Biodegradable resin composition and biodegradable nonwoven fabric including the same

Abstract

To provide a biodegradable resin composition having excellent biodegradability and improved spinning ability, and a biodegradable nonwoven fabric including the same.SOLUTION: The present invention provides a biodegradable resin composition comprising a biodegradable resin including a first repeating unit derived from a diol having 2 to 4 carbon atoms and a second repeating unit derived from an aliphatic dicarboxylic acid having 2 to 6 carbon atoms, and an inorganic nucleating agent, wherein the crystallinity measured by differential scanning calorimetry is 15% to 50%, as well as a biodegradable resin including a first repeating unit derived from a diol having 2 to 4 carbon atoms and a second repeating unit derived from an aliphatic dicarboxylic acid having 2 to 6 carbon atoms.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] Conventionally, polyethylene, polypropylene, and polyethylene terephthalate have been used as materials for clothing fibers, nonwoven 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 nonwoven fabrics used as disposable products have been demanded.

[0003] As solutions to these problems, research on biodegradable resins has been actively conducted. 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 into fibers or nonwoven fabrics.

[0005] Also, in order to improve the spinnability of biodegradable resins, various biodegradable resins were combined, but the kneadability between biodegradable resins with different physical properties decreased, and problems such as fusion occurring between fibers or the thread breaking after spinning occurred.

Summary of the Invention

Problems to be Solved by the Invention

[0006] The present invention provides a biodegradable resin composition excellent in biodegradability and improved in spinnability, and a biodegradable nonwoven fabric containing the same.

Means for Solving the Problems

[0007] The biodegradable resin composition according to the present invention includes a biodegradable resin containing a first repeating unit derived from a diol having 2 to 4 carbon atoms and a second repeating unit derived from an aliphatic dicarboxylic acid having 2 to 6 carbon atoms, and an inorganic nucleating agent, and the crystallinity measured using a differential scanning calorimeter is 15% to 50%.

[0008] In one embodiment of the present invention, the molar ratio of the first repeating unit to the second repeating unit may be 4:1 to 1:1.

[0009] In one embodiment of the present invention, the biodegradable resin may further include a third repeating unit derived from an aromatic dicarboxylic acid.

[0010] In one embodiment of the present invention, the molar ratio of the first repeating unit to the third repeating unit may be 10:3 to 10:7.

[0011] In one embodiment of the present invention, the molar ratio of the second repeating unit to the third repeating unit may be 3:2 to 2:3.

[0012] In one embodiment of the present invention, the content of the inorganic nucleating agent may be 10 ppm to 10,000 ppm with respect to the total weight of the biodegradable resin composition.

[0013] In one embodiment of the present invention, the inorganic nucleating agent may include 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.

[0014] In one embodiment of the present invention, the biodegradable resin composition may contain nanocellulose having an average length of 10 nm to 300 nm.

[0015] In one embodiment of the present invention, the content of the nanocellulose may be 10 ppm to 500 ppm based on the total weight of the biodegradable resin composition.

[0016] In one embodiment of the present invention, the biodegradable resin composition may contain a branching agent containing at least one of a polyhydric alcohol having three or more hydroxyl groups and a polycarboxylic acid having three or more carboxyl groups.

[0017] In one embodiment of the present invention, the content of the branching agent may be 500 ppm to 3,000 ppm based on the total weight of the biodegradable resin composition.

[0018] In one embodiment of the present invention, the biodegradable resin composition may have a melt flow rate value measured under the conditions of 190 °C and 2.16 kg of 10 g / 10 min to 25 g / 10 min.

[0019] In one embodiment of the present invention, the biodegradable resin composition may have an adhesive strength of 5 kgf or less according to the following measuring method 1.

[0020] [Measuring Method 1] 1) The biodegradable resin composition is compressed at a temperature of 210 °C and a pressure of 10 MPa for 3 minutes to produce a sheet having a width of 20 mm, a length of 100 mm, and a thickness of 0.3 mm.

[0021] 2) After the two sheets are butted against each other horizontally at a length of 75 mm, they are adhered at a temperature of 90 °C and a pressure of 5 MPa for 10 minutes.

[0022] 3) For the two adhered sheets, a 180° lap shear test is performed at a tensile speed of 100 mm / min to measure the adhesive strength.

[0023] In one embodiment of the present invention, the biodegradable resin composition may have an isothermal crystallization time at 70°C of 10 seconds to 300 seconds according to the following measurement method 2.

[0024] [Measurement method 2] 1) After heating the biodegradable resin composition to 220°C at a heating rate of 10°C / min, it is maintained for 5 minutes.

[0025] 2) Then, after cooling the biodegradable resin composition to 70°C at a cooling rate of 100°C / min, it is maintained in an isothermal state for 100 minutes.

[0026] 3) Using the 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.

[0027] The biodegradable nonwoven fabric according to the present invention includes a biodegradable resin composition containing a first repeating unit derived from a diol having 2 to 4 carbon atoms and a second repeating unit derived from an aliphatic dicarboxylic acid having 2 to 6 carbon atoms, and an inorganic nucleating agent. The biodegradable resin composition has a crystallinity of 15% to 50% measured using a differential scanning calorimeter.

Advantages of the Invention

[0028] The biodegradable resin composition according to the present invention may be one in which the types of monomers of the biodegradable resin are adjusted, an inorganic nucleating agent is included, and it has a crystallinity in the range of 15% to 50%.

[0029] Thereby, the biodegradable resin composition may have a melt flow rate, a melting point, an isothermal crystallization time, and an adhesion strength that may be produced into a nonwoven fabric by a spinning process.

[0030] As a result, the biodegradable resin composition can suppress the phenomenon of yarn breakage of fibers in the spinning process.

[0031] In addition, even when rapid quenching is not performed after spinning, the biodegradable resin composition can prevent fusion from occurring between fibers and can adjust the denier of the fibers.

[0032] Moreover, the fibers produced from the biodegradable resin composition can exhibit appropriate drape properties, can suppress the phenomenon of yarn breakage of fibers in the spinning process, and can improve the touch feeling of the produced fibers.

[0033] In addition, the biodegradable nonwoven fabric produced from the biodegradable resin composition is biodegradable naturally when its lifespan is exhausted, has the effect of not requiring incineration and not discharging harmful substances.

Brief Description of the Drawings

[0034]

Figure 1

Modes for Carrying Out the Invention

[0035] The structural or functional description regarding the embodiments disclosed in this specification or the application is merely exemplified for the purpose of explaining the embodiments according to the technical idea of the present invention. The embodiments according to the technical idea of the present invention can be implemented in various forms in addition to the embodiments disclosed in this specification or the application, and the technical idea of the present invention is not construed as being limited to the embodiments described in this specification or the application.

[0036] Also, when a component in this specification or application is described as "including", unless otherwise stated to the contrary, 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 application must be understood to be modified by the term "about" unless otherwise specified.

[0037] Also, "ppm" in this specification or application means a weight basis.

[0038] Also, "derived from" in this specification or application means a component, structure, or the substance itself that originates from a certain substance.

[0039] Hereinafter, the biodegradable resin composition according to the present invention and the biodegradable nonwoven fabric containing the same will be described.

[0040] The biodegradable resin composition according to the present invention includes a biodegradable resin containing a first repeating unit derived from a diol having 2 to 4 carbon atoms and a second repeating unit derived from an aliphatic dicarboxylic acid having 2 to 6 carbon atoms, and an inorganic nucleating agent, and the crystallinity measured using a differential scanning calorimeter is 15% to 50%.

[0041] The biodegradable resin composition according to the present invention includes a biodegradable resin. The biodegradable resin includes a first repeating unit derived from a diol having 2 to 4 carbon atoms and a second repeating unit derived from an aliphatic dicarboxylic acid having 2 to 6 carbon atoms.

[0042] The diol may be an aliphatic diol. The diol may also be a bio-derived diol. The diol may be at least one selected from the group consisting of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,4-butanediol, and derivatives thereof.

[0043] Preferably, the diol may contain at least one of ethylene glycol and 1,4-butanediol.

[0044] The biodegradable resin containing the first repeating unit derived from the C2-C4 diol can have an appropriate melt flow rate, melting point, isothermal crystallization time, and adhesion strength, and may be manufactured into a non-woven fabric by a spinning process.

[0045] The aliphatic dicarboxylic acid may be at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, and derivatives thereof.

[0046] Preferably, the aliphatic dicarboxylic acid may contain at least one of succinic acid and adipic acid.

[0047] The biodegradable resin containing the second repeating unit derived from the C2-C6 aliphatic dicarboxylic acid can have an appropriate melt flow rate, melting point, isothermal crystallization time, and adhesion strength, can suppress the phenomenon of fiber breakage in the spinning process, no fusion occurs between fibers, and the fineness of the fibers can be adjusted.

[0048] The biodegradable resin may further contain a third repeating unit derived from an aromatic dicarboxylic acid.

[0049] 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, and derivatives thereof.

[0050] 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, and derivatives thereof.

[0051] Preferably, the aromatic dicarboxylic acid may contain terephthalic acid, dimethyl terephthalate, and derivatives thereof.

[0052] The biodegradable resin containing the third repeating unit derived from the aromatic dicarboxylic acid can improve the tensile strength and elongation at break.

[0053] The molar ratio of the first repeating unit to the second repeating unit may be 4:1 to 1:1. The molar ratio of the first repeating unit to the second repeating unit may be 4:1.5 to 1:1. The molar ratio of the first repeating unit to the second repeating unit may be 4:2 to 1:1. Preferably, the molar ratio of the first repeating unit to the second repeating unit may be 4:2.12 to 1:1. When the above range is satisfied, the spinning ability of the biodegradable resin composition can be improved.

[0054] The molar ratio of the first repeating unit to the second repeating unit means the molar ratio of the first repeating unit derived from the diol having 2 to 4 carbon atoms and the second repeating unit derived from the aliphatic dicarboxylic acid having 2 to 6 carbon atoms.

[0055] The molar ratio of the first repeating unit to the third repeating unit may be 10:3 to 10:7. The molar ratio of the first repeating unit to the third repeating unit may be 10:3 to 10:6. The molar ratio of the first repeating unit to the third repeating unit may be 10:3 to 10:6. Preferably, the molar ratio of the first repeating unit to the third repeating unit may be 10:4 to 10:5. When the above range is satisfied, the tensile strength and elongation of the nonwoven fabric produced from the biodegradable resin composition can be improved.

[0056] The molar ratio of the first repeating unit to the third repeating unit means the molar ratio of the first repeating unit derived from the diol having 2 to 4 carbon atoms and the third repeating unit derived from the aromatic dicarboxylic acid.

[0057] The molar ratio of the second repeating unit to the third repeating unit may be 3:2 to 2:3. The molar ratio of the second repeating unit to the third repeating unit may be 3:2 to 2.5:3. The molar ratio of the second repeating unit to the third repeating unit may be 3:2 to 3:3. Preferably, the molar ratio of the second repeating unit to the third repeating unit may be 3:2 to 3:2.8. When the above range is satisfied, the spinning ability of the biodegradable resin composition is improved, and the tensile strength and elongation of the nonwoven fabric produced from the biodegradable resin composition can be improved.

[0058] The molar ratio of the second repeating unit to the third repeating unit means the molar ratio of the second repeating unit derived from the aliphatic dicarboxylic acid having 2 to 6 carbon atoms and the third repeating unit derived from the aromatic dicarboxylic acid.

[0059] The biodegradable resin may be polybutylene adipate terephthalate (PBAT).

[0060] The biodegradable resin may be polybutylene succinate terephthalate (PBST).

[0061] The biodegradable resin may be polybutylene adipate succinate (PBAS).

[0062] The biodegradable resin may be polybutylene adipate succinate terephthalate (PBAST).

[0063] The biodegradable resin may be polyethylene adipate succinate terephthalate (PEAST).

[0064] The number average molecular weight of the biodegradable resin may be 30,000 g / mol to 50,000 g / mol, 31,000 g / mol to 50,000 g / mol, 32,000 g / mol to 50,000 g / mol, 33,000 g / mol to 50,000 g / mol, 33,000 g / mol to 45,000 g / mol, 33,000 g / mol to 42,000 g / mol, or 33,000 g / mol to 40,000 g / mol.

[0065] The weight average molecular weight of the biodegradable resin may be 60,000 g / mol to 100,000 g / mol, 60,000 g / mol to 95,000 g / mol, 60,000 g / mol to 93,000 g / mol, 63,000 g / mol to 93,000 g / mol, 65,000 g / mol to 93,000 g / mol, or 70,000 g / mol to 90,000 g / mol.

[0066] The polydispersity index of the biodegradable resin may be 1.5 to 3.0, 1.8 to 3.0, 2.0 to 2.8, 2.0 to 2.7, 2.0 to 2.6, or 2.0 to 2.5.

[0067] When the ranges of the number average molecular weight, weight average molecular weight, and polydispersity index are satisfied, the spinning ability is excellent and the tensile strength can be improved.

[0068] The number average molecular weight, weight average molecular weight, and polydispersity index of the biodegradable resin can be measured under the following measurement conditions.

[0069] - Analytical instrument: Agilent 1260 Infinity - Detector: Agilent G1362A RI-detector - Column type: waters styragel(R) HR4 THF 7.8×300mm - Solvent: THF - Temperature: 40 °C - Flow rate: 1 mL / min - Concentration: 4 mg / mL

[0070] The biodegradable resin composition according to the present invention contains an inorganic nucleating agent. The inorganic nucleating agent may mean a nucleating agent composed of an inorganic compound. By including the inorganic nucleating agent, the biodegradable resin composition can improve the crystallization rate, suppress the fusion between fibers during the spinning process, and has the effect of being able to adjust the denier. In addition, a uniform nano-sized fiber phase can be formed, and the formation of beads can be suppressed during the production of non-woven fabrics.

[0071] The inorganic nucleating agent may include 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. Preferably, the inorganic nucleating agent may include titanium dioxide (TiO2). At least one of FD (Full Dull) TiO2 having almost no gloss and SD (Semi Dull) TiO2 having a little gloss can be used as the titanium dioxide.

[0072] The content of the inorganic nucleating agent may be 10 ppm to 10,000 ppm, 100 ppm to 10,000 ppm, 300 ppm to 10,000 ppm, 500 ppm to 10,000 ppm, 500 ppm to 5,000 ppm, or 1,000 ppm to 3,000 ppm based on the total weight of the biodegradable resin composition. When the above range is satisfied, the crystallinity of the biodegradable resin composition can be adjusted to the range of 15% to 50%, the phenomenon of yarn breakage of fibers in the spinning process can be suppressed, and the spinning process can be carried out smoothly.

[0073] The biodegradable resin composition may include 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. 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 based on the total weight of the biodegradable resin composition. When the above range is satisfied, the crystallization rate can be improved, the fusion between fibers during the spinning process can be suppressed, and the fineness can be adjusted.

[0074] The nanocellulose may be pre-treated with a bead mill or ultrasonic waves. The nanocellulose may be pre-treated with both a bead mill and ultrasonic waves. The nanocellulose is preferably pre-treated with ultrasonic waves after the bead mill pre-treatment to prevent re-aggregation and improve dispersibility.

[0075] The bead mill pre-treatment can be carried out using a vertical mill or a horizontal mill as a wet milling device. Although the horizontal mill is preferred in that it can hold a larger amount of beads inside the chamber, reducing mechanical eccentric wear, bead wear, and making maintenance easier, it is not limited thereto.

[0076] The bead mill pre-treatment can be carried out using one or more beads selected from the group consisting of zirconium, zircon, zirconia, quartz, and aluminum oxide.

[0077] The bead mill pre-treatment 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.

[0078] The ultrasonic pre-treatment means a method of physically closing or pulverizing nanoparticles by waves generated by emitting ultrasonic waves of 20 kHz into a solution.

[0079] The ultrasonic pre-treatment can be carried out at an output of 30,000 J / s or less for a time of less than 30 minutes. For example, the ultrasonic pre-treatment can be carried out at 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 pre-treatment, i.e., the improvement of dispersibility, can be maximized.

[0080] The biodegradable resin composition may contain a branching agent containing at least one of an alcohol having a valency of 3 or more and a carboxylic acid having a valency of 3 or more. 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 biodegradable resin.

[0081] The alcohol having a valency of 3 or more may be at least one selected from the group consisting of glycerol, pentaerythritol, or trimethylolpropane.

[0082] The carboxylic acid having a valency of 3 or more 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.

[0083] Preferably, the branching agent may contain glycerol.

[0084] 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 based on 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 its mechanical properties can be improved.

[0085] 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, triethylphosphonoacetate, phosphoric acid, phosphorous acid, polyphosphric acid, trimethyl phosphate (TMP), triethyl phosphate, trimethyl phosphine, and triphenyl phosphine.

[0086] Preferably, the heat stabilizer may contain triethylphosphonoacetate.

[0087] 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 degradation 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.

[0088] The biodegradable resin composition may contain a lubricant.

[0089] The lubricant may contain one or more selected from the group consisting of fatty acid-based lubricants containing stearic acid, aliphatic alcohol-based lubricants, aliphatic amide-based lubricants containing stearamide, n-butyl stearate, methyl hydroxystearate, polyhydric alcohol fatty acid esters, saturated fatty acid esters, aliphatic ester-based lubricants such as ester waxes, and fatty acid metal soap-based lubricants.

[0090] Preferably, the lubricant may be a stearate-based lubricant and may contain one or more selected from the group consisting of calcium stearate, zinc stearate, barium stearate, magnesium stearate, glycerin stearate, and butyl stearate.

[0091] Preferably, the lubricant may be a wax-based lubricant and may contain N,N-ethylenebisstearamide.

[0092] During the mixing, melting, and processing of the raw materials, the lubricant can reduce the generation of heat due to friction, is excellent in the dispersion effect on the biodegradable resin compared to the price, has an excellent lubricating effect, and can improve the manufacturing efficiency.

[0093] The content of the stearate-based lubricant may be 1,000 ppm to 10,000 ppm, 1,000 ppm to 8,000 ppm, 3,000 ppm to 8,000 ppm, or 4,000 ppm to 6,000 ppm based on the total weight of the biodegradable resin composition.

[0094] The content of the wax-based lubricant may be 1,000 ppm to 10,000 ppm, 1,000 ppm to 8,000 ppm, 3,000 ppm to 8,000 ppm, or 4,000 ppm to 6,000 ppm based on the total weight of the biodegradable resin composition.

[0095] 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.

[0096] The crystallinity of the biodegradable resin composition is 15% to 50% as measured using a differential scanning calorimeter (DSC).

[0097] Preferably, the crystallinity of the biodegradable resin composition may be 15% to 50%, 15% to 40%, 15% to 30%, or 15% to 25%. When the above range is satisfied, it is possible to suppress the phenomenon of yarn breakage of the fibers in the spinning process, no fusion occurs between the fibers, and the fineness of the fibers can be adjusted.

[0098] The crystallinity can be calculated by the following calculation formula using the crystal melting energy value and the crystal formation energy value measured using the differential scanning calorimeter.

[0099] [Calculation formula] Crystallinity (%) = [(Energy required for 1 g of the biodegradable resin composition to melt (crystal melting energy (J / g) / crystal formation energy (J / g))) / Energy required for 1 g to melt when the biodegradable resin composition has 100% crystallinity (J / g)] × 100

[0100] The fact that the biodegradable resin composition has a crystallinity range according to the calculation method means the crystallinity of the biodegradable resin composition produced into a non-woven fabric by a spinning process, and may also have a meaning as an index capable of suppressing the phenomenon of yarn breakage of the fibers in the spinning process and preventing fusion between the fibers.

[0101] The crystallinity of the biodegradable resin composition can be adjusted by the types and contents of the aforementioned diol, aliphatic dicarboxylic acid, and aromatic dicarboxylic acid, and whether or not an inorganic nucleating agent is included.

[0102] The melt flow rate value of the biodegradable resin composition measured under the conditions of 190 °C and 2.16 kg may be 10 g / 10 min to 25 g / 10 min, 10 g / 10 min to 20 g / 10 min, 10 g / 10 min to 15 g / 10 min, or 11 g / 10 min to 15 g / 10 min.

[0103] The melt flow rate value of the biodegradable resin composition measured under the conditions of 230 °C and 2.16 kg may be 20 g / 10 min to 50 g / 10 min, 25 g / 10 min to 50 g / 10 min, 25 g / 10 min to 40 g / 10 min, or 29 g / 10 min to 39 g / 10 min.

[0104] When the above range is satisfied, the discharge amount of the biodegradable resin composition is uniform during the spinning process, and it can have excellent spinning ability. The raw yarn of the biodegradable nonwoven fabric produced from the biodegradable resin composition is not cut, and the tensile strength and elongation rate can be improved.

[0105] The adhesive strength of the biodegradable resin composition according to the following measuring method 1 may be 5 kgf or less, 4.5 kgf or less, 4.4 kgf or less, or 0.2 kgf or more to 4.4 kgf or less. When the above range is satisfied, after the spinning process, the fibers produced from the biodegradable resin composition have the effect of not fusing with each other or the yarn not breaking.

[0106] [Measuring method 1] 1) Compress the biodegradable resin composition at a temperature of 210 °C and a pressure of 10 MPa for 3 minutes to produce a sheet with a width of 20 mm, a length of 100 mm, and a thickness of 0.3 mm.

[0107] 2) After butting the two sheets horizontally at a length of 75 mm, bond them at a temperature of 90 °C and a pressure of 5 MPa for 10 minutes.

[0108] 3) For the two adhered sheets, a 180° lap shear test is carried out at a tensile speed of 100 mm / min to measure the adhesion strength.

[0109] The adhesion strength can be adjusted according to the types and contents of the aforementioned diol, aliphatic dicarboxylic acid, and aromatic dicarboxylic acid, and whether or not an inorganic nucleating agent is included.

[0110] The biodegradable resin composition may have an isothermal crystallization time at 70 °C of 10 seconds to 300 seconds, 50 seconds to 300 seconds, 100 seconds to 300 seconds, or 114 seconds to 186 seconds according to the following measurement method 2. When the above range is satisfied, after the spinning process, the fibers produced from the biodegradable resin composition have the effect of fusing with each other or the yarn not breaking.

[0111] [Measurement method 2] 1) After heating the biodegradable resin composition to 220 °C at a heating rate of 10 °C / min, it is maintained for 5 minutes.

[0112] 2) Then, after cooling the biodegradable resin composition to 70 °C at a cooling rate of 100 °C / min, it is maintained in an isothermal state for 100 minutes.

[0113] 3) Using the differential scanning calorimeter, for the total area of the crystallization peak of the biodegradable resin composition, the time that becomes half of the total area of the crystallization peak of the biodegradable resin composition is measured.

[0114] The isothermal crystallization time evaluates the time until crystallization by rapidly cooling a polymer in a molten state.

[0115] A short isothermal crystallization time indicates that crystallization occurs quickly. Crystallization occurring quickly may mean that molecular motion in the early stage after cooling is suppressed and a crystalline part is formed.

[0116] The isothermal crystallization time can be adjusted according to the types and contents of the aforementioned diols, aliphatic dicarboxylic acids, and aromatic dicarboxylic acids, and whether or not an inorganic nucleating agent is included.

[0117] The biodegradable resin composition may have a melting temperature. The melting temperature of the biodegradable resin composition may be 120°C to 200°C, 130°C to 200°C, 150°C to 200°C, or 150°C to 190°C. When the above range is satisfied, the tensile strength and elongation of the biodegradable nonwoven fabric produced from the biodegradable resin composition can be improved.

[0118] The maximum load of the biodegradable resin composition may be 2 kgf to 5 kgf, 2.5 kgf to 5 kgf, 3 kgf to 5 kgf, or 4 kgf to 4.8 kgf.

[0119] The yield strength of the biodegradable resin composition may be 0.5 Mpa to 8 Mpa, 0.5 Mpa to 7 Mpa, 1 Mpa to 7 Mpa, 1.2 Mpa to 7 Mpa, or 1.2 Mpa to 5.4 Mpa.

[0120] The elongation of the biodegradable resin composition may be 300% to 700%, 350% to 700%, 400% to 700%, 450% to 700%, or 500% to 700%.

[0121] The maximum load, yield strength, and elongation of the biodegradable resin composition may be indicators showing the adhesion strength of the biodegradable resin composition. The maximum load, yield strength, and elongation of the biodegradable resin composition may vary depending on the content of the inorganic nucleating agent contained in the biodegradable resin composition. When the above range is satisfied, the adhesive force between the spun biodegradable resin compositions can be reduced, a uniform nano-sized fiber phase can be formed, and the formation of beads in the biodegradable nonwoven fabric can be suppressed.

[0122] The biodegradable nonwoven fabric according to the present invention may be manufactured by a step of spinning a biodegradable resin composition to produce biodegradable raw yarns, a step of cooling the biodegradable raw yarns, and a step of bonding the cooled biodegradable raw yarns to form a biodegradable raw yarn web.

[0123] FIG. 1 schematically shows an apparatus for manufacturing a biodegradable resin composition according to an embodiment. Referring to FIG. 1, the apparatus may include a slurry stirrer 100, an esterification reaction unit 200, a polycondensation reaction unit 300, a post-treatment unit 400, a first recovery unit 510, and a second recovery unit 520.

[0124] The step of manufacturing the biodegradable resin composition may include a step of manufacturing a first slurry containing the above-described diol and aromatic dicarboxylic acid.

[0125] The step of manufacturing the biodegradable resin composition may include a step of manufacturing a second slurry containing the above-described diol and aliphatic dicarboxylic acid.

[0126] In the step of manufacturing the first slurry, the diol and the aromatic dicarboxylic acid are introduced into the slurry stirrer 100 and stirred, and the first slurry can be manufactured. 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 accelerating the rate of the esterification reaction, so that the reaction efficiency can be increased. In particular, when the aromatic dicarboxylic acid such as terephthalic acid has complete crystallinity and is in the form of powder, 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.

[0127] 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 under normal pressure without a melting point. Its solubility in the diol is very low, and a homogeneous reaction may not easily occur. Therefore, when a pretreatment process is performed before the esterification reaction, it is possible to increase the surface area for reacting with the diol within the solid matrix of terephthalic acid and induce a uniform reaction.

[0128] When the aromatic dicarboxylic acid is dimethyl terephthalic acid, the pretreatment process can melt the dimethyl terephthalic acid at about 142 °C to 170 °C and react it with the diol, so that the esterification reaction rate can be made faster and more efficient.

[0129] In the pretreatment stage of manufacturing the first slurry, the structure and physical properties of the biodegradable resin composition may change depending on the particle size, particle size distribution, pretreatment reaction conditions, etc. of the aromatic dicarboxylic acid.

[0130] The aromatic dicarboxylic acid may include terephthalic acid. The terephthalic acid has an average particle size (D 50 ) measured by a particle size analyzer Microtrac S3500 in the particle size distribution (PSD) of 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 dispersion. 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.

[0131] In the pretreatment step, the diol and the aromatic dicarboxylic acid can be mixed and put into the slurry stirrer 100 (tank).

[0132] The slurry stirrer 100 has an anchor type at the bottommost 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.

[0133] The slurry stirrer 100 may have a height to the agitator of 20 mm or more, that is, there may be almost a connection between the reactor and the bottommost part of the agitator. 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.

[0134] The pretreatment step for manufacturing the first 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.

[0135] The diol may have the same characteristics as described above.

[0136] The diol may be charged all at once or in portions. The diol may be charged 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.

[0137] In the step of manufacturing the second slurry, the aromatic dicarboxylic acid is not used.

[0138] The diol and the aliphatic dicarboxylic acid may be charged into the slurry stirrer 100 and stirred to produce the second slurry.

[0139] The pretreatment step of manufacturing the second slurry may include a step of mixing the diol and the aliphatic dicarboxylic acid and stirring at about 30°C to about 100°C and at about 50 rpm to about 200 rpm for 10 minutes or more or for 10 minutes to 200 minutes.

[0140] The diol may have the same characteristics as described above.

[0141] The diol may be charged all at once or in portions. The diol may be charged separately when mixing with the aliphatic dicarboxylic acid. The aliphatic dicarboxylic acid may have the same characteristics as described above.

[0142] The step may include a step of manufacturing a prepolymer after the esterification reaction. The step of manufacturing the prepolymer can be carried out in the ester reaction unit 200.

[0143] The esterification reaction may be carried out all at once after the aliphatic dicarboxylic acid, or the diol and the aliphatic dicarboxylic acid are charged into the first slurry or the second slurry. That is, the first slurry or the second slurry is charged into the esterification reactor, and the aliphatic dicarboxylic acid alone, or the aliphatic dicarboxylic acid and the diol are charged into the esterification reaction unit 200 to carry out the esterification reaction.

[0144] The esterification reaction can be carried out at about 250°C or lower for about 0.5 hour to about 5 hours.

[0145] 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%.

[0146] Although 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, it is not limited thereto.

[0147] At least one of the polycarbonate diol and the polyether polyol can be mixed into the first slurry or the second slurry to carry out the first esterification reaction. Different from this, at least one of the polycarbonate diol and the polyether polyol may be introduced into the second esterification reaction.

[0148] 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 a 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.

[0149] The first ester reaction can be carried out at 250°C or lower for 1.25 hours to 4 hours.

[0150] 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%.

[0151] Although 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, it is not limited thereto.

[0152] 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%.

[0153] Although 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, it is not limited thereto.

[0154] When the ester reaction is carried out separately into the first ester reaction and the second ester reaction, the overall ester reaction can be precisely controlled. When the ester reaction is carried out separately, the reaction stability and reaction uniformity of the ester reaction can be improved.

[0155] A prepolymer can be formed by the esterification reaction.

[0156] The number average molecular weight of the prepolymer may be about 500 g / mol to about 10,000 g / mol. 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. When the above range is satisfied, the molecular weight of the polymer in the polycondensation reaction can be efficiently increased.

[0157] The number average molecular weight can be measured using gel permeation chromatography (GPC). Specifically, although the data calculated by gel permeation chromatography has various items such as Mn, Mw, and Mp, the molecular weight can be measured based on the number average molecular weight (Mn) among them.

[0158] The above-mentioned branching agent may be introduced into the esterification reaction section 200 during the esterification reaction.

[0159] 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 first slurry or the second slurry to carry out the esterification reaction.

[0160] Before the first esterification reaction, the titanium-based catalyst and / or the germanium-based catalyst may be added to the first slurry or the second slurry, and the titanium-based catalyst and / or the germanium-based catalyst may be further added to the product of the first esterification reaction.

[0161] 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 the content of the catalyst satisfying the above range, the physical properties can be further improved.

[0162] The above-described heat stabilizer may be introduced together with the slurry before the esterification reaction. The heat stabilizer may be introduced into the esterification reaction section 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 section 200 after the first ester reaction and before the second ester reaction.

[0163] The characteristics of the heat stabilizer are as described above.

[0164] 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, the additive and / or color corrector can be added and stabilized, and then the 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.

[0165] After the esterification reaction is completed, the above-mentioned inorganic nucleating agent may be added to the esterification reaction product. That is, after the esterification reaction is completed, the inorganic nucleating agent can be added and stabilized, and then the polycondensation reaction can be carried out. The characteristics of the inorganic nucleating agent are as described above. The inorganic nucleating agent can be introduced into the polycondensation reaction unit 300 together with the prepolymer to carry out the polycondensation step. Thereby, the inorganic nucleating agent may be uniformly dispersed in the biodegradable resin.

[0166] The first recovery unit 510 can recover reaction by-products such as water from the esterification reaction unit 200. The first recovery unit 510 can apply a vacuum pressure to the esterification reaction unit 200 or perform reflux to recover the by-products generated in the esterification reaction.

[0167] 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 unit 300. Also, the heat stabilizer may be introduced into the polycondensation reaction unit 300 together with the prepolymer.

[0168] 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, 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.

[0169] The polycondensation reaction may include a primary polycondensation and a secondary polycondensation.

[0170] The primary polycondensation can be carried out at about 260°C or less, about 250°C or less, 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, and 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.

[0171] The secondary 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 less, about 0.8 torr or less, about 0.6 torr or less, 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, and 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.

[0172] 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, additives such as silica, potassium, or magnesium; amine-based stabilizers such as trimethyl phosphate, triphenyl phosphate, trimethyl phosphine, phosphoric acid, phosphorous acid, or tetraethylenepentamine; and one or more selected from the group consisting of polymerization catalysts such as antimony trioxide, antimony trioxide, or tetrabutyl titanate can be further added to the prepolymer.

[0173] The number average molecular weight of the polymer may be about 40,000 g / mol or more. The number average molecular weight of the polymer may be 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. When the above range is satisfied, physical properties, impact resistance, durability, and moldability can be further improved.

[0174] 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.

[0175] 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.

[0176] The chain extender can be added to the polymer. The polymer and the chain extender can be uniformly mixed and maintained at a temperature of about 200°C to about 260°C for about 1 minute to about 15 minutes.

[0177] The above step may include the step 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 to produce pellets. The cutting step 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.

[0178] The pellets may be fed 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 fed into the post-treatment unit 400. Thereafter, the post-treatment unit 400 can melt the fed 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 step.

[0179] The manufactured biodegradable resin composition may be manufactured into biodegradable raw yarns by a spinning process.

[0180] The spinning process may include a process in which the biodegradable resin composition melts and is fed into a spinning block. In the spinning block, the melted biodegradable resin composition from an extruder may be spun from a nozzle. The spinning block can form filaments of the biodegradable resin composition. The filaments may be solidified and crystallized by cooling to produce undrawn biodegradable raw yarns.

[0181] There may be a plurality of the nozzles. The number of the nozzles may be 2fila - 30fila, 10fila - 30fila, or 18fila - 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 80kg / cm 2 ~120kg / cm 2 、90kg / cm 2 ~120kg / cm 2 、90kg / cm 2 ~110kg / cm 2 、or 95kg / cm 2 ~105kg / cm 2 and may be such. The spinning temperature in the spinning block may be 180°C - 250°C, 190°C - 250°C, 190°C - 240°C, or 190°C - 230°C.

[0182] The biodegradable resin composition in the spinning process may have a melt flow index within a specific range.

[0183] The biodegradable resin composition may have a melt flow rate value measured under the conditions of 190°C and 2.16 kg of 10g / 10min - 25g / 10min, 10g / 10min - 20g / 10min, 10g / 10min - 15g / 10min, or 11g / 10min - 15g / 10min.

[0184] The melt flow rate of the biodegradable resin composition, measured under the conditions of 230 °C and 2.16 kg, may be 20 g / 10 min to 50 g / 10 min, 25 g / 10 min to 50 g / 10 min, 25 g / 10 min to 40 g / 10 min, or 29 g / 10 min to 39 g / 10 min.

[0185] 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.

[0186] The above step may include the step of cooling the biodegradable raw yarn.

[0187] The biodegradable raw yarn may be an undrawn biodegradable raw yarn produced from the biodegradable resin composition.

[0188] 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.

[0189] When the above range is satisfied, the phenomenon of mutual fusion between adjacent undrawn biodegradable raw yarns can be suppressed.

[0190] The above step may include the step of stretching the cooled biodegradable raw yarn.

[0191] By the above stretching process, 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.

[0192] If necessary, the stretched biodegradable raw yarn may be heat-treated at an appropriate temperature.

[0193] 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.

[0194] 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 rate 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 rate 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 the biodegradable nonwoven fabric, and the mechanical strength of the biodegradable nonwoven fabric can be improved.

[0195] 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.

[0196] The step may include a step of combining the cooled biodegradable raw yarns to form a biodegradable raw yarn web.

[0197] The method of binding the biodegradable raw yarn may be by means of a carding, air laid, water suspension, or spun bond process.

[0198] The carding process may mean a process in which the biodegradable raw yarn is laminated on a collector by a device including a plurality of gears to form a biodegradable raw yarn web.

[0199] The air laid process may mean a process in which the biodegradable raw yarn is arranged on a collector by a device moved by an air flow to form a biodegradable raw yarn web.

[0200] The water suspension process may mean a process in which the biodegradable raw yarn is dispersed in water and transferred onto a wire screen or a perforated drum, and then the residual moisture of the transferred biodegradable raw yarn is sucked, pressurized, and dried to form a biodegradable raw yarn web.

[0201] The spun bond process may mean a process in which the biodegradable raw yarn is formed into a Venturi web on a collector and then formed into a biodegradable raw yarn web.

[0202] The stage may further include a stage of binding the biodegradable raw yarn web by at least one or more processes among needle punching, spun lace, stitch bonding, calendaring, and air through bonding.

[0203] By the above process, the bonding force between the biodegradable raw yarn 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.

[0204] 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.

[0205] 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.

[0206] The stitch bond process may mean a process of causing the biodegradable raw yarn web to bond by a sewing thread and needles.

[0207] The calendaring process may mean a process of heat-sealing the biodegradable raw yarn web after pressurizing it.

[0208] 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.

[0209] The biodegradable nonwoven fabric according to the present invention can be produced by the above process.

[0210] The biodegradable nonwoven fabric includes a biodegradable resin composition containing a first repeating unit derived from a diol having 2 to 4 carbon atoms and a second repeating unit derived from an aliphatic dicarboxylic acid having 2 to 6 carbon atoms, and an inorganic nucleating agent, and the biodegradable resin composition has a crystallinity of 15% to 50% measured using a differential scanning calorimeter.

[0211] The biodegradable nonwoven fabric is lightweight, has excellent strength, a high surface area and porosity, and can be used in products that require moisture absorption.

[0212] The biodegradable nonwoven fabric may include raw yarn 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.

[0213] 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 dewatered with a hydrophobic substance. The biodegradable nonwoven fabric may be dewatered with an antibacterial substance.

[0214] 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 article to which it is applied.

[0215] The present invention will be described in more detail below with reference to examples and comparative examples. However, the following examples and comparative examples are merely illustrative for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

[0216] Production Example - Production of Pretreated Nanocellulose Cellulose nanocrystals (NVC-100, manufacturer: Celluforce) in the form of dry powder with a particle size of about 1 μm to about 50 μm were dispersed in water at 1 wt % and then ultrasonicated for 2 minutes at an output of 20,000 J / s using a tip-type ultrasonic disperser to produce pretreated nanocellulose.

[0217] Example - Production of Biodegradable Resin Composition Example 1 - First step: Obtaining a prepolymer Into an esterification reaction tank of 5 kg size equipped with a nitrogen inlet and a stirrer, 1,4-butanediol (1,4-BDO), terephthalic acid (TPA), and tetrabutyl titanate (Dupont, Tyzor TnBT product), which is a titanium-based catalyst, were charged to produce a slurry. At this time, the molar (mol) ratio of the 1,4-butanediol:terephthalic acid was 100:47. 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.

[0218] Adipic acid (AA) was charged into the first prepolymer. At this time, the molar ratio of the 1,4-butanediol:adipic acid was 100:53, and the molar ratio of the terephthalic acid:adipic acid was 47:53.

[0219] Then, after charging the nanocellulose pretreated according to the production example, triethyl phosphonoacetate (TEPA) heat stabilizer, glycerol (Gly) branching agent, and titanium dioxide (TiO2) inorganic nucleating agent into the first prepolymer, an esterification reaction was carried out until about 90% or more of the by-product water was discharged. Then, tetrabutyl titanate (Dupont, Tyzor TnBT product), which is a titanium-based catalyst, was charged, and after stirring for 10 minutes, a second prepolymer was produced.

[0220] - Second stage: polycondensation reaction The second prepolymer produced in the reaction tank was transferred to a 5 kg size polycondensation reaction tank. Then, under a vacuum condition of about 1 torr or less, the temperature was gradually raised to 240 °C, and then a polycondensation reaction was carried out for about 200 minutes to obtain a biodegradable resin composition.

[0221] Examples 2 to 5 and Comparative Examples 1 to 4 A biodegradable resin composition was produced by the same process as in the production process of Example 1, except that the biodegradable resin composition was produced with the components and contents shown in Table 1 below.

[0222]

Table 1

[0223] Experimental Example Experimental Example 1 - Crystallinity For each of the biodegradable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4, the crystallinity was calculated by the following calculation formula using the crystal melting energy value and crystal formation energy value measured using a differential scanning calorimeter. The results are shown in Table 2 below.

[0224] [Calculation formula] Crystallinity (%) = [(Energy required for 1 g of the biodegradable resin composition to melt (crystal melting energy (J / g) / crystal formation energy (J / g))) / Energy required for 1 g to melt when the biodegradable resin composition has 100% crystallinity (J / g)] × 100

[0225] Experimental Example 2 - Melt Flow Rate Based on ASTM D1238, after pressing each of the biodegradable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 under a weight of 2.16 kg at temperature conditions of 190 °C and 230 °C respectively, the discharge amount for 10 minutes was measured, and the results are shown in Table 2 below.

[0226] Experimental Example 3 - Isothermal Crystallization Time Each of the biodegradable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 was heated to 220 °C at a heating rate of 10 °C / min and then maintained for 5 minutes. Thereafter, it was cooled to 70 °C at a cooling rate of 100 °C / min and then maintained in an isothermal state for 100 minutes.

[0227] Thereafter, the time when it became half of the total area of the crystallization peak measured using a differential scanning calorimeter was measured, and the results are shown in Table 2 below.

[0228] Experimental Example 4 - Spinnability Evaluation Each of the biodegradable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 was evaluated for spinnability according to the following criteria using a staple fiber spinning facility under the conditions of a spinning speed of 1,500 m / min, a melting temperature of 230°C, a nozzle temperature of 250°C, and a quenching air temperature of 20°C. The results are shown in Table 2 below.

[0229] - Excellent: During the spinning of staple fibers, the discharge from the nozzle is smooth. After quenching, no fiber fusion phenomenon occurs, and the fiber fineness deviation is within 20%. - Good: During the spinning of staple fibers, the discharge from the nozzle is smooth. After quenching, no fiber fusion phenomenon occurs, and the fiber fineness deviation is more than 20% and up to 40% or less. - Poor: During the spinning of staple fibers, it is impossible to discharge from the nozzle, or a fiber fusion phenomenon occurs after quenching.

[0230] Experimental Example 5 - Adhesion Strength Each of the biodegradable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 was compressed at a temperature of 210°C and a pressure of 10 MPa for 3 minutes to produce a sheet with a width of 20 mm, a length of 100 mm, and a thickness of 0.3 mm. After the two sheets were butted together at a length of 75 mm in the horizontal direction, they were adhered at a temperature of 90°C and a pressure of 5 MPa for 10 minutes.

[0231] Thereafter, for the two adhered sheets, a lap shear test was performed at a tensile speed of 100 mm / min and 180° to measure the adhesion strength, and the results are shown in Table 2 below.

[0232] Experimental Example 6 - Degree of Biodegradation For each of the biodegradable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4, the aerobic biodegradation degree carried out for 6 months under composting conditions was measured based on ISO 14855, and the results are shown in Table 2 below.

[0233]

Table 2

[0234] As can be confirmed from Tables 1 and 2 above, it was confirmed that the biodegradable resin compositions of Examples 1 to 5 exhibited a biodegradability equal to or higher than that of the biodegradable resin compositions of Comparative Examples 1 to 4.

[0235] In addition, the biodegradable resin compositions of Examples 1 to 5 exhibited appropriate melt flow index, isothermal crystallization time, and adhesion strength that could be manufactured into non-woven fabrics by a spinning process. After spinning, it was confirmed that there were no problems such as fusion occurring between the fibers or the yarn breaking, and the fineness of the fibers could be adjusted.

Explanation of Symbols

[0236] 100 Slurry stirrer 200 Esterification reaction section 300 Polycondensation reaction section 400 Post-treatment section 510 First recovery section 520 Second recovery section

Claims

1. a biodegradable resin including a first repeating unit derived from a diol having 2 to 4 carbon atoms and a second repeating unit derived from an aliphatic dicarboxylic acid having 2 to 6 carbon atoms; an inorganic nucleating agent; Including, The crystallinity, as measured by differential scanning calorimetry, is between 15% and 50%; Biodegradable resin composition.

2. the molar ratio of the first repeat unit to the second repeat unit is from 4:1 to 1:1; The biodegradable resin composition according to claim 1.

3. The biodegradable resin further includes a third repeating unit derived from an aromatic dicarboxylic acid. The biodegradable resin composition according to claim 1.

4. the molar ratio of the first repeat unit to the third repeat unit is 10:3 to 10:7; The biodegradable resin composition according to claim 3.

5. the molar ratio of the second repeat unit to the third repeat unit is from 3:2 to 2:3; The biodegradable resin composition according to claim 3.

6. The content of the inorganic nucleating agent is 10 ppm to 10,000 ppm based on the total weight of the biodegradable resin composition. The biodegradable resin composition according to claim 1.

7. The inorganic nucleating agent includes 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. The biodegradable resin composition according to claim 1.

8. The biodegradable resin composition contains nanocellulose having an average length of 10 nm to 300 nm. The biodegradable resin composition according to claim 1.

9. The content of the nanocellulose is 10 ppm to 500 ppm based on the total weight of the biodegradable resin composition; The biodegradable resin composition according to claim 8.

10. The biodegradable resin composition contains a branching agent containing at least one of a trivalent or higher alcohol and a trivalent or higher carboxylic acid. The biodegradable resin composition according to claim 1.

11. The content of the branching agent is 500 ppm to 3,000 ppm based on the total weight of the biodegradable resin composition. The biodegradable resin composition according to claim 10.

12. The biodegradable resin composition has a melt flow rate of 10 g / 10 min to 25 g / 10 min measured under conditions of 190° C. and 2.16 kg. The biodegradable resin composition according to claim 1.

13. The biodegradable resin composition has an adhesive strength of 5 kgf or less according to the following measurement method 1. The biodegradable resin composition according to claim 1. [Measurement method 1] 1) The biodegradable resin composition is compressed at a temperature of 210° C. and a pressure of 10 MPa for 3 minutes to produce a sheet having a width of 20 mm, a length of 100 mm and a thickness of 0.3 mm. 2) The two sheets are butted together horizontally at a length of 75 mm, and then bonded together at a temperature of 90° C. and a pressure of 5 MPa for 10 minutes. 3) The two adhered sheets were pulled at a tensile speed of 100 mm / min for 1 An 80° Lap shear test is performed to measure adhesive strength.

14. The biodegradable resin composition has an isothermal crystallization time at 70° C. of 10 seconds to more than 300 seconds, as measured by the following measurement method 2. The biodegradable resin composition according to claim 1: [Measurement method 2] 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 70° C. at a temperature lowering rate of 100° C. / min, and then the isothermal state is maintained for 100 minutes. 3) Using the differential scanning calorimeter, 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.

15. a biodegradable resin including a first repeating unit derived from a diol having 2 to 4 carbon atoms and a second repeating unit derived from an aliphatic dicarboxylic acid having 2 to 6 carbon atoms; an inorganic nucleating agent; Including, A biodegradable resin composition is included, The biodegradable resin composition has a crystallinity of 15% to 50% as measured by differential scanning calorimetry. Biodegradable non-woven fabric.

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