Biodegradable resin composition and blow-molded article comprising same

Abstract

The present invention provides a biodegradable resin composition and a blow-molded article comprising same, wherein the biodegradable resin composition comprises: a biodegradable resin comprising an aliphatic-aromatic polyester resin and an aliphatic polyester resin; an inorganic filler; a chain extender; and coffee grounds, and has a moisture content of less than 1 weight% as measured by a thermogravimetric analyzer (TGA).

Description

Biodegradable resin composition and blow molded product containing the same

[0001] The present invention relates to a biodegradable resin composition and a blow molded product 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] Meanwhile, only a small amount of coffee beans are used in coffee production, and the majority of the waste is coffee grounds. As coffee consumption increases, so does the amount of coffee grounds being produced. Furthermore, the organic matter remaining in the grounds has led to increased carbon emissions.

[0006] To solve these problems, molded products using resin compositions containing coffee grounds are being developed, but there are limitations in securing processability and mechanical properties of the molded products being manufactured.

[0007]

[0008] The present invention provides a biodegradable resin composition having excellent mechanical properties and ensuring blow molding processability, and a blow molded product comprising the same.

[0009]

[0010] A biodegradable resin composition according to the present invention comprises a biodegradable resin including an aliphatic-aromatic polyester resin and an aliphatic polyester resin, an inorganic filler, a chain extender, and coffee grounds, and has a moisture content of less than 1 wt % as determined by thermogravimetric analysis (TGA).

[0011] In one embodiment of the present invention, the weight ratio of the aliphatic-aromatic polyester resin to the aliphatic polyester resin may be 1:1 to 1:2.

[0012] In one embodiment of the present invention, the content of the inorganic filler may be 30 wt % to 60 wt % based on the total weight of the biodegradable resin composition.

[0013] In one embodiment of the present invention, the content of the chain extender may be 0.1 wt % to 1 wt % based on the total weight of the biodegradable resin composition.

[0014] In one embodiment of the present invention, the content of the coffee grounds may be 1 wt% to 20 wt% based on the total weight of the biodegradable resin composition.

[0015] In one embodiment of the present invention, the coffee grounds may have an ash content of less than 25 wt% at 900°C as determined by thermogravimetric analysis (TGA).

[0016] In one embodiment of the present invention, the biodegradable resin composition may further include lignin.

[0017] In one embodiment of the present invention, the moisture content of the lignin may be less than 5 wt %.

[0018] In one embodiment of the present invention, the lignin may have an ash content of less than 35 wt% at 900°C as determined by thermogravimetric analysis (TGA).

[0019] In one embodiment of the present invention, the biodegradable resin composition may further include an active agent including calcium.

[0020] In one embodiment of the present invention, the biodegradable resin composition may have a potassium content of 600 ppm to 1,000 ppm.

[0021] In one embodiment of the present invention, the biodegradable resin composition may have a magnesium content of 400 ppm to 3,000 ppm.

[0022] In one embodiment of the present invention, the biodegradable resin composition may have a melt index of 0.3 g / 10 min to 1.5 g / 10 min at 190° C. and 2.16 kg according to ASTM D1238.

[0023] A blow molded article according to the present invention comprises a biodegradable resin composition comprising an aliphatic-aromatic polyester resin and an aliphatic polyester resin, an inorganic filler, a chain extender, and coffee grounds, and having a moisture content of less than 1 wt % as determined by a thermogravimetric analyzer (TGA).

[0024] In one embodiment of the present invention, the time according to the following measurement method may be 10 seconds or more.

[0025] [measurement method]

[0026] 1) The pelletized biodegradable resin composition is fed into a blow molding machine (Samsung Hydraulic Machinery Co., Ltd., φ=50 mm) with a cylinder temperature of 160°C.

[0027] 2) The draw down occurrence time of the parison ejected from the die of the above blow molding machine is measured.

[0028]

[0029] The biodegradable resin composition according to the present invention and the blow molded product comprising the same include a biodegradable resin and coffee grounds, and thus can replace plastic materials and reduce the amount of coffee grounds waste generated in large quantities, making them environmentally friendly.

[0030] In addition, the biodegradable resin composition according to the present invention and the blow molded article comprising the same can minimize the problem of oxidation reaction promoted by residual moisture and the phenomenon of color change of the molded article by controlling the moisture content below a certain range. In addition, the problem of deterioration of the surface quality of the molded article due to bubble formation can be suppressed, and the mechanical properties such as tensile strength and impact strength can be improved. In addition, the biodegradable resin composition according to the present invention can have a melt index suitable for parison formation in the blow molding process, so that the blow molding processability can be secured.

[0031] In addition, the coffee grounds included in the biodegradable resin composition according to the present invention can have appropriate fluidity of the biodegradable resin composition by adjusting the potassium and magnesium contents through a pretreatment process, thereby improving the blow molding processability, and can serve as a UV stabilizer to prevent deterioration of the resin and improve mechanical strength. In addition, the coffee grounds can serve as an antioxidant, thereby improving tensile strength and impact strength.

[0032]

[0033] Figure 1 illustrates a photograph of a molded product according to Example 1.

[0034] Figure 2 shows a photograph in which a parison is not formed in Comparative Example 1.

[0035] Figure 3 shows a photograph of the outer surface of a molded product according to Comparative Example 2.

[0036] Figure 4 illustrates a photograph of the inner surface of a molded product according to Comparative Example 2.

[0037]

[0038] 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.

[0039] 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 properties, dimensions, etc. of the components described in this specification or application are to be understood as being modified by the term "about" in all cases, unless otherwise specified.

[0040] 'ppm' in this specification or application means weight basis.

[0041] The description of “A and / or B” in this specification or application means “A, B, or A and B.”

[0042]

[0043] The biodegradable resin composition according to the present invention comprises a biodegradable resin including an aliphatic-aromatic polyester resin and an aliphatic polyester resin.

[0044] The above aliphatic-aromatic polyester resin may include a diol-derived unit, an aliphatic dicarboxylic acid-derived unit, and an aromatic dicarboxylic acid-derived unit.

[0045] 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.

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

[0047] The aliphatic dicarboxylic acid may be at least one selected from the group consisting of oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid or derivatives thereof. The aliphatic dicarboxylic acid may be at least one selected from the group consisting of adipic acid, succinic acid, sebacic acid or derivatives thereof. The aliphatic dicarboxylic acid may include adipic acid or a derivative thereof.

[0048] 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. The above aromatic dicarboxylic acid may be at least one selected from the group consisting of terephthalic acid, dimethyl terephthalate, 2,6-naphthalene dicarboxylic acid, isophthalic acid, or derivatives thereof. The above aromatic dicarboxylic acid may include terephthalic acid, dimethyl terephthalate, or derivatives thereof.

[0049] In the above aliphatic-aromatic 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.

[0050] In the above aliphatic-aromatic 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.

[0051] The above aliphatic-aromatic 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.

[0052] The above aliphatic-aromatic polyester resin may include aromatic dicarboxylic acid residues 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.

[0053] The above aliphatic-aromatic 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.

[0054] The aliphatic-aromatic polyester resin may include a first block and a second block. The aliphatic-aromatic polyester resin may have a molecular structure in which the first block and the second block are alternately bonded.

[0055] 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.

[0056] 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.

[0057] In the aliphatic-aromatic polyester resin, the ratio (X / Y) of the number of the first blocks (X) to the number of the second blocks (Y) 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. The number of the 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. The number of the first blocks may vary depending on the content of the aromatic dicarboxylic acid, the molecular weight of the aliphatic-aromatic polyester resin, and the degree of alternation described below. That is, as the molar ratio of the aromatic dicarboxylic acid increases, as the molecular weight of the aliphatic-aromatic polyester resin increases, and as the degree of alternation described below increases, the number of the first blocks may increase.

[0058] The number of the 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. The number of the second blocks may vary depending on the content of the aliphatic dicarboxylic acid, the molecular weight of the aliphatic-aromatic polyester resin, and the degree of alternation described below.

[0059] When the aliphatic-aromatic polyester resin includes the first block and the second block in the above range, the coating layer including the aliphatic-aromatic polyester resin can have an appropriate mechanical strength while improving biodegradability.

[0060] The above aliphatic-aromatic polyester resin may include the following bonding structures 1 to 3.

[0061] [Combination Structure 1]

[0062] - Aromatic dicarboxylic acids - Diols - Aliphatic dicarboxylic acids -

[0063] [Combination Structure 2]

[0064] - Aromatic dicarboxylic acid - Diol - Aromatic dicarboxylic acid -

[0065] [Combination Structure 3]

[0066] - Aliphatic dicarboxylic acid - Diol - Aliphatic dicarboxylic acid -

[0067] 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.

[0068] 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.

[0069] 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.

[0070] The above aliphatic-aromatic polyester resin may have an alternating ratio. The alternating ratio is the ratio of the diol bonded between the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid among the diols. That is, the alternating ratio may be the ratio of the diol included in the bonding structure 1 among the diols. The alternating 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.

[0071] The above-mentioned exchange ratio may be the ratio of diols bonded between heterodicarboxylic acids among the total diols.

[0072] The above exchange ratio can be calculated using the following formula 1.

[0073] [Formula 1]

[0074]

[0075] 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.

[0076] In the above aliphatic-aromatic 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.

[0077] The above aliphatic-aromatic polyester resin may include a hard segment. The hard segment ratio is the ratio of the diol bonded between the aromatic dicarboxylic acid and the aromatic dicarboxylic acid among the diols.

[0078] 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.

[0079] The above hard segment ratio can be expressed by the following equation 2.

[0080] [Formula 2]

[0081]

[0082] 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.

[0083] 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.

[0084] The above aliphatic-aromatic polyester resin may include a soft segment.

[0085] 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.

[0086] 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.

[0087] The above soft segment ratio can be expressed by the following equation 3.

[0088] [Formula 3]

[0089]

[0090] 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.

[0091] 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.

[0092] The above soft segment ratio may be greater than the above hard segment ratio.

[0093] 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.

[0094] The above-mentioned alternation ratio, the hard segment ratio, and the soft segment ratio can be measured by nuclear magnetic resonance spectroscopy. The above-mentioned aliphatic-aromatic polyester resin composition is dissolved in a solvent such as CDCl3, 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.

[0095] 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 aliphatic-aromatic 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.

[0096] 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 aliphatic-aromatic 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.

[0097] 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.

[0098] -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.

[0099] Analysis of the aliphatic-aromatic 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] The above exchange ratio can be derived from the following equation 4 or equation 5.

[0106] [Formula 4]

[0107]

[0108] 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.

[0109] [Formula 5]

[0110]

[0111] 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.

[0112] The above hard segment ratio can be derived from the following equation 6 or equation 7.

[0113] [Formula 6]

[0114]

[0115] 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.

[0116] [Formula 7]

[0117]

[0118] 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.

[0119] The above soft segment ratio can be derived using Equation 8 or Equation 9 below.

[0120] [Formula 8]

[0121]

[0122] 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.

[0123] [Formula 9]

[0124]

[0125] 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.

[0126] The area of ​​the first peak may be about 0.35 to about 0.6, about 0.4 to about 0.55, about 0.43 to about 0.5, about 0.43 to about 0.52, or about 0.45 to about 0.49. The area of ​​the second peak may be about 0.37 to about 0.57, about 0.41 to about 0.54, about 0.45 to about 0.53, about 0.45 to about 0.55, or about 0.47 to about 0.53. The area of ​​the third peak may be about 0.37 to about 0.57, about 0.41 to about 0.54, about 0.45 to about 0.53, about 0.45 to about 0.55, or about 0.47 to about 0.53. The area of ​​the fourth peak may be about 0.4 to about 0.7, about 0.45 to about 0.65, about 0.48 to about 0.6, about 0.48 to about 0.60, or about 0.50 to about 0.58. 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. The area of ​​the sixth peak may be about 0.35 to about 0.6, about 0.4 to about 0.55, about 0.43 to about 0.5, about 0.45 to about 0.55, or about 0.47 to about 0.53. The area of ​​the seventh peak may be about 0.41 to about 0.71, about 0.45 to about 0.65, about 0.48 to about 0.6, about 0.45 to about 0.55, or about 0.47 to about 0.53. The area of ​​the eighth peak may be about 0.4 to about 0.7, about 0.45 to about 0.65, about 0.48 to about 0.6, or about 0.50 to about 0.58. The area of ​​the tenth peak may be about 0.7 to about 2.5, about 0.75 to about 2, about 0.8 to about 1.5, about 1.0 to about 1.15, or about 1.02 to about 1.13. The area of ​​the eleventh peak may be about 0.It may be from about 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.

[0127] 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 refer to the sum of the total number of ester bonds based on the number of terephthalic acids. 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 refer to the extent of extension of the molecular bond of the aliphatic-aromatic polyester resin. 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 from about 1.1 to about 1.3, from about 0.67 to about 2, from about 0.96 to about 1.40, or from 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 aliphatic-aromatic 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 aliphatic-aromatic polyester resin may have improved adhesive properties. 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. 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 from about 0.61 to about 1.62, from about 0.81 to about 1.11, from about 0.85 to about 0.95, or from about 0.86 to about 0.It may be 94. 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 about 0.61 to about 1.71, about 0.96 to about 1.40, about 0.8 to about 1.2, or about 0.9 to about 1.1. 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 about 0.58 to about 1.71, about 0.86 to about 1.16, about 0.8 to about 1.2, or about 0.9 to about 1.1. 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. 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.

[0128] The number average molecular weight of the above aliphatic-aromatic polyester resin may be 20,000 g / mol to 100,000 g / mol, 20,000 g / mol to 80,000 g / mol, 20,000 g / mol to 70,000 g / mol, or 30,000 g / mol to 62,000 g / mol. When the above range is satisfied, the blow molding processability may be improved while having an appropriate biodegradability. The number average molecular weight may be measured using gel permeation chromatography (GPC).

[0129] The crystallinity of the above aliphatic-aromatic polyester resin may be 10% to 30%, 10% to less than 30%, 12% to less than 30%, 12% to 28%, or 15% to 25%. When the above range is satisfied, the biodegradable resin composition can be provided with appropriate flowability in a blow molding process.

[0130] The above crystallinity is measured by melting enthalpy (ΔH) using differential scanning calorimetry (DSC) according to ASTM D-3417. m ) is the melting enthalpy (ΔH) at 100% determination c ) can be calculated as a percentage of the value divided by .

[0131] Specifically, it can be calculated according to the following calculation formula.

[0132] [Calculation formula]

[0133] Crystallinity (%) = [Energy required to melt 1g of aliphatic-aromatic polyester resin (crystal melting energy (J / g) - crystal formation energy (J / g)) / Energy required to melt 1g of aliphatic-aromatic polyester resin with 100% crystallinity (J / g)] × 100

[0134] The content of the aliphatic-aromatic polyester resin may be 2 wt% to 10 wt%, 3 wt% to 10 wt%, 5 wt% to 10 wt%, or 7 wt% to 10 wt% based on the total weight of the biodegradable resin composition. When the above range is satisfied, the blow molding processability may be improved and the mechanical properties may be improved.

[0135] The aliphatic polyester resin may have a glass transition temperature (Tg) of 50°C or higher. The glass transition temperature of the aliphatic polyester resin may be 50°C or higher, 50°C to 80°C, 50°C to 75°C, 50°C to 70°C, 55°C to 70°C, or 55°C to 65°C. When the above range is satisfied, the chain fluidity of the polymer may be reduced during the process of cooling the biodegradable resin composition, so that the change in volume after molding of the biodegradable resin composition may be minimized.

[0136] The above aliphatic polyester resin may include polylactic acid.

[0137] The above polylactic acid may include a unit represented by the following chemical formula 1.

[0138] [Chemical Formula 1]

[0139]

[0140] The above polylactic acid may be a high-melting-point polylactic acid having a stereocomplex crystal. In addition, the polylactic acid may be formed by solution mixing or melt mixing of L-lactic acid and D-lactic acid.

[0141] The polylactic acid may be a polymer comprising L-lactic acid and / or D-lactic acid. The polylactic acid may comprise L-lactic acid and / or D-lactic acid.

[0142] Preferably, the polylactic acid comprises D-lactic acid, and the D-lactic acid may be present in an amount of 1 wt% to 5 wt%, 2 wt% to 5 wt%, 3 wt% to 5 wt%, or 4 wt% to 5 wt% based on the total weight of the polylactic acid. When the above range is satisfied, the heat resistance properties of the blow molded product can be improved.

[0143] The above aliphatic polyester resin can be modified by a surface treatment agent.

[0144] The surface of the above-mentioned aliphatic polyester resin can be modified by the above-mentioned surface treatment agent. By including the aliphatic polyester resin modified by the surface treatment agent, the biodegradable resin composition can improve compatibility with the aliphatic-aromatic polyester resin, and the bleeding phenomenon in which the aliphatic polyester resin flows out onto the surface of the blow molded product can be suppressed.

[0145] The surface treatment agent may contain an amide group. The surface treatment agent may contain a fatty acid amide. The surface treatment agent containing the amide group can easily bond with the functional group of the aliphatic polyester resin, so that the surface of the aliphatic polyester resin can be more easily modified, thereby improving compatibility with the aliphatic-aromatic polyester resin and further suppressing the bleeding phenomenon.

[0146] The above surface-modified aliphatic polyester resin can be manufactured by the following method.

[0147] A surface treatment agent is added to the above aliphatic polyester resin, and the aliphatic polyester resin and the surface treatment agent are stirred so that the surface treatment agent can be bonded to the surface of the aliphatic polyester resin.

[0148] The stirring temperature may be from the melting point of the surface treatment agent to the melting point of the surface treatment agent + 50°C. The amount of the surface treatment agent added may be 0.1 parts by weight to 5 parts by weight, 0.1 parts by weight to 4 parts by weight, 0.1 parts by weight to 3 parts by weight, or 0.5 parts by weight to 3 parts by weight relative to 100 parts by weight of the aliphatic polyester resin.

[0149] The stirring time may be from about 1 minute to about 60 minutes, from about 1 minute to about 50 minutes, from about 5 minutes to about 50 minutes, or from about 5 minutes to about 40 minutes.

[0150] The above biodegradable resin composition may have different weight average molecular weights and number average molecular weights depending on the content ratio of the aliphatic-aromatic polyester resin and the aliphatic polyester resin.

[0151] The content of the aliphatic-aromatic polyester resin may be 10 wt% to 40 wt%, 10 wt% to 35 wt%, 15 wt% to 35 wt%, or 15 wt% to 30 wt% based on the total weight of the biodegradable resin composition.

[0152] The content of the aliphatic polyester resin may be 20 wt% to 50 wt%, 25 wt% to 50 wt%, 25 wt% to 45 wt%, or 25 wt% to 40 wt% based on the total weight of the biodegradable resin composition.

[0153] The weight ratio of the aliphatic-aromatic polyester resin to the aliphatic polyester resin may be 1:1 to 1:2, 1:1 to 1:1.9, 1:1.1 to 1:1.9, or 1:1.3 to 1:1.7.

[0154] When the above range is satisfied, processability, flexural strength and flexural modulus can be improved.

[0155] The above biodegradable resin composition comprises an inorganic filler.

[0156] The above-mentioned inorganic filler can be used as a support for the aliphatic-aromatic polyester resin, the aliphatic polyester resin, or the aliphatic-aromatic polyester resin and the aliphatic polyester resin included in the above-mentioned biodegradable resin composition, so that dimensional stability can be improved.

[0157] The content of the above-mentioned inorganic filler may be 30 wt % to 60 wt %, 35 wt % to 60 wt %, 40 wt % to 60 wt %, or 40 wt % to 50 wt % based on the total weight of the biodegradable resin composition. When the above range is satisfied, the flowability of the biodegradable resin can be improved without deteriorating the mechanical properties of the molded product according to the blow molding process, so that the processability of temperature, parison formation, etc. in the blow molding process can be implemented. In addition, dimensional stability can be improved, and the appearance quality of the molded product can be improved.

[0158] The above-mentioned inorganic filler may include heavy calcium carbonate having an average particle size of 0.1 μm to 5 μm, 0.1 μm to 4 μm, 0.1 μm to 3 μm, or 0.1 μm to 2 μm. The above-mentioned average particle size may be calculated from the measurement results of the specific surface area by the air permeation method using a specific surface area measuring device. The above-mentioned heavy calcium carbonate is obtained by mechanically crushing natural calcium carbonate, and may be distinguished from light calcium carbonate produced through a chemical precipitation reaction.

[0159] When the inorganic filler comprises heavy calcium carbonate having the above-described average particle size range, the dispersibility in the biodegradable resin composition can be improved, and excessive viscosity increase of the biodegradable resin composition can be suppressed. In addition, the tensile strength can be increased compared to light calcium carbonate, so that the mechanical properties can be improved. In addition, the inorganic filler can be suppressed from protruding or falling off from the surface of the molded product according to the blow molding process, thereby damaging the surface properties and mechanical strength of the molded product. In addition, the acid component that may be generated during biodegradation of the molded product can react with the heavy calcium carbonate to generate CO2 and H2O, so that the biodegradation rate of the molded product can be further improved at a molecular level. In addition, the heavy calcium carbonate can neutralize the acid component, thereby reducing the environmental load and preventing acidification of the soil.

[0160] The specific surface area of ​​the above heavy calcium carbonate is 0.1 m 2 / g to 10.0 m 2 / g, 0.1 m 2 / g to 9.0 m 2 / g, 0.1 m 2 / g to 8.0 m 2 / g, 0.1 m 2 / g to 7.0 m 2 / g, 0.1 m 2 / g to 6.0 m 2 / g, 0.1 m 2 / g to 5.0 m 2 / g, 0.1 m 2 / g to 4.0 m 2 / g, or 0.1 m 2 / g to 3.0 m 2 / g. The above specific surface area can be measured by a nitrogen gas adsorption method. When the above range is satisfied, it can be easily dispersed in a biodegradable resin, thereby promoting the biodegradability of the biodegradable resin and improving processability.

[0161] The sphericity of the above-mentioned heavy calcium carbonate may be 0.30 to 0.95, 0.30 to 0.93, 0.30 to 0.90, 0.50 to 0.95, 0.50 to 0.93, 0.50 to 0.90, 0.60 to 0.95, 0.60 to 0.93, or 0.60 to 0.90. When the above range is satisfied, a large number of fine pores generated at the interface between the biodegradable resin and the inorganic filler may be included, so that biodegradability may be improved and the strength of the molded product may be increased.

[0162] The above heavy calcium carbonate may be surface-treated with an organic acid. By surface-treating the heavy calcium carbonate with the organic acid, the dispersibility within the biodegradable resin composition may be increased, and the reactivity with the biodegradable resin may be improved. The surface treatment may be performed by a physical method such as plasma treatment or corona treatment, or a chemical method such as a silane coupling agent, a titanium coupling agent, or a surfactant. The organic acid may include a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher fatty acid, and the like, and may be, for example, calcium stearate.

[0163] The above surface-treated heavy calcium carbonate can be manufactured by the following method.

[0164] First, calcium carbonate powder can be produced through a grinding process. Thereafter, the calcium carbonate powder can be classified to obtain calcium carbonate having a desired particle size.

[0165] Thereafter, the calcium carbonate can be heat treated at about 200°C to about 800°C by a heating device selected from a kiln, an electric furnace, or a microwave. The heat treatment time can be about 5 minutes to about 30 minutes, about 7 minutes to about 15 minutes, or about 7 minutes to about 14 minutes. The heat treatment temperature can be about 250°C to about 700°C or about 300°C to about 600°C. By heat treating the calcium carbonate under the above conditions, moisture within the calcium carbonate can be easily removed, the organic acid can be easily bound to the surface of the calcium carbonate, and agglomeration of the calcium carbonate can be minimized.

[0166] Thereafter, an organic acid may be added to the heat-treated calcium carbonate to perform a process of treating the surface of the calcium carbonate. The process temperature may be 70°C to about 130°C. The amount of the organic acid added may be about 0.5 parts by weight to about 5 parts by weight, about 0.5 parts by weight to about 4 parts by weight, about 0.5 parts by weight to about 3 parts by weight, about 0.5 parts by weight to about 2 parts by weight, about 0.6 parts by weight to about 5 parts by weight, about 0.6 parts by weight to about 4 parts by weight, about 0.6 parts by weight to about 3 parts by weight, about 0.6 parts by weight to about 2 parts by weight, about 0.7 parts by weight to about 5 parts by weight, about 0.7 parts by weight to about 4 parts by weight, about 0.7 parts by weight to about 3 parts by weight, or about 0.7 parts by weight to about 2 parts by weight, based on 100 parts by weight of the calcium carbonate. The process time may be from about 1 minute to about 60 minutes, from about 10 minutes to about 30 minutes, or from about 5 minutes to about 20 minutes.

[0167] Thereafter, the surface-treated calcium carbonate may undergo an additional process of crushing and classifying the aggregates aggregated in the surface treatment process. In the surface-treated calcium carbonate, the content of the organic acid may be about 0.1 wt% to about 3 wt%, about 0.1 wt% to about 2 wt%, about 0.1 wt% to about 1 wt%, about 0.2 wt% to about 3 wt%, about 0.2 wt% to about 2 wt%, about 0.2 wt% to about 1 wt%, about 0.3 wt% to about 3 wt%, about 0.3 wt% to about 2 wt%, or about 0.3 wt% to about 1 wt%, based on the total weight.

[0168] The above-mentioned calcium carbonate surface-treated with an organic acid may be partially oxidized. The above-mentioned surface-treated calcium carbonate may partially include calcium oxide (CaO). The proportion of the calcium oxide may be 5% by volume or less, 4% by volume or less, 3% by volume or less, 2% by volume or less, 1% by volume or less, 0.01% by volume or more to 5% by volume or less, 0.01% by volume or more to 4% by volume or less, 0.01% by volume or more to 3% by volume or less, 0.01% by volume or more to 2% by volume or less, or 0.01% by volume or more to 1% by volume, based on 100% by volume of the surface-treated calcium carbonate particles. The proportion of the calcium oxide may be measured by the EDTA (Ethylene diamine tetra acetic acid) titration method according to JIS R 9011. When the above range is satisfied, the uniformity of the surface of the calcium carbonate can be improved, and the phenomenon of organic acid being eluted from the surface of the calcium carbonate can be minimized, so that the water resistance can be improved.

[0169] The biodegradable resin composition includes a chain extender. By including the chain extender, the molecular weight of the biodegradable resin increases, thereby improving the tensile strength and impact strength of the biodegradable resin composition. Furthermore, the flowability of the biodegradable resin composition is improved, thereby enhancing the blow molding processability. Furthermore, resistance to acids, alkalis, solvents, and the like can be improved, thereby suppressing an increase in the moisture content of the biodegradable resin composition.

[0170] The above chain extender may include at least one selected from the group consisting of aromatic diisocyanate, aliphatic diisocyanate, isocyanurate, bisoxazoline, carboxylic anhydride, and epoxide.

[0171] The above aromatic diisocyanate may include at least one selected from the group consisting of tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthylene 1,5-diisocyanate, and xylylene diisocyanate.

[0172] The above aliphatic diisocyanate may include at least one selected from the group consisting of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and methylenebis(4-isocyanatocyclohexane).

[0173] The above isocyanurate may include isophorone diisocyanate or methylenebis(4-isocyanatocyclohexane).

[0174] The above bisoxazoline may include at least one selected from the group consisting of 2,2'-bis(2-oxazoline), bis(2-oxazolinyl)methane, 1,2-bis(2-oxazolinyl)ethane, 1,3-bis(2-oxazolinyl)propane, and 1,4-bis(2-oxazolinyl)butane.

[0175] The above epoxide means an epoxy-containing copolymer based on at least one of styrene, acrylic acid ester and methacrylic acid ester, and a copolymer having a copolymer content of glycidyl (meth)acrylate of more than 20, more than 30, or more than 50 wt% is preferred.

[0176] The chain extender may be present in an amount of 0.1 wt% to 1 wt%, 0.1 wt% to 0.8 wt%, 0.1 wt% to 0.5 wt%, or 0.2 wt% to 0.4 wt% based on the total weight of the biodegradable resin composition. When the above range is satisfied, the biodegradable resin composition may have a melt index that allows it to be manufactured into a molded product by a blown mold process.

[0177] The biodegradable resin composition comprises coffee grounds. By including coffee grounds in the biodegradable resin composition, mechanical properties such as tensile strength and wear resistance can be improved. Furthermore, the cost of raw materials for the biodegradable resin can be reduced, and coffee grounds, a waste product, can be recycled, thereby reducing costs and improving environmental friendliness. Furthermore, the coffee grounds contain natural antibacterial ingredients, which can impart antibacterial properties to molded articles manufactured from the biodegradable resin composition.

[0178] The content of the coffee grounds may be 1 wt % to 20 wt %, 2 wt % to 20 wt %, 3 wt % to 20 wt %, or 5 wt % to 20 wt % based on the total weight of the biodegradable resin composition. When the above range is satisfied, the specific gravity of a molded article manufactured from the biodegradable resin composition can be appropriately controlled, and the problem of deterioration of the surface quality of the molded article can be suppressed.

[0179] The above coffee grounds may have a moisture content of less than 5 wt %, less than 4.5 wt %, less than 4 wt %, or from 1 wt % to 3 wt % as determined by thermogravimetric analysis (TGA). The moisture content may be calculated as a mass of the coffee grounds reduced at about 105° C. compared to the initial mass of the coffee grounds as determined by thermogravimetric analysis (TGA). When the above range is satisfied, the moisture content of the biodegradable resin composition is controlled, so that generation of volatile organic compound gases due to moisture can be suppressed, and bubble generation can be minimized, so that mechanical properties can be improved.

[0180] The coffee grounds may have an ash content at 900°C as measured by thermogravimetric analysis (TGA) of less than 25 wt%, less than 22 wt%, 20 wt% or less, or 5 wt% to 20 wt%. When the above range is satisfied, the chemical resistance, mechanical strength, and surface quality of a molded product manufactured from the biodegradable resin composition may be improved.

[0181] The above coffee grounds may have a potassium content of 4,000 ppm to 10,000 ppm, 5,000 ppm to 10,000 ppm, 6,000 ppm to 10,000 ppm, or 6,500 ppm to 10,000 ppm based on the total weight of the coffee grounds, as determined by inductively coupled plasma optical emission spectrometry (ICP-OES).

[0182] The coffee grounds may have a magnesium content of 1,300 ppm to 2,000 ppm, 1,400 ppm to 2,000 ppm, 1,400 ppm to 1,900 ppm, or 1,400 ppm to 1,800 ppm according to the inductively coupled plasma optical emission spectrometry (ICP-OES).

[0183] When the above range is satisfied, the potassium and magnesium contents of the biodegradable resin composition including the coffee grounds can be adjusted to a certain content range, so that the processability and mechanical strength of the biodegradable resin composition can be improved.

[0184] The above coffee grounds may be pretreated. After being pretreated, the coffee grounds may have the moisture content, ash content, potassium content, and / or magnesium content as described above.

[0185] The above coffee grounds may be obtained by physically treating the raw coffee grounds by grinding and sieving. The above coffee grounds may be obtained by chemically treating the raw coffee grounds by using an alkaline solution or an acid solution. The above coffee grounds may be obtained by hydrothermal treatment by immersing and drying in high-temperature water. The above coffee grounds may be obtained by heat treatment using high-temperature steam and rapid decompression. The above coffee grounds may be obtained by solvent extraction and distillation. The above coffee grounds may be obtained by biological treatment by hydrolysis using enzymes or fermentation.

[0186] The biodegradable resin composition may further comprise lignin. The biodegradable resin composition may exhibit enhanced mechanical strength due to the polymer chain structure of the lignin. This may result in enhanced tensile strength, hardness, and wear resistance. Furthermore, thermal stability may be imparted by the lignin, thereby allowing the biodegradable resin composition to remain stable even at high temperatures. Furthermore, the lignin may function as a natural antioxidant, thereby preventing oxidation of the biodegradable resin composition. Furthermore, the lignin may be readily decomposed in nature, thereby enhancing the biodegradation rate of the biodegradable resin composition.

[0187] The content of the lignin may be 0.01 wt % to 5 wt %, 0.01 wt % to 4 wt %, 0.1 wt % to 4 wt %, or 0.1 wt % to 3 wt % based on the total weight of the biodegradable resin composition. When the above range is satisfied, the processability of the biodegradable resin composition is not reduced, and an increase in moisture content can be minimized.

[0188] The above lignin may have a moisture content of less than 5 wt %, less than 4.5 wt %, less than 4 wt %, or from 1 wt % to 3 wt % as determined by thermogravimetric analysis (TGA). The moisture content may be calculated as a mass of the lignin reduced at about 105° C. compared to the initial mass of the lignin as determined by thermogravimetric analysis (TGA). When the above range is satisfied, the moisture content of the biodegradable resin composition is controlled, so that generation of volatile organic compound gases due to moisture can be suppressed, and bubble generation can be minimized, so that mechanical properties can be improved.

[0189] The lignin may have an ash content at 900°C as determined by thermogravimetric analysis (TGA) of less than 35 wt%, less than 30 wt%, 25 wt% or less, or 5 wt% to 25 wt%. When the above range is satisfied, the chemical resistance, mechanical strength, and surface quality of a molded article manufactured from the biodegradable resin composition may be improved.

[0190] The biodegradable resin composition has a moisture content of less than 1 wt% as determined by thermogravimetric analysis (TGA). Preferably, the moisture content may be less than 1 wt%, less than 0.95 wt%, less than 0.9 wt%, or between 0.1 wt% and 0.8 wt%. When the above ranges are satisfied, chemical and mechanical durability may be improved.

[0191] The above moisture content may be calculated as the reduced mass of the biodegradable resin composition at about 105°C compared to the initial mass of the biodegradable resin composition by the thermogravimetric analysis (TGA).

[0192] When coffee grounds are included in the biodegradable resin composition, it is environmentally friendly in terms of recycling coffee ground waste, but there is a problem that the moisture content increases due to the coffee grounds and other ingredients included in the biodegradable resin composition, which causes bubbles to be generated, resulting in a deterioration in the surface properties of the molded product and a deterioration in the blow molding processability. In addition, there is a problem that it is difficult to maintain the physical properties when the biodegradable resin composition is stored for a long period of time. In addition, there is a problem that the chemical reaction increases, reacting with additives to promote an oxidation reaction, or causing a deterioration in physical properties due to hydrolysis, and mechanical properties such as tensile strength and impact strength to deteriorate.

[0193] To address these issues, the inventors of the present invention used a biodegradable resin as a base resin, added an inorganic filler, a chain extender, and coffee grounds, and controlled the types, content ratios, and physical properties of the biodegradable resin, inorganic filler, chain extender, and coffee grounds, thereby controlling the moisture content of the biodegradable resin composition within a specific range. This allows the use of an environmentally friendly biodegradable resin composition that can replace plastic materials, while minimizing the problem of oxidation reactions being promoted by residual moisture and the phenomenon of color changes in molded products. Furthermore, the surface quality of the molded product can be improved, and mechanical properties such as tensile strength and impact strength can be enhanced. Furthermore, the composition can have a melt index suitable for parison formation in a blow molding process, thereby ensuring blow molding processability.

[0194] The biodegradable resin composition may have a potassium content of 600 ppm to 1,000 ppm, 650 ppm to 1,000 ppm, 700 ppm to 1,000 ppm, or 750 ppm to 1,000 ppm. The potassium content may be measured by inductively coupled plasma optical emission spectrometry (ICP-OES). When the above range is satisfied, the fluidity of the biodegradable resin composition may increase, thereby improving the blow molding processability. In addition, the potassium may act as a UV stabilizer, thereby preventing the biodegradable resin composition from deteriorating and improving the mechanical strength.

[0195] The biodegradable resin composition may have a magnesium content of 400 ppm to 3,000 ppm, 500 ppm to 3,000 ppm, 1,000 ppm to 3,000 ppm, or 1,500 ppm to 3,000 ppm. The magnesium content may be measured by inductively coupled plasma optical emission spectrometry (ICP-OES). When the above range is satisfied, the viscosity of the biodegradable resin composition may be controlled, thereby improving the blow molding processability. In addition, the magnesium may act as an antioxidant, thereby improving the tensile strength and impact strength of the biodegradable resin composition.

[0196] The biodegradable resin composition may have a melt index of 0.3 g / 10 min to 1.5 g / 10 min, 0.3 g / 10 min to 1.4 g / 10 min, 0.3 g / 10 min to 1.3 g / 10 min, or 0.3 g / 10 min to 1 g / 10 min at 190° C. and 2.16 kg according to ASTM D1238. When the above range is satisfied, the composition may have a viscosity suitable for forming a parison in a blow molding process, thereby ensuring blow molding processability.

[0197] The above biodegradable resin composition may further include an activator.

[0198] The above-mentioned lubricant may include at least one selected from the group consisting of a fatty acid-based lubricant including stearic acid, an aliphatic alcohol-based lubricant, an aliphatic amide-based lubricant including stearamide, an aliphatic ester-based lubricant such as n-butyl stearate, methyl hydroxystearate, a polyhydric alcohol fatty acid ester, a saturated fatty acid ester, an ester-based wax, and a fatty acid metal soap-based lubricant. Specifically, the above-mentioned lubricant may be a stearate-based lubricant.

[0199] Preferably, the biodegradable resin composition may further comprise a calcium-containing lubricant. Specifically, the lubricant may be calcium stearate. The calcium stearate-based lubricant has the same calcium content as the inorganic filler, heavy calcium carbonate, and thus exhibits excellent compatibility, reduces heat generation due to friction during raw material mixing, melting, and processing, has an excellent dispersion effect for the biodegradable resin relative to its price, and has an excellent lubricating effect, thereby improving manufacturing efficiency.

[0200] More preferably, the biodegradable resin composition may further include a calcium-containing lubricant and a stearyl stearate-based lubricant. The weight ratio of the calcium-containing lubricant: the stearyl stearate-based lubricant may be 1:3 to 3:1, 1:2.5 to 2.5:1, 1:2 to 2:1, or 1:1.5 to 1.5:1. When the above range is satisfied, the compatibility between the calcium-containing lubricant and the heavy calcium carbonate is improved, and due to the excellent lubricity of the stearyl stearate-based lubricant, friction is minimized in the blow molding process, and the production speed of the molded product according to the process can be improved.

[0201] The content of the above-mentioned active agent may be 0.1 wt % to 5 wt %, 0.1 wt % to 4 wt %, 0.1 wt % to 3 wt %, or 0.1 wt % to 2 wt % based on the total weight of the biodegradable resin composition. When the above range is satisfied, the manufacturing efficiency can be improved without deteriorating the physical properties of the biodegradable resin composition.

[0202] The above biodegradable resin composition may include an antioxidant. The antioxidant may include at least one selected from the group consisting of a phosphorus-based antioxidant, a phenol-based antioxidant, and a pentaerythritol-based antioxidant.

[0203] The above-mentioned phosphorus antioxidant may be at least one selected from the group consisting of triesters, diesters, monoesters of phosphorous acid, such as triphenyl phosphite, trisnonylphenyl phosphite, and tris(2,4-di-t-butylphenyl)phosphite, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl)phosphate, and 2-ethylphenyl diphenyl phosphate.

[0204] The above phenolic antioxidants are α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-t-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-t-butyl-4-hydroxybenzyl phosphonate diethyl ester, 2,2-bis(((3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl)oxy)methyl)propane-1,3-diyl It may be at least one selected from the group consisting of bis(3-(3,5-di-tert)-butyl-4-hydroxyphenyl)propanoate), pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane.

[0205] The above antioxidant may further include at least one selected from the group consisting of BHT, ascorbic acid, catechin, quercetin, dodecyl gallate, TBHQ, Ralox, Irganox 1135, Irganox 1076, nordihydroguaiaretic acid, epicatechin gallate, epigallocatechin gallate, epigallocatein, propyl gallate, 2,3,5-trihydroxybutyrophenone, butylated hydroxyanisole, 4-hydroxymethyl-2,6-di-tert-butylphenol, α-tocopherol, resveratrol, rutin, astaxanthin, lycopene, beta-carotene, and melatonin.

[0206] Preferably, the biodegradable resin composition further comprises a phenolic antioxidant and a phosphorus antioxidant, and the weight ratio of the phenolic antioxidant to the phosphorus antioxidant may be 1:1 to 1:5, 1:1 to 1:4.5, 1:1 to 1:4, or 1:2 to 1:4. When the above range is satisfied, the phenolic antioxidant can capture and neutralize free radicals, and the oxidation reaction can be suppressed by decomposing peroxides generated when oxidation is initiated by the phosphorus antioxidant. As a result, the thermal stability, color stability, and long-term storage stability of a molded product manufactured by a blow molding process can be improved.

[0207] The content of the antioxidant may be 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1.5 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.3 wt% or less, 0 to 5 wt%, 0.01 to 4 wt%, 0.1 to 3 wt%, 1 to 3 wt%, 1 to 2 wt%, 0.01 to 0.3 wt%, 0.05 to 0.3 wt%, 0.15 to 0.3 wt%, or 0.2 to 0.3 wt%, based on the total weight of the biodegradable resin composition.

[0208] The biodegradable resin composition may further comprise a reinforcing material. The reinforcing material may be a fiber derived from biomass. The reinforcing material may comprise nanocellulose. The nanocellulose may be a natural material nanocellulose in the form of a gel or dry powder, and the dispersion stability, strength, and processability of the biodegradable resin comprising the nanocellulose may all be improved.

[0209] The diameter of the nanocellulose may be 1 nm to 100 nm, 1 nm to 95 nm, 5 nm to 90 nm, 10 nm to 80 nm, 5 nm to 60 nm, or 15 nm to 60 nm. The length of the nanocellulose may be 5 nm to 5 ㎛, 5 nm to 1 ㎛, 10 nm to 700 nm, 20 nm to 500 nm, 60 nm to 300 nm, 80 nm to 200 nm, or 100 nm to 250 nm. When the above ranges are satisfied, the strength and tear strength of the biodegradable resin composition may be further improved.

[0210] The nanocellulose may be in the form of a dry powder or gel having aggregated secondary particles rather than single particles, and the size of the secondary particles may be 1 μm to 50 μm, 2 μm to 45 μm, or 5 μm to 50 μm. The nanocellulose may be in the form of a freeze-dried powder to reduce the volume for easy storage and transportation.

[0211] The average particle size of the above nanocellulose may be 200 nm or less, 190 nm or less, or 185 nm or less, and the particle size deviation may be 20% or less, 18% or less, or 16% or less. When the above ranges are satisfied, the dispersibility and durability of the nanocellulose may be improved.

[0212] The above nanocellulose can perform a crystal nucleating function, thereby improving the crystallization speed of the biodegradable resin composition and increasing the crystallization temperature of the biodegradable resin composition. The nanocellulose may be at least one selected from the group consisting of cellulose nanocrystals, cellulose nanofibers, and microfibrillated cellulose. In terms of strength and thermal properties, the cellulose nanocrystals or the cellulose nanofibers are preferable.

[0213] The above nanocellulose can perform UV resistance function, thereby providing the biodegradable resin with appropriate UV resistance properties, biodegradation rate, and hydrolysis rate. The above nanocellulose may be at least one selected from the group consisting of 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.

[0214] The above nanocellulose may be bead mill pretreated or ultrasonically pretreated. The above nanocellulose may be water-dispersed nanocellulose that has been bead mill pretreated or ultrasonically pretreated.

[0215] The above nanocellulose may be obtained by dispersing cellulose nanocrystals in a dry powder or gel form having a particle size of 1 μm to 50 μm in water and then pretreating them with a bead mill or ultrasonic pretreatment. If the above nanocellulose dispersed in water is pretreated with a bead mill or ultrasonic pretreatment, the number of nanocellulose particles may increase and dispersibility may be maximized.

[0216] The above nanocellulose may be pretreated with a silane coupling agent in an amount of 0.01 to 10 wt%, 0.05 to 8 wt%, 0.1 to 8 wt%, 0.5 to 6 wt%, or 0.7 to 6 wt% based on the total weight of the nanocellulose. When the above range is satisfied, interfacial adhesion, dispersibility, and compatibility can be maximized, and thus the mechanical properties and durability of the biodegradable resin composition including the same can be further improved.

[0217] The biodegradable resin composition may include a flame retardant. The flame retardant may include at least one selected from the group consisting of halogen-based flame retardants, phosphorus-based flame retardants, and non-phosphorus halogen-based flame retardants such as metal hydrates.

[0218] The above halogenated flame retardant may include at least one selected from the group consisting of halogenated bisphenol compounds such as halogenated bisphenyl alkanes, halogenated bisphenyl ethers, halogenated bisphenyl thioethers, and halogenated bisphenyl sulfones, and bisphenol-bis(alkyl ether) compounds such as brominated bisphenol A, brominated bisphenol S, chlorinated bisphenol A, and chlorinated bisphenol S.

[0219] The above-mentioned phosphorus flame retardant may include at least one selected from the group consisting of tris(diethyl phosphinic acid)aluminum, bisphenol A bis(diphenyl phosphate), triaryl isopropyl phosphate, cresyl di-2,6-xylenyl phosphate, and aromatic condensed phosphate esters.

[0220] The metal hydrate may include aluminum trihydrate, magnesium dihydrate, or a combination thereof.

[0221] The above flame retardant may include at least one selected from the group consisting of antimony oxide, such as antimony trioxide or antimony pentoxide, zinc oxide, iron oxide, aluminum oxide, molybdenum oxide, titanium oxide, calcium oxide, and magnesium oxide, as a flame retardant additive to improve the flame retardant effect.

[0222] The biodegradable resin composition may include a dispersant. The dispersant may improve the dispersibility of solvents and solutes. The dispersant may include at least one selected from the group consisting of aliphatic polyester, polylactic acid, polyglycolic acid, polycaprolactone, and polyhydroxyalkanoate.

[0223] The dispersant may be included in an amount of 1 to 20 wt%, 1 to 15 wt%, 1 to 13 wt%, 1 to 11 wt%, 2 to 10 wt%, 5 to 15 wt%, 7 to 12 wt%, 2 to 8 wt%, 5 to 8 wt%, or 2 to 5 wt% based on the total weight of the biodegradable resin composition.

[0224] The biodegradable resin composition may include a hydrolysis inhibitor. When the weight average molecular weight (Mw) of the hydrolysis inhibitor is large, volatility may be low and hydrolysis resistance may be improved. When the weight average molecular weight (Mw) of the hydrolysis inhibitor is small, compatibility with the biodegradable resin may be increased.

[0225] The above hydrolysis inhibitor may be two types of hydrolysis inhibitors having different weight average molecular weights. In order to increase compatibility with a biodegradable resin, one type of hydrolysis inhibitor having a weight average molecular weight (Mw) of 10,000 g / mol or less, 9,000 g / mol or less, 8,000 g / mol or less, 7,000 g / mol or less, 6,000 g / mol or less, or 5,000 g / mol or less may be used, and in order to lower volatility and improve hydrolysis resistance, one type of hydrolysis inhibitor having a weight average molecular weight of 10,000 g / mol or more, 20,000 g / mol or more, 30,000 g / mol or more, 40,000 g / mol or more, or 50,000 g / mol or more may be used. The above weight average molecular weight can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC using THF as an eluent. When the above range is satisfied, the mechanical properties and water resistance of the biodegradable resin composition can be improved.

[0226] The above hydrolysis inhibitor may include a carbodiimide-based compound. The carbodiimide-based compound may react with moisture and acid to convert into a urea structure, thereby reducing the reactivity between moisture and acid and the ester group contained in the biodegradable resin. As a result, the phenomenon of the biodegradable resin being hydrolyzed by moisture and acid may be reduced, and consequently, the hydrolysis resistance of the biodegradable resin composition may be improved.

[0227] The above carbodiimide compound may include a compound represented by the following chemical formula.

[0228] [chemical formula]

[0229]

[0230] In the above chemical formula, n is an integer from 1 to 20.

[0231] The above carbodiimide compounds are N,N'-di-o-tolylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-dioctyldecylcarbodiimide, N,N'-di-2,6-diketylphenylcarbodiimide, N-tolyl-N'cyclohexylcarbodiimide, N,N'-di-2,6-diisopropylphenylcarbodiimide, N,N'-di-2,6-di-tert-butylphenylcarbodiimide, N-tolyl-N'-phenylcarbodiimide, N,N'-di-p-nitrophenylcarbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N'-di-p-hydroxyphenylcarbodiimide, N,N'-di-cyclohexylcarbodiimide, It may be at least one selected from the group consisting of N,N'-di-p-tolylcarbodiimide, p-phenylene-bis-di-o-tolylcarbodiimide, p-phenylene-bisdicyclohexylcarbodiimide, hexamethylene-bisdicyclohexylcarbodiimide, ethylene-bisdiphenylcarbodiimide, and copolymers of benzene-2,4-diisocyanato-1,3,5-tris(1-methylethyl) homopolymer, 2,4-diisocyanato-1,3,5-tris(1-methylethyl) and 2,6-diisopropyl diisocyanate.

[0232] The weight average molecular weight of the above carbodiimide compound may be 500 g / mol to 100,000 g / mol, 600 g / mol to 100,000 g / mol, 700 g / mol to 100,000 g / mol, 800 g / mol to 90,000 g / mol, 900 g / mol to 80,000 g / mol, 1,000 g / mol to 70,000 g / mol, 1,000 g / mol to 60,000 g / mol, or 1,000 g / mol to 50,000 g / mol.

[0233] In the above carbodiimide-based compound, the content of the NCN group may be 1 wt% to 20 wt%, 1 wt% to 19 wt%, 1 wt% to 18 wt%, 1 wt% to 17 wt%, 1 wt% to 16 wt%, 1 wt% to 15 wt%, 2 wt% to 15 wt%, 3 wt% to 15 wt%, 4 wt% to 15 wt%, 5 wt% to 15 wt%, or 6 wt% to 15 wt%. The content of the NCN group in the carbodiimide-based compound can be measured by titration with oxalic acid. When the above range is satisfied, compatibility with a biodegradable resin is not reduced, and the water resistance of the biodegradable resin composition can be improved.

[0234] The content of the hydrolysis inhibitor may be 0.1 wt% to 5.0 wt%, 0.1 wt% to 4.0 wt%, 0.1 wt% to 3.0 wt%, 0.1 wt% to 2.0 wt%, 0.1 wt% to 1.5 wt%, or 0.1 wt% to 1.0 wt% based on the total weight of the biodegradable resin composition. When the above range is satisfied, the hydrolysis resistance and odor reduction effect of the biodegradable resin composition may be improved.

[0235] The content of the compound including the urea group may be 0.01 wt% to 10.00 wt%, 0.01 wt% to 9.00 wt%, 0.01 wt% to 8.00 wt%, 0.01 wt% to 7.00 wt%, 0.01 wt% to 6.00 wt%, 0.01 wt% to 5.00 wt%, 0.01 wt% to 4.00 wt%, or 0.01 wt% to 3.00 wt%, based on the total weight of the biodegradable resin composition. When the above range is satisfied, the proportion of the ester group included in the biodegradable resin that can react with moisture or acid is reduced, so that water resistance can be improved.

[0236] A blow molded article according to the present invention comprises a biodegradable resin composition comprising an aliphatic-aromatic polyester resin and an aliphatic polyester resin, an inorganic filler, a chain extender, and coffee grounds, and having a moisture content of less than 1 wt % as determined by a thermogravimetric analyzer (TGA).

[0237] The above biodegradable resin composition may be the same as the biodegradable resin composition described above.

[0238] The blow molding molded product may have a time of 10 seconds or more, 11 seconds or more, 12 seconds or more, or 10 to 30 seconds according to the following measurement method. The drawdown occurrence time may refer to the time during which the biodegradable resin composition maintains the parison shape without being drawn down. The drawdown occurrence time may be closely related to the melt index of the biodegradable resin composition, and may be controlled according to the content of the inorganic filler and chain extender included in the biodegradable resin composition. When the above range is satisfied, the biodegradable resin composition can be efficiently manufactured into a molded product through a blow molding process.

[0239] [measurement method]

[0240] 1) The pelletized biodegradable resin composition is fed into a blow molding machine (Samsung Hydraulic Machinery Co., Ltd., φ=50 mm) with a cylinder temperature of 160°C.

[0241] 2) The draw down occurrence time of the parison ejected from the die of the above blow molding machine is measured.

[0242] The volume of the blow molded article may be less than 2 L, less than 1.5 L, less than 1.2 L, or less than 1 L. The properties of the biodegradable resin composition described above may be designed to be more suitable when manufactured within the volume range of the molded article.

[0243] The blow molded product may have a specific gravity of 1.5 to 1.65, 1.51 to 1.65, 1.52 to 1.65, or 1.52 to 1.63 according to ASTM D792. When the above range is satisfied, the product may be suitably used in products requiring durability and light weight.

[0244] The above blow molded product has a tensile strength of 200 kgf / cm according to ASTM D638. 2 Up to 300 kgf / cm 2 , 210 kgf / cm 2 Up to 300 kgf / cm 2 , 220 kgf / cm 2 Up to 300 kgf / cm 2 , or 225 kgf / cm 2 Up to 280 kgf / cm 2 It could be.

[0245] The blow molded article may have an elongation of 10% to 60%, 15% to 60%, 20% to 60%, or 40% to 60% as determined by ASTM D638.

[0246] The above blow molded product has a flexural strength of 300 kgf / cm according to ASTM D790. 2 Up to 500 kgf / cm 2, 305 kgf / cm 2 Up to 500 kgf / cm 2 , 310 kgf / cm 2 Up to 500 kgf / cm 2 , or 315 kgf / cm 2 Up to 400 kgf / cm 2 It could be.

[0247] The above blow molded product has a flexural modulus of 10,000 kgf / cm according to ASTM D790. 2 Up to 25,000 kgf / cm 2 , 12,000 kgf / cm 2 Up to 25,000 kgf / cm 2 , 14,000 kgf / cm 2 Up to 25,000 kgf / cm 2 , or 14,000 kgf / cm 2 Up to 22,000 kgf / cm 2 It could be.

[0248] The above blow molded product may have an Izod impact strength of 7 kgf·cm / cm to 40 kgf·cm / cm, 8 kgf·cm / cm to 40 kgf·cm / cm, 8 kgf·cm / cm to 35 kgf·cm / cm, or 8 kgf·cm / cm to 33 kgf·cm / cm according to ASTM D256.

[0249] When the above range is satisfied, blow molding processability and mechanical properties can be secured.

[0250] The blow molded product may have a biodegradability of 90% to 100%, 91% to 100%, 91% to 99%, or 92% to 99% according to the evaluation method below. When the above range is satisfied, the molded product can be easily decomposed after being discarded.

[0251] [Biodegradability Evaluation Method]

[0252] 1) A sample is prepared by crushing the above biodegradable resin composition.

[0253] 2) Prepare an inoculum container containing only compost (Manufacturer: Taeheung F&G, Product Name: Jisengto (Grade 1 Compost, By-product Fertilizer)). Separately, prepare a test container containing a 6:1 weight ratio of compost to sample, based on the dry weight of the compost.

[0254] 3) The above inoculum container and test container are cultured for 180 days under conditions of temperature 58±2℃, pH 8±1, moisture content 50%, and oxygen concentration 6% or higher.

[0255] 4) After capturing the CO2 generated from each container, the amount of CO2 generated from each container is measured by titration with an aqueous phenolphthalein solution. The biodegradability of the reference (cellulose), which serves as the basis for evaluating biodegradability, is calculated according to Equation 1 below. The biodegradability of the above samples is calculated according to Equation 1 below, and then calculated as a relative biodegradability value based on the biodegradability of 100% of the reference.

[0256] [Formula 1]

[0257] Biodegradability (%) = [(CO2 generation in test vessel) - (CO2 generation in inoculation vessel)] / (theoretical CO2 generation in test vessel) × 100

[0258]

[0259] 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.

[0260]

[0261] Manufacturing example

[0262] - Aliphatic-aromatic polyester resin: PBAT (Kingpa A400)

[0263] - Aliphatic polyester resin: PLA (Nature Works 2003D)

[0264] - Inorganic filler: Calcium carbonate (Omia)

[0265] - Chain extender: BASF Joncryl

[0266] - Active ingredient #1: Calcium stearate

[0267] - Active ingredient #2: Stearyl stearate

[0268] - Antioxidant #1: Phenolic antioxidant (Adeca Korea AO-60)

[0269] Antioxidant #2: Phosphorus Antioxidant (Adeca Korea 2112)

[0270] - Coffee grounds #1: Refined coffee grounds (moisture content of about 3 wt%, ash content of about 20 wt%)

[0271] - Coffee grounds #2: Unrefined coffee grounds (moisture content of about 50 wt%, ash content of about 40 wt%)

[0272]

[0273] Manufacturing Example 1

[0274] A mixture comprising an aliphatic-aromatic polyester resin, an aliphatic polyester resin, an inorganic filler, a chain extender, a lubricant #1, a lubricant #2, an antioxidant #1, an antioxidant #2, and coffee grounds #1 according to the compositions described in Table 1 below was kneaded at a temperature of 175°C, and the kneaded product was extruded for about 3 minutes by an extruder equipped with a twin screw.

[0275] Thereafter, the extruded biodegradable resin composition was cut and cooled using a hot-cut pellet cutter to produce a pelletized biodegradable resin composition.

[0276]

[0277] Manufacturing Examples 2 to 5 and Comparative Manufacturing Examples 1 to 2

[0278] A biodegradable resin composition was prepared with the composition described in Table 1 below.

[0279]

[0280] Classification Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Comparative Manufacturing Example 1 Comparative Manufacturing Example 2 Aliphatic-aromatic polyester resin 19 wt% 19 wt% 19 wt% 23.6 wt% 25.6 wt% 48.8 wt% 19 wt% Aliphatic polyester resin 30 wt% 30 wt% 30 wt% 30 wt% 33 wt% 40 wt% 30 wt% Inorganic filler 44.6 wt% 39.6 wt% 29.6 wt% 40 wt% 35 wt% -19.6 wt% Chain extender 0.2 wt% 0.2 wt% 0.2 wt% 0.2 wt% -0.2 wt% Lubricant #10.4 wt% 0.4 wt% 0.4 wt% 0.4 wt% 0.4 wt% 0.4 wt% Lubricant #20.6 wt% 0.6 wt% 0.6 wt% 0.6 wt% 0.6 wt% 0.6 wt% 0.6 wt% Antioxidant #10.05 wt% 0.05 wt% 0.05 wt% 0.05 wt% 0.05 wt% 0.05 wt% 0.05 wt% 0.05 wt% Antioxidant #20.15 wt% 0.15 wt% 0.15 wt% 0.15 wt% 0.15 wt% 0.15 wt% 0.15 wt% Coffee grounds #15 wt% 10 wt% 20 wt% 5 wt% 5 wt% 30 wt% - Coffee grounds #2------ 30 wt%

[0281]

[0282] Example - Manufacturing of blow molded products

[0283] Example 1

[0284] The biodegradable resin composition manufactured in the above Manufacturing Example 1 was introduced into a blow molding machine (Samsung Hydraulic Machinery Co., Ltd., φ=50 mm) with a cylinder temperature of approximately 160°C. Thereafter, the composition was blow molded into a parison shape discharged from the die of the blow molding machine, and then cooled to manufacture a molded product having a volume of approximately 500 ml.

[0285]

[0286] Examples 2 to 5 and Comparative Examples 1 to 2

[0287] A molded product was manufactured by the same process as Example 1, except that the biodegradable resin composition described in Table 2 below was used.

[0288]

[0289] Experimental example

[0290] Experimental Example 1 - Moisture Content

[0291] For each biodegradable resin composition used in Examples 1 to 5 and Comparative Examples 1 to 2, the reduced mass at about 105°C compared to the initial mass was calculated as the moisture content by thermogravimetric analysis (TGA), and the results are shown in Table 2 below.

[0292]

[0293] Experimental Example 2 - Specific Gravity

[0294] For the molded products or separate samples manufactured in Examples 1 to 5 and Comparative Examples 1 to 2, the specific gravity was measured according to ASTM D792, and the results are shown in Table 2 below.

[0295]

[0296] Experimental Example 3 - Melt Index

[0297] For each biodegradable resin composition used in Examples 1 to 5 and Comparative Examples 1 to 2, the melt index at 190°C and 2.16 kg was measured according to ASTM D1238, and the results are shown in Table 2 below.

[0298]

[0299] Experimental Example 4 - Potassium and Magnesium Content

[0300] After each biodegradable resin composition used in Examples 1 to 5 and Comparative Examples 1 to 2 was dissolved in 65 wt% nitric acid, the potassium and magnesium contents were measured using inductively coupled plasma optical emission spectrometry (ICP-OES) under the following measurement conditions, and the results are shown in Table 2 below.

[0301] [Measurement conditions]

[0302] - Device: Agilent 5110 SVDV

[0303] - RF power: 1.2 kW

[0304] - Nebulizer flow: 0.7 L / min

[0305] - Plasma flow: 12 L / min

[0306] - Aux flow: 1 L / min

[0307] - Read time: 5 s

[0308]

[0309] Experimental Example 5 - Tensile strength and elongation

[0310] For the molded products or separate samples manufactured in Examples 1 to 5 and Comparative Examples 1 to 2, tensile strength and elongation were measured according to ASTM D638, and the results are shown in Table 2 below.

[0311]

[0312] Experimental Example 6 - Flexural Strength and Flexural Modulus

[0313] For the molded products or separate samples manufactured in Examples 1 to 5 and Comparative Examples 1 to 2, the flexural strength and flexural modulus were measured according to ASTM D790, and the results are shown in Table 2 below.

[0314]

[0315] Experimental Example 7 - Izod Impact Strength

[0316] For the molded products or separate samples manufactured in Examples 1 to 5 and Comparative Examples 1 to 2, the Izod impact strength was measured according to ASTM D256, and the results are shown in Table 2 below.

[0317]

[0318] Experimental Example 8 - Drawdown Occurrence Time of the Parison

[0319] Each of the biodegradable resin compositions used in Examples 1 to 5 and Comparative Examples 1 to 2 was introduced into a blow molding machine (Samsung Hydraulic Machinery Co., Ltd., φ=50 mm) with a cylinder temperature of approximately 160°C. Thereafter, the drawdown occurrence time of the parison ejected from the die of the blow molding machine was measured, and the results are shown in Table 2 below.

[0320]

[0321] Experimental Example 9 - Molding Reliability

[0322] For the molded products manufactured in Examples 1 to 5 and Comparative Examples 1 to 2, the molding reliability was evaluated based on the following criteria, and the results are shown in Table 2 below.

[0323] - ○: No coffee grounds dissolution on the outside or inside of the molded product.

[0324] - ×: Coffee grounds eluting from the outside or inside of the molded product

[0325]

[0326] Classification Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 1) Comparative Example 2 Biodegradable resin composition Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Manufacturing Example 4 Manufacturing Example 5 Comparative Manufacturing Example 1 Comparative Manufacturing Example 2 Moisture content 0.15 wt% 0.2 wt% 0.3 wt% 0.18 wt% 0.19 wt% 1.5 wt% 1.8 wt% Specific gravity 1.6 1 1.6 0 1.5 5 1.6 1 1.5 9-1.44 Melt Index 0.91g / 10min 0.94g / 10min 0.98g / 10min 0.92g / 10min 0.94g / 10min 2.5g / 10min 1.55g / 10min Potassium 821ppm 930ppm 970ppm 830ppm 822ppm 1,205ppm 544ppm Magnesium 1,705ppm 1,950ppm 1,975ppm 1,695ppm 1,723ppm 2,209ppm 371ppm Tensile strength 242 kgf / cm 2 239kgf / cm 2 235kgf / cm 2 241kgf / cm 2 240kgf / cm 2-190kgf / cm 2 Elongation 44% 40% 35% 42% 41% -3% Flexural strength 350 kgf / cm 2 325kgf / cm 2 305kgf / cm 2 345kgf / cm 2 330kgf / cm 2 -275kgf / cm 2 Flexural modulus: 14,800 kgf / cm 2 13,600 kgf / cm 2 12,900 kgf / cm 2 14,200 kgf / cm 2 14,000 kgf / cm 2 -11,500kgf / cm 2 Izod impact strength 33kgf·cm / cm 26kgf·cm / cm 22kgf·cm / cm 31kgf·cm / cm 29kgf·cm / cm -7kgf·cm / cm Drawdown occurrence time 18s 15s 10s 16s 15s -5s Molding reliability ○○○○○-×1) Comparative example 1: No molded product was manufactured because the parison was not formed

[0327]

[0328] Fig. 1 illustrates a photograph of a molded product according to Example 1, and Fig. 2 illustrates a photograph of a molded product not manufactured because a parison was not formed in Comparative Example 1. Fig. 3 illustrates a photograph of the outer surface of a molded product according to Comparative Example 2, and Fig. 4 illustrates a photograph of the inner surface of a molded product according to Comparative Example 2.

[0329] As can be seen from the above FIGS. 1 to 4, Tables 1 and 2, the molded products according to Examples 1 to 5 have a melt index suitable for parison formation in a blow molding process by controlling the composition and moisture content of the biodegradable resin composition, thereby ensuring blow molding processability. In addition, it was confirmed that the tensile strength, elongation, flexural strength, flexural modulus, and impact strength were improved. In addition, it was confirmed that the molding reliability was improved because there was no coffee grounds dissolution phenomenon on the outside and inside of the molded products.

[0330]

[0331] The embodiment can be applied to a biodegradable resin composition and a blow molded product comprising the same.

Claims

1. Biodegradable resin comprising aliphatic-aromatic polyester resin and aliphatic polyester resin; Weapon refill; chain extender; and Contains coffee grounds, A biodegradable resin composition having a moisture content of less than 1 wt% as determined by thermogravimetric analysis (TGA).

2. In paragraph 1, A biodegradable resin composition wherein the weight ratio of the aliphatic-aromatic polyester resin to the aliphatic polyester resin is 1:1 to 1:

2.

3. In paragraph 1, A biodegradable resin composition wherein the content of the inorganic filler is 30 wt% to 60 wt% based on the total weight of the biodegradable resin composition.

4. In paragraph 1, A biodegradable resin composition wherein the content of the chain extender is 0.1 wt% to 1 wt% based on the total weight of the biodegradable resin composition.

5. In paragraph 1, A biodegradable resin composition wherein the content of the coffee grounds is 1 wt% to 20 wt% based on the total weight of the biodegradable resin composition.

6. In paragraph 1, A biodegradable resin composition wherein the coffee grounds have an ash content of less than 25 wt% at 900°C as determined by thermogravimetric analysis (TGA).

7. In paragraph 1, A biodegradable resin composition further comprising lignin.

8. In paragraph 7, A biodegradable resin composition wherein the moisture content of the lignin is less than 5 wt%.

9. In paragraph 7, A biodegradable resin composition wherein the lignin has an ash content of less than 35 wt% at 900°C as determined by thermogravimetric analysis (TGA).

10. In paragraph 1, A biodegradable resin composition further comprising an active agent containing calcium.

11. In paragraph 1, The above biodegradable resin composition is a biodegradable resin composition having a potassium content of 600 ppm to 1,000 ppm.

12. In paragraph 1, The above biodegradable resin composition is a biodegradable resin composition having a magnesium content of 400 ppm to 3,000 ppm.

13. In paragraph 1, The biodegradable resin composition has a melt index of 0.3 g / 10 min to 1.5 g / 10 min at 190° C. and 2.16 kg according to ASTM D1238.

14. Biodegradable resins including aliphatic-aromatic polyester resins and aliphatic polyester resins; Weapon refill; chain extender; and Contains coffee grounds, A blow molded article comprising a biodegradable resin composition having a moisture content of less than 1 wt% as determined by a thermogravimetric analyzer (TGA).

15. In paragraph 14, Blow molded products having a time of 10 seconds or more according to the following measurement method: [measurement method] 1) The pelletized biodegradable resin composition is fed into a blow molding machine (Samsung Hydraulic Machinery Co., Ltd., φ=50 mm) with a cylinder temperature of 160°C. 2) The draw down occurrence time of the parison ejected from the die of the above blow molding machine is measured.

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