Biodegradable resin composition, method for preparing same, and biodegradable molded article comprising same

Abstract

The present invention comprises: a first biodegradable resin; a second biodegradable resin; a radical initiator; and a third biodegradable resin having a structure in which a part or the whole of the first biodegradable resin and a part or the whole of the second biodegradable resin are bonded, wherein the melt flow index measured at a temperature of 190 °C and a weight of 2.16 kg according to ASTM D1238 is less than 1.0 g / 10 min.

Description

Biodegradable resin composition, method for manufacturing the same, and biodegradable molded article comprising the same

[0001] The present invention relates to a biodegradable resin composition, a method for manufacturing the same, and a biodegradable molded article comprising the same.

[0002]

[0003] With the recent increase in concerns regarding environmental issues, there is a growing demand for solutions to the disposal problems of various household goods, particularly 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, they have disadvantages: harmful substances are released during incineration when used products reach the end of their lifespan, and depending on the type, it takes hundreds of years for them to completely decompose naturally.

[0004] In order to overcome the limitations of these petroleum-based polymer materials, research on biodegradable resins that decompose within a relatively short period of time is actively underway. As biodegradable resins, polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), and polybutylene succinate (PBS) are being introduced as alternatives.

[0005] However, PLA lacked flexibility, and PBAT had poor mechanical properties, limiting its applications.

[0006] Meanwhile, in the field of polymers, it is well known that specially customized polymers are required to achieve individually required characteristics depending on the different application. For example, polymers used in blow molding must inevitably have different properties from those used in injection molding.

[0007] For example, the blow molding process is a very special process that allows for the flexible and inexpensive manufacturing of different types of bottles in terms of size and shape.

[0008] In the blow molding process, a polymer melt is first extruded with air through a tubular die to form a polymer tube, and then the polymer tube (typically referred to as a "parison" in this field) is blown up until it reaches the boundary of the outer mold. Completely covering the mold walls with the blown-up polymer tube is somewhat more difficult than in injection molding because it is a demanding process step requiring the complete removal of air between the polymer tube and the mold. Additionally, since the interior of the polymer tube does not come into contact with the mold, there is little possibility of affecting the internal surface structure of the tube.

[0009] In particular, to manufacture medium to large blow-molded products of 2L or more, a polymer melt having a certain level of viscosity and molecular weight is required.

[0010]

[0011] The present invention provides a biodegradable resin composition having excellent flexibility and mechanical properties that allows for medium to large-sized blow molding, a method for manufacturing the same, and a biodegradable molded article comprising the same.

[0012]

[0013] The biodegradable resin composition according to the present invention comprises a first biodegradable resin comprising an aliphatic-aromatic polyester resin, a second biodegradable resin comprising an aliphatic polyester resin, a polyol, and a third biodegradable resin comprising a structure in which part or all of the first biodegradable resin and part or all of the second biodegradable resin are combined, and has a melt index of 1 g / 10 min or less at 190 ℃ and 2.16 kg according to ASTM D1238.

[0014] In one embodiment of the present invention, the weight ratio of the first biodegradable resin to the second biodegradable resin may be 1:1 to 1:9.

[0015] In one embodiment of the present invention, the polyol may have a hydroxyl value (OH value) of 1,830 mgKOH / g to 2,000 mgKOH / g.

[0016] In one embodiment of the present invention, the polyol may have a solubility in water of 50 g / 100 ml to 300 g / 100 ml at 25 ℃.

[0017] In one embodiment of the present invention, the content of the polyol may be greater than 0 weight % and less than 0.1 weight % based on the total weight of the biodegradable resin composition.

[0018] In one embodiment of the present invention, the third biodegradable resin may include a structure represented by the following chemical formula 1.

[0019] [Chemical Formula 1]

[0020]

[0021] In the above chemical formula 1, n1 is an integer from 1 to 200, and A1 is derived from the above polyol.

[0022] In one embodiment of the present invention, the biodegradable resin composition may include a radical initiator.

[0023] In one embodiment of the present invention, the radical initiator may be in a solid state at room temperature.

[0024] In one embodiment of the present invention, the content of the radical initiator may be greater than 0.01 weight % and less than 1 weight % based on the total weight of the biodegradable resin composition.

[0025] In one embodiment of the present invention, the biodegradable resin composition may include a fourth biodegradable resin comprising a structure represented by the following chemical formula 2.

[0026] [Chemical Formula 2]

[0027]

[0028] In the above chemical formula 2, n2 is an integer from 1 to 200, X1 is derived from the first biodegradable resin, and A2 is derived from the polyol.

[0029] In one embodiment of the present invention, the biodegradable resin composition may include a fifth biodegradable resin comprising a structure represented by the following chemical formula 3.

[0030] [Chemical Formula 3]

[0031]

[0032] In the above chemical formula 3, n3 is an integer from 1 to 200, X2 is derived from the second biodegradable resin, and A3 is derived from the polyol.

[0033] In one embodiment of the present invention, the biodegradable resin composition may include a chain extender.

[0034] A method for manufacturing a biodegradable resin composition according to the present invention comprises the steps of: melt-mixing a first biodegradable resin comprising an aliphatic-aromatic polyester resin, a second biodegradable resin comprising an aliphatic polyester resin, and a polyol; and reacting the first biodegradable resin and the second biodegradable resin with the polyol to form a third biodegradable resin, wherein the melt index of the biodegradable resin composition manufactured according to ASTM D1238 at 190°C and 2.16 kg is 1 g / 10 min or less.

[0035] In one embodiment of the present invention, in the step of forming the third biodegradable resin, the first biodegradable resin and the second biodegradable resin may be reacted under a temperature condition of 170°C to 190°C.

[0036] In one embodiment of the present invention, the step of melt mixing may include a step in which a radical initiator is melt mixed, and the first biodegradable resin and the third biodegradable resin are reacted by the radical initiator to form a fourth biodegradable resin.

[0037] In one embodiment of the present invention, the method may include a step in which a radical initiator is melt-mixed in the melt-mixing step, and the second biodegradable resin and the third biodegradable resin are reacted by the radical initiator to form a fifth biodegradable resin.

[0038] A biodegradable molded article according to the present invention comprises a biodegradable resin composition comprising a first biodegradable resin comprising an aliphatic-aromatic polyester resin, a second biodegradable resin comprising an aliphatic polyester resin, a polyol, and a third biodegradable resin comprising a structure in which part or all of the first biodegradable resin and part or all of the second biodegradable resin are combined, wherein the biodegradable resin composition has a melt index of 1 g / 10 min or less at 190 ℃ and 2.16 kg according to ASTM D1238.

[0039] The biodegradable resin composition according to the present invention comprises a first biodegradable resin; a second biodegradable resin; a radical initiator; and a third biodegradable resin comprising a structure in which part or all of the first biodegradable resin and part or all of the second biodegradable resin are combined, and the melt flow index measured at a temperature of 190°C and a weight of 2.16 kg according to ASTM D1238 is less than 1.0 g / 10 min.

[0040] The above melt flow index may be 0.2g / 10min to 0.8g / 10min.

[0041] The first biodegradable resin comprises polylactic acid, and the second biodegradable resin comprises polybutylene adipate terephthalate, and the weight ratio of the first biodegradable resin and the second biodegradable resin may be 1:1 to 9:1.

[0042] The above third biodegradable resin may include a structure represented by the following chemical formula 1.

[0043] [Chemical Formula 1]

[0044]

[0045] In the above chemical formula 1, k is 1 to 50000, and X1 is derived from the second biodegradable resin.

[0046] In the above chemical formula 1, X1 may include at least one of the repeating units represented by the following chemical formulas B'-1 to B'-3.

[0047] [Chemical Formula B'-1]

[0048]

[0049] [Chemical Formula B'-2]

[0050]

[0051] [Chemical Formula B'-3]

[0052]

[0053] In the above chemical formulas B'-1 to B'-3, q is 1 to 20.

[0054] It may include a fourth biodegradable resin comprising a structure represented by the following chemical formula 2.

[0055] [Chemical Formula 2]

[0056]

[0057] In the above chemical formula 2, l is 1 to 50000, and X2 is derived from the first biodegradable resin.

[0058] In the above chemical formula 2, the X2 may include a repeating unit represented by the following chemical formula A'.

[0059] [Chemical Formula A']

[0060]

[0061] In the above chemical formula A', p is 1 to 20.

[0062] The above radical initiator includes an organic peroxide and may be in a solid state at room temperature.

[0063] The above radical initiator may include a compound represented by the following chemical formula 3.

[0064] [Chemical Formula 3]

[0065]

[0066] In the above chemical formula 3,

[0067] R1 to R4 are each independently selected from the group consisting of hydrogen atoms, hydrocarbon groups, heteroatoms, and combinations thereof, n is 1 to 20, and m is 1 to 20.

[0068] The content of the radical initiator may be 0.01% to 1% by weight based on the total weight of the biodegradable resin composition.

[0069] The above biodegradable resin composition may further include a chain extender in an amount of 1% by weight or less based on the total weight.

[0070] The above biodegradable resin composition may further include an antioxidant in an amount of 1% by weight or less based on the total weight.

[0071] Meanwhile, a method for manufacturing a biodegradable resin composition according to the present invention comprises the steps of: melt-mixing a first biodegradable resin, a second biodegradable resin, and a radical initiator; and reacting the first biodegradable resin and the second biodegradable resin using the radical initiator to form a third biodegradable resin, wherein the melt flow index measured at a temperature of 190°C and a weight of 2.16 kg according to ASTM D1238 is less than 1.0 g / 10 min.

[0072] In the step of forming the third biodegradable resin, the first biodegradable resin and the second biodegradable resin can react with each other at a temperature of 150°C to 200°C.

[0073] After forming the third biodegradable resin, the method may further include a step of removing by-products derived from the radical initiator.

[0074] Meanwhile, the biodegradable molded article according to the present invention comprises a biodegradable resin composition comprising a first biodegradable resin; a second biodegradable resin; a radical initiator; and a third biodegradable resin having a structure in which part or all of the first biodegradable resin and part or all of the second biodegradable resin are combined, wherein in the biodegradable resin composition, the melt flow index measured at a temperature of 190°C and a weight of 2.16 kg according to ASTM D1238 is less than 1.0 g / 10 min.

[0075]

[0076] The biodegradable resin composition according to the present invention comprises a third biodegradable resin produced by reacting a part or all of a first biodegradable resin and a part or all of a second biodegradable resin with a polyol. As the molecular weight of the biodegradable resin composition increases and the melt index is lowered to below a specific value, mechanical properties such as tensile strength, elongation, flexural strength, flexural modulus, and impact strength suitable for medium to large blow molding can be improved.

[0077] The above biodegradable resin composition may include radicals generated by the radical initiator. Accordingly, the biodegradable resin composition can be effectively biodegraded. The radicals can promote biodegradation by cleaving the first biodegradable resin, the second biodegradable resin, and / or the third biodegradable resin, thereby providing an environmentally friendly biodegradable molded article.

[0078] The above biodegradable resin composition may include an antioxidant. The antioxidant acts as a radical scavenger to remove unstable free radicals from the manufactured final biodegradable resin composition, thereby improving the thermal stability of the final biodegradable resin composition.

[0079]

[0080] Figure 1 is a simplified diagram showing the blow molding process.

[0081] FIG. 2 is a partial cross-sectional view of an extruder used according to one embodiment.

[0082]

[0083] 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 concept of the present invention. Embodiments according to the technical concept of the present invention may be implemented in various forms other than those disclosed in this specification or application, and the technical concept of the present invention is not to be interpreted as being limited to the embodiments described in this specification or application.

[0084] When a component is described as "comprising" in this specification or application, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. Furthermore, all numerical ranges representing physical properties, dimensions, etc., of components described in this specification or application should be understood to be modified by the term "approximately" in all cases, unless otherwise specifically stated.

[0085] In this specification or application, 'ppm' refers to a weight basis.

[0086] In this specification or application, the description of "A and / or B" means "A, B, or A and B".

[0087]

[0088] <1st Example>

[0089] The biodegradable resin composition according to the present invention comprises a first biodegradable resin comprising an aliphatic-aromatic polyester resin. By including the first biodegradable resin, the biodegradable resin composition can be easily decomposed in soil by microorganisms, etc.

[0090] 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.

[0091] 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.

[0092] The above diol may be selected from at least one of 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 at least one of 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.

[0093] The above aliphatic dicarboxylic acid may be selected from at least one of the group consisting of oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, servenic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, or derivatives thereof. The above aliphatic dicarboxylic acid may be selected from at least one of the group consisting of adipic acid, succinic acid, sebacic acid, or derivatives thereof. The above aliphatic dicarboxylic acid may include adipic acid or a derivative thereof.

[0094] The aromatic dicarboxylic acid may be selected from at least one 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 aromatic dicarboxylic acid may be selected from at least one group consisting of terephthalic acid, dimethyl terephthalate, 2,6-naphthalenedicarboxylic acid, isophthalic acid, or derivatives thereof. The aromatic dicarboxylic acid may include terephthalic acid, dimethyl terephthalate, or derivatives thereof.

[0095] 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 about 1:0.9 to about 1:1.1, or about 1:0.95 to about 1:1.05.

[0096] In the above aliphatic-aromatic polyester resin, the molar ratio of the aromatic dicarboxylic acid residue and the aliphatic dicarboxylic acid residue may be about 3:7 to about 7:3, about 3.3:6.7 to about 6.7:3.3, about 4:6 to about 6:4, or about 4.2:5.8 to about 5:5.

[0097] The above aliphatic-aromatic polyester resin may contain diol residues 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.

[0098] The above aliphatic-aromatic polyester resin may contain 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.

[0099] The above aliphatic-aromatic polyester resin may contain aliphatic dicarboxylic acid residues 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.

[0100] The above aliphatic-aromatic polyester resin may include a first block and a second block. The above aliphatic-aromatic polyester resin may have a molecular structure in which the first block and the second block are alternately bonded.

[0101] 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 the repeating unit formed by the esterification reaction of the diol and the aromatic dicarboxylic acid. The first block may refer to the sum of the repeating units of the diol and the aromatic dicarboxylic acid up to the point of aliphatic dicarboxylic acid bonding.

[0102] 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 the repeating unit formed by the esterification reaction of the diol and the aliphatic dicarboxylic acid. The second block may refer to the sum of the repeating units of the diol and the aliphatic dicarboxylic acid up to the point of being bonded to the aromatic dicarboxylic acid.

[0103] In the above aliphatic-aromatic polyester resin, the ratio (X / Y) of the number of the first block (X) and the number of the second block (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 block may be smaller than the number of the second block. The number of the first block 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 block may vary depending on the content of the aromatic dicarboxylic acid, the molecular weight of the aliphatic-aromatic polyester resin, and the degree of substitution 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 substitution described later increases, the number of the first blocks may increase.

[0104] 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 substitution described below.

[0105] When the aliphatic-aromatic polyester resin comprises the first block and the second block within the above range, the biodegradable molded article comprising the aliphatic-aromatic polyester resin can have appropriate mechanical strength while improving biodegradability.

[0106] The above aliphatic-aromatic polyester resin may include the following bonding structures 1 to 3.

[0107] [Coupling Structure 1]

[0108] - Aromatic dicarboxylic acid - Diol - Aliphatic dicarboxylic acid -

[0109] [Combination Structure 2]

[0110] - Aromatic dicarboxylic acid - Diol - Aromatic dicarboxylic acid -

[0111] [Combination Structure 3]

[0112] - Aliphatic dicarboxylic acid - Diol - Aliphatic dicarboxylic acid -

[0113] 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 bonded between the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid, and to the aromatic dicarboxylic acid and the aliphatic dicarboxylic acid.

[0114] 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 bonded between the aromatic dicarboxylic acid and the aromatic dicarboxylic acid, and to the aromatic dicarboxylic acid and the aromatic dicarboxylic acid.

[0115] 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 bonded between the aliphatic dicarboxylic acid and the aliphatic dicarboxylic acid, and to the aliphatic dicarboxylic acid and the aliphatic dicarboxylic acid.

[0116] 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.

[0117] The above replacement ratio may be the ratio of the diol in which the heterocyclic acid is bonded between the diols among the total diols.

[0118] The above alternating ratio can be calculated using the following Formula 1.

[0119] [Formula 1]

[0120]

[0121] 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.

[0122] In the above aliphatic-aromatic polyester resin, the alteration 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.

[0123] The above aliphatic-aromatic polyester resin may include hard segments. The ratio of the hard segments is the ratio of the aromatic dicarboxylic acid and the diol bonded between the aromatic dicarboxylic acid among the diols.

[0124] The hard segment ratio may be the molar ratio of the diol included in the bonding structure 2 among the total diol. The hard segment ratio may be the 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.

[0125] The above hard segment ratio can be expressed by the following formula 2.

[0126] [Equation 2]

[0127]

[0128] 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.

[0129] The above hard segment ratio may be about 0.15 to about 0.35, about 0.2 to about 0.3, about 0.21 to about 0.29, or about 0.22 to about 0.28.

[0130] The above aliphatic-aromatic polyester resin may include soft segments.

[0131] The above soft segment ratio is the ratio of the aliphatic dicarboxylic acid and the diol bonded between the aliphatic dicarboxylic acid among the above diols.

[0132] The above soft segment ratio may be the molar ratio of the diol included in the bonding structure 3 among the total diol. The above soft segment ratio may be the 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.

[0133] The above soft segment ratio can be expressed by the following formula 3.

[0134] [Equation 3]

[0135]

[0136] 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.

[0137] The above soft segment ratio may be about 0.16 to about 0.36, about 0.21 to about 0.31, about 0.22 to about 0.30, or about 0.23 to about 0.29.

[0138] The above soft segment ratio may be larger than the above hard segment ratio.

[0139] 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.

[0140] The above-mentioned alteration ratio, the above-mentioned hard segment ratio, and the above-mentioned soft segment ratio can be measured by nuclear magnetic resonance spectroscopy. The above-mentioned aliphatic-aromatic polyester resin 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.

[0141] When the above diol is 1,4-butanediol, the above aromatic dicarboxylic acid is terephthalic acid or dimethyl terephthalate, and the above aliphatic dicarboxylic acid is adipic acid, the analysis of the above 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.

[0142] When the above diol is 1,4-butanediol, the above aromatic dicarboxylic acid is terephthalic acid or dimethyl terephthalate, and the above aliphatic dicarboxylic acid is adipic acid, the analysis of the above aliphatic-aromatic polyester resin by nuclear magnetic resonance spectroscopy may include a peak derived from the diol of the above bonding structure 1, a peak derived from the diol of the above bonding structure 2, and a peak derived from the above bonding structure 3 at about 3.5 ppm to about 4.6 ppm.

[0143] 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. Additionally, based on the ppm of the ninth peak, in the range of about -3.4 ppm to about -4.3 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.

[0144] The -ppm direction can be the upfield direction or the shielding direction. For example, -3.4 ppm may mean a location of 3.4 ppm in the upfield direction. For example, -3.4 ppm may mean a location of 3.4 ppm in the shielding direction.

[0145] Analysis of the aliphatic-aromatic polyester resin by the above nuclear magnetic resonance spectroscopy may include peaks derived from the diol of the bonding structure 1, peaks derived from the diol of the bonding structure 2, and peaks derived from the bonding structure 3, even at about 1.0 ppm to about 2.5 ppm.

[0146] In the range of about 1.0 ppm to about 2.5 ppm, the 10th peak, the 5th peak, the 6th peak, the 7th peak, the 8th peak, and the 11th peak may be defined in order from high ppm to low ppm. Based on the ppm of the 9th peak, in the range of about -6.0 ppm to about -6.7 ppm, the 5th peak, the 6th peak, the 7th peak, the 8th peak, and the 11th peak may be defined in order from high ppm to low ppm.

[0147] The ninth peak may be formed in the range of about 7.5 ppm to about 8.5 ppm. The ninth peak may be derived from the aromatic dicarboxylic acid. The ninth peak may be derived from an aromatic ring contained in the aromatic dicarboxylic acid. The ninth peak may be derived from an aromatic ring contained in the terephthalic acid or dimethyl terephthalate.

[0148] The above 10th peak and the above 11th peak may be derived from the above aliphatic dicarboxylic acid. The above 10th peak and the above 11th peak may be derived from the above adipic acid.

[0149] The first peak may be located at approximately -3.6 ppm to approximately -3.68 ppm based on the ppm of the ninth peak. The second peak may be located at approximately -3.69 ppm to approximately -3.75 ppm based on the ppm of the ninth peak. The third peak may be located at approximately -3.9 ppm to approximately -3.97 ppm based on the ppm of the ninth peak. The fourth peak may be located at approximately -3.98 ppm to approximately -4.1 ppm based on the ppm of the ninth peak. The fifth peak may be located at approximately -6.0 ppm to approximately -6.19 ppm based on the ppm of the ninth peak. The sixth peak may be located at approximately -6.2 ppm to approximately -6.26 ppm based on the ppm of the ninth peak. The 7th peak may be located at approximately -6.27 ppm to approximately -6.34 ppm based on the ppm of the 9th peak. The 8th peak may be located at approximately -6.35 ppm to approximately -6.42 ppm based on the ppm of the 9th peak. The 10th peak may be located at approximately -5.6 ppm to approximately -5.8 ppm based on the ppm of the 9th peak. The 11th peak may be located at approximately -6.421 ppm to approximately -6.5 ppm based on the ppm of the 9th peak. The position based on the ppm of the 9th peak may be the position of each peak when the position of the 9th peak is 0 ppm.

[0150] 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 determined relatively.

[0151] The above alternating ratio can be derived using the following Equation 4 or Equation 5.

[0152] [Equation 4]

[0153]

[0154] In the above formula 4, PA1 is the area of ​​the first peak, PA2 is the area of ​​the second peak, PA3 is the area of ​​the third peak, and PA4 is the area of ​​the fourth peak.

[0155] [Formula 5]

[0156]

[0157] In the above formula 5, PA5 is the area of ​​the fifth peak, PA6 is the area of ​​the sixth peak, PA7 is the area of ​​the seventh peak, and PA8 is the area of ​​the eighth peak.

[0158] The above hard segment ratio can be derived using the following formula 6 or the following formula 7.

[0159] [Equation 6]

[0160]

[0161] In the above formula 6, PA1 is the area of ​​the first peak, PA2 is the area of ​​the second peak, PA3 is the area of ​​the third peak, and PA4 is the area of ​​the fourth peak.

[0162] [Equation 7]

[0163]

[0164] In the above formula 7, PA5 is the area of ​​the fifth peak, PA6 is the area of ​​the sixth peak, PA7 is the area of ​​the seventh peak, and PA8 is the area of ​​the eighth peak.

[0165] The above soft segment ratio can be derived using the following formula 8 or formula 9.

[0166] [Equation 8]

[0167]

[0168] In the above formula 8, PA1 is the area of ​​the first peak, PA2 is the area of ​​the second peak, PA3 is the area of ​​the third peak, and PA4 is the area of ​​the fourth peak.

[0169] [Formula 9]

[0170]

[0171] In the above formula 9, PA5 is the area of ​​the fifth peak, PA6 is the area of ​​the sixth peak, PA7 is the area of ​​the seventh peak, and PA8 is the area of ​​the eighth peak.

[0172] 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 7 to about 3.5, about 0.7 to about 3, about 0.8 to about 2.5, about 1.0 to about 1.15, or about 1.02 to about 1.13.

[0173] The sum of the areas of the first peak, the second peak, the third peak, and the fourth peak may be about 1.49 to about 2.44, about 1.81 to about 2.16, about 1.9 to about 2.2, or about 1.95 to about 2.1. Here, the sum of the areas of the first peak, the second peak, the third peak, and the fourth peak may represent the sum of the total number of ester bonds based on the number of terephthalic acid groups. The sum of the areas of the second peak and the third peak may be about 0.95 to about 1.10, or about 0.98 to about 1.07. Here, the sum of the areas of the first peak and the third peak may represent the degree of extension of the molecular bonds 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 about 1.1 to about 1.3, about 0.67 to about 2, about 0.96 to about 1.40, or about 1.15 to about 1.25. The ratio of the area of ​​the fourth peak to the area of ​​the first peak may refer to the ratio of the soft segment to the hard segment within the molecular structure of the 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 about 0.7 to about 1.89, about 0.91 to about 1.33, about 1.0 to about 1.2, or 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 about 0.61 to about 1.62, about 0.81 to about 1.11, about 0.85 to about 0.95, or about 0.86 to about 0.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.

[0174] The number average molecular weight of the 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, processability can be improved while having appropriate biodegradability. The number average molecular weight can be measured using gel permeation chromatography (GPC).

[0175] The degree of crystallization of the aliphatic-aromatic polyester resin may be 10% to 30%, less than 10% to 30%, less than 12% to 30%, 12% to 28%, or 15% to 25%. If the above range is satisfied, processability may be improved.

[0176] The above degree of crystallinity is the melting enthalpy (ΔH) measured using Differential Scanning Calorimetry (DSC) according to ASTM D-3417. m ) enthalpy of melting in 100% crystal (ΔH c It can be calculated as a percentage of the value divided by ).

[0177] Specifically, it can be calculated according to the following formula.

[0178] [Calculation Formula]

[0179] Degree of 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% degree of crystallinity (J / g)] × 100

[0180] The above aliphatic-aromatic polyester resin may have a melt index at 190°C and 2.16 kg according to ASTM D1238 of greater than 3 g / 10 min to less than 50 g / 10 min, 3.5 g / 10 min to 45 g / 10 min, 3.5 g / 10 min to 40 g / 10 min, or 3.5 g / 10 min to 30 g / 10 min. If the above range is satisfied, processability may be improved and the mechanical properties of the biodegradable molded article produced may be secured.

[0181] The content of the aliphatic-aromatic polyester resin may be 10% to 50% by weight, 15% to 50% by weight, 20% to 50% by weight, or 20% to 45% by weight based on the total weight of the biodegradable resin composition. When the above range is satisfied, processability may be improved, and water resistance may be improved without deterioration of mechanical properties.

[0182] The first biodegradable resin may further include a reinforcing material. The reinforcing material may be a fiber derived from biomass. The reinforcing material may include 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 first biodegradable resin containing the nanocellulose may be improved.

[0183] 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 µm, 5 nm to 1 µm, 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.

[0184] 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 volume for easy storage and transportation.

[0185] The average particle size of the 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. If the above ranges are satisfied, the dispersibility and durability of the nanocellulose may be improved.

[0186] The nanocellulose above performs the function of a crystal nucleating agent, which can increase the crystallization rate and crystallization temperature of the biodegradable resin composition. The nanocellulose may be one or more selected from the group consisting of cellulose nanocrystals, cellulose nanofibers, and microfibrillated cellulose. In terms of strength and thermal properties, it may preferably be the cellulose nanocrystals or the cellulose nanofibers.

[0187] The above nanocellulose performs a UV resistance function, thereby imparting appropriate UV resistance, biodegradation rate, and hydrolysis rate to the above biodegradable resin. The above nanocellulose may be one or more 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.

[0188] The above nanocellulose may be bead mill pretreated or ultrasonically pretreated. The above nanocellulose may be water-dispersed nanocellulose that is bead mill pretreated or ultrasonically pretreated.

[0189] The above nanocellulose may be obtained by dispersing cellulose nanocrystals in the form of dry powder or gel having a particle size of 1 μm to 50 μm in water, and then pretreating them with a bead mill or ultrasonic treatment. When the water-dispersed nanocellulose is pretreated with a bead mill or ultrasonic treatment, the number of nanocellulose particles may increase, and dispersibility may be maximized.

[0190] 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 ranges are satisfied, interfacial adhesion, dispersibility, and compatibility can be maximized, thereby further improving the mechanical properties and durability of the biodegradable resin composition containing it.

[0191] The first biodegradable resin may contain the nanocellulose in an amount of 0.01 to 3 weight%, 0.01 to 2.5 weight%, 0.05 to 2 weight%, 0.07 to 1.8 weight%, 0.1 to 1.2 weight%, 0.1 to 1 weight%, or 0.15 to 0.7 weight% based on the total weight of the biodegradable resin composition. When the above range is satisfied, the biodegradability and mechanical strength of the biodegradable resin composition may be further improved.

[0192] The biodegradable resin composition according to the present invention comprises a second biodegradable resin comprising an aliphatic polyester resin. By including the second biodegradable resin, the strength and stiffness of the first biodegradable resin can be supplemented.

[0193] 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 cooling process of the biodegradable resin composition, thereby minimizing the volume change of the biodegradable resin composition.

[0194] The content of the aliphatic polyester resin may be greater than 50% by weight and less than 90% by weight, 55% by weight and less than 90% by weight, 55% by weight and 85% by weight, or 60% by weight and 80% by weight, based on the total weight of the biodegradable resin composition. If the above range is satisfied, the mechanical properties of the biodegradable molded article produced may be improved.

[0195] The above aliphatic polyester resin may contain polylactic acid.

[0196] The above polylactic acid may include units represented by the following chemical formula.

[0197] [Chemical Formula]

[0198]

[0199] The above polylactic acid may be a high-melting-point polylactic acid having stereocomplex crystals. Additionally, the above polylactic acid may be formed by solution mixing or melt mixing of L-lactic acid and D-lactic acid.

[0200] The above polylactic acid may be a polymer comprising L-lactic acid and / or D-lactic acid. The above polylactic acid may comprise L-lactic acid and / or D-lactic acid.

[0201] Preferably, the polylactic acid comprises D-lactic acid, and the D-lactic acid may be 1% to 5% by weight, 2% to 5% by weight, 3% to 5% by weight, or 4% to 5% by weight based on the total weight of the polylactic acid. If the above range is satisfied, the heat resistance of the biodegradable molded article produced may be improved.

[0202] The number average molecular weight (Mn) of the aliphatic polyester resin may be about 20,000 g / mol to about 160,000 g / mol. The number average molecular weight of the aliphatic polyester resin may be about 30,000 g / mol to about 140,000 g / mol. The number average molecular weight of the aliphatic polyester resin may be about 40,000 g / mol to about 120,000 g / mol.

[0203] The weight-average molecular weight (Mw) of the aliphatic polyester resin may be about 40,000 g / mol to about 200,000 g / mol. The weight-average molecular weight of the aliphatic polyester resin may be about 50,000 g / mol to about 180,000 g / mol. The weight-average molecular weight of the aliphatic polyester resin may be about 70,000 g / mol to about 160,000 g / mol.

[0204] The polydispersity index (Mw / Mn) of the aliphatic polyester resin may be about 1.0 to about 3.0. The polydispersity index of the aliphatic polyester resin may be about 1.1 to about 2.0. The polydispersity index of the aliphatic polyester resin may be about 1.2 to about 1.8. The weight average molecular weight and the number average molecular weight may be measured by methods known to those skilled in the art. For example, the weight average molecular weight and the number average molecular weight may be measured by gel permeation chromatography (GPC). The weight average molecular weight and the number average molecular weight may be measured by standard monodisperse polystyrene.

[0205] The above aliphatic polyester resin may have an apparent viscosity of about 50 Pascal·seconds (Pa·s) to about 600 Pa·s measured at a temperature of about 190°C and a shear rate of 1000 / s. The above aliphatic polyester resin may have an apparent viscosity of about 100 Pa·s to about 500 Pa·s measured at a temperature of about 190°C and a shear rate of 1000 / s. The above aliphatic polyester resin may have an apparent viscosity of about 200 Pa·s to about 400 Pa·s measured at a temperature of about 190°C and a shear rate of 1000 / s.

[0206] The above aliphatic polyester resin may have a melt index of less than 100g / 10min, 90g / 10min or less, 80g / 10min or less, 10g / 10min to 80g / 10min, 20g / 10min to 70g / 10min, or 25g / 10min to 75g / 10min at a temperature of about 190℃.

[0207] The above aliphatic polyester resin may have a melt index of about 30g / 10min to about 90g / 10min, about 35g / 10min to about 85g / 10min at a temperature of about 220℃, or about 40g / 10min to about 80g / 10min at a temperature of about 250℃.

[0208] The above melt flow index can be measured according to ASTM D1238.

[0209] The weight ratio of the first biodegradable resin to the second biodegradable resin may be 1:1 to 1:9, 1:1 to 1:8.5, 1:1 to 1:8, or 1:1 to 1:5. When the above weight ratio is satisfied, the impact strength of the biodegradable molded article may be improved.

[0210] The above aliphatic polyester resin can be modified by a surface treatment agent.

[0211] The surface of the aliphatic polyester resin can be modified by the surface treatment agent. By including an aliphatic polyester resin modified by the surface treatment agent, the biodegradable resin composition can improve compatibility with an aliphatic-aromatic polyester resin and suppress the bleeding phenomenon in which the aliphatic polyester resin flows out onto the surface of the biodegradable molded article being manufactured.

[0212] The surface treatment agent may include an amide group. The surface treatment agent may include a fatty acid amide. The surface treatment agent containing the amide group can be easily bonded to 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 bleeding phenomena.

[0213] The above surface-modified aliphatic polyester resin can be manufactured by the following method.

[0214] A surface treatment agent is added to the 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.

[0215] 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 to 5 parts by weight, 0.1 to 4 parts by weight, 0.1 to 3 parts by weight, or 0.5 to 3 parts by weight relative to 100 parts by weight of the aliphatic polyester resin.

[0216] The above stirring time may be about 1 minute to about 60 minutes, about 1 minute to about 50 minutes, about 5 minutes to about 50 minutes, or about 5 minutes to about 40 minutes.

[0217] The biodegradable resin composition according to the present invention comprises a polyol. The polyol is a compound containing two or more hydroxyl groups (-OH) within one molecule. The first biodegradable resin and the second biodegradable resin may be bonded by the hydroxyl groups contained in the polyol. The hydroxyl groups contained in the polyol may be bonded to the terminal carboxyl groups of the first biodegradable resin. The hydroxyl groups contained in the polyol may be bonded to the terminal carboxyl groups of the second biodegradable resin. The first biodegradable resin and the second biodegradable resin may be crosslinked by the polyol bonded to the terminal carboxyl groups of the first biodegradable resin and the terminal carboxyl groups of the second biodegradable resin. Accordingly, the mechanical properties of the first biodegradable resin and the second biodegradable resin crosslinked by the polyol may be improved, and the melt index may be reduced due to an increase in molecular weight.

[0218] The above polyol may include at least one of a diol having two hydroxyl groups, a triol having three hydroxyl groups, a tetraol having four hydroxyl groups, and a hexaol having six hydroxyl groups.

[0219] The above polyol may have a hydroxyl value (OH value) of 1,830 mgKOH / g to 2,000 mgKOH / g, 1,830 mgKOH / g to 1,900 mgKOH / g, 1,830 mgKOH / g to 1,880 mgKOH / g, or 1,830 mgKOH / g to 1,850 mgKOH / g. The above hydroxyl value represents the amount of potassium hydroxide (KOH) required to neutralize the hydroxyl groups contained in 1 g of the above polyol. When the above range is satisfied, the crosslinking reactivity between the first biodegradable resin and the second biodegradable resin may be improved, thereby improving the mechanical properties of the biodegradable resin composition and significantly reducing the melt index with increasing molecular weight.

[0220] The above polyol may have a solubility in water at 25°C of 50 g / 100ml to 300 g / 100ml, 100 g / 100ml to 300 g / 100ml, 150 g / 100ml to 300 g / 100ml, or 200 g / 100ml to 300 g / 100ml. When the above range is satisfied, the mixing properties with the first biodegradable resin and the second biodegradable resin are improved, and the dispersibility within the biodegradable resin composition may be improved.

[0221] The content of the polyol may be greater than 0 weight % and less than 0.1 weight %, 0.1 weight % and less than 0.1 weight %, 0.15 weight % and less than 0.1 weight %, or 0.15 weight % and 0.9 weight % based on the total weight of the biodegradable resin composition. When the above range is satisfied, the melt index of the final-produced biodegradable resin composition can be adjusted to have a target range, thereby enabling the realization of a biodegradable resin composition suitable for medium to large-sized blow molding.

[0222] The biodegradable resin composition according to the present invention comprises a third biodegradable resin having a structure in which part or all of the first biodegradable resin and part or all of the second biodegradable resin are combined.

[0223] The third biodegradable resin may be formed by combining part or all of the first biodegradable resin and part or all of the second biodegradable resin with the polyol.

[0224] The above third biodegradable resin may include a structure represented by the following chemical formula 1.

[0225] [Chemical Formula 1]

[0226]

[0227] In the above chemical formula 1, n1 may be an integer of 1 to 200, 1 to 100, 10 to 100, or 20 to 50, and A1 may be derived from the above polyol.

[0228] The above A1 may be selected from structures represented by the following chemical formulas 1-1 to 1-4.

[0229] [Chemical Formula 1-1]

[0230]

[0231] [Chemical Formula 1-2]

[0232]

[0233] [Chemical Formula 1-3]

[0234]

[0235] [Chemical Formula 1-4]

[0236]

[0237] In the above chemical formulas 1-1 to 1-4, * indicates a bonding position with an oxygen atom in the above chemical formula 1. Some or all of the hydroxyl groups in the above chemical formulas 1-2 to 1-4 may be bonded to some or all of the first biodegradable resin and some or all of the second biodegradable resin.

[0238] The molecular weight of the third biodegradable resin may be increased compared to the molecular weight of the first biodegradable resin or the second biodegradable resin. Accordingly, the biodegradable resin composition containing the third biodegradable resin may have a reduced melt index value, thereby possessing physical properties suitable for blow molding.

[0239] The weight-average molecular weight (Mw) of the third biodegradable resin may be about 100,000 g / mol to about 1,000,000 g / mol, about 100,000 g / mol to about 800,000 g / mol, about 100,000 g / mol to about 700,000 g / mol, or about 200,000 g / mol to about 500,000 g / mol.

[0240] The weight-average molecular weight of the third biodegradable resin may be greater than the weight-average molecular weight of the first biodegradable resin by about 50,000 g / mol to about 900,000 g / mol, about 100,000 g / mol to about 900,000 g / mol, about 150,000 g / mol to about 900,000 g / mol, or about 200,000 g / mol to about 900,000 g / mol.

[0241] The weight-average molecular weight of the third biodegradable resin may be greater than the weight-average molecular weight of the second biodegradable resin by about 5,000 g / mol to about 900,000 g / mol, about 100,000 g / mol to about 800,000 g / mol, about 100,000 g / mol to about 700,000 g / mol, or about 100,000 g / mol to about 500,000 g / mol.

[0242] The content of the third biodegradable resin may be 1% to 20% by weight, 3% to 20% by weight, 3% to 15% by weight, or 5% to 15% by weight based on the total weight of the biodegradable resin composition.

[0243] If the above range is satisfied, the biodegradable resin composition may have physical properties suitable for medium to large blow molding.

[0244] The above biodegradable resin composition may include a radical initiator.

[0245] The above radical initiator may decompose to generate radicals. Weak chemical bonds among the chemical bonds present in the above radical initiator may be broken by heat, chemical reactions, radiation, etc. The above radical initiator may react with the above first biodegradable resin, the above second biodegradable resin, and / or the above third biodegradable resin to generate radicals.

[0246] The radical initiator may have a number average molecular weight of 150 g / mol or more, 160 g / mol or more, 170 g / mol or more, 180 g / mol or more, 180 g / mol to 400 g / mol, or 200 g / mol to 350 g / mol. When the above range is satisfied, over-reaction can be suppressed, and the melt index of the biodegradable resin composition can be controlled.

[0247] The melting point of the above radical initiator may be 30 ℃ or higher, 31 ℃ or higher, 32 ℃ or higher, 35 ℃ to 150 ℃, or 35 ℃ to 100 ℃.

[0248] The radical initiator may be in a solid state at room temperature. When the radical initiator is in a solid state at room temperature, overreaction may be suppressed, making it suitable for manufacturing the biodegradable resin composition.

[0249] The above radical initiator may include an organic peroxide. The above radical initiator may include a ROO-R' type and may generate an RO· type radical.

[0250] The above radical initiator may include a compound represented by the following chemical formula.

[0251] [Chemical Formula]

[0252]

[0253] In the above chemical formula, R1 to R4 may each be independently selected from the group consisting of hydrogen atoms, hydrocarbon groups, heteroatoms, and combinations thereof. n may be 1 to 20, 2 to 19, or 3 to 18, and m may be 1 to 20, 2 to 19, or 3 to 18.

[0254] The content of the radical initiator may be greater than 0.01 wt% to less than 1 wt%, greater than 0.01 wt% to 0.9 wt%, greater than 0.01 wt% to 0.8 wt%, greater than 0.01 wt% to 0.7 wt%, or 0.1 wt% to 0.5 wt% based on the total weight of the biodegradable resin composition. When the above range is satisfied, the radical reaction of the first biodegradable resin, the second biodegradable resin, and / or the third biodegradable resin can be controlled, and the melt index of the biodegradable resin composition can have a target range, thereby enabling the realization of a biodegradable resin composition suitable for medium to large blow molding.

[0255] The above radical initiator may be selected from at least one of the group consisting of benzoyl peroxide, azobisisobutyronitrile, and dicumyl peroxide.

[0256] The above biodegradable resin composition may contain radicals. The radicals may be generated from the radical initiator, the first biodegradable resin, the second biodegradable resin, and / or the third biodegradable resin in a reaction extrusion process. The radicals may be generated by the decomposition of the radical initiator.

[0257] The above biodegradable resin composition may include at least one of the compounds represented by the following chemical formulas A-1 to A-5. The compounds represented by the following chemical formulas A-1 to A-5 may be radicals derived from the first biodegradable resin.

[0258] [Chemical Formula A-1]

[0259]

[0260] [Chemical Formula A-2]

[0261]

[0262] [Chemical Formula A-3]

[0263]

[0264] [Chemical Formula A-4]

[0265]

[0266] [Chemical Formula A-5]

[0267]

[0268] The above radical may include at least one of the repeating units represented by the following chemical formulas A'-1 to A'-3.

[0269] [Chemical Formula A'-1]

[0270]

[0271] [Chemical Formula A'-2]

[0272]

[0273] [Chemical Formula A'-3]

[0274]

[0275] In the above chemical formulas A'-1 to A'-3, q may be an integer from 1 to 20, 2 to 19, or 3 to 18.

[0276] The above biodegradable resin composition may include at least one of the compounds represented by the following chemical formulas B-1 and B-2. The compounds represented by the following chemical formulas B-1 and B-2 may be radicals derived from the second biodegradable resin.

[0277] [Chemical Formula B-1]

[0278]

[0279] [Chemical Formula B-2]

[0280]

[0281] The above radical may include a repeating unit represented by the following chemical formula B'.

[0282] [Chemical Formula B']

[0283]

[0284] In the above chemical formula B', p may be an integer from 1 to 20, 2 to 19, or 3 to 18.

[0285] The above biodegradable resin composition may include a compound represented by the following chemical formula C. The compound represented by the following chemical formula C may be a radical derived from the third biodegradable resin.

[0286] [Chemical Formula C]

[0287]

[0288] The content of the radical may be about 0.001 weight % to about 1 weight %, about 0.01 weight % to about 1 weight %, or about 0.05 weight % to about 1 weight % based on the total weight of the biodegradable resin composition.

[0289] The above biodegradable resin composition may include a fourth biodegradable resin comprising a structure represented by the following chemical formula 2.

[0290] [Chemical Formula 2]

[0291]

[0292] In the above chemical formula 2, n2 may be an integer of 1 to 200, 1 to 100, 10 to 100, or 20 to 50, X1 may be derived from the first biodegradable resin, and A2 may be derived from the polyol.

[0293] The above A2 may be selected from structures represented by the aforementioned chemical formulas 1-1 to 1-4.

[0294] The molecular weight of the fourth biodegradable resin may be increased compared to the molecular weight of the third biodegradable resin. Accordingly, the biodegradable resin composition containing the fourth biodegradable resin may have a reduced melt index value, thereby possessing physical properties suitable for blow molding.

[0295] The weight-average molecular weight (Mw) of the fourth biodegradable resin may be about 100,000 g / mol to about 1,500,000 g / mol, about 100,000 g / mol to about 1,000,000 g / mol, about 200,000 g / mol to about 1,000,000 g / mol, or about 300,000 g / mol to about 1,000,000 g / mol.

[0296] The content of the fourth biodegradable resin may be greater than 0 weight % to 20 weight %, greater than 0 weight % to 15 weight %, greater than 0 weight % to 12 weight %, or greater than 0 weight % to 10 weight % based on the total weight of the biodegradable resin composition.

[0297] If the above range is satisfied, the biodegradable resin composition may have physical properties suitable for medium to large blow molding.

[0298] The above biodegradable resin composition may include a fifth biodegradable resin comprising a structure represented by the following chemical formula 3.

[0299] [Chemical Formula 3]

[0300]

[0301] In the above chemical formula 3, n3 may be an integer of 1 to 200, 1 to 100, 10 to 100, or 20 to 50, X2 may be derived from the second biodegradable resin, and A3 may be derived from the polyol.

[0302] The above A3 may be selected from structures represented by the aforementioned chemical formulas 1-1 to 1-4.

[0303] The molecular weight of the fifth biodegradable resin may be increased compared to the molecular weight of the third biodegradable resin. Accordingly, the biodegradable resin composition containing the fifth biodegradable resin may have a reduced melt index value, thereby possessing physical properties suitable for blow molding.

[0304] The weight-average molecular weight (Mw) of the fifth biodegradable resin may be about 100,000 g / mol to about 1,500,000 g / mol, about 100,000 g / mol to about 1,000,000 g / mol, about 200,000 g / mol to about 1,000,000 g / mol, or about 300,000 g / mol to about 1,000,000 g / mol.

[0305] The content of the fifth biodegradable resin may be greater than 0 weight % to 20 weight %, greater than 0 weight % to 15 weight %, greater than 0 weight % to 12 weight %, or greater than 0 weight % to 10 weight % based on the total weight of the biodegradable resin composition.

[0306] If the above range is satisfied, the biodegradable resin composition may have physical properties suitable for medium to large blow molding.

[0307] The above biodegradable resin composition may include a sixth biodegradable resin comprising a structure represented by the following chemical formula 4.

[0308] [Chemical Formula 4]

[0309]

[0310] In the above chemical formula 4, k may be an integer from 1 to 50,000, 10 to 30,000, 100 to 25,000, or 150 to 20,000.

[0311] In the above chemical formula 4, X1 may be derived from the first biodegradable resin. X1 may be selected from structures represented by the aforementioned chemical formulas A-1 to A-5. X1 may include at least one repeating unit represented by the above chemical formulas A'-1 to A'-3.

[0312] If the value of k in Chemical Formula 4 is greater than the value of q in Chemical Formulas A'-1 to A'-3, it means that the length of the main chain is longer than the length of the side chain, so the weight-average molecular weight of the 6th biodegradable resin may increase. Accordingly, the biodegradable resin composition may have physical properties suitable for blow molding.

[0313] The above biodegradable resin composition may include a seventh biodegradable resin comprising a structure represented by the following chemical formula 5.

[0314] [Chemical Formula 5]

[0315]

[0316] In the above chemical formula 5, l may be an integer of 1 to 50,000, 10 to 30,000, 100 to 25,000, or 150 to 20,000.

[0317] In the above chemical formula 5, X2 may be derived from the second biodegradable resin. X2 may be selected from structures represented by the aforementioned chemical formulas B-1 to B-2. X2 may include a repeating unit represented by the above chemical formula B'.

[0318] If the value of l in Chemical Formula 5 above is greater than the value of p in Chemical Formula A' above, it means that the length of the main chain is longer than the length of the side chain, so the weight-average molecular weight of the seventh biodegradable resin may increase. Accordingly, the biodegradable resin composition may have physical properties suitable for blow molding.

[0319] The above biodegradable resin composition may include a chain extender. The chain extender increases the molecular weight of the biodegradable resin composition, thereby enabling the realization of a biodegradable resin composition having a target melt index.

[0320] The above chain extender may include one or more selected from the group consisting of aromatic diisocyanates, aliphatic diisocyanates, isocyanurates, bisoxazolins, carboxylic acid anhydrides, and epoxides.

[0321] The above aromatic diisocyanate may include one or more 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.

[0322] The above aliphatic diisocyanate may include one or more selected from the group consisting of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and methylenebis(4-isocyanatocyclohexane).

[0323] The above isocyanurate may include isophorone diisocyanate or methylenebis(4-isocyanatocyclohexane).

[0324] The above bis-oxazolin may include one or more selected from the group consisting of 2,2'-bis(2-oxazolin), bis(2-oxazolinyl)methane, 1,2-bis(2-oxazolinyl)ethane, 1,3-bis(2-oxazolinyl)propane, and 1,4-bis(2-oxazolinyl)butane.

[0325] The above epoxy refers to 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 greater than 20, greater than 30, or greater than 50 weight% is preferred.

[0326] The chain extender may be 1.5 wt% or less, 1.4 wt% or less, 1.3 wt% or less, 1.2 wt% or less, 1.1 wt% or less, 1 wt% or less, 0.9 wt% or less, 0.8 wt% or less, 0.7 wt% or less, 0.6 wt% or less, 0.5 wt% or less, 0.4 wt% or less, or 0.3 wt% or less, based on the total weight of the biodegradable resin composition, or 0 wt% to 1.5 wt%, 0.01 wt% to 1.5 wt%, 0.1 wt% to 1.5 wt%, 0.1 wt% to 1.0 wt%, 0.1 wt% to 0.9 wt%, 0.1 wt% to 0.8 wt%, 0.1 wt% to 0.7 wt%, 0.1 wt% to 0.6 wt%, or 0.1 wt% to 0.5 wt%. It can be weight %.

[0327] The above biodegradable resin composition may include an antioxidant. The antioxidant acts as a radical scavenger to remove unstable free radicals in the biodegradable resin composition, thereby improving the thermal stability of the biodegradable resin composition.

[0328] The above antioxidant may include one or more selected from the group consisting of phosphorus-based antioxidants, phenol-based antioxidants, and pentaerythritol-based antioxidants.

[0329] The above phosphorus-based antioxidant may be one or more selected from the group consisting of triesters, diesters, monoesters of phosphoric 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.

[0330] The above-mentioned phenolic antioxidants are α-tocopherol, butylhydroxytoluene, cinnafil 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 bis(3-(3,5-di-tert)-butyl-4-hydroxyphenyl)propanoate), It may be one or more selected from the group consisting of 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-t-butyl-4-hydroxyphenyl)propionyloxymethyl]methane.

[0331] The above antioxidant may further include one or more 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.

[0332] The content of the antioxidant may be 1% by weight or less, 0.5% by weight or less, 0.3% by weight or less, 0 to 5% by weight, 0.01 to 4% by weight, 0.1 to 3% by weight, 1 to 3% by weight, 1 to 2% by weight, 0.01 to 0.5% by weight, or 0.1 to 0.5% by weight based on the total weight of the biodegradable resin composition.

[0333] The above antioxidant may include both the phosphorus-based antioxidant and the phenolic antioxidant. When the above antioxidant includes both the phosphorus-based antioxidant and the phenolic antioxidant, the weight ratio of the phosphorus-based antioxidant to the phenolic antioxidant may be 1:10 to 10:1, 1:5 to 5:1, 1:1 to 5:1, 2:1 to 4:1, 2.5:1 to 3.5:1, 1:5 to 1:1, 1:2 to 1:4, or 1:2.5 to 1:3.5. When the above range is satisfied, there is an effect of delaying the oxidation phenomenon of the biodegradable resin composition over various temperature ranges.

[0334] The above biodegradable resin composition may include a lubricant. The lubricant may include one or more selected from the group consisting of fatty acid-based lubricants including stearic acid, aliphatic alcohol-based lubricants, aliphatic amide-based lubricants including stearamide, aliphatic ester-based lubricants such as stearate-n-butyl stearate, methyl hydroxystearate, polyhydric alcohol fatty acid esters, saturated fatty acid esters, and ester-based waxes, and fatty acid metal soap-based lubricants. The lubricant may be a stearate-based lubricant and may include one or more selected from the group consisting of calcium stearate, zinc stearate, barium stearate, magnesium stearate, glycerin stearate, and butyl stearate. The stearate-based lubricant reduces heat generation due to friction during raw material mixing, melting, and processing, provides excellent dispersion effects on the biodegradable resin relative to cost, and offers superior lubrication effects, thereby improving manufacturing efficiency.

[0335] The content of the above-mentioned active agent may be 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, 1% by weight or less, or 0.1% to 1% by weight based on the total weight of the above-mentioned biodegradable resin composition. When the above range is satisfied, manufacturing efficiency can be improved without deterioration of the physical properties of the above-mentioned biodegradable resin composition.

[0336] The above biodegradable resin composition may include an inorganic filler. The inorganic filler may include calcium carbonate. By including the inorganic filler in the above biodegradable resin composition, the relative ratio of the first biodegradable resin and the second biodegradable resin may be reduced, thereby improving economic efficiency.

[0337] The content of the inorganic filler may be greater than 30% by weight and less than 60% by weight, 35% by weight and less than 60% by weight, 40% by weight and less than 60% by weight, or 40% by weight and 50% by weight, based on the total weight of the biodegradable resin composition. When the above range is satisfied, production costs can be reduced, biodegradability and water resistance can be improved by increasing the biodegradation point, and the mechanical properties of the molded article can be improved by preventing a decrease in the dispersibility of the inorganic filler. In addition, the specific gravity of the biodegradable molded article does not increase significantly, allowing it to be used in a wider variety of products, and product reliability can be ensured by improving the mechanical properties of the product.

[0338] The above inorganic filler may include 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 average particle size may be calculated from the results of measuring the specific surface area by the air permeation method using a specific surface area measuring device. When the above inorganic filler includes calcium carbonate having the above average particle size range, dispersibility in the biodegradable resin composition may be improved, and an excessive increase in viscosity of the biodegradable resin composition may be suppressed.

[0339] The calcium carbonate mentioned above may be heavy calcium carbonate. The heavy calcium carbonate is obtained by mechanically grinding natural calcium carbonate and can be distinguished from light calcium carbonate produced by a chemical precipitation reaction. The heavy calcium carbonate may have increased tensile strength compared to light calcium carbonate, thereby improving the mechanical properties of the biodegradable resin composition. Furthermore, the heavy calcium carbonate can neutralize the acidic component, thereby reducing the environmental burden and preventing soil acidification.

[0340] The specific surface area of ​​the above heavy calcium carbonate is 0.1 m² 2 / g to 10.0 m2 / 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 It may be / g. The above specific surface area can be measured by the nitrogen gas adsorption method. If the above range is satisfied, it can be easily dispersed in the first biodegradable resin and / or the second biodegradable resin, thereby promoting biodegradability.

[0341] The sphericity of the 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, it may contain a large number of fine pores generated at the interface between the first biodegradable resin and the second biodegradable resin and the inorganic filler, thereby improving biodegradability.

[0342] The 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 first biodegradable resin and / or the second biodegradable resin may be improved. The surface treatment may be performed using physical methods such as plasma treatment or corona treatment, or chemical methods such as silane coupling agents, titanium coupling agents, or surfactants. Examples of the organic acid include higher fatty acids, higher fatty acid esters, higher fatty acid amides, and higher fatty acids, and may be, for example, calcium stearate.

[0343] The above-mentioned surface-treated heavy calcium carbonate can be manufactured by the following method.

[0344] First, calcium carbonate powder can be manufactured by a grinding process. Subsequently, the calcium carbonate powder is classified to obtain calcium carbonate of a desired particle size.

[0345] Subsequently, the calcium carbonate may be heat-treated at approximately 200°C to approximately 800°C by a heating device selected from a kiln, an electric furnace, or a microwave furnace. The heat treatment time may be approximately 5 minutes to approximately 30 minutes, approximately 7 minutes to approximately 15 minutes, or approximately 7 minutes to approximately 14 minutes. The heat treatment temperature may be approximately 250°C to approximately 700°C or approximately 300°C to approximately 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 bonded to the surface of the calcium carbonate, and the aggregation of the calcium carbonate can be minimized.

[0346] Subsequently, 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, based on 100 parts by weight of the calcium carbonate. The above process time may be about 1 minute to about 60 minutes, about 10 minutes to about 30 minutes, or about 5 minutes to about 20 minutes.

[0347] Subsequently, the surface-treated calcium carbonate may undergo an additional process of crushing and classifying aggregates aggregated during the surface treatment process. In the surface-treated calcium carbonate, the content of the organic acid may be about 0.1% to about 3% by weight, about 0.1% to about 2% by weight, about 0.1% to about 1% by weight, about 0.2% to about 3% by weight, about 0.2% to about 2% by weight, about 0.2% to about 1% by weight, about 0.3% to about 3% by weight, about 0.3% to about 2% by weight, or about 0.3% to about 1% by weight, based on the total weight.

[0348] The calcium carbonate surface-treated with the above organic acid may be partially oxidized. The above surface-treated calcium carbonate may partially contain calcium oxide (CaO). The proportion of the calcium oxide may be 5 volume% or less, 4 volume% or less, 3 volume% or less, 2 volume% or less, 1 volume% or less, 0.01 volume% or more to 5 volume% or less, 0.01 volume% or more to 4 volume% or less, 0.01 volume% or more to 3 volume% or less, 0.01 volume% or more to 2 volume% or less, or 0.01 volume% or more to 1 volume% or less, based on 100 volume% of the above surface-treated calcium carbonate particles. The proportion of the calcium oxide may be measured by the EDTA (Ethylene diamine tetra acetic acid) titration method in accordance with JIS R 9011. When the above range is satisfied, the uniformity of the calcium carbonate surface can be improved, and the phenomenon of organic acid leaching from the surface of the calcium carbonate can be minimized, thereby improving water resistance.

[0349] The above biodegradable resin composition may have a melt index of 1 g / 10 min or less, 0.95 g / 10 min or less, 0.5 g / 10 min or less, or 0.47 g / 10 min or less at 190 ℃ and 2.16 kg according to ASTM D1238. When satisfying the above ranges, the biodegradable resin composition may have appropriate viscosity and molecular weight for medium to large blow molding processes. Accordingly, a biodegradable molded article made from the above biodegradable resin composition may have appropriate mechanical properties.

[0350]

[0351] A biodegradable molded article according to the present invention comprises a biodegradable resin composition comprising a first biodegradable resin comprising an aliphatic-aromatic polyester resin, a second biodegradable resin comprising an aliphatic polyester resin, a polyol, and a third biodegradable resin comprising a structure in which part or all of the first biodegradable resin and part or all of the second biodegradable resin are combined, wherein the biodegradable resin composition has a melt index of 1 g / 10 min or less at 190 ℃ and 2.16 kg according to ASTM D1238.

[0352] The above biodegradable resin composition may be the same as the biodegradable resin composition described above.

[0353] The above biodegradable molded article may be manufactured from the above biodegradable resin composition. The above biodegradable molded article may be manufactured by molding the above biodegradable resin composition by methods known in the art, such as extrusion or injection molding, and the above biodegradable molded article may be an injection molded article, an extrusion molded article, a thin film molded article, or a blow molded article. Preferably, the above biodegradable molded article may be a blow molded article.

[0354] Figure 1 is a simplified diagram showing the blow molding process.

[0355] Referring to FIG. 1, the blow molding process can form a parison (30) by melting a biodegradable resin composition using the extruder (10) and extruding it with air through a tubular die (20) attached to the end of the extruder (10). Then, the parison (30) is introduced into an open blow mold (40), and can be inflated by injecting air into the parison (30) until it reaches the boundary of the blow mold (40). Afterward, it can be cooled, removed from the blow mold (40), and the edges trimmed to produce a biodegradable resin molded article.

[0356] In order to manufacture medium to large blow-molded articles of 2L or more, it can be determined by the formation of a parison with a diameter of a certain level or larger. This can be confirmed by satisfying the flow of the parison for manufacturing medium to large blow-molded articles when the melt index of the manufactured biodegradable resin composition is satisfied.

[0357] The above-mentioned biodegradable molded article may be a soil fertilization material, specifically an agricultural mulching film, disposable gloves, food packaging material, woven fabric, knitted fabric, nonwoven fabric, rope, or food packaging container. Since the above-mentioned biodegradable molded article can be manufactured from a biodegradable resin composition capable of inducing soil fertilization and neutralizing acidic components, excellent properties can be exhibited when applied to packaging materials or mulching films used for crop cultivation, etc.

[0358] The above biodegradable molded article may be a biodegradable container. The thickness of the above biodegradable container may be 0.01 mm to 2.0 mm, 0.1 mm to 1.5 mm, or 0.2 mm to 1.0 mm.

[0359] The tensile strength of the above biodegradable container is 100 kgf / cm 2 Up to 500 kgf / cm² 2 , 150kgf / cm 2 Up to 480 kgf / cm² 2 , or 200 kgf / cm² 2 Up to 450 kgf / cm² 2 It could be.

[0360] The elongation of the above biodegradable container may be 10% to 1,000%, 20% to 500%, or 40% to 400%.

[0361] The flexural strength of the above biodegradable container is 200 kgf / cm 2 Up to 800 kgf / cm² 2 , 300kgf / cm 2 Up to 700 kgf / cm² 2 , or 400 kgf / cm² 2Up to 600 kgf / cm² 2 It could be.

[0362] The flexural modulus of the above biodegradable container is 10,000 kgf / cm 2 Up to 30,000 kgf / cm² 2 , 11,000kgf / cm 2 Up to 25,000 kgf / cm² 2 , or 12,000 kgf / cm² 2 Up to 22,000 kgf / cm² 2 It could be.

[0363] The Izod impact strength of the above biodegradable container may be 5 kgf·cm / cm to 100 kgf·cm / cm, 10 kgf·cm / cm to 90 kgf·cm / cm, or 20 kgf·cm / cm to 85 kgf·cm / cm.

[0364] If the tensile strength, elongation, flexural strength, flexural modulus, or impact strength of the above-mentioned biodegradable molded article each satisfy the above ranges, it can possess mechanical properties equivalent to those of a PET plastic molded article, and at the same time, the biodegradable molded article can be easily decomposed when disposed of.

[0365]

[0366] A method for manufacturing a biodegradable resin composition according to the present invention comprises the steps of: melt-mixing a first biodegradable resin comprising an aliphatic-aromatic polyester resin, a second biodegradable resin comprising an aliphatic polyester resin, and a polyol; and reacting the first biodegradable resin and the second biodegradable resin with the polyol to form a third biodegradable resin, wherein the melt index of the biodegradable resin composition manufactured according to ASTM D1238 at 190°C and 2.16 kg is 1 g / 10 min or less.

[0367] In the step of forming the third biodegradable resin, the first biodegradable resin and the second biodegradable resin may be reacted under temperature conditions of 170°C to 190°C.

[0368] The method may include a step in which a radical initiator is melt-mixed in the above melt-mixing step, and the first biodegradable resin and the third biodegradable resin are reacted by the radical initiator to form a fourth biodegradable resin.

[0369] The method may include a step in which a radical initiator is melt-mixed in the above melt-mixing step, and the second biodegradable resin and the third biodegradable resin are reacted by the radical initiator to form a fifth biodegradable resin.

[0370] The above biodegradable resin composition may be the same as the biodegradable resin composition described above.

[0371] The above biodegradable resin composition can be extruded into a form suitable for the intended use. For example, a biodegradable molded article can be manufactured by extruding the above biodegradable resin composition after providing it in the form of pellets, or a biodegradable molded article can be manufactured by extruding the above biodegradable resin composition directly.

[0372] FIG. 2 is a partial cross-sectional view of an extruder used according to one embodiment.

[0373] Referring to FIG. 2, the extruder (100) may include a material supply section (110), a compression section (120), a screw (130), a head section (140), and a die (150).

[0374] The above extrusion molding conditions may vary depending on the application of the biodegradable molded article, and the extrusion may be performed by a commonly used process.

[0375] The first biodegradable resin and the second biodegradable resin can be uniformly mixed from the pressure and shear force generated by the rotation of the screw (130) of the extruder (100).

[0376] The above material supply unit (110) may be a space into which the first biodegradable resin, the second biodegradable resin, and the polyol are introduced. Additionally, the above material supply unit (110) may be a space into which the radical initiator is introduced.

[0377] The screw (130) can uniformly mix the first biodegradable resin, the second biodegradable resin, and the polyol introduced into the material supply unit (110). The screw (130) can uniformly mix the first biodegradable resin, the second biodegradable resin, the polyol, and the radical initiator introduced into the material supply unit (110).

[0378] The screw (130) may be a single screw. The screw (130) may be a twin screw. Preferably, to improve the mixing and processing properties of the first biodegradable resin, the second biodegradable resin, the polyol, and the radical initiator, the screw may be a twin screw.

[0379] The screw (130) may have an L / D value of 10 to 60, 10 to 50, 20 to 50, or 25 to 45. The L / D value is the compression ratio of the screw, where L represents the length of the screw and D represents the diameter of the screw. When the above range is satisfied, the mixing properties of the first biodegradable resin, the second biodegradable resin, the polyol, and the radical initiator may be improved.

[0380] In the step of forming the third biodegradable resin, the first biodegradable resin and the second biodegradable resin may react with each other at a temperature of 170°C to 190°C. That is, the reaction extrusion molding may be performed at a temperature of 170°C to 190°C.

[0381] The above reaction extrusion molding can be performed at a speed of 100 rpm to 300 rpm, 120 rpm to 290 rpm, 150 rpm to 280 rpm, or 170 rpm to 250 rpm.

[0382] When extrusion molding is performed at the above temperature and speed, a parison capable of producing medium to large biodegradable molded articles can be manufactured.

[0383] The method for manufacturing the above biodegradable resin composition may include the step of removing by-products derived from the radical initiator after forming the above fourth biodegradable resin and / or the above fifth biodegradable resin.

[0384] The above byproduct may include radicals formed by the radical initiator. The above byproduct may be discharged in gaseous form through a vent provided in the extruder (100).

[0385] The manufactured biodegradable resin composition can be discharged through the die (150). The manufactured biodegradable resin composition can be extruded and discharged through the die (150). The manufactured biodegradable resin composition can be pelletized through the die (150).

[0386] The discharge rate of the above biodegradable resin composition may be 100 kg / h or more, 110 kg / h or more, 120 kg / h or more, 120 kg / h to 500 kg / h, or 130 kg / h to 400 kg / h. When the above discharge rate is satisfied, excellent mechanical properties can be achieved as a suitable amount for medium to large blow molding.

[0387]

[0388] Examples

[0389] - 1st Biodegradable Resin: Aliphatic-Aromatic Polyester Resin (PBAT, SK Livio)

[0390] - 2nd Biodegradable Resin: Aliphatic Polyester Resin (PLA, NatureWorks 4032D)

[0391] - Polyol: Sorbitol (OH value 1,847 mgKOH / g, solubility 235 g / 100ml (based on water, 25 ℃))

[0392] - Radical initiator: Dicumyl peroxide (DCP, Sigma-Aldrich)

[0393] - Chain extender: BASF's Joncryl

[0394] - Lubricant #1: Calcium Stearate

[0395] - Lubricant #2: Stearyl Stearate

[0396] - Antioxidant #1: Phenolic antioxidant (Adeka, AO-80)

[0397] - Antioxidant #2: Phosphorus-based antioxidant (Adeka 2112)

[0398]

[0399] Example 1-1

[0400] A raw material composition was prepared by mixing a resin composition in a weight ratio of 30:70:0.05:0.1:0.5:0.5:0.1:0.1 of a first biodegradable resin: second biodegradable resin: polyol: chain extender: lubricant #1: lubricant #2: antioxidant #1: antioxidant #2 at a weight ratio of 30:70:0.05:0.1:0.5:0.5:0.1:0.1 and kneading it at a temperature of about 180°C.

[0401] Subsequently, the above raw material composition was fed into an extruder equipped with a twin screw (19Φ L / D 40 Twin Extruder, Ecotec Co.) and reactively extruded, and the process byproduct was discharged through the vent of the extruder. In the reactive extrusion process, the temperature was approximately 180 ℃ and the speed was approximately 220 rpm.

[0402] Subsequently, the resin composition after reaction extrusion was cut and cooled using a hot-cut pellet cutter to produce a pelletized resin composition.

[0403]

[0404] Examples 1-2 to 1-6 and Comparative Examples 1-1 to 1-3

[0405] A pelletized resin composition was prepared by the same process as in Example 1-1, except that the composition, content, and reaction extrusion conditions listed in Table 1 below were applied.

[0406]

[0407] Classification Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 Example 1-6 Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 First biodegradable resin 30 parts by weight 30 parts by weight 30 parts by weight 30 parts by weight 30 parts by weight 30 parts by weight 30 parts by weight 30 parts by weight Second biodegradable resin 70 parts by weight 70 parts by weight 70 parts by weight 70 parts by weight 70 parts by weight 70 parts by weight 70 parts by weight 70 parts by weight Polyol 0.05 parts by weight 0.08 parts by weight 0.1 parts by weight 0.1 parts by weight 0.2 parts by weight 0.2 parts by weight - 0.1 parts by weight 0.2 parts by weight Radical initiator -- 0.1 parts by weight 0.2 parts by weight 0.1 parts by weight 0.2 parts by weight --- chain Extender 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.5 parts by weight 0.1 #20.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight 0.1 parts by weight Temperature 180 ℃ 175 ℃ 180 ℃ 180 ℃ 180 ℃ 180 ℃ 175 ℃ 180 ℃ 180 ℃ Speed ​​220 rpm 210 rpm 220 rpm 220 rpm 220 rpm 210 rpm 220 rpm 220 rpm

[0408]

[0409] Experimental Example 1

[0410] Each pelletized resin composition prepared in Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-3 was melted at a temperature of about 160°C. Subsequently, molded product samples having a thickness of about 1.2 mm, a diameter of about 15 cm, and a height of about 30 cm were each produced by a blow molding process.

[0411]

[0412] Experimental Example 1-1 - Melt Index

[0413] For each resin composition of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-3 above, the melt index at 190°C and 2.16 kg according to ASTM D1238 was measured, and the results are shown in Table 2 below.

[0414]

[0415] Experimental Example 1-2 - Viscosity

[0416] For each resin composition of Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-3 above, using a rotational rheometer, at approximately 190 °C and a shear rate of approximately 10 s -1 Viscosity was measured using the frequency sweep method. The results are shown in Table 2 below.

[0417]

[0418] Experimental Example 1-3 - Tensile Strength and Elongation

[0419] For each molded product sample prepared in Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-3 above, tensile strength and elongation were measured according to ASTM D638, and the results are shown in Table 2 below.

[0420]

[0421] Experimental Example 1-4 - Flexural Strength and Flexural Modulus

[0422] For each molded product sample prepared in Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-3 above, flexural strength and flexural modulus were measured according to ASTM D790, and the results are shown in Table 2 below.

[0423]

[0424] Experimental Example 1-5 - Izod Impact Strength

[0425] For each molded product sample prepared in Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-3 above, the Izod impact strength was measured according to ASTM D256 (based on 1 / 8 inch), and the results are shown in Table 2 below.

[0426]

[0427] Experimental Example 1-6 - Parison Drawdown Evaluation

[0428] After each pelletized resin composition prepared in Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-3 was melted at a temperature of about 160°C, the draw-down time of the parison discharged from the die of a blow molding machine (Samsung Hydraulic Machinery, Φ=50mm) during the blow molding process was measured. It was evaluated according to the following criteria, and the results are shown in Table 2 below.

[0429] - ○: 10 seconds or more

[0430] - △: 5 seconds or more but less than 10 seconds

[0431] - ×: Less than 5 seconds or no parison formed

[0432]

[0433] Classification Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 Example 1-6 Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 Melt Index 0.95g / 10min 1.0g / 10min 1.0g / 10min 0.13g / 10min 0.47g / 10min 0.29g / 10min 3.4g / 10min 2.8g / 10min 3.1g / 10min Viscosity 2.18 × 107 mPa·s1.92 × 10 7 mPa·s1.93 × 10 7 mPa·s9.28 × 10 7 mPa·s6.65× 10 7 mPa·s4.59 × 10 7 mPa·s2.91 × 10 5 mPa·s9.12 × 10 6 mPa·s6.72 × 10 5 mPa·s인장강도350kgf / cm 2 345kgf / cm 2 378kgf / cm 2 375kgf / cm 2 382kgf / cm 2 377kgf / cm 2 330kgf / cm 2 341kgf / cm 2 340kgf / cm 2 신율80 %79 %79 %75 %77 %76 %42 %58 %46 %굴곡강도557kgf / cm 2 559kgf / cm 2 571kgf / cm 2 576kgf / cm 2 567kgf / cm 2 559kgf / cm 2 529kgf / cm 2 548kgf / cm 2 530kgf / cm 2 굴곡탄성율18,283kgf / cm 2 18,328kgf / cm 2 18,542kgf / cm 2 18,610kgf / cm 2 18,490kgf / cm 2 18,503kgf / cm 2 18,002kgf / cm 2 18,050kgf / cm 2 17.980kgf / cm 2Izod Impact Strength 40kgf·cm / cm 41kgf·cm / cm 45kgf·cm / cm 44kgf·cm / cm 42kgf·cm / cm 43kgf·cm / cm 7kgf·cm / cm 17kgf·cm / cm 8kgf·cm / cm Parison Draw Down Rating ○○○○○○×△×

[0434]

[0435] As can be seen in Tables 1 to 2 above, it was confirmed that the resin compositions according to Examples 1-1 to 1-6 and the molded articles prepared therefrom exhibited tensile strength, flexural strength, and flexural modulus equal to or greater than those of Comparative Examples 1-1 to 1-3. In addition, it was confirmed that Examples 1-1 to 1-6 showed significantly improved elongation and Izod impact strength, which are important physical properties for blow-molded articles, compared to Comparative Examples 1-1 to 1-3. Furthermore, it was confirmed that Examples 1-1 to 1-6 had longer parison draw-down times compared to Comparative Examples 1-1 to 1-3, indicating that they possess physical properties suitable for the blow process.

[0436]

[0437] <2nd Example>

[0438] <Biodegradable resin composition>

[0439] The biodegradable resin composition according to the present invention comprises a first biodegradable resin, a second biodegradable resin, a radical initiator, and a third biodegradable resin having a structure in which part or all of the first biodegradable resin and part or all of the second biodegradable resin are combined, and the melt flow index measured at a temperature of 190°C and a weight of 2.16 kg according to ASTM D1238 is less than 1.0 g / 10 min.

[0440]

[0441] The above biodegradable resin composition includes a biodegradable resin.

[0442] The above biodegradable resin includes a first biodegradable resin, a second biodegradable resin, and a third biodegradable resin.

[0443]

[0444] First biodegradable resin and second biodegradable resin

[0445] The first biodegradable resin may be the same as the second biodegradable resin in the first embodiment. The second biodegradable resin may be the same as the first biodegradable resin in the first embodiment.

[0446]

[0447] radical initiator

[0448] The radical initiator above may be the same as the radical initiator in the first embodiment.

[0449]

[0450] radical

[0451] The biodegradable resin composition according to the example may include radicals. That is, when the first biodegradable resin, the second biodegradable resin, and the radical initiator are mixed and reacted by extrusion, the radicals may be generated from the radical initiator, the first biodegradable resin, or the second biodegradable resin.

[0452] In addition, the above radical initiator can be decomposed to generate the above radical.

[0453] In one embodiment, when the first biodegradable resin is polylactic acid, a radical comprising at least one of the structures represented by the following chemical formulas A-1 and A-2 may be generated. That is, the radical may be derived from the polylactic acid and may include a compound represented by the following chemical formula A-1 or A-2.

[0454] [Chemical Formula A-1]

[0455]

[0456] [Chemical Formula A-2]

[0457]

[0458] The above radical may include a repeating unit represented by the following chemical formula A'.

[0459] [Chemical Formula A']

[0460]

[0461] In the above chemical formula A', p can be 1 to 20, 2 to 19, or 3 to 18.

[0462] In one embodiment, when the second biodegradable resin composition is polybutylene adipate terephthalate, a radical comprising at least one of the structures represented by the following chemical formulas B-1 to B-5 may be generated. That is, the radical may be derived from the polybutylene adipate terephthalate and may include a compound represented by the following chemical formulas B-1 to B-5.

[0463] [Chemical Formula B-1]

[0464]

[0465] [Chemical Formula B-2]

[0466]

[0467] [Chemical Formula B-3]

[0468]

[0469] [Chemical Formula B-4]

[0470]

[0471] [Chemical Formula B-5]

[0472]

[0473] The above radical may include at least one of the repeating units represented by the following chemical formulas B'-1 to B'-3.

[0474] [Chemical Formula B'-1]

[0475]

[0476] [Chemical Formula B'-2]

[0477]

[0478] [Chemical Formula B'-3]

[0479]

[0480] In the above chemical formulas B'-1 to B'-3, q may be 1 to 20, 2 to 19, or 3 to 18.

[0481] The biodegradable resin composition according to the example may contain the radical in an amount of about 0.001 wt% to about 1 wt%, about 0.01 wt% to about 1 wt%, about 0.05 wt% to about 1.5 wt%, or about 0.05 wt% to about 1 wt% based on the total weight of the resin composition.

[0482]

[0483] Third biodegradable resin

[0484] The third biodegradable resin may include a structure in which part or all of the first biodegradable resin and part or all of the second biodegradable resin are combined. The third biodegradable resin may be formed by the reaction of the first biodegradable resin and the radical.

[0485] The above third biodegradable resin may include a structure represented by the following chemical formula 1.

[0486] [Chemical Formula 1]

[0487]

[0488] In the above chemical formula 1, k may be 1 to 50000, 10 to 30000, 100 to 25000, or 150 to 20000.

[0489] In the above chemical formula 1, X1 may be derived from the second biodegradable resin. X1 may be a structure represented by the above chemical formulas B-1 to B-5. X1 may include at least one of the repeating units represented by the above chemical formulas B'-1 to B'-3.

[0490] If the value of k in Chemical Formula 1 is greater than the value of q in Chemical Formulas B'-1 to B'-3, it means that the length of the main chain is longer than the length of the side chain, so the weight-average molecular weight of the third biodegradable resin may increase. Accordingly, the biodegradable resin composition according to the example may have physical properties suitable for blow molding.

[0491] The weight-average molecular weight (Mw) of the third biodegradable resin may be about 50,000 g / mol to about 300,000 g / mol. The weight-average molecular weight of the third biodegradable resin may be about 60,000 g / mol to about 250,000 g / mol. The weight-average molecular weight of the third biodegradable resin may be about 80,000 g / mol to about 200,000 g / mol.

[0492] The weight-average molecular weight of the third biodegradable resin may be greater than the weight-average molecular weight of the polylactic acid by about 2,000 g / mol to about 200,000 g / mol, about 5,000 g / mol to about 150,000 g / mol, about 10,000 g / mol to about 200,000 g / mol, about 20,000 g / mol to about 200,000 g / mol, or about 30,000 g / mol to about 200,000 g / mol.

[0493] In addition, the weight-average molecular weight of the third biodegradable resin may be about 1.1 to about 2 times, about 1.2 to about 2 times, about 1.3 to about 2 times, about 1.4 to about 2 times, or about 1.5 to about 2 times with respect to the weight-average molecular weight of the first biodegradable resin.

[0494] The biodegradable resin composition according to the example may include the third biodegradable resin in an amount of about 1 wt% to about 10 wt%, about 0.5 wt% to about 10 wt%, about 1 wt% to about 5 wt%, about 2 wt% to about 5 wt%, about 5 wt% to about 10 wt%, or about 5 wt% to about 15 wt% based on the total weight of the resin composition.

[0495] Since the third biodegradable resin has the same molecular weight as described above, the biodegradable resin composition according to the example contains a high proportion of high molecular weight resin. Accordingly, the biodegradable resin composition according to the example can have physical properties suitable for blow molding. Preferably, the biodegradable resin composition can have physical properties suitable for medium to large blow molding.

[0496]

[0497] 4th biodegradable resin

[0498] The above biodegradable resin composition may further include a fourth biodegradable resin. The fourth biodegradable resin may include a structure in which part or all of the first biodegradable resin is combined with part or all of the first biodegradable resin.

[0499] The above-mentioned fourth biodegradable resin may include a structure represented by the following chemical formula 2.

[0500] [Chemical Formula 2]

[0501]

[0502] In the above chemical formula 2, l may be 1 to 50000, 10 to 30000, 100 to 25000, or 150 to 20000.

[0503] In the above chemical formula 2, X2 may be derived from the first biodegradable resin. X2 may be a structure represented by the above chemical formulas A-1 to A-2. X2 may include a repeating unit represented by the above chemical formula A'.

[0504] If the value of l in Chemical Formula 2 above is greater than the value of p in Chemical Formula A' above, it means that the length of the main chain is longer than the length of the side chain, so the weight-average molecular weight of the fourth biodegradable resin may increase. Accordingly, the biodegradable resin composition according to the example may have physical properties suitable for blow molding.

[0505] The weight-average molecular weight (Mw) of the fourth biodegradable resin may be about 50,000 g / mol to about 300,000 g / mol. The weight-average molecular weight of the fourth biodegradable resin may be about 60,000 g / mol to about 250,000 g / mol. The weight-average molecular weight of the fourth biodegradable resin may be about 80,000 g / mol to about 200,000 g / mol.

[0506] The weight-average molecular weight of the fourth biodegradable resin may be greater than the weight-average molecular weight of the polylactic acid by about 2,000 g / mol to about 200,000 g / mol, about 5,000 g / mol to about 150,000 g / mol, about 10,000 g / mol to about 200,000 g / mol, about 20,000 g / mol to about 200,000 g / mol, or about 30,000 g / mol to about 200,000 g / mol.

[0507] In addition, the weight-average molecular weight of the fourth biodegradable resin may be about 1.1 to about 2 times, about 1.2 to about 2 times, about 1.3 to about 2 times, about 1.4 to about 2 times, or about 1.5 to about 2 times with respect to the weight-average molecular weight of the first biodegradable resin.

[0508] The biodegradable resin composition according to the example may include the fourth biodegradable resin in an amount of about 1 wt% to about 10 wt%, about 0.5 wt% to about 10 wt%, about 1 wt% to about 5 wt%, about 2 wt% to about 5 wt%, about 5 wt% to about 10 wt%, or about 5 wt% to about 15 wt% based on the total weight of the resin composition.

[0509] Since the above-mentioned fourth biodegradable resin has a molecular weight as described above, the biodegradable resin composition according to the example contains a high proportion of high molecular weight resin. Accordingly, the biodegradable resin composition according to the example can manufacture medium to large-sized molded articles by blow molding, and said molded articles can have improved mechanical properties.

[0510]

[0511] The melt flow index of the above biodegradable resin composition may be less than 1.0 g / 10 min, 0.9 g / 10 min or less, 0.8 g / 10 min or less, 0.2 g / 10 min to 0.8 g / 10 min, 0.2 g / 10 min to 0.6 g / 10 min, or 0.2 g / 10 min to 0.4 g / 10 min. Accordingly, the biodegradable resin composition according to the example may have appropriate viscosity and molecular weight in a medium-to-large blow molding process. Accordingly, the biodegradable resin composition according to the example may realize a molded article having appropriate mechanical properties. The melt flow index may be measured according to ASTM D1238 at a temperature of 190°C and a weight of 2.16 kg.

[0512]

[0513] Chain extender

[0514] The chain extender may be the same as the chain extender in the first embodiment.

[0515]

[0516] additives

[0517] The above additive may be selected from at least one of the group consisting of an antioxidant and a lubricant, and the antioxidant and lubricant may be the same as the antioxidant and lubricant in the first embodiment.

[0518]

[0519] Weapon filler

[0520] The above-mentioned inorganic filler may be the same as the inorganic filler in the first embodiment.

[0521]

[0522] Biodegradable molded product

[0523] The above biodegradable molded article comprises a biodegradable resin, an inorganic filler, and one or more selected from the group consisting of iron, magnesium, manganese, and calcium, wherein the content of the inorganic filler is 30% by weight or more based on the total weight of the biodegradable resin composition. The biodegradable resin, inorganic filler, iron, magnesium, manganese, and calcium may be the same as the biodegradable resin, inorganic filler, iron, magnesium, manganese, and calcium in the aforementioned biodegradable resin composition. Additionally, the above molded article may have the same physical properties as the molded article of the first embodiment.

[0524]

[0525] Method for manufacturing a biodegradable resin composition

[0526] A method for preparing a biodegradable resin composition according to the present invention comprises the steps of: melt-mixing a first biodegradable resin, a second biodegradable resin, and a radical initiator; and reacting the first biodegradable resin and the second biodegradable resin using the radical initiator to form a third biodegradable resin, wherein the melt flow index measured at a temperature of 190°C and a weight of 2.16 kg according to ASTM D1238 is less than 1.0 g / 10 min.

[0527] The first biodegradable resin, the second biodegradable resin, the radical initiator, and the third biodegradable resin may be the same as the first biodegradable resin, the second biodegradable resin, the radical initiator, and the third biodegradable resin described above. Additionally, the manufacturing method may be the same as the manufacturing method of the first embodiment.

[0528]

[0529] Examples

[0530] Preparation Example

[0531] - Biodegradable Resin #1: Polylactic Acid (PLA, NatureWorks, 4032D)

[0532] - Biodegradable Resin #2: Polybutylene Adipate Terephthalate (PBAT, SK Livio)

[0533] - Radical initiator: Dicumyl peroxide (DCP, Sigma-Aldrich)

[0534] - Chain extender: Joncryl (BASF)

[0535] - Antioxidant #1: Phenolic antioxidant (Adeka Korea AO-60)

[0536] - Antioxidant #2: Phosphorus-based antioxidant (Adeka Korea 2112)

[0537] - Lubricant: Stearyl stearate

[0538]

[0539] Example 2-1

[0540] A raw material composition was prepared by adding biodegradable resin #1 : biodegradable resin #2 : radical initiator : chain extender : antioxidant #1 : antioxidant #2 : lubricant in a weight ratio of 60 : 40 : 0.1 : 0.1 : 0.15 : 0.15 : 0.1 and mixing at a temperature of 185°C.

[0541] Subsequently, the above raw material composition was fed into an extruder equipped with a twin screw (58Φ L / D 40 Twin Extruder, Ecotec Co.) and reactively extruded. In addition, after the reaction of the above-described biodegradable resin mixture was completed, the process byproduct was discharged through the vent of the extruder.

[0542] Subsequently, the biodegradable resin composition, after the reaction extrusion was completed, was cut and cooled using a hot-cut pellet cutter to produce a pelletized biodegradable resin composition. In the above reaction extrusion process, the reaction temperature and rate are as shown in Table 3 below.

[0543]

[0544] Examples 2-2 to 2-7

[0545] A biodegradable resin composition was prepared in the same manner as in Example 2-1, except that biodegradable resin #1 : biodegradable resin #2 : radical initiator : chain extender were added in the ratios shown in Table 3 below and reacted and extruded under the conditions shown in Table 3 below.

[0546]

[0547] Classification Biodegradable Resin #1 (parts by weight) Biodegradable Resin #2 (parts by weight) Radical Initiator (parts by weight) Chain Extender (parts by weight) Temperature (°C) Speed ​​(rpm) Example 2-1 60.000 400.10.1180-190220 Example 2-259.820 400.09 0.09 180-190220 Example 2-369.800 300.10.1180-190220 Example 2-469.760 300.120.12180-190220 Example 2-569.900 300.05 0.05 170-180220 Example 2-669.825 300.10.07 5170-180200 Example 2-769.820 300.09 0.09 180-190200

[0548]

[0549] Comparative Examples 2-1 and 2-2

[0550] A biodegradable resin composition was prepared in the same manner as in Example 2-1, except that biodegradable resin #1 : biodegradable resin #2 : radical initiator : chain extender were added in the ratios shown in Table 4 below and reacted and extruded under the conditions shown in Table 4 below.

[0551]

[0552] Classification Biodegradable Resin #1 (parts by weight) Biodegradable Resin #2 (parts by weight) Radical Initiator (parts by weight) Chain Extender (parts by weight) Temperature (°C) Speed ​​(rpm) Comparative Example 2-1 69.825300.10.075170-180220 Comparative Example 2-2 69.900300.050.05180-190220

[0553]

[0554] Experimental Example 2-1 - Viscosity of Biodegradable Resin Composition

[0555] The viscosity of the biodegradable resin compositions prepared in Examples 2-1 to 2-7 and Comparative Examples 2-1 and 2-2 was measured. The viscosity was measured using a rotational rheometer via the 190°C frequency sweep method. Additionally, when the viscosity was measured, the shear rate was approximately 10 s⁻¹. -1 It may be. The above viscosity is listed in Table 5 below.

[0556]

[0557] Classification Viscosity (mPa·s) Example 2-16.32 X 10 7 Example 2-25.29 X 10 7 Example 2-34.56 X 10 7 Example 2-45.70 X 10 7 Example 2-52.48 X 10 7 Example 2-62.99 X 10 7 Example 2-74.13 X 10 7 Comparative Example 2-11.77 X 10 7 Comparative Example 2-28.64 X 10 6

[0558]

[0559] Experimental Example 2-2 - Melt flow index of biodegradable resin composition

[0560] The melt flow index was measured by measuring the weight of the biodegradable resin composition produced when the biodegradable resin compositions prepared in Examples 2-1 to 2-7 and Comparative Examples 2-1 and 2-2 were extruded for 10 minutes at a temperature of 190°C and a weight of 2.16 kg using a melt indexer (G-01, TOYOSEIKI) in accordance with ASTM D1238, ISO 1133, and JIS K7210 standards. The melt flow index is listed in Table 6 below.

[0561]

[0562] Classification Molten Flow Index (g / 10min) Example 2-10.23 Example 2-20.27 Example 2-30.30 Example 2-40.25 Example 2-50.83 Example 2-60.8 Example 2-70.34 Comparative Example 2-11.1 Comparative Example 2-21.6

[0563]

[0564] Referring to Tables 5 and 6 above, it can be seen that the biodegradable resin composition with a melt flow index of less than 1.0 g / 10 min has a higher viscosity compared to the comparative examples.

[0565]

[0566] Experimental Example 2-3 - Tensile Strength and Elongation of Biodegradable Molded Article

[0567] Manufacture of Biodegradable Molded Products

[0568] Subsequently, the biodegradable resin compositions prepared in Examples 2-1 to 2-7 and Comparative Examples 2-1 and 2-2 were melted at a temperature of about 160°C, and by a blow molding process, a cylindrical container having a thickness of about 1.2 mm, a diameter of about 15 cm, and a height of about 30 cm was manufactured.

[0569] For each of the biodegradable molded articles of Examples 2-1 to 2-7 and Comparative Examples 2-1 and 2-2 above, tensile strength and elongation were measured according to ISO 527, and the results are listed in Table 7 below.

[0570]

[0571] Experimental Example 2-4 - Flexural Strength and Flexural Modulus of Biodegradable Molded Article

[0572] For each of the biodegradable molded articles of Examples 2-1 to 2-7 and Comparative Examples 2-1 and 2-2 above, flexural strength and flexural modulus were measured according to ISO178, and the results are listed in Table 7 below.

[0573]

[0574] Experimental Example 2-5 - Impact strength of biodegradable molded articles

[0575] For each of the biodegradable molded articles of Examples 2-1 to 2-7 and Comparative Examples 2-1 and 2-2 above, the impact strength was measured according to ISO 180 (1 / 8 inch standard), and the results are listed in Table 7 below.

[0576]

[0577] Classification tensile strength (kgf / cm²) 2 Elongation (%) Flexural Strength (kgf / cm²) 2 Flexural modulus (kgf / cm²) 2 Impact Strength (kgf·cm / cm) Example 2-130 317 344 715,383 82 Example 2-23 2015 74 5015,456 75 Example 2-340 3615 8718,760 38 Example 2-439 880 55618,723 40 Example 2-540 30 58218,920 25 Example 2-639 125 56218,592 25 Example 2-740 763 53918,630 43 Comparative Example 2-138 127 53818,346 15 Comparative Example 2-23 7615 56219,020 8

[0578]

[0579] Referring to Table 7 above, it can be confirmed that a biodegradable molded article manufactured with a biodegradable resin composition having a melt flow index of less than 1.0 g / 10 min can achieve tensile strength, flexural strength, and flexural modulus at an equivalent level compared to the comparative examples, while achieving very high levels of elongation and impact strength, which is most important for blow containers.

[0580]

[0581] The examples may be applied to a biodegradable resin composition, a method for manufacturing the same, and a biodegradable molded article containing the same.

Claims

A first biodegradable resin comprising an aliphatic-aromatic polyester resin; A second biodegradable resin comprising an aliphatic polyester resin; polyol; and It comprises a third biodegradable resin having a structure in which part or all of the first biodegradable resin and part or all of the second biodegradable resin are combined, A biodegradable resin composition having a melt index of 1 g / 10 min or less at 190 ℃ and 2.16 kg according to ASTM D1238. In paragraph 1, A biodegradable resin composition in which the weight ratio of the first biodegradable resin to the second biodegradable resin is 1:1 to 1:

9. In paragraph 1, The above polyol is a biodegradable resin composition having a hydroxyl value (OH value) of 1,830 mgKOH / g to 2,000 mgKOH / g. In paragraph 1, A biodegradable resin composition in which the content of the polyol is greater than 0 weight % and less than 0.1 weight % based on the total weight of the biodegradable resin composition. In paragraph 1, A biodegradable resin composition wherein the third biodegradable resin comprises a structure represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, n1 is an integer from 1 to 200, and A1 is derived from the above polyol. In paragraph 1, The above biodegradable resin composition is a biodegradable resin composition comprising a radical initiator. In paragraph 6, The above radical initiator is a biodegradable resin composition that is in a solid state at room temperature. In paragraph 6, A biodegradable resin composition having a content of the radical initiator of greater than 0.01 weight % and less than 1 weight % based on the total weight of the biodegradable resin composition. In paragraph 6, The above biodegradable resin composition comprises a fourth biodegradable resin having a structure represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, n2 is an integer from 1 to 200, X1 is derived from the first biodegradable resin, and A2 is derived from the polyol. In paragraph 6, The above biodegradable resin composition comprises a fifth biodegradable resin having a structure represented by the following chemical formula 3: [Chemical Formula 3] In the above chemical formula 3, n3 is an integer from 1 to 200, X2 is derived from the second biodegradable resin, and A3 is derived from the polyol. A first biodegradable resin comprising an aliphatic-aromatic polyester resin; A second biodegradable resin comprising an aliphatic polyester resin; polyol; and A biodegradable resin composition comprising a third biodegradable resin having a structure in which part or all of the first biodegradable resin and part or all of the second biodegradable resin are combined, The above biodegradable resin composition is a biodegradable molded article having a melt index of 1 g / 10 min or less at 190 ℃ and 2.16 kg according to ASTM D1238. First biodegradable resin; Second biodegradable resin; Radical initiator; and A third biodegradable resin comprising a structure in which part or all of the first biodegradable resin and part or all of the second biodegradable resin are combined, A biodegradable resin composition having a melt flow index of less than 1.0 g / 10 min as measured at a temperature of 190°C and a weight of 2.16 kg according to ASTM D1238. In Paragraph 12, The first biodegradable resin above comprises polylactic acid, and The second biodegradable resin above comprises polybutylene adipate terephthalate, and A biodegradable resin composition in which the weight ratio of the first biodegradable resin and the second biodegradable resin is 1:1 to 9:

1. A biodegradable resin composition according to claim 13, wherein the third biodegradable resin comprises a structure represented by the following chemical formula 1. [Chemical Formula 1] In the above chemical formula 1, k is 1 to 50000, and X1 is derived from the second biodegradable resin. In Paragraph 14, A biodegradable resin composition in which, in the above chemical formula 1, X1 comprises at least one repeating unit represented by the following chemical formulas B'-1 to B'-3. [Chemical Formula B'-1] [Chemical Formula B'-2] [Chemical Formula B'-3] In the above chemical formulas B'-1 to B'-3, q is 1 to 20. In Paragraph 12, A biodegradable resin composition further comprising a fourth biodegradable resin having a structure represented by the following chemical formula 2. [Chemical Formula 2] In the above chemical formula 2, l is 1 to 50000, and X2 is derived from the first biodegradable resin. In Paragraph 16, A biodegradable resin composition in which, in the above chemical formula 2, X2 comprises a repeating unit represented by the following chemical formula A'. [Chemical Formula A'] In the above chemical formula A', p is 1 to 20. In Paragraph 12, The above radical initiator comprises an organic peroxide and is a biodegradable resin composition that is in a solid state at room temperature. In Paragraph 12, A biodegradable resin composition in which the radical initiator comprises a compound represented by the following chemical formula 3. [Chemical Formula 3] In the above chemical formula 3, R1 to R4 are each independently selected from the group consisting of hydrogen atoms, hydrocarbon groups, heteroatoms, and combinations thereof, and n is 1 to 20, and m is 1 to 20. In Paragraph 12, A biodegradable resin composition in which the content of the radical initiator is 0.01% to 1% by weight based on the total weight of the biodegradable resin composition.

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