin composition, the discharge amount after being pressed with a weight of about 2.16 kg at a temperature of about 250°C for 10 minutes may be 100 g / 10 min to 200 g / 10 min, 100 g / 10 min to 190 g / 10 min, 100 g / 10 min to 180 g / 10 min, 110 g / 10 min to 180 g / 10 min, or 110 g / 10 min to 170 g / 10 min.

[0379] When the above range is satisfied, the discharge amount of the biodegradable resin composition during the spinning process may be uniform and have excellent spinning ability, and the raw yarn of the biodegradable nonwoven fabric produced from the biodegradable resin composition can be improved in tensile strength and elongation without being cut.

[0380] The biodegradable resin composition may be produced into a biodegradable nonwoven fabric by a dry method (Dry laid), a wet method (Wet laid), or a direct spinning (Spun laid).

[0381] The dry method may be a carding process in which short fiber raw materials produced from the biodegradable resin composition are laminated on a collector by a device including a plurality of gears, or an air laid process in which short fiber raw materials produced from the biodegradable resin composition are arranged on a collector by a device moved by an air flow.

[0382] The wet method may be a water suspension process in which short fiber raw materials produced from the biodegradable resin composition are dispersed in water, transferred onto a wire screen or a perforated drum, and then the residual moisture is sucked, pressurized, and dried.

[0383] The direct spinning may be a spun bond process in which long fiber raw materials produced from the biodegradable resin composition are formed into a venturi web on a collector, a melt blown process in which the biodegradable resin composition is produced into ultrafine fibers by high-temperature air, or an electro spinning process in which the biodegradable resin composition is produced into ultrafine fibers by electrospinning.

[0384] The biodegradable resin composition according to the present invention can be produced into a biodegradable nonwoven fabric not only by the dry method or the wet method, but also by a direct spinning process. The biodegradable nonwoven fabric contains ultrafine fibers and can exhibit a soft touch feeling.

[0385] After the dry method (Dry laid), wet method (Wet laid) or direct spinning (Spun laid) process, the biodegradable resin composition can be subjected to at least one or more processes among needle punch (Needle punch), spun lace (Spun lace), stitch bond (Stitch bond), calendaring (Calendaring), and air through bonding (Air through bonding).

[0386] By the above processes, the bonding strength between the biodegradable nonwoven fabric filaments can be enhanced, the tensile strength and elongation rate can be improved, and the generation of fluff on the biodegradable nonwoven fabric can be prevented.

[0387] The needle punch process may mean a process of passing needles through the biodegradable raw fiber web so that the biodegradable raw fibers are entangled with each other by the barbs of the needles.

[0388] The spun lace process may mean a process of causing the biodegradable raw fiber web to bond by, on the one hand, injecting a high-pressure water stream and, on the other hand, absorbing the high-pressure water stream.

[0389] The stitch bond process may mean a process of causing the biodegradable raw fiber web to be bonded by a sewing thread and a needle.

[0390] The calendaring process may mean a process of pressurizing the biodegradable raw fiber web and then thermally fusing it.

[0391] The air-through bonding step may mean a step of bonding the biodegradable raw fiber web with hot air at a high temperature.

[0392] The biodegradable nonwoven fabric may be processed. The biodegradable nonwoven fabric may be antistatic-treated with an antistatic agent. The biodegradable nonwoven fabric may be water-repellent-treated with a hydrophobic substance. The biodegradable nonwoven fabric may be water-repellent-treated with an antibacterial substance.

[0393] The biodegradable nonwoven fabric may be embossed. The biodegradable nonwoven fabric may be printed. The biodegradable nonwoven fabric may be embossed or printed with a thickness and size suitable for the article to which it is applied.

[0394] Hereinafter, the present invention will be described more specifically based on examples and comparative examples. However, the following examples and comparative examples are only examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

[0395] First Production Example Production Example 1-1 - Production of Nanocellulose Crystallization Promoter After dispersing dry powder-like cellulose nanocrystals (NVC-100, manufacturer: Celluforce) having a particle size of about 1 μm to about 50 μm in water at 1% by weight, ultrasonic treatment was performed for 2 minutes at an output of 20,000 J / s using a tip-type ultrasonic disperser to produce a nanocellulose crystallization promoter.

[0396] Production Example 1-2 - Production of Titanium Dioxide Crystallization Promoter Titanium dioxide (TiO having a particle size of about 0.2 μm and in an anatase-type crystal form 2) was dispersed in 1,4-butanediol (1,4-BDO) at 5% by weight to produce a slurry. Then, the slurry was stirred at a speed of 1,000 rpm for 2 hours and filtered through a 500-mesh filter to produce a titanium dioxide crystallization accelerator.

[0397] First Example - Production of Biodegradable Resin Composition Example 1-1 - First stage: Obtaining a prepolymer 1,4-butanediol (1,4-BDO) and terephthalic acid (TPA) were charged into a 5-kg-sized esterification reactor equipped with a nitrogen inlet and a stirrer to produce a slurry. At this time, the molar ratio of the 1,4-butanediol (1,4-BDO) to terephthalic acid (TPA) was 1.4:1, and the D 50 of the terephthalic acid (TPA) was 130 μm.

[0398] The slurry was charged into a reactor through a supply line, and tetrabutyl titanate (product of Dupont, Tyzor TnBT), which is a titanium-based catalyst, was charged at 250 ppm. Then, the temperature of the slurry was raised to 210 °C, and an esterification reaction was carried out until about 90% or more of the by-product water was discharged to produce a first prepolymer.

[0399] Based on the total number of moles of the diol component in the product of the primary esterification reaction, 53 mol% of 1,4-butanediol (1,4-BDO) was charged. Based on the total number of moles of the dicarboxylic acid component, 53 mol% of adipic acid (AA) was charged. Based on the total weight of the diol component and the dicarboxylic acid component, tetrabutyl titanate (product of Dupont, Tyzor TnBT), which is a titanium-based catalyst, was charged at 200 ppm. Also, 100 ppm of the nanocellulose crystallization accelerator according to Production Example 1 was charged into the product of the primary esterification. Then, at 220 °C and normal pressure, a secondary esterification reaction was carried out for about 2 hours and 30 minutes until 95% of the by-product water was discharged to produce a second prepolymer having a number average molecular weight of 5,500 g / mol.

[0400] - Second stage: Polycondensation reaction The second prepolymer was transferred to a 5 kg-sized polycondensation reaction tank. Based on the total weight of the second prepolymer, 150 ppm of tetrabutyl titanate (manufactured by Dupont, Tyzor TnBT), a titanium-based catalyst, and 500 ppm of triethylene phosphate stabilizer were added, and then it was stabilized for about 10 minutes.

[0401] Thereafter, after raising the temperature to 240°C, a polycondensation reaction was carried out at 0.5 torr for 2 hours to produce a biodegradable resin composition.

[0402] Example 1-2 A biodegradable resin composition was produced by the same process as in the production process of Example 1-1, except that 500 ppm of the nanocellulose crystallization promoter according to Production Example 1-1 was added to the primary esterification product in Example 1-1 instead of adding 100 ppm of the nanocellulose crystallization promoter according to Production Example 1-1.

[0403] Example 1-3 A biodegradable resin composition was produced by the same process as in the production process of Example 1-1, except that 200 ppm of the nanocellulose crystallization promoter according to Production Example 1-1 and 3,000 ppm of the titanium dioxide crystallization promoter according to Production Example 2 were added to the product of the primary esterification in Example 1-1, and 1,000 ppm of calcium stearate external lubricant was added in the polycondensation reaction instead of adding 100 ppm of the nanocellulose crystallization promoter according to Production Example 1-1.

[0404] Example 1-4 The biodegradable resin composition according to Example 1-1, 500 ppm of the titanium dioxide crystallization accelerator according to Production Example 1-2, and 2,000 ppm of an external lubricant of calcium stearate were put into a T-die extrusion molding apparatus (φ20 mm, L / D = 25) of a product of an extrusion molding machine (Toyo Seiki Seisaku-sho, Ltd.) equipped with a twin-screw, kneaded at a temperature of about 140°C, and a biodegradable resin composition was produced.

[0405] Example 1-5 A biodegradable resin composition was produced by the same process as the production process of Example 1-4, except that 6,000 ppm of the titanium dioxide crystallization accelerator according to Production Example 1-2 and 500 ppm of an external lubricant of calcium stearate were added instead of 500 ppm of the titanium dioxide crystallization accelerator according to Production Example 1-2 and 2,000 ppm of an external lubricant of calcium stearate in Example 1-4.

[0406] Example 1-6 500 ppm of the titanium dioxide crystallization accelerator according to Production Example 1-2 and 2,000 ppm of an external lubricant of calcium stearate were put into a composition obtained by mixing the biodegradable resin composition according to Example 1-1 and PLA (Total Corbion, L130) at a weight ratio of 8:2, into a T-die extrusion molding apparatus (φ20 mm, L / D = 25) of a product of an extrusion molding machine (Toyo Seiki Seisaku-sho, Ltd.) equipped with a twin-screw, kneaded at a temperature of about 140°C, and a biodegradable resin composition was produced.

[0407] Comparative Example 1-1 A biodegradable resin composition was produced by the same process as the production process of Example 1-1, except that the nanocellulose crystallization accelerator according to Production Example 1-1 was not added to the primary esterification product in Example 1-1.

[0408] Comparative Example 1-2 The biodegradable resin composition according to Example 1-1 and 8,000 ppm of the nanocellulose crystallization accelerator according to Production Example 1-1 were put into a T-die extrusion molding device (φ20 mm, L / D = 25) of a product of an extrusion molding machine (Toyo Seiki Seisaku-sho, Ltd.) equipped with a twin-screw, kneaded at a temperature of about 140°C, and a biodegradable resin composition was produced.

[0409] Comparative Example 1-3 The biodegradable resin composition according to Example 1-1 and 63,000 ppm of the titanium dioxide crystallization accelerator according to Production Example 1-2 were put into a T-die extrusion molding device (φ20 mm, L / D = 25) of a product of an extrusion molding machine (Toyo Seiki Seisaku-sho, Ltd.) equipped with a twin-screw, kneaded at a temperature of about 140°C, and a biodegradable resin composition was produced.

[0410] Comparative Example 1-4 To the composition in which the biodegradable resin composition according to Example 1-1 and PLA (Total Corbion, L130) were mixed at a weight ratio of 8:2, 63,000 ppm of the titanium dioxide crystallization accelerator according to Production Example 1-2 and 2,000 ppm of an external lubricant of calcium stearate were put into a T-die extrusion molding device (φ20 mm, L / D = 25) of a product of an extrusion molding machine (Toyo Seiki Seisaku-sho, Ltd.), kneaded at a temperature of about 140°C, and a biodegradable resin composition was produced.

[0411] First Experimental Example Experimental Example 1-1 - Isothermal Crystallization Time Each of the biodegradable resin compositions of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4 was heated to 220°C at a heating rate of 10°C / min and then maintained for 5 minutes. Then, after cooling to 70°C at a cooling rate of 100°C / min, an isothermal state was maintained for 100 minutes.

[0412] Subsequently, using a differential scanning calorimeter, the time that is half of the total area of the crystallization peak of the biodegradable resin composition was measured with respect to the total area of the crystallization peak of the biodegradable resin composition, and the results are shown in Table 1 below.

[0413] Experimental Example 1-2 - Glass transition temperature, crystallization temperature, melting temperature Using the differential scanning calorimeter of Experimental Example 1-1, the glass transition temperature (Tg), crystallization temperature (Tc), and melting temperature (Tm) of each of the biodegradable resin compositions of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4 were measured, and the results are shown in Table 1 below.

[0414] Experimental Example 1-3 - Melt Flow Rate Based on ASTM D1238, after pressing each of the biodegradable resin compositions of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4 under a temperature condition of 190 °C using a 2.16 kg weight, the discharge amount for 10 minutes was measured, and the results are shown in Table 1 below.

[0415] Experimental Example 1-4 - Tensile strength, elongation at break Each of the biodegradable resin compositions of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4 was manufactured into a specimen with a thickness of 300 μm based on KSM6518. Subsequently, for the said specimen, using a universal testing machine (UTM, model 4206-001) of INSTRON, the tensile strength (kgf / mm 2 = 9.8 MPa) and elongation at break were measured at a speed of 100 mm / min based on ASTM D638. The results are shown in Table 1 below.

[0416] Experimental Example 1-5 - Spinnability evaluation Each of the biodegradable resin compositions of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4 was evaluated for spinnability according to the following criteria using a melt spinning (Filament) facility under the conditions of a spinning speed of 24 g / min, a melting temperature of 210 °C, a winder draw ratio of 2.2, and a quenching air temperature of 10 °C. The results are shown in Table 1 below.

[0417] - ◎: Nozzle spinning is smooth, and there is no fiber breakage or fiber joining. - Δ: Although nozzle spinning is smooth, the fiber is broken or joined. - ×: The nozzle is clogged and spinning is impossible.

[0418] Experimental Example 1-6 - Injection Moldability Evaluation After maintaining each of the biodegradable resin compositions of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4 in a mold at 200 °C for 5 minutes, the injection moldability was evaluated according to the following criteria. The results are shown in Table 1 below.

[0419] - ◎: Excellent mold release property, and the shape of the injection molded product is maintained. - Δ: Although there is no residue in the mold, flow marks are generated on the injection molded product. - ×: Residue is generated in the mold, or carbonization marks are generated on the injection molded product.

[0420] Experimental Example 1-7 - Foaming Property Evaluation After charging a composition in which each of the biodegradable resin compositions of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4 and PLA (NatureWorks, 4032D) were mixed at a weight ratio of 3:7 into a gas foaming equipment, the foaming property was evaluated according to the following criteria. The results are shown in Table 1 below.

[0421] - ◎: Maximum foaming ratio is 5 times or more - ○: Maximum foaming ratio is 3 times or more and less than 5 times - Δ: Maximum foaming ratio is 1 time or more and less than 3 times - ×: Not foamed

[0422] Experimental Example 1-8 - Biodegradability For each of the biodegradable resin compositions of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-4, the aerobic biodegradability measured under composting conditions for 6 months based on ISO 14855 was measured, and the results are shown in Table 1 below.

[0423]

Table 1

[0424] As can be confirmed from Table 1 above, it was confirmed that the biodegradable resin compositions of Examples 1-1 to 1-6 exhibited the same or higher biodegradability compared to the biodegradable resin compositions of Comparative Examples 1-1 to 1-4.

[0425] In addition, the biodegradable resin compositions of Examples 1-1 to 1-6 contain a crystallization accelerator at a content of 100 ppm to 50,000 ppm, and the isothermal crystallization time at 90 °C satisfies 10 seconds to 900 seconds, so it was confirmed that they are excellent in spinnability, injectability, and foamability, and have excellent mechanical properties.

[0426] Second Production Example <Production of Pretreated Nanocellulose> Cellulose nanocrystals (NVC-100, manufacturer: Celluforce) in the form of dry powder having a particle size of about 1 μm to about 50 μm were dispersed in water at 1 wt%, and then ultrasonic treatment was performed for 2 minutes at an output of 20,000 J / s using a tip-type ultrasonic disperser to produce pretreated nanocellulose.

[0427] <Production of PBAT Resin> Production of PBAT Resin #1 - First stage: The stage of obtaining a slurry by pretreatment In the catalyst-free state, the pretreated nanocellulose according to the above production example, 1,4-butanediol (1,4-BDO), and terephthalic acid (TPA) were mixed and charged into a slurry tank (the bottom of the slurry tank has a height of 40 mm up to an anchor-type agitator and is equipped with three rotating blades). At this time, the molar ratio of the 1,4-butanediol (1,4-BDO) to the terephthalic acid (TPA) was 1.4:1, and the D 50 of the terephthalic acid (TPA) was 130 μm. The mixture charged into the slurry tank was pretreated by stirring at 60 °C and 100 rpm for 1 hour to obtain a slurry without phase separation.

[0428] - Second stage: Obtaining a prepolymer The slurry obtained in the first stage was charged into a reactor through a supply line. After charging 250 ppm of tetrabutyl titanate (product of Dupont, Tyzor TnBT), which is a titanium-based catalyst, based on the total weight of the slurry into the reactor, a primary esterification reaction was carried out at 220 °C and normal pressure for about 1 hour and 30 minutes until 95% of the by-product water was discharged.

[0429] Based on the total number of moles of the diol component in the primary esterification reaction product, 53 mol% of 1,4-butanediol (1,4-BDO) was charged. Based on the total number of moles of the dicarboxylic acid component, 53 mol% of adipic acid (AA) was charged. Based on the total weight of the diol component and the dicarboxylic acid component, 200 ppm of tetrabutyl titanate (product of Dupont, Tyzor TnBT), which is a titanium-based catalyst, was charged. Then, a secondary esterification reaction was carried out at 220 °C and normal pressure for about 2 hours and 30 minutes until 95% of the by-product water was discharged to produce a prepolymer having a number average molecular weight of 5,500 g / mol.

[0430] - Third stage: Performing a polycondensation reaction Based on the total weight of the prepolymer produced in the second stage, 150 ppm of tetrabutyl titanate (product of Dupont, Tyzor TnBT), which is a titanium-based catalyst, and 500 ppm of triethylene phosphate stabilizer were added, and then it was stabilized for about 10 minutes. Then, after raising the temperature to 240 °C, a polycondensation reaction was carried out at 0.5 torr for 2 hours to produce a polymer having a number average molecular weight of 34,000 g / mol. Then, the polymer was cooled to 5 °C and cut with a pellet cutter to obtain PBAT resin #1 pellets.

[0431] Production of PBAT Resin #2 to #5 PBAT resin #2 to #5 pellets were produced by the same process as the production process of the PBAT resin #1, except for the components and contents shown in Table 2 below, the temperatures and times of the primary and secondary esterification reactions shown in Table 3 below, and the temperature and time of the polycondensation reaction.

[0432]

Table 2

[0433]

Table 3

[0434] <Production of Biodegradable Resin Composition> Production of Biodegradable Resin Composition #1 A raw material composition was prepared with the components and contents shown in Table 4 below. Then, the raw material composition was put into a T-die extrusion molding device (φ20 mm, L / D = 25) of a product of an extrusion molding machine (manufactured by Toyo Seiki Seisaku-sho, Ltd.) equipped with a twin-screw and kneaded at a temperature of 160 °C to produce biodegradable resin composition #1 in pellet form.

[0435] Production of Biodegradable Resin Composition #2 to #9 Biodegradable resin compositions #2 to #9 were produced by the same process as the production process of the biodegradable resin composition #1, except for the components and contents shown in Table 4 below.

[0436]

Table 4

[0437] Second Example Example 2-1 The biodegradable resin composition #1 was supplied to the die of a melt blown manufacturing apparatus. The set temperature of the die was 230°C. Using a melt blown nozzle (0.32 mmφ, distance between holes of each nozzle: 0.20 mm), the biodegradable resin composition #1 was ejected from both sides of the nozzle at a discharge rate of 0.52 g / min per single hole of the nozzle, together with high-temperature and high-speed air (250°C, air volume: 600 m 3 / hr). Thereafter, a cooling and dispersion process was carried out by cooling air (15°C, air volume 6,000 m 3 / hr), and a melt blown nonwoven fabric was manufactured by ejecting it onto a carrier film so that the basis weight of the melt blown nonwoven fabric at a distance (DCD) from the surface of the spinneret to the collector of 120 mm was 70 g / m 2 .

[0438] Example 2-2 A melt blown nonwoven fabric was manufactured by the same process as in Example 2-1, except that the biodegradable resin composition #2 was used instead of the biodegradable resin composition #1 in Example 2-1.

[0439] Example 2-3 A melt blown nonwoven fabric was manufactured by the same process as in Example 2-1, except that the biodegradable resin composition #3 was used instead of the biodegradable resin composition #1 in Example 2-1.

[0440] Example 2-4 A melt blown nonwoven fabric was manufactured by the same process as in Example 2-1, except that the biodegradable resin composition #4 was used instead of the biodegradable resin composition #1 in Example 2-1.

[0441] Example 2-5 A melt-blown nonwoven fabric was produced by the same process as in Example 2-1, except that biodegradable resin composition #5 was used instead of biodegradable resin composition #1 of Example 2-1.

[0442] Example 2-6 A melt-blown nonwoven fabric was produced by the same process as in Example 2-1, except that biodegradable resin composition #6 was used instead of biodegradable resin composition #1 of Example 2-1.

[0443] Comparative Example 2-1 A melt-blown nonwoven fabric was produced by the same process as in Example 2-1, except that biodegradable resin composition #7 was used instead of biodegradable resin composition #1 of Example 2-1.

[0444] Comparative Example 2-2 A melt-blown nonwoven fabric was produced by the same process as in Example 2-1, except that biodegradable resin composition #8 was used instead of biodegradable resin composition #1 of Example 2-1.

[0445] Comparative Example 2-3 A melt-blown nonwoven fabric was produced by the same process as in Example 2-1, except that biodegradable resin composition #9 was used instead of biodegradable resin composition #1 of Example 2-1.

[0446] Comparative Example 2-4 A melt-blown nonwoven fabric was produced by the same process as in Example 2-1, except that biodegradable resin composition #10 was used instead of biodegradable resin composition #1 of Example 2-1.

[0447] Second Experimental Example Experimental Example 2-1 - Irreversible deformation rate Each of the biodegradable resin compositions #1 to #10 was placed between a pair of flat stainless steel molds and compressed at a temperature of 200 °C and a pressure of 20 MPa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0448] Thereafter, the sheet of the biodegradable resin composition was cut to produce a sample including a test portion having a width of 3.18 mm and a length of 25 mm.

[0449] Thereafter, the test portion was pulled at a rate of 10 mm / min in the longitudinal direction at room temperature, and at this time, it was further pulled by 40%, 30%, 20%, or 10% with respect to the total length of the test portion.

[0450] Thereafter, the test portion recovered at room temperature for 5 minutes in the absence of an external force, and then, using a universal testing machine (UTM, model 4206 - 001) manufactured by INSTRON, the first to fourth irreversible deformation rates were derived according to the following formulas 1 to 4. The results are shown in Table 5 below.

[0451] [Formula 1] The first irreversible deformation rate = (the length of the test portion after recovery - 25 mm) / 25 mm

[0452] The length of the test portion in Formula 1 means the length of the test portion after recovery after being pulled by 40% with respect to the total length of the test portion.

[0453] [Formula 2] The second irreversible deformation rate = (the length of the test portion after recovery - 25 mm) / 25 mm

[0454] The length of the test portion in Formula 2 means the length of the test portion after recovery after being pulled by 30% with respect to the total length of the test portion.

[0455] [Formula 3] The third irreversible deformation rate = (the length of the test portion after recovery - 25 mm) / 25 mm

[0456] The length of the test part in the formula 3 means the length of the recovered test part after being stretched by 20% with respect to the total length of the test part.

[0457] [Formula 4] The fourth non-reversible deformation rate = (the length of the test part after recovery - 25 mm) / 25 mm

[0458] The length of the test part in the formula 4 means the length of the recovered test part after being stretched by 10% with respect to the total length of the test part.

[0459] Experimental Example 2-2 - Dynamic Mechanical Analysis Each of the biodegradable resin compositions #1 to #10 was placed between a pair of flat stainless steel molds and compressed at a temperature of 200 °C and a pressure of 20 Mpa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm.

[0460] Thereafter, the sheet of the biodegradable resin composition was cut to produce a sample including a test part having a width of 5 mm and a length of 12 mm.

[0461] Thereafter, the maximum loss tangent temperature and the minimum temperature of the rubber plateau region were derived for the test part by dynamic mechanical analysis under the following conditions. The rubber plateau region was derived as a temperature range that is larger than the maximum loss tangent temperature and has a change rate of the loss tangent of less than 0.025 / 10 °C. The results are shown in Table 5 below.

[0462] - Measuring instrument: Dynamic Mechanical Analyzer (DMA) TA2980 / Q800 - Heating temperature: from -40 °C to 80 °C - Heating rate: 10 °C / min

[0463] Experimental Example 2-3 - Crystallization Temperature For each of the biodegradable resin compositions #1 to #10, the crystallization temperature and the melting temperature were measured based on ASTM D3417. Specifically, using a Differential Scanning Calorimeter (DSC), after heating from 40°C to 220°C at a rate of 10°C / min, it was isothermal for 5 minutes to perform a primary heat history removal process, cooled from 200°C to -50°C at a rate of 10°C / min, isothermal for 5 minutes to perform a secondary cooling process, and further heated from -50°C to 220°C at a rate of 10°C / min. Through the above process, the crystallization temperature and the melting temperature were confirmed, and the results are shown in Table 5 below.

[0464] Experimental Example 2-4 - Melt Index For each of the biodegradable resin compositions #1 to #10, after pressing with a 2.16 kg weight under temperature conditions of 190°C, 230°C, and 250°C based on ASTM D1238, the discharge amount for 10 minutes was measured, and the results are shown in Table 5 below.

[0465] Experimental Example 2-5 - Degree of Biodegradability For each of the nonwoven fabrics produced in Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-4, the amount of carbon dioxide generated was measured according to KS M3100-1, and the degree of biodegradability was measured. Specifically, an inoculation source container with only compost produced in a compost factory was prepared, and a test container was prepared by putting nonwoven fabric accounting for 5% by weight of the dry weight of the compost into the compost. Then, it was cultured for 180 days under conditions of a temperature of about 58 ± 2°C, a humidity of 50%, and an oxygen concentration of 6% or more, and the carbon dioxide generated in each test container was collected and titrated with an aqueous phenolphthalein solution to measure the amount of carbon dioxide generated in each test container. The degree of biodegradability was calculated by Calculation Formula 1 using the measured amount of carbon dioxide generated, and the results are shown in Table 5 below.

[0466] [Calculation Formula 1]

[0467] Experimental Example 2-6 - Touch The touch of each nonwoven fabric produced in Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-4 was evaluated by hand by 10 users. Each user assigned a score on a scale of 1 to 10, with a higher score indicating a softer touch. The results for the average scores of the 10 users are shown in Table 5 below.

[0468]

Table 5

[0469] As can be confirmed from Table 5 above, the biodegradable nonwoven fabrics of Examples 2-1 to 2-6 have an irreversible deformation rate below a specific range and have a rubber flat region in the temperature range of about 15°C to 40°C where nonwoven fabrics are generally used, compared to the biodegradable nonwoven fabrics of Comparative Examples 2-1 to 2-4. It was confirmed that they are excellent in stretchability and have a soft touch. Therefore, when the biodegradable nonwoven fabrics of Examples 2-1 to 2-6 are applied as sanitary materials that are environmentally friendly and directly touch the human body, the wearing comfort can be improved.

Industrial Applicability

[0470] The examples can be applied to biodegradable resin compositions and biodegradable molded articles containing the same.

Claims

1. a first biodegradable resin including a first repeating unit derived from a diol, a second repeating unit derived from an aromatic dicarboxylic acid, and a third repeating unit derived from an aliphatic dicarboxylic acid; A crystallization promoter; Including, The crystallization promoter is included in an amount of 100 ppm to 50,000 ppm, The isothermal crystallization time at 90° C. is 10 seconds to 900 seconds according to the following measurement method 1. Biodegradable resin composition. [Measurement method 1] 1) The biodegradable resin composition is heated to 220° C. at a heating rate of 10° C. / min, and then maintained at that temperature for 5 minutes. 2) Thereafter, the temperature of the biodegradable resin composition is lowered to 90° C. at a temperature lowering rate of 100° C. / min, and then the isothermal state is maintained for 100 minutes. 3) Using a differential scanning calorimetry, the time required for the total area of ​​the crystallization peak of the biodegradable resin composition to become half of the total area of ​​the crystallization peak of the biodegradable resin composition is measured.

2. The biodegradable resin composition further comprises one or more second biodegradable resins selected from the group consisting of polybutylene succinate, polylactic acid, polybutylene adipate, polybutylene succinate-adipate, polybutylene succinate-terephthalate, polyhydroxybutyrate-valerate, polycaprolactone, polybutylene adipate-co-butylene succinate terephthalate, and polybutylene succinate adipate terephthalate. The biodegradable resin composition according to claim 1.

3. The crystallization promoter includes at least one of an organic nucleating agent and an inorganic nucleating agent. The biodegradable resin composition according to claim 1.

4. The biodegradable resin composition contains the organic nucleating agent in an amount of 10 ppm to 5,000 ppm. The biodegradable resin composition according to claim 3.

5. The biodegradable resin composition contains the inorganic nucleating agent in an amount of 100 ppm to 10,000 ppm. The biodegradable resin composition according to claim 3.

6. The inorganic nucleating agent includes at least one of rutile titanium dioxide and anatase titanium dioxide. The biodegradable resin composition according to claim 3.

7. The average diameter of the inorganic nucleating agent (D ５０ ) is 0.1 μm to 0.5 μm; The biodegradable resin composition according to claim 3.

8. The biodegradable resin composition further contains an external lubricant. The biodegradable resin composition according to claim 1.

9. The biodegradable resin composition contains the external lubricant in an amount of 100 ppm to 5,000 ppm. The biodegradable resin composition according to claim 8.

10. The biodegradable resin composition has a crystallization temperature (Tc) of 35° C. to 90° C. as measured using the differential scanning calorimeter. The biodegradable resin composition according to claim 1.

11. The biodegradable resin composition has a melt flow rate of 2 g / 10 min to 60 g / 10 min measured under conditions of 190° C. and 2.16 kg. The biodegradable resin composition according to claim 1.

12. The biodegradable resin composition has a tensile strength of 25 MPa or more, measured by the following measurement method 2. The biodegradable resin composition according to claim 1. [Measurement method 2] 1) The biodegradable resin composition is prepared into a test piece having a thickness of 300 μm. 2) The tensile strength of the test piece is measured at a speed of 100 mm / min using a universal testing machine.

13. The breaking elongation of the specimen measured using the universal testing machine is 800% to 1,200%. The biodegradable resin composition according to claim 12.

14. The isothermal crystallization time is from 40 seconds to more than 800 seconds; The biodegradable resin composition according to claim 1.

15. The present invention includes a biodegradable resin composition including a first biodegradable resin including a diol, an aromatic dicarboxylic acid, and an aliphatic dicarboxylic acid, The biodegradable resin composition has a first irreversible deformation rate measured by the following measurement method 3 of less than 30%. Biodegradable non-woven fabric. [Measurement method 3] 1) The biodegradable resin composition is placed between a pair of flat stainless steel molds and compressed at a temperature of 200° C. and a pressure of 20 MPa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm. 2) The sheet of biodegradable resin composition is cut to produce a sample including a test section having a width of 3.18 mm and a length of 25 mm. 3) The test piece is pulled at room temperature in the length direction at a speed of 10 mm / min, and is pulled further by 40% of the total length of the test piece. 4) The test part is allowed to recover for 5 minutes at room temperature in the absence of external forces. 5) The first irreversible deformation ratio is derived by the following Equation 1. [Formula 1] First irreversible deformation rate=(length of the test portion after recovery−25 mm) / 25 mm

16. The biodegradable resin composition has a second irreversible deformation rate measured by the following measurement method 4 of less than 20%. The biodegradable nonwoven fabric according to claim 15. [Measurement method 4] 1) The biodegradable resin composition is placed between a pair of flat stainless steel molds and compressed at a temperature of 200° C. and a pressure of 20 MPa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm. 2) The sheet of biodegradable resin composition is cut to produce a sample including a test section having a width of 3.18 mm and a length of 25 mm. 3) The test part is pulled in the length direction at room temperature at a speed of 10 mm / min, and is pulled further by 30% of the total length of the test part. 4) The test part is allowed to recover for 5 minutes at room temperature in the absence of external forces. 5) The second irreversible deformation ratio is derived by the following Equation 2. [Formula 2] Second irreversible deformation rate=(length of the test portion after recovery−25 mm) / 25 mm

17. The biodegradable resin composition has a third irreversible deformation rate measured by the following measurement method 5 of less than 10%. The biodegradable nonwoven fabric according to claim 15. [Measurement method 5] 1) The biodegradable resin composition is placed between a pair of flat stainless steel molds and compressed at a temperature of 200° C. and a pressure of 20 MPa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm. 2) The sheet of biodegradable resin composition is cut to produce a sample including a test section having a width of 3.18 mm and a length of 25 mm. 3) The test part is pulled at room temperature in the length direction at a speed of 10 mm / min, and is pulled further by 20% of the total length of the test part. 4) The test part is allowed to recover for 5 minutes at room temperature in the absence of external forces. 5) The third irreversible deformation ratio is derived by the following Equation 3. [Formula 3] Third irreversible deformation rate=(length of the test portion after recovery−25 mm) / 25 mm

18. The biodegradable resin composition has a fourth irreversible deformation rate measured by the following measurement method 6 of less than 5%. The biodegradable nonwoven fabric according to claim 15. [Measurement method 6] 1) The biodegradable resin composition is placed between a pair of flat stainless steel molds and compressed at a temperature of 200° C. and a pressure of 20 MPa to produce a sheet of the biodegradable resin composition having a thickness of 300 μm. 2) The sheet of biodegradable resin composition is cut to produce a sample including a test section having a width of 3.18 mm and a length of 25 mm. 3) The test part is pulled in the length direction at room temperature at a speed of 10 mm / min, and is further pulled by 10% of the total length of the test part. 4) The test part is allowed to recover for 5 minutes at room temperature in the absence of external forces. 5) The fourth irreversible deformation ratio is derived by the following Equation 4. [Formula 4] Fourth irreversible deformation rate=(length of the test portion after recovery−25 mm) / 25 mm

19. The biodegradable resin composition further comprises a second biodegradable resin, The second biodegradable resin includes one or more selected from the group consisting of polybutylene succinate, polylactic acid, polybutylene adipate, polybutylene succinate-adipate, polybutylene succinate-terephthalate, polyhydroxybutyrate-valerate, polycaprolactone, and polybutylene succinate adipate terephthalate. The biodegradable nonwoven fabric according to claim 15.

20. a first biodegradable resin comprising a diol, an aromatic dicarboxylic acid, and an aliphatic dicarboxylic acid; The temperature of maximum loss tangent by dynamic mechanical analysis is −40° C. to 0° C., and the minimum temperature of the rubber plateau is less than 30° C.; The rubber flat region is a temperature range in which the temperature is higher than the maximum loss tangent temperature and the rate of change of the loss tangent is less than 0.025 / 10°C. Biodegradable resin composition.

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