Biodegradable polyester resin composition and biodegradable nonwoven fabric comprising same

Abstract

The present invention provides a biodegradable polyester resin composition and a biodegradable nonwoven fabric comprising same, wherein the biodegradable polyester resin composition comprises: a biodegradable polyester resin comprising diol-derived units, aromatic dicarboxylic acid-derived units, and aliphatic dicarboxylic acid-derived units; and a melt strength enhancer, and the crystallization time at 90 °C according to measurement method 1 is 2 min or less. [Measurement method 1] (see the description of the invention)

Description

Biodegradable polyester resin composition and biodegradable nonwoven fabric comprising the same

[0001] The present invention relates to a biodegradable polyester resin composition and a biodegradable nonwoven fabric comprising the same.

[0002]

[0003] With growing concerns about environmental issues, solutions are being sought for the disposal of various household goods, especially disposable products. Specifically, petroleum-based polymer materials are widely used in the manufacture of various products such as films, fibers, packaging materials, bottles, and containers due to their low cost and excellent processability. However, when incinerated at the end of their useful life, they emit hazardous substances, and depending on the type, they can take hundreds of years to completely decompose naturally.

[0004] To overcome the limitations of these petroleum-based polymer materials, active research is being conducted on biodegradable resins that decompose in a relatively short period of time. Biodegradable resins such as polylactic acid (PLA), polybutyleneadipate terephthalate (PBAT), and polybutylene succinate (PBS) are being introduced as alternatives.

[0005]

[0006] The present invention provides a biodegradable polyester resin composition having excellent biodegradability and improved radiation processability, and a biodegradable nonwoven fabric comprising the same.

[0007]

[0008] A biodegradable polyester resin composition according to the present invention comprises a biodegradable polyester resin including a diol-derived unit, an aromatic dicarboxylic acid-derived unit, and an aliphatic dicarboxylic acid-derived unit, and a melt strength enhancer, and has a crystallization time at 90°C of 2 minutes (min) or less according to the following measurement method 1.

[0009] [Measurement Method 1]

[0010] 1) The biodegradable polyester resin composition is heated to 220°C at a heating rate of 10°C / min, and then maintained for 5 minutes.

[0011] 2) The biodegradable polyester resin composition is cooled to 90°C at a cooling rate of 100°C / min, and then maintained in an isothermal state for 60 minutes.

[0012] 3) Using a differential scanning calorimeter (DSC), the time taken for the total area of ​​the crystallization peak of the biodegradable polyester resin composition to become half of the total area of ​​the crystallization peak of the biodegradable polyester resin composition is measured.

[0013] In one embodiment of the present invention, the melt strength enhancer may include a saturated fatty acid amide.

[0014] In one embodiment of the present invention, the melt strength enhancer may have a thermal decomposition temperature of 200°C or higher when heated to 900°C at a rate of 20°C / min in a nitrogen atmosphere using a thermogravimetric analyzer (TGA), and a weight reduction rate of 20% or less when heated to 240°C at a rate of 20°C / min for 360 minutes at an isothermal temperature.

[0015] In one embodiment of the present invention, the melt strength enhancer may have a weight average molecular weight of 500 g / mol to 800 g / mol.

[0016] In one embodiment of the present invention, the biodegradable polyester resin composition may further include an anti-adhesive agent.

[0017] In one embodiment of the present invention, the anti-adhesive agent may include an unsaturated fatty acid amide.

[0018] In one embodiment of the present invention, the anti-adhesive agent may have a weight average molecular weight of 200 g / mol to 500 g / mol.

[0019] In one embodiment of the present invention, the solubility of the melt strength enhancer in the biodegradable polyester resin may be lower than the solubility of the anti-adhesion agent in the biodegradable polyester resin.

[0020] In one embodiment of the present invention, the total content of the melt strength enhancer and the anti-adhesive agent may be 0.1 phr to 3 phr relative to the biodegradable polyester resin.

[0021] In one embodiment of the present invention, the biodegradable polyester resin composition may further include a nucleating agent.

[0022] In one embodiment of the present invention, the content of the nucleating agent may be 0.1 phr to 4 phr relative to the biodegradable polyester resin.

[0023] In one embodiment of the present invention, the biodegradable polyester resin composition may have a first melt index of 10 g / 10 min to 40 g / 10 min measured under conditions of 190° C. and 2.16 kg, and a second melt index of 30 g / 10 min to 100 g / 10 min measured under conditions of 230° C. and 2.16 kg.

[0024] A biodegradable nonwoven fabric according to the present invention comprises a biodegradable polyester resin comprising a diol-derived unit, an aromatic dicarboxylic acid-derived unit, and an aliphatic dicarboxylic acid-derived unit, and a melt strength reinforcing agent, and comprises a biodegradable polyester resin composition having a crystallization time of 2 minutes (min) or less at 90° C. according to the following measurement method 1.

[0025] [Measurement Method 1]

[0026] 1) The biodegradable polyester resin composition is heated to 220°C at a heating rate of 10°C / min, and then maintained for 5 minutes.

[0027] 2) The biodegradable polyester resin composition is cooled to 90°C at a cooling rate of 100°C / min, and then maintained in an isothermal state for 60 minutes.

[0028] 3) Using a differential scanning calorimeter (DSC), the time taken for the total area of ​​the crystallization peak of the biodegradable polyester resin composition to become half of the total area of ​​the crystallization peak of the biodegradable polyester resin composition is measured.

[0029]

[0030] The biodegradable polyester resin composition according to the present invention comprises a type of biodegradable polyester resin selected and a melt strength enhancer.

[0031] The nonwoven fabric manufactured using the above biodegradable polyester resin has excellent biodegradability and can be naturally biodegraded, so it does not require incineration or emit harmful substances.

[0032] In addition, by the above melt strength reinforcing agent, the flow stability within the yarn can be strengthened and the elongation of the yarn can be improved, so that the phenomenon of the yarn breaking during the spinning process can be suppressed.

[0033] In addition, the biodegradable polyester resin composition further includes an anti-adhesive agent, so that the adhesive properties are reduced and the phenomenon of yarns being twisted together during the spinning process can be suppressed.

[0034] In addition, the biodegradable polyester resin composition is selected from the type of biodegradable polyester resin, includes a melt strength enhancer, and optionally includes a nucleating agent, thereby controlling the crystallization time, so that a smooth spinning process can be performed without deterioration of mechanical properties such as tensile strength and elongation at break.

[0035]

[0036] The structural or functional descriptions of the embodiments disclosed in this specification or application are merely illustrative for the purpose of explaining embodiments according to the technical idea of ​​the present invention, and the embodiments according to the technical idea of ​​the present invention can be implemented in various forms other than the embodiments disclosed in this specification or application, and the technical idea of ​​the present invention is not construed as being limited to the embodiments described in this specification or application.

[0037] Additionally, when a component is referred to as "including" in this specification or application, unless otherwise specifically stated, this does not exclude other components, but rather implies the inclusion of additional components. Furthermore, all numerical ranges indicating physical property values, dimensions, etc. of the components described in this specification or application should be understood to be modified by the term "about" in all cases, unless otherwise specified.

[0038] Additionally, 'ppm' in this specification or application means weight basis.

[0039] Additionally, the term 'derived from' in this specification or application means a component, structure, or substance itself derived from a substance.

[0040]

[0041] Hereinafter, a biodegradable polyester resin composition according to the present invention and a biodegradable nonwoven fabric comprising the same will be described.

[0042]

[0043] A biodegradable polyester resin composition according to the present invention comprises a biodegradable polyester resin comprising a diol-derived unit, an aliphatic dicarboxylic acid-derived unit, and an aromatic dicarboxylic acid-derived unit.

[0044] The above diol may be an aliphatic diol. The above diol may be a bio-derived diol. The above diols are 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, At least one may be selected from the group consisting of 1,9-nonanediol, 1,10-decanediol and 1,12-octadecanediol or derivatives thereof.

[0045] The above diol may be selected from the group consisting of 1,4-butanediol, 1,2-ethanediol, 1,3-propanediol, diethylene glycol, neopentyl glycol or derivatives thereof.

[0046] The above diol may be selected from the group consisting of 1,4-butanediol, 1,2-ethanediol, 1,3-propanediol or derivatives thereof.

[0047] The above diol may include 1,4-butanediol or a derivative thereof.

[0048] The above aliphatic dicarboxylic acid may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, terbric acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid or derivatives thereof.

[0049] The above aliphatic dicarboxylic acid may be selected from the group consisting of adipic acid, succinic acid, sebacic acid or derivatives thereof.

[0050] The above aliphatic dicarboxylic acid may include adipic acid or a derivative thereof.

[0051] The above 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.

[0052] The above aromatic dicarboxylic acid may be selected from the group consisting of terephthalic acid, dimethyl terephthalate, 2,6-naphthalene dicarboxylic acid, isophthalic acid or derivatives thereof.

[0053] The above aromatic dicarboxylic acid may include terephthalic acid, dimethyl terephthalate or derivatives thereof.

[0054] In the biodegradable polyester resin, the molar ratio of the total diol residues including the diol and the total dicarboxylic acid residues including the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid may be from about 1:0.9 to about 1:1.1, or from about 1:0.95 to about 1:1.05.

[0055] In the biodegradable polyester resin, the molar ratio of the aromatic dicarboxylic acid residue and the aliphatic dicarboxylic acid residue may be from about 3:7 to about 7:3, from about 3.3:6.7 to about 6.7:3.3, from about 4:6 to about 6:4, or from about 4.2:5.8 to about 5:5.

[0056] The biodegradable polyester resin may include a diol residue derived from 1,4-butanediol in an amount of about 90 mol% or more, about 95 mol% or more, or about 98 mol% or more based on the total diol.

[0057] The biodegradable polyester resin may include an aromatic dicarboxylic acid residue derived from terephthalic acid or dimethyl terephthalate in an amount of about 30 mol% to about 70 mol%, about 35 mol% to about 65 mol%, about 40 mol% to about 60 mol%, or about 43 mol% to about 53 mol% based on the total dicarboxylic acid.

[0058] The biodegradable polyester resin may include an aliphatic dicarboxylic acid residue derived from adipic acid in an amount of about 30 mol% to about 70 mol%, about 35 mol% to about 65 mol%, about 40 mol% to about 60 mol%, or about 47 mol% to about 57 mol% based on the total dicarboxylic acid.

[0059] The biodegradable polyester resin may include a first block and a second block. The biodegradable polyester resin may have a molecular structure in which the first block and the second block are alternately bonded.

[0060] The first block may include the diol residue and the aromatic dicarboxylic acid residue. The first block may be formed by an esterification reaction of the diol and the aromatic dicarboxylic acid. The first block may include only the diol residue and the aromatic dicarboxylic acid residue. The first block may include only repeating units formed by an esterification reaction of the diol and the aromatic dicarboxylic acid. The first block may refer to the sum of repeating units of the diol and the aromatic dicarboxylic acid before the aliphatic dicarboxylic acid is bonded.

[0061] The second block may include the diol residue and the aliphatic dicarboxylic acid residue. The second block may be formed by an esterification reaction of the diol and the aliphatic dicarboxylic acid. The second block may include only the diol residue and the aliphatic dicarboxylic acid residue. The second block may include only repeating units formed by an esterification reaction of the diol and the aliphatic dicarboxylic acid. The second block may refer to the sum of repeating units of the diol and the aliphatic dicarboxylic acid before the aromatic dicarboxylic acid is bonded.

[0062] In the biodegradable polyester resin, the ratio (X / Y) of the number (X) of the first blocks and the number (Y) of the second blocks may be about 0.5 to about 1.5, about 0.6 to about 1.4, about 0.7 to about 1.3, about 0.75 to about 1.2, or about 0.8 to about 1. The number of the first blocks may be smaller than the number of the second blocks.

[0063] The number of said first blocks may be about 30 to about 300, about 40 to about 250, about 50 to about 220, about 60 to about 200, about 70 to about 200, or about 75 to about 200.

[0064] The number of the first blocks may vary depending on the content of the aromatic dicarboxylic acid, the number average molecular weight of the biodegradable polyester resin, and the degree of alternation described below.

[0065] The number of said second blocks may be about 30 to about 300, about 40 to about 250, about 50 to about 220, about 60 to about 200, about 70 to about 200, or about 75 to about 200.

[0066] The number of the second blocks may vary depending on the content of the aliphatic dicarboxylic acid, the molecular weight of the biodegradable polyester resin, and the degree of alternation described below.

[0067] When the biodegradable polyester resin includes the first block and the second block in the above range, a biodegradable polyester resin composition including the biodegradable polyester resin can have appropriate biodegradability and improved mechanical properties.

[0068] The above biodegradable polyester resin may include the following bonding structures 1 to 3.

[0069] [Combination Structure 1]

[0070] - Aromatic dicarboxylic acids - Diols - Aliphatic dicarboxylic acids -

[0071] [Combination Structure 2]

[0072] - Aromatic dicarboxylic acid - Diol - Aromatic dicarboxylic acid -

[0073] [Combination Structure 3]

[0074] - Aliphatic dicarboxylic acid - Diol - Aliphatic dicarboxylic acid -

[0075] The diol included in the above bonding structure 1 is bonded between the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid, and to the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid. The diol included in the above bonding structure 1 can be directly esterified between the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid, and to the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid.

[0076] The diol included in the above bonding structure 2 is bonded between the aromatic dicarboxylic acid and the aromatic dicarboxylic acid, and to the aromatic dicarboxylic acid and the aromatic dicarboxylic acid. The diol included in the above bonding structure 2 can be directly esterified between the aromatic dicarboxylic acid and the aromatic dicarboxylic acid, and to the aromatic dicarboxylic acid and the aromatic dicarboxylic acid.

[0077] The diol included in the above bonding structure 3 is bonded between the aliphatic dicarboxylic acid and the aliphatic dicarboxylic acid, and to the aliphatic dicarboxylic acid and the aliphatic dicarboxylic acid. The diol included in the above bonding structure 3 can be directly esterified between the aliphatic dicarboxylic acid and the aliphatic dicarboxylic acid and the aliphatic dicarboxylic acid.

[0078] The above biodegradable polyester resin may have an alternating ratio.

[0079] The above-mentioned alternation ratio is the ratio of the diol bonded between the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid among the diols. That is, the above-mentioned alternation ratio may be the ratio of the diol included in the bonding structure 1 among the diols. The above-mentioned alternation ratio may be a value obtained by dividing the number of moles of the diol included in the bonding structure 1 by the sum of the number of moles of the diol included in the bonding structure 1, the number of moles of the diol included in the bonding structure 2, and the number of moles of the diol included in the bonding structure 3.

[0080] The above-mentioned exchange ratio may be the ratio of diols bonded between heterodicarboxylic acids among the total diols.

[0081] The above exchange ratio can be calculated using the following formula 1.

[0082] [Formula 1]

[0083]

[0084] In the above formula 1, DM1 is the molar ratio of the diol included in the bonding structure 1, DM2 is the molar ratio of the diol included in the bonding structure 2, and DM3 is the molar ratio of the diol included in the bonding structure 3.

[0085] In the biodegradable polyester resin, the alternation ratio may be about 0.3 to about 0.7, about 0.37 to about 0.59, about 0.4 to about 0.56, or about 0.45 to about 0.53.

[0086] The biodegradable polyester resin may include a hard segment ratio. The hard segment ratio is the ratio of the diol bonded between the aromatic dicarboxylic acid and the aromatic dicarboxylic acid among the diols.

[0087] The above hard segment ratio may be the molar ratio of the diol included in the bonding structure 2 among the total diols. The above hard segment ratio may be a value obtained by dividing the number of moles of the diol included in the bonding structure 2 by the sum of the number of moles of the diol included in the bonding structure 1, the number of moles of the diol included in the bonding structure 2, and the number of moles of the diol included in the bonding structure 3.

[0088] The above hard segment ratio can be expressed by the following equation 2.

[0089] [Formula 2]

[0090]

[0091] In the above formula 2, DM1 is the molar ratio of the diol included in the bonding structure 1, DM2 is the molar ratio of the diol included in the bonding structure 2, and DM3 is the molar ratio of the diol included in the bonding structure 3.

[0092] The hard segment ratio may be from about 0.15 to about 0.35, from about 0.2 to about 0.3, from about 0.21 to about 0.29, or from about 0.22 to about 0.28.

[0093] The above biodegradable polyester resin composition may include a soft segment.

[0094] The above soft segment ratio is the ratio of the diol bonded between the aliphatic dicarboxylic acid and the aliphatic dicarboxylic acid among the diols.

[0095] The above soft segment ratio may be the molar ratio of the diol included in the bonding structure 3 among the total diols. The above soft segment ratio may be a value obtained by dividing the number of moles of the diol included in the bonding structure 3 by the sum of the number of moles of the diol included in the bonding structure 1, the number of moles of the diol included in the bonding structure 2, and the number of moles of the diol included in the bonding structure 3.

[0096] The above soft segment ratio can be expressed by the following equation 3.

[0097] [Formula 3]

[0098]

[0099] In the above formula 3, DM1 is the molar ratio of the diol included in the bonding structure 1, DM2 is the molar ratio of the diol included in the bonding structure 2, and DM3 is the molar ratio of the diol included in the bonding structure 3.

[0100] The soft segment ratio may be from about 0.16 to about 0.36, from about 0.21 to about 0.31, from about 0.22 to about 0.30, or from about 0.23 to about 0.29.

[0101] The above soft segment ratio may be greater than the above hard segment ratio.

[0102] The ratio of the hard segment to the soft segment may be about 0.92 to about 0.99. That is, the value obtained by dividing the DM2 by the DM3 may be about 0.92 to about 0.99.

[0103] The above-mentioned alternation ratio, the hard segment ratio, and the soft segment ratio can be measured by nuclear magnetic resonance spectroscopy. The biodegradable polyester resin composition is dissolved in a solvent such as CDCl-3, and at room temperature, by a nuclear magnetic resonance (NMR) device, 1 H-NMR and / or 13 It can be analyzed by C-NMR analysis.

[0104] When the diol is 1,4-butanediol, the aromatic dicarboxylic acid is terephthalic acid or dimethyl terephthalate, and the aliphatic dicarboxylic acid is adipic acid, the analysis of the biodegradable polyester resin by nuclear magnetic resonance spectroscopy may include a first peak, a second peak, a third peak, a fourth peak, a fifth peak, a sixth peak, a seventh peak, an eighth peak, a ninth peak, a tenth peak, and an eleventh peak.

[0105] When the diol is 1,4-butanediol, the aromatic dicarboxylic acid is terephthalic acid or dimethyl terephthalate, and the aliphatic dicarboxylic acid is adipic acid, analysis of the biodegradable polyester resin by nuclear magnetic resonance spectroscopy may include a peak derived from the diol of the bonding structure 1, a peak derived from the diol of the bonding structure 2, and a peak derived from the bonding structure 3 at about 3.5 ppm to about 4.6 ppm.

[0106] In the range of about 3.5 ppm to about 4.6 ppm, the first peak, the second peak, the third peak, and the fourth peak may be defined in order from high ppm to low ppm. In addition, based on the ppm of the ninth peak, the first peak, the second peak, the third peak, and the fourth peak may be defined in order from high ppm to low ppm in the range of about -3.4 ppm to about -4.3 ppm.

[0107] -ppm direction can be upfield or shielded. For example, -3.4 ppm can mean 3.4 ppm upfield. For example, -3.4 ppm can mean 3.4 ppm shielded.

[0108] Analysis of the biodegradable polyester resin by the nuclear magnetic resonance spectroscopy may include a peak derived from the diol of the bonding structure 1, a peak derived from the diol of the bonding structure 2, and a peak derived from the bonding structure 3 at about 1.0 ppm to about 2.5 ppm.

[0109] In the range of about 1.0 ppm to about 2.5 ppm, the tenth peak, the fifth peak, the sixth peak, the seventh peak, the eighth peak, and the eleventh peak may be defined in order from high ppm to low ppm. In the range of about -6.0 ppm to about -6.7 ppm based on the ppm of the ninth peak, the fifth peak, the sixth peak, the seventh peak, the eighth peak, and the eleventh peak may be defined in order from high ppm to low ppm.

[0110] In the range of about 7.5 ppm to about 8.5 ppm, the ninth peak may be formed. The ninth peak may be derived from the aromatic dicarboxylic acid. The ninth peak may be derived from an aromatic ring included in the aromatic dicarboxylic acid. The ninth peak may be derived from an aromatic ring included in the terephthalic acid or dimethyl terephthalate.

[0111] The above tenth peak and the above eleventh peak may be derived from the aliphatic dicarboxylic acid. The above tenth peak and the above eleventh peak may be derived from the adipic acid.

[0112] The first peak may be located at about -3.6 ppm to about -3.68 ppm based on the ppm of the ninth peak. The second peak may be located at about -3.69 ppm to about -3.75 ppm based on the ppm of the ninth peak. The third peak may be located at about -3.9 ppm to about -3.97 ppm based on the ppm of the ninth peak. The fourth peak may be located at about -3.98 ppm to about -4.1 ppm based on the ppm of the ninth peak. The fifth peak may be located at about -6.0 ppm to about -6.19 ppm based on the ppm of the ninth peak. The sixth peak may be located at about -6.2 ppm to about -6.26 ppm based on the ppm of the ninth peak. The seventh peak may be located at about -6.27 ppm to about -6.34 ppm based on the ppm of the ninth peak. The eighth peak may be located at about -6.35 ppm to about -6.42 ppm based on the ppm of the ninth peak. The tenth peak may be located at about -5.6 ppm to about -5.8 ppm based on the ppm of the ninth peak. The eleventh peak may be located at about -6.421 ppm to about -6.5 ppm based on the ppm of the ninth peak. The positions based on the ppm of the ninth peak may be the positions of each peak when the position of the ninth peak is 0 ppm.

[0113] The areas of the first peak, the second peak, the third peak, the fourth peak, the fifth peak, the sixth peak, the seventh peak, the eighth peak, the tenth peak, and the eleventh peak can be normalized based on the area of ​​the ninth peak. That is, when the area of ​​the ninth peak is 1, the areas of the first peak, the second peak, the third peak, the fourth peak, the fifth peak, the sixth peak, the seventh peak, the eighth peak, the tenth peak, and the eleventh peak can be relatively determined.

[0114] The above exchange ratio can be derived from the following equation 4 or equation 5.

[0115] [Formula 4]

[0116]

[0117] In the above formula 4, the PA1 is the area of ​​the first peak, the PA2 is the area of ​​the second peak, the PA3 is the area of ​​the third peak, and the PA4 is the area of ​​the fourth peak.

[0118] [Formula 5]

[0119]

[0120] In the above formula 5, the PA5 is the area of ​​the fifth peak, the PA6 is the area of ​​the sixth peak, the PA7 is the area of ​​the seventh peak, and the PA8 is the area of ​​the eighth peak.

[0121] The above hard segment ratio can be derived from the following equation 6 or equation 7.

[0122] [Formula 6]

[0123]

[0124] In the above formula 6, the PA1 is the area of ​​the first peak, the PA2 is the area of ​​the second peak, the PA3 is the area of ​​the third peak, and the PA4 is the area of ​​the fourth peak.

[0125] [Formula 7]

[0126]

[0127] In the above formula 7, the PA5 is the area of ​​the fifth peak, the PA6 is the area of ​​the sixth peak, the PA7 is the area of ​​the seventh peak, and the PA8 is the area of ​​the eighth peak.

[0128] The above soft segment ratio can be derived using Equation 8 or Equation 9 below.

[0129] [Formula 8]

[0130]

[0131] In the above formula 8, the PA1 is the area of ​​the first peak, the PA2 is the area of ​​the second peak, the PA3 is the area of ​​the third peak, and the PA4 is the area of ​​the fourth peak.

[0132] [Formula 9]

[0133]

[0134] In the above formula 9, the PA5 is the area of ​​the fifth peak, the PA6 is the area of ​​the sixth peak, the PA7 is the area of ​​the seventh peak, and the PA8 is the area of ​​the eighth peak.

[0135] The area of ​​the first peak may be from about 0.35 to about 0.6, from about 0.4 to about 0.55, from about 0.43 to about 0.5, from about 0.43 to about 0.52, or from about 0.45 to about 0.49.

[0136] The area of ​​the second peak may be from about 0.37 to about 0.57, from about 0.41 to about 0.54, from about 0.45 to about 0.53, from about 0.45 to about 0.55, or from about 0.47 to about 0.53.

[0137] The area of ​​the third peak may be from about 0.37 to about 0.57, from about 0.41 to about 0.54, from about 0.45 to about 0.53, from about 0.45 to about 0.55, or from about 0.47 to about 0.53.

[0138] The area of ​​the fourth peak may be from about 0.4 to about 0.7, from about 0.45 to about 0.65, from about 0.48 to about 0.6, from about 0.48 to about 0.60, or from about 0.50 to about 0.58.

[0139] The area of ​​the fifth peak may be about 0.35 to about 0.6, about 0.4 to about 0.55, about 0.43 to about 0.53, about 0.43 to about 0.52, or about 0.45 to about 0.49.

[0140] The area of ​​the sixth peak may be from about 0.35 to about 0.6, from about 0.4 to about 0.55, from about 0.43 to about 0.5, from about 0.45 to about 0.55, or from about 0.47 to about 0.53.

[0141] The area of ​​the seventh peak may be from about 0.41 to about 0.71, from about 0.45 to about 0.65, from about 0.48 to about 0.6, from about 0.45 to about 0.55, or from about 0.47 to about 0.53.

[0142] The area of ​​the eighth peak may be from about 0.4 to about 0.7, from about 0.45 to about 0.65, from about 0.48 to about 0.6, or from about 0.50 to about 0.58.

[0143] The area of ​​the above tenth peak may be from about 0.7 to about 2.5, from about 0.75 to about 2, from about 0.8 to about 1.5, from about 1.0 to about 1.15, or from about 1.02 to about 1.13.

[0144] The area of ​​the eleventh peak may be from about 0.7 to about 3.5, from about 0.7 to about 3, from about 0.8 to about 2.5, from about 1.0 to about 1.15, or from about 1.02 to about 1.13.

[0145] The sum of the area of ​​the first peak, the area of ​​the second peak, the area of ​​the third peak, and the area of ​​the fourth peak may be from about 1.49 to about 2.44, from about 1.81 to about 2.16, from about 1.9 to about 2.2, or from about 1.95 to about 2.1. Here, the sum of the area of ​​the first peak, the area of ​​the second peak, the area of ​​the third peak, and the area of ​​the fourth peak may mean the sum of the total number of ester bonds based on the number of terephthalic acids.

[0146] The sum of the area of ​​the second peak and the area of ​​the third peak may be from about 0.95 to about 1.10, or from about 0.98 to about 1.07. Here, the sum of the area of ​​the first peak and the area of ​​the third peak may indicate the extent of extension of the molecular bond of the biodegradable polyester resin.

[0147] The ratio of the area of ​​the fourth peak to the area of ​​the first peak (area of ​​the fourth peak / area of ​​the first peak) may be about 1.1 to about 1.3, about 0.67 to about 2, about 0.96 to about 1.40, or about 1.15 to about 1.25. The ratio of the area of ​​the fourth peak to the area of ​​the first peak may refer to the ratio of the soft segment to the hard segment within the molecular structure of the biodegradable polyester resin. That is, the higher the ratio of the area of ​​the fourth peak to the area of ​​the first peak, the more the biodegradable polyester resin may have improved adhesive properties.

[0148] The ratio of the area of ​​the fourth peak to the area of ​​the third peak (area of ​​the fourth peak / area of ​​the third peak) may be from about 0.7 to about 1.89, from about 0.91 to about 1.33, from about 1.0 to about 1.2, or from about 1.01 to about 1.1.

[0149] The ratio of the area of ​​the first peak to the area of ​​the second peak (area of ​​the first peak / area of ​​the second peak) may be about 0.61 to about 1.62, about 0.81 to about 1.11, about 0.85 to about 0.95, or about 0.86 to about 0.94.

[0150] The ratio of the area of ​​the fifth peak to the area of ​​the first peak (area of ​​the fifth peak / area of ​​the first peak) may be from about 0.61 to about 1.71, from about 0.96 to about 1.40, from about 0.8 to about 1.2, or from about 0.9 to about 1.1.

[0151] The ratio of the area of ​​the sixth peak to the area of ​​the second peak (area of ​​the sixth peak / area of ​​the second peak) may be from about 0.58 to about 1.71, from about 0.86 to about 1.16, from about 0.8 to about 1.2, or from about 0.9 to about 1.1.

[0152] The ratio of the area of ​​the seventh peak to the area of ​​the third peak (area of ​​the seventh peak / area of ​​the third peak) may be about 0.72 to about 1.92, about 0.91 to about 1.33, about 0.8 to about 1.2, or about 0.9 to about 1.1.

[0153] The ratio of the area of ​​the eighth peak to the area of ​​the fourth peak (area of ​​the eighth peak / area of ​​the fourth peak) may be about 0.59 to about 1.75, about 0.80 to about 1.2, or about 0.9 to about 1.1.

[0154] The number average molecular weight of the biodegradable polyester resin may be 20,000 g / mol to 100,000 g / mol, 20,000 g / mol to 90,000 g / mol, 20,000 g / mol to 80,000 g / mol, or 30,000 g / mol to 70,000 g / mol. When the above range is satisfied, the biodegradability is excellent, and changes in mechanical properties due to environmental changes can be minimized.

[0155] The above biodegradable polyester resin composition includes a melt strength enhancer.

[0156] Biodegradable polyester resins containing diol-derived units, aliphatic dicarboxylic acid-derived units, and aromatic dicarboxylic acid-derived units typically exhibit low crystallization temperatures and slow crystallization rates. Consequently, flow stability within the yarn is not maintained during spinning processes at temperatures exceeding 200°C, leading to yarn breakage.

[0157] To address the above issues, the inventors of the present invention introduced a melt strength enhancer that enhances the flow stability within the yarn. This enhances the yarn's stretchability during the spinning process, thereby suppressing yarn breakage.

[0158] The melt strength enhancer may have a weight average molecular weight of 500 g / mol to 2,000 g / mol, 500 g / mol to 1,000 g / mol, 500 g / mol to 800 g / mol, or 500 g / mol to 600 g / mol. The melt strength enhancer may have a melting point (Tm) of 140°C to 147°C, 141°C to 147°C, 142°C to 147°C, or 145°C to 147°C. The melt strength enhancer may have a crystallization temperature (Tc) of 100°C to 150°C, 110°C to 150°C, 130°C to 150°C, or 140°C to 150°C.

[0159] The above melt strength enhancer may have a thermal decomposition temperature of 200°C or higher when heated to 900°C at a rate of 20°C / min in a nitrogen atmosphere using a thermogravimetric analyzer (TGA), and a weight loss rate of 20% or less when heated isothermally for 360 minutes after heating to 240°C at a rate of 20°C / min. The above melt strength enhancer may have a thermal decomposition temperature of 200°C or higher when heated to 900°C at a rate of 20°C / min in a nitrogen atmosphere using a thermogravimetric analyzer (TGA), and a weight loss rate of 18% or less when heated isothermally for 360 minutes after heating to 240°C at a rate of 20°C / min. The above melt strength enhancer may have a thermal decomposition temperature of 200°C or higher when heated to 900°C at a rate of 20°C / min in a nitrogen atmosphere using a thermogravimetric analyzer (TGA), and may have a weight loss rate of 16% or less when heated to 240°C at a rate of 20°C / min and isothermally for 360 minutes.

[0160] The above weight reduction rate can be calculated according to the following formula.

[0161] [ceremony]

[0162] Weight loss rate (%) = {1 - (TGA sample weight (g) / initial sample weight (g))} × 100

[0163] In the above formula, the initial sample weight is the sample weight (g) at the initial room temperature of the TGA, and the TGA sample weight is the sample weight (g) at 900°C after the TGA temperature is raised.

[0164] When the above range is satisfied, the properties of the melt strength enhancer can be prevented from deteriorating during a high-temperature radiation process.

[0165] The above melt strength enhancer may have a LogP (distribution coefficient) value of 10 to 20, 11 to 20, 11 to 19, or 11 to 18.

[0166] The above LogP value is the octanol / water partition coefficient (P ow ) may mean the logarithmic value of the compound. The LogP value may be a parameter value indicating the hydrophilicity / hydrophobicity of the compound. When the above range is satisfied, the dispersibility of the biodegradable polyester resin may be improved.

[0167] The above melt strength enhancer may include a saturated fatty acid amide.

[0168] The above saturated fatty acid amide may have two or more amide groups per molecule.

[0169] The above saturated fatty acid amide may not contain an amide group at the molecular terminal.

[0170] The above saturated fatty acid amide may be a compound whose molecules have a symmetrical structure.

[0171] When the above melt strength enhancer includes a saturated fatty acid amide having the above characteristics, it can exhibit a polarity that is easily reactive with the biodegradable polyester resin, and excessive polarization is suppressed, so that dispersibility for the biodegradable polyester resin can be improved.

[0172] The above melt strength enhancer may include at least one selected from the group consisting of Ethylenebis(stearamide), Ethylenebis-12-hydroxystearamide, and Stearyl Erucamide.

[0173] The above biodegradable polyester resin composition may further include an anti-adhesive agent.

[0174] By using the above anti-adhesive agent, surface friction is reduced, and the adhesive properties are lowered, so that the phenomenon of yarns being twisted together in the spinning process can be suppressed.

[0175] The anti-adhesion agent may have a weight average molecular weight of 200 g / mol to 1,000 g / mol, 200 g / mol to 800 g / mol, 200 g / mol to 500 g / mol, or 300 g / mol to 400 g / mol. The anti-adhesion agent may have a melting point (Tm) of 75°C to 85°C, 77°C to 85°C, 79°C to 85°C, or 80°C to 85°C. The anti-adhesion agent may have a crystallization temperature (Tc) of 50°C to 100°C, 60°C to 100°C, 70°C to 100°C, or 70°C to 90°C.

[0176] The above anti-sticking agent may have a LogP value of 5 to less than 10, 5.5 to less than 10, 5.5 to 9.5, or 6 to 9.5. When the above range is satisfied, the phenomenon of yarns being twisted during the spinning process can be more effectively suppressed.

[0177] The anti-adhesion agent may include an alkene. The anti-adhesion agent may include an amide group at a molecular terminal group. The anti-adhesion agent may include an amide group at one of the molecular terminal groups. The anti-adhesion agent may include a compound in the cis form. The anti-adhesion agent may include an unsaturated fatty acid amide. The anti-adhesion agent may include an unsaturated fatty acid amide in the cis form.

[0178] The anti-adhesive agent as described above has a carbon-carbon double bond, so that the polarity of the molecule can be increased and the slip property between the biodegradable polyester resins can be improved, thereby imparting an anti-blocking function.

[0179] The above anti-adhesive agent may include at least one selected from the group consisting of erucamide and oleamide.

[0180] The solubility of the melt strength enhancer in the biodegradable polyester resin may be lower than the solubility of the anti-adhesion agent in the biodegradable polyester resin.

[0181] The above biodegradable polyester resin composition includes a melt strength enhancer having relatively low solubility in the biodegradable polyester resin, thereby enhancing flow stability within the yarn and improving the stretchability of the yarn, thereby suppressing the phenomenon of the yarn breaking during the spinning process.

[0182] Meanwhile, the biodegradable polyester resin composition can have a relatively fast surface release rate of the yarn by including an anti-adhesive agent having a relatively high solubility in the biodegradable polyester resin, thereby reducing surface friction of the yarn, thereby lowering the adhesive properties between the yarns, and thus suppressing the phenomenon of the yarns being twisted during the spinning process.

[0183] The total content of the above melt strength enhancer and the above anti-adhesive agent may be 0.1 phr to 3 phr, 0.8 phr to 3 phr, 1 phr to 3 phr, or 1.5 phr to 3 phr relative to the biodegradable polyester resin. When the above range is satisfied, a smooth spinning process can be implemented without deterioration of the mechanical properties of the nonwoven fabric being manufactured.

[0184] The above biodegradable polyester resin composition may further include a nucleating agent.

[0185] The above nucleating agent may be a substance that forms a nucleus for the formation of a crystal nucleus.

[0186] When the nucleating agent is included in the biodegradable polyester resin composition, the crystallization speed can be improved. In addition, the crystallization temperature of the biodegradable polyester resin composition can be controlled by the nucleating agent.

[0187] The content of the nucleating agent may be 0.1 phr to 4 phr, 0.5 phr to 4 phr, 0.5 phr to 4 phr, or 0.5 phr to 3 phr relative to the biodegradable polyester resin. When the above range is satisfied, the nucleating agent can be uniformly dispersed in the biodegradable polyester resin composition, and the mechanical properties of a nonwoven fabric manufactured from the biodegradable polyester resin composition can be improved.

[0188] The nucleating agent may include an inorganic material. The inorganic material may include at least one of mica, talc, silica, titanium dioxide (TiO2), and calcium carbonate (CaCO3).

[0189] The nucleating agent may be a fiber derived from biomass. The nucleating agent may be a fiber composed of organic matter. The nucleating agent may be a fibrous nucleating agent. The fibrous nucleating agent may be nanocellulose.

[0190] The above nanocellulose may be at least one selected from the group consisting of nanocrystalline cellulose, cellulose nanofibers, microfibrillated cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, cellulose acetate, methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, pentyl cellulose, hexyl cellulose, and cyclohexyl cellulose.

[0191] The nanocellulose may contain an ionically bonded metal. The nanocrystalline cellulose may contain an alkali metal. The nanocellulose may contain elemental sodium. In addition, the nanocellulose may contain a sulfate. The nanocellulose may contain a carboxylic acid salt. The nanocellulose may be cellulose hydrogen sulfate sodium salt.

[0192] The above nanocellulose can be represented by the following chemical formula 1.

[0193] [Chemical Formula 1]

[0194]

[0195] Here, x may be 1 to 35, and y may be 1 to 10. x may be 15 to 35, and y may be 1 to 10.

[0196] The sulfur content of the nanocellulose may be about 0.1 wt% to about 1.2 wt%, about 0.5 wt% to about 1.2 wt%, or about 0.75 wt% to about 1.1 wt% based on the entire nanocellulose. The sulfur content of the nanocellulose may be measured by ASTM D2622.

[0197] The above nanocellulose may include a surface treatment agent. The surface treatment agent may include at least one selected from the group consisting of sulfates and carboxylates. That is, the nanocellulose may be surface treated with the sulfates or carboxylates.

[0198] The zeta potential of the nanocellulose may be about -50 mV to about -25 mV, about -45 mV to about -30 mV, about -60 mV to about -25 mV, or about -55 mV to about -30 mV. The zeta potential of the cellulose may be measured by a zeta potential meter (e.g., Zetasizer Nano ZS, Malvern).

[0199] Since the above nanocellulose has the above-described characteristics, it can be uniformly dispersed in the biodegradable polyester resin composition, and the mechanical properties of a nonwoven fabric manufactured from the biodegradable polyester resin composition can be improved.

[0200] The above biodegradable polyester resin composition may have a crystallization time at 90°C of 2 minutes (min) or less, 1.8 minutes or less, 1.6 minutes or less, 1.54 minutes or less, 1 minute or less, or 0.5 to 1 minute according to the following measurement method 1.

[0201] [Measurement Method 1]

[0202] 1) The biodegradable polyester resin composition is heated to 220°C at a heating rate of 10°C / min, and then maintained for 5 minutes.

[0203] 2) The biodegradable polyester resin composition is cooled to 90°C at a cooling rate of 100°C / min, and then maintained in an isothermal state for 60 minutes.

[0204] 3) Using a differential scanning calorimeter (DSC), the time taken for the total area of ​​the crystallization peak of the biodegradable polyester resin composition to become half of the total area of ​​the crystallization peak of the biodegradable polyester resin composition is measured.

[0205] The above crystallization time is to rapidly cool the biodegradable polyester resin composition in a molten state and evaluate the time until crystallization.

[0206] A short crystallization time indicates rapid crystallization. Rapid crystallization may imply that molecular motion is suppressed and crystals are formed in the early stages after cooling.

[0207] The above crystallization time can be adjusted depending on whether or not the aforementioned melt strength enhancer, anti-adhesive agent, and nucleating agent are included, the content, etc.

[0208] The fact that the biodegradable polyester resin composition has a crystallization time according to the above measurement method not only indicates a crystallization speed at which the biodegradable polyester resin composition can be manufactured into a nonwoven fabric through a spinning process, but also serves as an indicator that the occurrence of inter-yarn fusion and yarn breakage during the spinning process can be suppressed. When the crystallization time within the above range is satisfied, a smooth spinning process can be performed without deterioration of the mechanical properties of the nonwoven fabric manufactured from the biodegradable polyester resin composition.

[0209] The biodegradable polyester resin composition may have a first melt index of 10 g / 10 min to 40 g / 10 min measured under conditions of 190° C. and 2.16 kg, and a second melt index of 30 g / 10 min to 100 g / 10 min measured under conditions of 230° C. and 2.16 kg. The biodegradable polyester resin composition may have a first melt index of 10 g / 10 min to 38 g / 10 min measured under conditions of 190° C. and 2.16 kg, and a second melt index of 30 g / 10 min to 80 g / 10 min measured under conditions of 230° C. and 2.16 kg. The biodegradable polyester resin composition may have a first melt index of 10 g / 10 min to 30 g / 10 min measured under conditions of 190° C. and 2.16 kg, and a second melt index of 30 g / 10 min to 60 g / 10 min measured under conditions of 230° C. and 2.16 kg.

[0210] When the above range is satisfied, smooth execution of the spinning process can be achieved, which generally exhibits an extruder temperature of about 190°C and a spinning nozzle temperature of about 230°C.

[0211] A biodegradable nonwoven fabric according to the present invention comprises a biodegradable polyester resin comprising a diol-derived unit, an aromatic dicarboxylic acid-derived unit, and an aliphatic dicarboxylic acid-derived unit, and a melt strength reinforcing agent, and comprises a biodegradable polyester resin composition having a crystallization time of 2 minutes (min) or less at 90° C. according to the following measurement method 1.

[0212] [Measurement Method 1]

[0213] 1) The biodegradable polyester resin composition is heated to 220°C at a heating rate of 10°C / min, and then maintained for 5 minutes.

[0214] 2) The biodegradable polyester resin composition is cooled to 90°C at a cooling rate of 100°C / min, and then maintained in an isothermal state for 60 minutes.

[0215] 3) Using a differential scanning calorimeter (DSC), the time taken for the total area of ​​the crystallization peak of the biodegradable polyester resin composition to become half of the total area of ​​the crystallization peak of the biodegradable polyester resin composition is measured.

[0216] The above biodegradable polyester resin composition may be the same as the biodegradable polyester resin composition described above.

[0217] The above nonwoven fabric may include a step of producing a biodegradable yarn by a spinning process using the biodegradable polyester resin composition, a step of cooling the biodegradable yarn, a step of drawing the biodegradable yarn, and a step of forming a biodegradable yarn web by combining the cooled biodegradable yarn.

[0218] The above spinning process may include a process in which the biodegradable polyester resin composition is melted and injected into a spinning block. In the spinning block, the biodegradable polyester resin composition melted from an extruder can be spun from a nozzle. Filaments of the biodegradable polyester resin composition can be formed by the spinning block. The filaments can be solidified and crystallized by cooling to produce an undrawn biodegradable yarn.

[0219] The above step may include a step of cooling the biodegradable yarn.

[0220] The above biodegradable yarn may be an unstretched biodegradable yarn manufactured from the above biodegradable polyester resin composition.

[0221] The cooling may be performed 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 may be performed in a quenching chamber. The length of the quenching 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.

[0222] When the above range is satisfied, the phenomenon of adjacent non-stretched biodegradable yarns fusing with each other can be suppressed.

[0223] The above step may include a step of stretching the cooled biodegradable yarn.

[0224] By the above stretching process, a biodegradable yarn stretched 1.1 to 3 times, 1.2 to 3 times, 1.2 to 2.7 times, 1.2 to 2.6 times, or 1.2 to 2.5 times compared to an unstretched biodegradable yarn can be produced.

[0225] The above-mentioned elongated biodegradable yarn can be heat treated at an appropriate temperature.

[0226] The above-described elongated biodegradable yarn can be wound. The above-described elongated biodegradable yarn can be wound by a winder. The winding speed of the winder can be 300 m / min to 4,000 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 of the biodegradable yarns being fused or cut off from each other can be suppressed.

[0227] The biodegradable 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 4.0 g / de, or 0.5 g / de to 3.0 g / de. The biodegradable yarn may have an elongation of 20% to 400%, 20% to 300%, 25% to 300%, 25% to 250%, or 30% to 250%.

[0228] When the above range is satisfied, the biodegradable yarns can be easily pressed together and easily applied to a biodegradable nonwoven fabric, and the mechanical strength of the biodegradable nonwoven fabric can be improved.

[0229] The above step may include a step of combining the cooled biodegradable yarns to form a biodegradable yarn web.

[0230] The above biodegradable yarn can be made into a nonwoven fabric by a spun bond process or a drawing-crimping-cutting process of filament long fibers to form short fibers. Furthermore, a web can be formed through a carding, airlaid, or water suspension process. Furthermore, a short fiber nonwoven fabric can be made by bonding the web through a calendaring, spunlace, or air-through bonding process.

[0231] By the above process, the bonding force between the biodegradable yarn webs can be strengthened, the tensile strength and elongation can be improved, and the generation of fluff in the biodegradable nonwoven fabric can be prevented.

[0232] The above biodegradable nonwoven fabric is lightweight, has excellent strength, and has a high surface area and porosity, so it can be applied to products requiring hygroscopicity.

[0233] The biodegradable nonwoven fabric may include 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.

[0234] The biodegradable nonwoven fabric may be processed. The biodegradable nonwoven fabric may be treated with an antistatic agent to prevent static electricity. The biodegradable nonwoven fabric may be treated with a water-repellent agent to prevent water leakage. The biodegradable nonwoven fabric may be treated with an antibacterial agent to prevent water leakage.

[0235] The biodegradable nonwoven fabric may be embossed. The biodegradable nonwoven fabric may be printed. The biodegradable nonwoven fabric may be embossed or printed in a thickness and size suitable for the product to which it is applied.

[0236]

[0237] Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the following examples and comparative examples are merely illustrative examples for further explaining the present invention, and the present invention is not limited to the following examples and comparative examples.

[0238]

[0239] Manufacturing example

[0240] - Biodegradable polyester resin: PBAT (SK Livio)

[0241] - Melt strength enhancer #1: Ethylenebis(stearamide) (Mw 593 g / mol, LogP 13.9)

[0242] - Melt strength enhancer #2: Ethylenebis-12-hydroxystearamide (Mw 625 g / mol, LogP 11.3)

[0243] - Melt strength enhancer #3: Stearyl Erucamide (Mw 590 g / mol, LogP 17.7)

[0244] - Anti-adhesive agent #1: Erucamide (Mw 338 g / mol, LogP 8)

[0245] - Anti-adhesive agent #2: Oleamide (Mw 281 g / mol, LogP 6.9)

[0246] - Nucleating agent: TiO2 (average particle size: approximately 0.2 ㎛)

[0247]

[0248] Manufacturing Example 1

[0249] A raw material composition was prepared with the components and contents shown in Table 1 below. Thereafter, the raw material composition was fed into a T-die extrusion molding device (φ20 mm, L / D=25) manufactured by Toyo Seiki Seisaku-sho, Ltd. and equipped with a twin screw, and kneaded at a temperature of approximately 160°C to produce a pelletized biodegradable polyester resin composition.

[0250]

[0251] Manufacturing Examples 2 to 6 and Comparative Manufacturing Examples 1 to 3

[0252] A biodegradable polyester resin composition was manufactured by the same process as Manufacturing Example 1, except that the raw material composition was prepared with the components and contents shown in Table 1 below.

[0253]

[0254] Classification Unit Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Manufacturing Example 6 Manufacturing Example 7 Comparative Manufacturing Example 1 Comparative Manufacturing Example 2 Biodegradable polyester resin weight part 100 100 100 100 100 100 100 100 100 Anti-adhesive agent #1----121-1 #2-121-----Melt strength enhancer #111--122--#2--1------#3---1-----Nucleating agent 0.6 0.6 0.6 0.6 0.6 0.6 0.6-0.6

[0255]

[0256] Example

[0257] Example 1

[0258] The biodegradable polyester resin composition of Manufacturing Example 1 was melted and introduced into a spinning block. Thereafter, a biodegradable yarn was produced from the biodegradable polyester resin composition under the spinning conditions shown in Table 2 below.

[0259]

[0260] Examples 2 to 9 and Comparative Examples 1 to 2

[0261] Biodegradable yarn was manufactured by the same process as Example 1, except for the type of biodegradable polyester resin composition and process conditions shown in Table 2 below.

[0262]

[0263] Classification Biodegradable polyester resin composition Spinning block Nozzle Extruder temperature Spinning nozzle temperature Output Spinning speed Unit -fila℃ g / min, hole m / min Example 1 Manufacturing example 1 36 190 2 30 0.91,500 Example 2 Manufacturing example 1 36 190 2 30 0.62,600 Example 3 Manufacturing example 2 36 190 2 30 0.62,600 Example 4 Manufacturing example 3 36 190 2 30 0.91,500 Example 5 Manufacturing example 4 36 190 2 30 0.91,500 Example 6 Manufacturing example 53 61902300.62,950 Example 7 Manufacturing Example 5361902300.91,500 Example 8 Manufacturing Example 6361902300.91,500 Example 9 Manufacturing Example 7361902300.91,500 Comparative Example 1 Comparative Manufacturing Example 1361902300.91,000 Comparative Example 2 Comparative Manufacturing Example 2361902300.61,500

[0264]

[0265] Experimental example

[0266] Experimental Example 1 - Melt Index (MI)

[0267] Each biodegradable polyester resin composition used in Examples 1 to 9 and Comparative Examples 1 to 2 was pressed with a 2.16 kg weight at a temperature of 190°C according to ASTM D1238, and the discharge amount for 10 minutes was measured to measure the first melt index. In addition, the biodegradable polyester resin composition was pressed with a 2.16 kg weight at a temperature of 230°C according to ASTM D1238, and the discharge amount for 10 minutes was measured to measure the second melt index. The results are shown in Table 3 below.

[0268]

[0269] Experimental Example 2 - Crystallization Time

[0270] Each of the biodegradable polyester resin compositions used in Examples 1 to 9 and Comparative Examples 1 to 2 was heated to 220°C at a heating rate of 10°C / min and maintained for 5 minutes. Thereafter, the temperature was lowered to 90°C at a cooling rate of 100°C / min and maintained in an isothermal state for 60 minutes.

[0271] Thereafter, using differential scanning calorimetry (DSC), the time for the total area of ​​the crystallization peak of the biodegradable polyester resin composition to become half of the total area of ​​the crystallization peak of the biodegradable polyester resin composition was measured, and the results are shown in Table 3 below.

[0272]

[0273] Experimental Example 3 - Tensile strength, elongation at break

[0274] Each of the biodegradable polyester resin compositions used in Examples 1 to 9 and Comparative Examples 1 to 2 was manufactured into a 300 μm thick specimen according to KSM6518. Thereafter, for each specimen, the tensile strength (kgf / mm2 = 9.8 MPa) and elongation at break were measured at room temperature and a speed of 100 mm / min according to ASTM D638 using a universal testing machine (UTM, model number 4206-001) manufactured by INSTRON.

[0275] Separately, after adjusting each of the above specimens to 0.5 cm, the chamber temperature was increased to 100°C for 1 minute, and the tensile strength (kgf / mm2=9.8 MPa) and elongation at break at a speed of 1,000 mm / min were measured. The results are shown in Table 3 below.

[0276]

[0277] Experimental Example 4 - Adhesive Strength

[0278] Each specimen according to the above Experimental Example 3 was adjusted to 2.54 cm × 5 cm and then bonded under a pressure of 0.2 MPa. Thereafter, using a 180-degree peel tester (CK TRADING), the ends of the bonded specimens were separated, bitten into a jig, and then pulled in a 180-degree direction at a speed of 300 mm / min. At this time, the average value of the applied load was measured as the bonding strength, and the results are shown in Table 3 below.

[0279]

[0280] Experimental Example 5 - Radioactivity Evaluation

[0281] In manufacturing the biodegradable yarns of Examples 1 to 9 and Comparative Examples 1 to 2, the radioactivity was evaluated according to the following criteria, and the results are shown in Table 3 below.

[0282] - ◎: ​​Nozzle radiation is smooth, and fiber breakage and merging do not occur.

[0283] - △: Nozzle radiation is smooth, but fibers are cut or combined.

[0284] - ×: Nozzle is blocked and cannot be emitted.

[0285]

[0286] Experimental Example 6 - Properties of Biodegradable Yarn

[0287] The fineness of the biodegradable yarns of Examples 1 to 9 and Comparative Examples 1 to 2 was measured according to KSK ISO 6939, and the tensile strength and elongation at break were measured at a breaking distance of 300 mm and a tensile speed of 2,000 mm / min according to KSK ISO 2062. The results are shown in Table 3 below.

[0288]

[0289] Classification Biodegradable polyester resin composition MI crystallization time tensile strength elongation at break adhesive strength radioactivity evaluation yarn properties 190 ℃230℃Room temperatureHigh temperatureRoom temperatureHigh temperatureFinenessTensile strengthElongation at breakUnit-g / 10minminMPa%kg / inch-deg / de%Example 1Manufacturing example 129.475.41.5428.54.5338831,7620.2◎5.21.1123Example 2Manufacturing example 129.475.41.5428.54.5338831,7620.2◎1.91.399Example 3Manufacturing example 231.688.60.724.84.17902,1050.1◎1.61.680Example 4Manufacturing example 332.589.50.723.83.9417401,913- 1) ◎5.00.8160 Example 5 Manufacturing Example 431.688.60.724.84.17902,105- 2) ◎4.91.0210Embodiment 6 Manufacturing Example 531.552.30.725.73.9387952,0840.1◎5.11.1220Embodiment 7 Manufacturing Example 531.552.30.725.73.9387952,0840.1◎1.51.580Embodiment 8 Manufacturing Example 635.958.90.824.947441,924- 3) ◎4.90.8162 Example 9 Manufacturing Example 734.154.90.7523.23.787032,539- 4)◎5.00.9173Comparative Example 1Comparative Manufacturing Example 1294810.931.53.738902,7903.8×Unable to be measured due to non-radiationComparative Example 2Comparative Manufacturing Example 230.247.70.525.94.1687721,9352.4△Unable to be measured due to fiber breakage after radiation1),2),3),4) -: Not adhered

[0290]

[0291] As can be confirmed from Tables 1 to 3 above, the biodegradable polyester resin compositions of Examples 1 to 9 can strengthen the flow stability inside the yarn and improve the stretchability of the yarn compared to the biodegradable polyester resin compositions of Comparative Examples 1 to 2, and it can be confirmed that the phenomenon of the yarn breaking during the spinning process is suppressed.

[0292] Additionally, the biodegradable polyester resin compositions of Examples 1 to 9 can have a crystallization time sufficient to be manufactured into a nonwoven fabric by a spinning process due to their enhanced crystallization rate. Furthermore, it was confirmed that the phenomenon of yarns being twisted or broken during the spinning process was suppressed due to a decrease in adhesive properties.

[0293]

[0294] The embodiment can be applied to a biodegradable polyester resin composition and a biodegradable nonwoven fabric comprising the same.

Claims

1. A biodegradable polyester resin comprising a diol-derived unit, an aromatic dicarboxylic acid-derived unit, and an aliphatic dicarboxylic acid-derived unit; and Contains a melting strength enhancer, A biodegradable polyester resin composition having a crystallization time of 2 minutes (min) or less at 90°C according to the following measurement method 1: [Measurement Method 1] 1) The biodegradable polyester resin composition is heated to 220°C at a heating rate of 10°C / min, and then maintained for 5 minutes. 2) The biodegradable polyester resin composition is cooled to 90°C at a cooling rate of 100°C / min, and then maintained in an isothermal state for 60 minutes. 3) Using a differential scanning calorimeter (DSC), the time taken for the total area of ​​the crystallization peak of the biodegradable polyester resin composition to become half of the total area of ​​the crystallization peak of the biodegradable polyester resin composition is measured.

2. In paragraph 1, A biodegradable polyester resin composition wherein the above melt strength reinforcing agent comprises a saturated fatty acid amide.

3. In paragraph 1, The above melt strength enhancer is a biodegradable polyester resin composition having a thermal decomposition temperature of 200°C or higher when heated to 900°C at a rate of 20°C / min in a nitrogen atmosphere using a thermogravimetric analyzer (TGA), and a weight loss rate of 20% or less when heated to 240°C at a rate of 20°C / min for 360 minutes at an isothermal temperature.

4. In paragraph 1, A biodegradable polyester resin composition wherein the above melt strength enhancer has a weight average molecular weight of 500 g / mol to 800 g / mol.

5. In paragraph 1, A biodegradable polyester resin composition further comprising an anti-adhesive agent.

6. In paragraph 1, A biodegradable polyester resin composition wherein the above-mentioned anti-adhesive agent comprises an unsaturated fatty acid amide.

7. In paragraph 1, A biodegradable polyester resin composition wherein the above-mentioned anti-adhesive agent has a weight average molecular weight of 200 g / mol to 500 g / mol.

8. In paragraph 5, A biodegradable polyester resin composition wherein the solubility of the melt strength enhancer in the biodegradable polyester resin is lower than the solubility of the anti-adhesion agent in the biodegradable polyester resin.

9. In paragraph 5, A biodegradable polyester resin composition wherein the total content of the melt strength enhancer and the anti-adhesive agent is 0.1 phr to 3 phr relative to the biodegradable polyester resin.

10. In paragraph 1, A biodegradable polyester resin composition further comprising a nucleating agent.

11. In paragraph 10, A biodegradable polyester resin composition having a nucleating agent content of 0.1 phr to 4 phr relative to the biodegradable polyester resin.

12. In paragraph 1, The biodegradable polyester resin composition has a first melt index of 10 g / 10 min to 40 g / 10 min measured under conditions of 190° C. and 2.16 kg, and a second melt index of 30 g / 10 min to 100 g / 10 min measured under conditions of 230° C. and 2.16 kg.

13. A biodegradable nonwoven fabric comprising a biodegradable polyester resin composition comprising a diol-derived unit, an aromatic dicarboxylic acid-derived unit, and an aliphatic dicarboxylic acid-derived unit, and a melt strength reinforcing agent, and having a crystallization time of 2 minutes (min) or less at 90° C. according to the following measurement method 1: [Measurement Method 1] 1) The biodegradable polyester resin composition is heated to 220°C at a heating rate of 10°C / min, and then maintained for 5 minutes. 2) The biodegradable polyester resin composition is cooled to 90°C at a cooling rate of 100°C / min, and then maintained in an isothermal state for 60 minutes. 3) Using a differential scanning calorimeter (DSC), the time taken for the total area of ​​the crystallization peak of the biodegradable polyester resin composition to become half of the total area of ​​the crystallization peak of the biodegradable polyester resin composition is measured.

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