Biodegradable resin composition for breathable film and breathable film comprising same

Abstract

The present invention provides a biodegradable resin composition for a breathable film and a breathable film comprising same, the biodegradable resin composition comprising: a biodegradable resin comprising an aliphatic-aromatic polyester resin; and an inorganic filler comprising calcium carbonate, wherein the biodegradable resin has a melt index of greater than 3 g / 10 min and less than 30 g / 10 min at 190°C and 2.16 kg according to ASTM D1238, and the calcium carbonate has a water contact angle of less than 90°.

Description

Biodegradable resin composition for breathable films and breathable film comprising the same

[0001] The present invention relates to a biodegradable resin composition for a breathable film and a breathable film 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, when manufacturing biodegradable resins into breathable films for use in sanitary products, there were difficulties in securing the breathability required by the industry. Consequently, even when breathability was secured by adjusting the type of biodegradable resin and / or additives, it was difficult to secure the mechanical properties required for the film.

[0006]

[0007] The present invention provides an eco-friendly biodegradable resin composition for a breathable film with improved breathability and mechanical properties, and a breathable film comprising the same.

[0008]

[0009] The biodegradable resin composition for a breathable film according to the present invention comprises a biodegradable resin comprising an aliphatic-aromatic polyester resin and an inorganic filler comprising calcium carbonate, wherein the biodegradable resin has a melt index at 190°C and 2.16kg according to ASTM D1238 of greater than 3 g / 10min and less than 30 g / 10min, and the water contact angle of the calcium carbonate is less than 90°.

[0010] In one embodiment of the present invention, the biodegradable resin may include a crystallization promoter.

[0011] In one embodiment of the present invention, the average particle size (D) of the calcium carbonate is 50 ) may be greater than 2 μm or less than 8 μm.

[0012] In one embodiment of the present invention, the span (D) of the calcium carbonate is 90 -D 10 / D 50 ) may be greater than 5 or less than 20.

[0013] In one embodiment of the present invention, the calcium oxide content may be less than 0.01 volume % based on 100 volume % of the calcium carbonate.

[0014] In one embodiment of the present invention, the surface free energy of the calcium carbonate may be greater than 100 mN / m and less than 300 mN / m.

[0015] In one embodiment of the present invention, the content of the inorganic filler may be 40% by weight to 70% by weight based on the total weight of the biodegradable resin composition for the breathable film.

[0016] In one embodiment of the present invention, the content of the inorganic filler may be 80 to 200 parts by weight based on 100 parts by weight of the biodegradable resin.

[0017] In one embodiment of the present invention, the biodegradable resin composition for the breathable film may include a lubricant containing calcium.

[0018] The breathable film according to the present invention comprises a biodegradable resin comprising an aliphatic-aromatic polyester resin and an inorganic filler comprising calcium carbonate, wherein the biodegradable resin has a melt index at 190°C and 2.16kg according to ASTM D1238 greater than 3 g / 10min and less than 30 g / 10min, and the water contact angle of the calcium carbonate is less than 90°.

[0019] In one embodiment of the present invention, the breathable film has a basis weight of 30 g / m² 2 Based on the standard Water vapor transmission rate (WVTR) is 200 g / m 2 · May exceed 24 hours.

[0020] In one embodiment of the present invention, the breathable film has a basis weight of 30 g / m² 2 The tensile strength in the longitudinal direction (MD) at the standard may exceed 1,300 g / inch.

[0021] In one embodiment of the present invention, the breathable film has a basis weight of 30 g / m² 2 The elongation in the longitudinal direction (MD) from the standard may exceed 120%.

[0022]

[0023] The biodegradable resin composition for a breathable film according to the present invention comprises a biodegradable resin including an aliphatic-aromatic polyester resin. As a result, the breathable film produced from the biodegradable resin composition can be biodegraded within a short period after disposal, thereby reducing product disposal costs and preventing environmental pollution.

[0024] The above-described biodegradable resin composition for breathable films includes an inorganic filler containing calcium carbonate. As a result, the content of the biodegradable resin can be relatively reduced, thereby providing a cost-saving effect. In addition, the thermal stability of the biodegradable resin can be improved, which can suppress the degradation of the biodegradable resin during the blown film extrusion process.

[0025] The above biodegradable resin is selected such that its melt index is controlled to be greater than 3 g / 10 min and less than 30 g / 10 min, and the water contact angle of the calcium carbonate is less than 90°. As a result, processability for manufacturing a blown film can be ensured, excellent breathability can be achieved, and at the same time, mechanical properties such as tensile strength and elongation required for the film can be improved.

[0026]

[0027] 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.

[0028] 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.

[0029] In this specification or application, 'ppm' refers to a weight basis.

[0030] In this specification or application, the description of "A and / or B" means "A, B, or A and B".

[0031]

[0032] The biodegradable resin composition for a breathable film according to the present invention comprises a biodegradable resin comprising an aliphatic-aromatic polyester resin.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] When the aliphatic-aromatic polyester resin comprises the first block and the second block within the above range, the breathable film containing the aliphatic-aromatic polyester resin can have appropriate mechanical strength while improving biodegradability.

[0049] The above aliphatic-aromatic polyester resin may include the following bonding structures 1 to 3.

[0050] [Coupling Structure 1]

[0051] - Aromatic dicarboxylic acid - Diol - Aliphatic dicarboxylic acid -

[0052] [Combination Structure 2]

[0053] - Aromatic dicarboxylic acid - Diol - Aromatic dicarboxylic acid -

[0054] [Combination Structure 3]

[0055] - Aliphatic dicarboxylic acid - Diol - Aliphatic dicarboxylic acid -

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] The above-mentioned alternation ratio can be calculated using the following formula 1.

[0062] [Formula 1]

[0063]

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] The above hard segment ratio can be expressed by the following formula 2.

[0069] [Equation 2]

[0070]

[0071] 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.

[0072] 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.

[0073] The above aliphatic-aromatic polyester resin may include soft segments.

[0074] 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.

[0075] 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.

[0076] The above soft segment ratio can be expressed by the following formula 3.

[0077] [Equation 3]

[0078]

[0079] 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.

[0080] 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.

[0081] The above soft segment ratio may be larger than the above hard segment ratio.

[0082] 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.

[0083] 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 composition is dissolved in a solvent such as CDCl3, and at room temperature, by a nuclear magnetic resonance (NMR) device, 1 H-NMR and / or 13 It can be analyzed by C-NMR analysis.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] The above alternating ratio can be derived using the following Equation 4 or Equation 5.

[0095] [Equation 4]

[0096]

[0097] 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.

[0098] [Formula 5]

[0099]

[0100] 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.

[0101] The above hard segment ratio can be derived using the following formula 6 or the following formula 7.

[0102] [Equation 6]

[0103]

[0104] 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.

[0105] [Equation 7]

[0106]

[0107] 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.

[0108] The above soft segment ratio can be derived using the following formula 8 or formula 9.

[0109] [Equation 8]

[0110]

[0111] 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.

[0112] [Formula 9]

[0113]

[0114] 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.

[0115] 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.

[0116] 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.

[0117] The number average molecular weight of the aliphatic-aromatic polyester resin may be greater than 20,000 g / mol and less than 45,000 g / mol, 22,000 g / mol and 44,000 g / mol, 25,000 g / mol and 44,000 g / mol, or 25,000 g / mol and 42,000 g / mol. When the above range is satisfied, mechanical properties and moldability may be improved while having appropriate biodegradability. The number average molecular weight may be measured using gel permeation chromatography (GPC).

[0118] The degree of crystallinity 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.

[0119] 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 ).

[0120] Specifically, it can be calculated according to the following formula.

[0121] [Calculation Formula]

[0122] 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

[0123] The content of the aliphatic-aromatic polyester resin may be 30% to 90% by weight, 40% to 90% by weight, 40% to 80% by weight, or 50% to 70% by weight based on the total weight of the biodegradable resin composition for the breathable film. When the above range is satisfied, moldability may be improved, and mechanical properties that allow for functionality as a breathable film may be satisfied.

[0124] The above biodegradable resin may include a crystallization promoter. The crystallization promoter may be mixed in the polymerization reaction of the aliphatic-aromatic polyester resin and / or in the compounding process with the aliphatic-aromatic polyester resin.

[0125] The crystallization promoter may be included in an amount of 100 ppm to 50,000 ppm, 100 ppm to 40,000 ppm, 100 ppm to 30,000 ppm, 100 ppm to 10,000 ppm, or 100 ppm to 6,000 ppm based on the total weight of the biodegradable resin. When the above range is satisfied, the melt index of the biodegradable resin can be appropriately controlled, thereby ensuring processability for manufacturing into a breathable film and realizing mechanical properties.

[0126] The crystallization promoter may include at least one of an organic nucleating agent and an inorganic nucleating agent.

[0127] The above organic nucleating agent may refer to a nucleating agent composed of an organic compound.

[0128] The above biodegradable resin may contain the above organic nucleating agent in an amount of 10 ppm to 5,000 ppm, 10 ppm to 3,000 ppm, 10 ppm to 1,000 ppm, or 100 ppm to 500 ppm.

[0129] The above organic nucleating agent may include nanocellulose having an average length of 10 nm to 300 nm, 10 nm to 200 nm, 20 nm to 200 nm, or 30 nm to 200 nm.

[0130] The above nanocellulose may be bead mill pretreated or ultrasonically pretreated. The above nanocellulose may be subjected to both bead mill pretreatment and ultrasonically pretreatment. It is preferable to perform ultrasonically pretreatment on the nanocellulose after bead mill pretreatment in order to prevent re-aggregation and improve dispersibility.

[0131] The above bead mill pretreatment can be performed using a wet milling device, either a vertical mill or a horizontal mill. The horizontal mill is preferable in that it allows for a larger amount of beads to be filled inside the chamber, reduces uneven wear of the machine and beads, and makes maintenance easier, but it is not limited thereto.

[0132] The above bead mill pretreatment can be performed using one or more beads selected from the group consisting of zirconium, zircon, zirconia, quartz, and aluminum oxide.

[0133] The above bead mill pretreatment can be performed using beads having a diameter of about 0.3 mm to about 1 mm. For example, the diameter of the beads may be about 0.3 mm to about 0.9 mm, about 0.4 mm to about 0.8 mm, about 0.45 mm to about 0.7 mm, or about 0.45 mm to about 0.6 mm. If the above range is satisfied, the dispersibility of the nanocellulose may be improved.

[0134] The above ultrasonic pretreatment refers to a method of physically closing or crushing nanoparticles with waves generated by emitting 20 kHz ultrasonic waves into a solution.

[0135] The above ultrasonic pretreatment may be performed for a time of less than 30 minutes at an output of 30,000 J / s or less. For example, the above ultrasonic pretreatment may be performed for a time of 25 minutes or less, 20 minutes or less, or 18 minutes or less at an output of 25,000 J / s or less or 22,000 J / s or less. When the above range is satisfied, the effect of the ultrasonic pretreatment, that is, the improvement of dispersibility, can be maximized.

[0136] The above-mentioned inorganic nucleating agent may refer to a nucleating agent composed of an inorganic compound.

[0137] The above biodegradable resin may contain the above inorganic nucleating agent in an amount of 100 ppm to 10,000 ppm, 100 ppm to 8,000 ppm, 300 ppm to 8,000 ppm, 500 ppm to 8,000 ppm, or 500 ppm to 6,000 ppm.

[0138] The above-mentioned inorganic nucleating agent may include one or more selected from the group consisting of titanium dioxide, talc, kaolinite, montmorillonite, mica, clay, zeolite, silica, graphite, carbon black, mica, barium sulfate, calcium silicate, calcium carbonate, calcium sulfide, calcium titanate, zinc oxide, aluminum oxide, magnesium oxide, neodymium oxide, and boron nitride.

[0139] The above-mentioned inorganic nucleating agent may include at least one of rutile-phase titanium dioxide and anatase-phase titanium dioxide.

[0140] Preferably, the inorganic nucleating agent may include anatase-phase titanium dioxide. The anatase-phase titanium dioxide exhibits high photoactivity, which can further enhance biodegradability.

[0141] Average diameter (D) of the above-mentioned inorganic nucleating agent 50 ) may be 0.1 μm to 0.5 μm, 0.1 μm to 0.4 μm, 0.15 μm to 0.4 μm, 0.15 μm to 0.3 μm, or 0.15 μm to 0.25 μm. When the above range is satisfied, the kneading ability with the aliphatic-aromatic polyester resin may be improved.

[0142] The above biodegradable 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 30 g / 10 min, 3.5 g / 10 min to 28 g / 10 min, 3.5 g / 10 min to 25 g / 10 min, 3.5 g / 10 min to 20 g / 10 min, or 4 g / 10 min to 20 g / 10 min. When the above range is satisfied, appropriate blown and stretching processes of the biodegradable resin composition for the breathable film can be carried out, and mechanical properties such as tensile strength and elongation of the breathable film produced can be secured.

[0143] The biodegradable resin composition for a breathable film according to the present invention comprises an inorganic filler comprising calcium carbonate.

[0144] Since the content of the biodegradable resin can be relatively reduced due to the inclusion of the above-mentioned inorganic filler, there is an economic effect. In addition, the thermal stability of the above-mentioned biodegradable resin can be improved, so the phenomenon of degradation of the above-mentioned biodegradable resin during the blown film extrusion process can be suppressed. Furthermore, the above-mentioned inorganic filler can provide an anti-blocking agent effect, so blocking problems that may occur during the processing of the above-mentioned breathable film can be suppressed.

[0145] The water contact angle of the calcium carbonate may be less than 90°, 30° to 80°, 30° to 70°, 30° to 75°, or 30° to 60°. The water contact angle may be measured as the contact angle with water according to ASTM D7334. The inventors noted that when calcium carbonate is included in a breathable film, the water vapor permeability and oxygen permeability vary depending on the degree of hydrophilicity or hydrophobicity of the surface of the calcium carbonate. When the above ranges are satisfied, the spacing between the calcium carbonate particles can be maintained uniformly, allowing a fine pore structure to be formed. As a result, the pores provide a path for water vapor to pass through, thereby improving breathability.

[0146] Average particle size (D of the above calcium carbonate) 50 ) may be greater than 2 μm to less than 8 μm, 3 μm to 7.5 μm, 3 μm to 7 μm, 3 μm to 6 μm, or 3 μm to 5 μm.

[0147] The span (D) of the above calcium carbonate 90 -D 10 / D 50 ) may be greater than 5 to less than 20, 5.5 to less than 20, 5.5 to 19, or 6 to 18.

[0148] The above span is D, the particle size corresponding to 10% of the volume accumulation in the particle size distribution curve derived using laser diffraction. 10 , particle size corresponding to 50% of the volume accumulation D 50 , and particle size corresponding to 90% of the volume accumulation D 90 It can be calculated as.

[0149] If the above range is satisfied, biodegradability may be further improved, the dispersibility of the calcium carbonate within the biodegradable resin may be improved, and the breathability of the breathable film produced from the biodegradable resin composition for the breathable film may be improved.

[0150] The surface free energy of the calcium carbonate may be greater than 100 mN / m and less than 300 mN / m, 150 mN / m and less than 300 mN / m, 200 mN / m and less than 300 mN / m, or 200 mN / m and 280 mN / m. The surface free energy may be measured according to DIN 53364 and may vary depending on the surface treatment, average particle size, and / or span of the calcium carbonate.

[0151] When the above range is satisfied, the hydrophilicity of the calcium carbonate is improved, and a fine pore structure can be formed, thereby improving breathability.

[0152] The calcium carbonate mentioned above may be heavy calcium carbonate. When the inorganic filler includes heavy calcium carbonate, the dispersibility of the biodegradable resin may be improved, and an excessive increase in viscosity of the biodegradable resin composition for the breathable film may be suppressed. In addition, the tensile strength may be increased compared to light calcium carbonate, thereby improving mechanical properties.

[0153] The specific surface area of ​​the above heavy calcium carbonate is 0.1 m² 2 / g to 10.0 m 2 / g, 0.1 m 2 / g to 9.0 m 2 / g, 0.1 m 2 / g to 8.0 m 2 / g, 0.1 m 2 / g to 7.0 m 2 / g, 0.1 m 2 / g to 6.0 m 2 / g, 0.1 m 2 / g to 5.0 m 2 / g, 0.1 m 2 / g to 4.0 m 2 / g, or 0.1 m 2 / g to 3.0 m 2It can 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 biodegradable resin and moldability can be improved.

[0154] 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 biodegradable resin and the inorganic filler, thereby improving air permeability and biodegradability.

[0155] The calcium carbonate may contain calcium oxide. The calcium oxide may be formed when a portion of the surface of the calcium carbonate is oxidized upon surface treatment. The content of the calcium oxide may be less than 0.01 volume%, less than 0.009 volume%, or less than 0.008 volume% based on 100 volume% of the calcium carbonate. Preferably, the calcium carbonate may not contain calcium oxide. The ratio of calcium oxide may be measured by the EDTA (Ethylene diamine tetraacetic acid) titration method in accordance with JIS R 9011. The calcium carbonate may not be surface-treated with organic and / or inorganic materials. By not surface-treating the calcium carbonate, the interaction between calcium carbonate particles is enhanced, allowing for the formation of a fine pore structure. Additionally, the surface free energy of the calcium carbonate increases, allowing for the formation of aggregates between calcium carbonate particles, thereby creating more pore structures. Consequently, the breathability of the breathable film containing the calcium carbonate may be improved.

[0156] The content of the inorganic filler may be 40% to 70% by weight, 40% to 65% by weight, 40% to 55% by weight, or 45% to 50% by weight based on the total weight of the biodegradable resin composition for the breathable film. When the above range is satisfied, the water resistance of the breathable film may be improved, and processability in the blown film extrusion process may be improved, thereby improving the productivity of the breathable film.

[0157] Based on 100 parts by weight of the above biodegradable resin, the content of the above inorganic filler may be 80 to 200 parts by weight, 80 to 150 parts by weight, 80 to 120 parts by weight, or 80 to 100 parts by weight. When the above range is satisfied, the above inorganic filler can be uniformly dispersed in the above biodegradable resin, so that the mechanical properties of the breathable film produced can be improved.

[0158] The above biodegradable resin composition for breathable films may include a lubricant.

[0159] The above biodegradable resin composition for breathable films may include a lubricant containing calcium. Since the lubricant contains the same calcium component as the calcium carbonate, which is the inorganic filler, it exhibits excellent compatibility, reduces heat generation due to friction during raw material mixing, melting, and processing, and can improve manufacturing efficiency.

[0160] The above lubricant may include one or more selected from the group consisting of fatty acid-based lubricants containing stearic acid, aliphatic alcohol-based lubricants, aliphatic amide-based lubricants containing stearamide, stearate-n-butyl, methyl hydroxystearate, polyhydric alcohol fatty acid esters, saturated fatty acid esters, ester-based waxes, and fatty acid metal soap-based lubricants.

[0161] The content of the above-mentioned lubricant may be 0.1% by weight to 5% by weight, 0.1% by weight to 4% by weight, 0.1% by weight to 3% by weight, or 0.1% by weight to 2% by weight based on the total weight of the biodegradable resin composition for the breathable film. When the above range is satisfied, manufacturing efficiency can be improved without deterioration of the mechanical and chemical properties of the breathable film.

[0162] The above biodegradable resin composition for breathable films may include an antioxidant.

[0163] The above antioxidant may include one or more selected from the group consisting of phosphorus-based antioxidants, phenol-based antioxidants, and pentaerythritol-based antioxidants.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] The biodegradable resin composition for the above-described breathable film further comprises a phenolic antioxidant and a phosphorus-based antioxidant, and the weight ratio of the phenolic antioxidant to the phosphorus-based antioxidant may be 1:1 to 1:5, 1:1 to 1:4.5, 1:1 to 1:4, or 1:2 to 1:4. When the above ranges are satisfied, the phenolic antioxidant can capture and neutralize free radicals, and the oxidation reaction can be suppressed by decomposing peroxides generated when oxidation begins by the phosphorus-based antioxidant. As a result, the thermal stability, color stability, and long-term storage stability of the breathable film can be improved.

[0168] The content of the antioxidant may be 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, 1.5 wt% or less, 1 wt% or less, 0.5 wt% or less, 0.3 wt% or less, 0 to 5 wt%, 0.01 to 4 wt%, 0.1 to 3 wt%, 1 to 3 wt%, 1 to 2 wt%, 0.01 to 0.3 wt%, 0.05 to 0.3 wt%, 0.15 to 0.3 wt%, or 0.2 to 0.3 wt% based on the total weight of the biodegradable resin composition for the breathable film.

[0169] The above biodegradable resin composition for breathable films may include a flame retardant. The flame retardant may include one or more selected from the group consisting of halogen-based flame retardants, phosphorus-based flame retardants, and non-phosphorus halogen-based flame retardants such as metal hydrates.

[0170] The above halogenated flame retardant may include one or more selected from the group consisting of halogenated bisphenyl alkanes, halogenated bisphenyl ethers, halogenated bisphenyl thioethers, halogenated bisphenyl sulfones, halogenated bisphenol-based compounds such as brominated bisphenol A, brominated bisphenol S, chlorinated bisphenol A, and chlorinated bisphenol S.

[0171] The above-mentioned phosphorus-based flame retardant may include one or more selected from the group consisting of tris(diethylphosphinic acid)aluminum, bisphenol A bis(diphenyl phosphate), triaryl isopropyl phosphate, cresyl di2,6-xylenyl phosphate, and aromatic condensed phosphate esters.

[0172] The above metal hydrate may include aluminum trihydrate, magnesium dihydrate, or a combination thereof.

[0173] The above flame retardant may include one or more selected from the group consisting of antimony oxide (such as antimony trioxide and antimony pentoxide), zinc oxide, iron oxide, aluminum oxide, molybdenum oxide, titanium oxide, calcium oxide, and magnesium oxide as flame retardant additives to enhance the flame retardant effect.

[0174] The above biodegradable resin composition for breathable films may include a dispersant. The dispersant may improve the dispersibility of the solvent and the solute. The dispersant may include one or more selected from the group consisting of aliphatic polyesters, polylactic acid, polyglycolic acid, polycaprolactone, and polyhydroxyalkanoates.

[0175] The above dispersant may be included in an amount of 1 to 20 weight%, 1 to 15 weight%, 1 to 13 weight%, 1 to 11 weight%, 2 to 10 weight%, 5 to 15 weight%, 7 to 12 weight%, 2 to 8 weight%, 5 to 8 weight%, or 2 to 5 weight% based on the total weight of the biodegradable resin composition for the breathable film.

[0176] The above biodegradable resin composition for a breathable film may include a hydrolysis inhibitor. If the weight-average molecular weight (Mw) of the hydrolysis inhibitor is large, volatility may be low and water resistance may be improved, and if the weight-average molecular weight (Mw) of the hydrolysis inhibitor is small, compatibility between the components included in the biodegradable resin composition for a breathable film may be increased.

[0177] The above hydrolysis inhibitor may include a carbodiimide-based compound.

[0178] The above carbodiimide-based compound may include a compound represented by the following chemical formula.

[0179] [Chemical Formula]

[0180]

[0181] In the above chemical formula, n is an integer from 1 to 20.

[0182] The above carbodiimide compounds are N,N'-di-o-tolylcarbodiimide, N,N'-diphetylcarbodiimide, N,N'-dioctyldecylcarbodiimide, N,N'-di-2,6-diketylphenylcarbodiimide, N-tolyl-N'cyclohexylcarbodiimide, N,N'-di-2,6-diisopropylphenylcarbodiimide, N,N'-di-2,6-di-tertiary-butylphenylcarbodiimide, N-tolyl-N'-phenylcarbodiimide, N,N'-di-p-nitrophenylcarbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N'-di-p-hydroxyphenylcarbodiimide, N,N'-di-cyclohexylcarbodiimide, It may be one or more selected from the group consisting of N,N'-di-p-tolylcarbodiimide, p-phenylene-bis-di-o-tolylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, hexamethylene-bis-dicyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, benzene-2,4-diisocyanato-1,3,5-tris(1-methylethyl) homopolymer, and copolymers of 2,4-diisocyanato-1,3,5-tris(1-methylethyl) and 2,6-diisopropyl diisocyanate.

[0183] The weight-average molecular weight of the above carbodiimide compound may be 500 g / mol to 100,000 g / mol, 600 g / mol to 100,000 g / mol, 700 g / mol to 100,000 g / mol, 800 g / mol to 90,000 g / mol, 900 g / mol to 80,000 g / mol, 1,000 g / mol to 70,000 g / mol, 1,000 g / mol to 60,000 g / mol, or 1,000 g / mol to 50,000 g / mol.

[0184] The content of NCN groups in the above carbodiimide-based compound may be 1 wt% to 20 wt%, 1 wt% to 19 wt%, 1 wt% to 18 wt%, 1 wt% to 17 wt%, 1 wt% to 16 wt%, 1 wt% to 15 wt%, 2 wt% to 15 wt%, 3 wt% to 15 wt%, 4 wt% to 15 wt%, 5 wt% to 15 wt%, or 6 wt% to 15 wt%. The content of NCN groups in the above carbodiimide-based compound may be measured by titration with oxalic acid. When the above range is satisfied, the water resistance of the biodegradable resin composition for the breathable film may be improved.

[0185] The content of the hydrolysis inhibitor may be 0.1% to 5.0% by weight, 0.1% to 4.0% by weight, 0.1% to 3.0% by weight, 0.1% to 2.0% by weight, 0.1% to 1.5% by weight, or 0.1% to 1.0% by weight, based on the total weight of the biodegradable resin composition for the breathable film. When the above range is satisfied, the water resistance and odor reduction effect of the biodegradable resin composition for the breathable film may be improved.

[0186] The content of the compound containing the urea group may be 0.01 wt% to 10.00 wt%, 0.01 wt% to 9.00 wt%, 0.01 wt% to 8.00 wt%, 0.01 wt% to 7.00 wt%, 0.01 wt% to 6.00 wt%, 0.01 wt% to 5.00 wt%, 0.01 wt% to 4.00 wt%, or 0.01 wt% to 3.00 wt% based on the total weight of the biodegradable resin composition for the breathable film. When the above range is satisfied, the proportion of functional groups included in the biodegradable resin composition for the breathable film that can react with moisture or acid is reduced, and water resistance may be improved.

[0187] The above-mentioned biodegradable resin composition for breathable films may include a slip agent. The slip agent may provide lubrication during or after the processing process, thereby reducing the coefficient of friction.

[0188] The slip agent may be selected from one or more of the group consisting of oleamide, erucamide, oleyl palmitamide, stearyl erucamide, and ethylene bis oleamide.

[0189] The content of the slip agent may be 1% to 10% by weight, 1% to 8% by weight, 1% to 6% by weight, or 1% to 5% by weight based on the total weight of the biodegradable resin composition for the breathable film. When the above range is satisfied, the manufacturing efficiency of the breathable film may be improved.

[0190] The above biodegradable resin composition for a breathable film may further include an anti-blocking agent. The occurrence of fine wrinkles in the breathable film can be prevented by the anti-blocking agent.

[0191] The above anti-blocking agent may be selected from one or more of the group consisting of silica, silicon, talc, and talc.

[0192] The biodegradable resin composition for the above-mentioned breathable film may include a chain extender. The mechanical properties of the breathable film, such as tensile strength and elongation at break, may be improved by the chain extender.

[0193] The above chain extender may be selected from one or more of the group consisting of aromatic diisocyanates, aliphatic diisocyanates, isocyanurates, bisoxazolins, carboxylic acid anhydrides, and epoxides.

[0194] The above aromatic diisocyanate may be selected from one or more of 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.

[0195] The above aliphatic diisocyanate may be selected from one or more of the group consisting of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and methylenebis(4-isocyanatocyclohexane).

[0196] The above isocyanurate may include isophorone diisocyanate or methylenebis(4-isocyanatocyclohexane).

[0197] 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.

[0198] 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.

[0199] The content of the chain extender may be 0.1% to 1% by weight, 0.1% to 0.9% by weight, 0.1% to 0.8% by weight, 0.1% to 0.7% by weight, or 0.1% to 0.5% by weight based on the total weight of the biodegradable resin composition for the breathable film. When the above range is satisfied, mechanical properties such as tensile strength and elongation at break of the breathable film may be improved.

[0200] The breathable film according to the present invention comprises a biodegradable resin comprising an aliphatic-aromatic polyester resin and an inorganic filler comprising calcium carbonate, wherein the biodegradable resin has a melt index at 190°C and 2.16kg according to ASTM D1238 greater than 3 g / 10min and less than 30 g / 10min, and the water contact angle of the calcium carbonate is less than 90°.

[0201] The above biodegradable resin and inorganic filler may be the same as the biodegradable resin and inorganic filler described above.

[0202] The above breathable film has a basis weight of 30 g / m² 2 Based on the standard Water vapor transmission rate (WVTR) is 200 g / m 2 · Over 24 hours, 500 g / m² 2 · Over 24 hours, 600 g / m² 2 · Over 24 hours, or 700 g / m² 2 · 24hr to 1,000 g / m² 2· It may be 24hr. The above WVTR may be a value obtained by measuring water vapor permeability using a WVTR measuring instrument (Mocon, Permatran W 3 / 61) according to ASTM E96.

[0203] The above breathable film has an OTR (oxygen transmission rate) of 0.1 cc / m 2 · Less than 24hr, 0.05 cc / m 2 · Less than 24hr, 0.001 cc / m 2 · It may be less than 24 hours or may not be measured. The above OTR may be a value of oxygen permeability measured using an OTR meter (Mocon, OX-TRAN) according to ASTM D3985.

[0204] As the above WVTR value increases and the above OTR value decreases, it indicates an indicator of improved breathability, and when the above range is satisfied, breathability can be secured so that it can be used as a breathable film without degradation of mechanical properties.

[0205] The above breathable film has a basis weight of 30 g / m² 2 The tensile strength in the longitudinal direction (MD) at the standard may be greater than 1,300 g / inch, greater than 1,350 g / inch, greater than 1,370 g / inch, or between 1,370 g / inch and 1,500 g / inch.

[0206] The above breathable film has a basis weight of 30 g / m² 2 The elongation in the longitudinal direction (MD) at the standard may be greater than 120%, greater than 125%, 130% or more, or between 130% and 200%.

[0207] The tensile strength and elongation of the above breathable film may be the average value measured 5 times at room temperature at a test speed of 200 mm / min using an INSTRON universal testing machine (4206-001, manufacturer: UTM) in accordance with ASTM D882.

[0208] If the above range is satisfied, the mechanical properties and manufacturing efficiency of the breathable film can be improved, and thus product reliability can be improved.

[0209]

[0210] The present invention will be described in more detail below based on examples and comparative examples. However, the following examples and comparative examples are merely illustrative for further explaining the present invention, and the present invention is not limited by the following examples and comparative examples.

[0211]

[0212] Example of preparation of crystallization promoter

[0213] A crystallization promoter was prepared by dispersing cellulose nanocrystals (NVC-100, manufacturer: Celluforce) in the form of dry powder having a particle size of about 1 μm to about 50 μm in water at 1 wt%, and then ultrasonically treating them for 2 minutes at an output of 20,000 J / s using a tip-type ultrasonic disperser.

[0214]

[0215] Example of preparing biodegradable resin

[0216] Preparation Example 1

[0217] - Step 1: Obtaining a prepolymer

[0218] A slurry was prepared by introducing 1,4-butanediol (1,4-BDO) and terephthalic acid (TPA) into a 5 kg esterification reactor equipped with a nitrogen inlet and a stirrer. At this time, the molar ratio of the 1,4-butanediol (1,4-BDO) and terephthalic acid (TPA) was 1.4:1, and the D of the terephthalic acid (TPA) 50 It was 130 µm.

[0219] The above slurry was introduced into a reactor through a supply line, and 250 ppm of tetrabutyl titanate (Dupont, Tyzor TnBT product), a titanium-based catalyst, was introduced. Subsequently, the temperature of the slurry was raised to 210 ℃, and an esterification reaction was carried out until more than 90% of the byproduct, water, was discharged to produce a first prepolymer.

[0220] 53 mol% of 1,4-butanediol (1,4-BDO) was added to the first esterification reaction product based on the total molar amount of the diol component, 53 mol% of adipic acid (AA) was added based on the total molar amount of the dicarboxylic acid component, and 200 ppm of tetrabutyl titanate (Dupont, Tyzor TnBT product), a titanium-based catalyst, was added based on the total weight of the diol component and the dicarboxylic acid component. In addition, 100 ppm of a crystallization promoter according to the above preparation example was added to the first esterification product. Subsequently, a second esterification reaction was carried out at 220°C and atmospheric pressure for about 2 hours and 30 minutes until 95% of the byproduct water was discharged, thereby producing a second prepolymer having a number average molecular weight of 5,500 g / mol.

[0221] - Step 2: Polycondensation reaction

[0222] The above second prepolymer was transferred to a 5 kg polycondensation reactor. Based on the total weight of the second prepolymer, 150 ppm of the titanium-based catalyst tetrabutyl titanate (Dupont, Tyzor TnBT product) and 500 ppm of triethylene phosphate stabilizer were added, and the mixture was stabilized for about 10 minutes.

[0223] Subsequently, after raising the temperature to 240 ℃, a polycondensation reaction was carried out at 0.5 torr for 2 hours to produce an aliphatic-aromatic polyester resin with a number average molecular weight of approximately 42,000 g / mol.

[0224] Preparation Example 2

[0225] An aliphatic-aromatic polyester resin having a number average molecular weight of about 32,000 g / mol was prepared by the same process as in Preparation Example 1, except that 150 ppm of crystallization promoter was added instead of 100 ppm of crystallization promoter in Preparation Example 1, and the condensation reaction was carried out for 1 hour and 40 minutes instead of 2 hours.

[0226] Preparation Example 3

[0227] An aliphatic-aromatic polyester resin having a number average molecular weight of about 25,000 g / mol was prepared by the same process as in Preparation Example 1, except that 120 ppm of crystallization promoter was added instead of 100 ppm of crystallization promoter in Preparation Example 1, and the condensation reaction was carried out for 1 hour and 30 minutes instead of 2 hours.

[0228] Preparation Example 4

[0229] An aliphatic-aromatic polyester resin having a number average molecular weight of about 45,000 g / mol was prepared by the same process as in Preparation Example 1, except that instead of adding 100 ppm of crystallization promoter as in Preparation Example 1, no crystallization promoter was added, and instead of carrying out the condensation reaction for 2 hours and 30 minutes, the condensation reaction was carried out for 2 hours and 30 minutes.

[0230] Preparation Example 5

[0231] An aliphatic-aromatic polyester resin having a number average molecular weight of about 20,000 g / mol was prepared by the same process as in Preparation Example 4, except that the polycondensation reaction was carried out for 1 hour instead of 2 hours in Preparation Example 4.

[0232]

[0233] Examples

[0234] - Biodegradable Resin #1: Preparation Example 1

[0235] - Biodegradable Resin #2: Preparation Example 2

[0236] - Biodegradable Resin #3: Preparation Example 3

[0237] - Biodegradable Resin #4: Preparation Example 4

[0238] - Biodegradable Resin #5: Preparation Example 5

[0239] - Inorganic Filler #1: Heavy Calcium Carbonate (Average Particle Size (D 50 ) Approx. 4 µm, water contact angle approx. 60° according to ASTM D7334)

[0240] - Inorganic Filler #2: Heavy Calcium Carbonate (Average Particle Size (D 50 ) Approx. 3.5 µm, water contact angle approx. 50° according to ASTM D7334)

[0241] - Inorganic Filler #3: Hard calcium carbonate surface-treated with a silane coupling agent (average particle size (D 50 ) Approx. 0.5 µm, water contact angle approx. 90° according to ASTM D7334)

[0242] - Inorganic Filler #4: Heavy calcium carbonate surface-treated with stearic acid (average particle size (D 50 ) Approx. 3 µm, water contact angle approx. 110° according to ASTM D7334)

[0243] - Lubricant #1: Calcium Stearate

[0244] - Lubricant #2: Stearyl Stearate

[0245] - Antioxidant #1: Phenolic antioxidant (Adeka Korea AO-60)

[0246] - Antioxidant #2: Phosphorus-based antioxidant (Adeka Korea 2112)

[0247]

[0248] Example 1

[0249] A resin composition mixed with 51.8 wt% of biodegradable resin #1, 47 wt% of inorganic filler #1, 0.4 wt% of lubricant #1, 0.6 wt% of lubricant #2, 0.07 wt% of antioxidant #1, and 0.13 wt% of antioxidant #1 was kneaded at a temperature of 175 ℃, and the mixture was extruded for about 3 minutes by an extrusion molding machine equipped with a twin-screw.

[0250] Subsequently, the extruded resin composition was cut and cooled using a hot-cut pellet cutter to produce a pelletized biodegradable resin composition.

[0251]

[0252] Examples 2 to 6 and Comparative Examples 1 to 3

[0253] A pelletized biodegradable resin composition was prepared using the same content and process as in Example 1, except that the biodegradable resin composition was prepared with the composition listed in Table 1 below.

[0254]

[0255] Classification Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Biodegradable Resin #1----#1----#2--#2------#3#3-----------#4---------#5#5 Inorganic Filler #1#1#1----#1----#2#2#2---------#3----------#4 Lubricant #1#1#1#1#1#1#1#1#1#1#2#2#2#2#2#2#2#2#2 Antioxidant #1#1#1#1#1#1#1#1#1#1#1#2#2#2#2#2#2#2#2#2

[0256]

[0257] Experimental Example

[0258] Breathable film manufacturing

[0259] The pelletized biodegradable resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were melt-extruded and stretched using a 1,470 mm × 600 mm blown film extruder (Blown Film Extrusion Line, Manufacturer: Eugene Engineering) at a temperature of 160°C and a speed of 36 m / min, resulting in a basis weight of approximately 30 g / m² 2 A film was manufactured.

[0260]

[0261] Experimental Example 1 - Melt Index

[0262] For the biodegradable resins used in Examples 1 to 6 and Comparative Examples 1 to 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.

[0263]

[0264] Experimental Example 2 - Tensile Strength and Elongation

[0265] For the breathable films or separate samples prepared in Examples 1 to 6 and Comparative Examples 1 to 3 above, the tensile strength and elongation in the longitudinal direction (MD) were each measured five times at room temperature using an INSTRON universal testing machine (4206-001, manufacturer: UTM) at a test speed of 200 mm / min in accordance with ASTM D882, and the respective average values ​​are shown in Table 2 below.

[0266]

[0267] Experimental Example 3 - WVTR (water vapor transmission rate)

[0268] For the breathable films or separate samples prepared in Examples 1 to 6 and Comparative Examples 1 to 3 above, water vapor permeability was measured using a WVTR meter (Mocon, Permatran W 3 / 61) according to ASTM E96, and the results are shown in Table 2 below.

[0269]

[0270] Experimental Example 4 - OTR (oxygen transmission rate)

[0271] For the breathable films or separate samples prepared in Examples 1 to 6 and Comparative Examples 1 to 3 above, oxygen permeability was measured using an OTR measuring instrument (Mocon, OX-TRAN) according to ASTM D3985, and the results are shown in Table 2 below.

[0272]

[0273] Experimental Example 5 - Biodegradability

[0274] Samples of the breathable films prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were prepared. Subsequently, an inoculum container containing only compost (Manufacturer: Taeheung F&G, Product Name: Jisengto (Grade 1 By-product Fertilizer Compost)) was prepared. Separately, a test container was prepared by mixing the compost and the sample in a weight ratio of 6:1 based on the dry weight of the compost. Subsequently, the inoculum container and the test container were cultured for 180 days under conditions of a temperature of 58±2℃, pH of 8±1, moisture content of 50%, and oxygen concentration of 6% or higher. Afterward, CO2 generated from each container was collected, and the amount of CO2 generated from each container was measured by titration with an aqueous phenolphthalein solution. Subsequently, the biodegradability of the reference (cellulose), which serves as the evaluation standard for biodegradability, was calculated according to the following formula. The biodegradability of the above samples was calculated according to the following formula, and then calculated as a relative biodegradability value based on the biodegradability of the above reference of 100%. The results are shown in Table 1 below.

[0275] [ceremony]

[0276] Biodegradability (%) = [(CO2 emissions from test container) - (CO2 emissions from inoculum container)] / (Theoretical CO2 emissions from test container) × 100

[0277]

[0278] Classification Melt Index Calcium Carbonate Water Contact Angle Tensile Strength Elongation WV TROTR Biodegradability Unit g / 10 min° g / inch % g / m 2 ·24hrcc / m 2 · 24hr% Example 14601, 400130790 Measurement impossible 1) 95 Example 2 10601,360125770 Unmeasurable 95 Example 3 20601,320122780 Unmeasurable 95 Example 4 20501,320122750 Unmeasurable 95 Example 5 10501,350125745 Unmeasurable 95 Example 6 4501,390130750 Unmeasurable 95 Comparative Example 1 3901,4501302000.1 95 Comparative Example 2 306095095780 Unmeasurable 95 Comparative Example 3 30110940951900.1 95 Reference Example 2) --1,300130800 Unmeasured NA 3) 1) Unmeasurable: Oxygen permeability could not be measured due to good air permeability. 2) Reference example: Basis weight approx. 30 g / m² 2 LDPE film (Daemyung Chemical Co.) 3) NA: Not biodegradable

[0279]

[0280] As can be seen in Tables 1 and 2 above, it was confirmed that the breathable films according to Examples 1 to 6 have superior breathability compared to the breathable films according to Comparative Examples 1 to 3, and that the mechanical properties of tensile strength and elongation required for the film are improved.

[0281] In addition, the breathable films according to Examples 1 to 6 have mechanical properties equivalent to those of the conventional films according to the reference examples, while being biodegradable, so that the mechanical properties of conventionally used films can be satisfied, and environmental pollution caused by waste can be prevented.

[0282]

[0283] The example can be applied to a biodegradable resin composition for a breathable film and a breathable film containing the same.

Claims

1. A biodegradable resin comprising an aliphatic-aromatic polyester resin; and It includes an inorganic filler containing calcium carbonate, The above biodegradable resin has a melt index of greater than 3 g / 10 min and less than 30 g / 10 min at 190 ℃ and 2.16 kg according to ASTM D1238, and A biodegradable resin composition for a breathable film having a water contact angle of less than 90° of the calcium carbonate.

2. In Paragraph 1, The above biodegradable resin is a biodegradable resin composition for a breathable film that includes a crystallization promoter.

3. In Paragraph 1, Average particle size (D of the above calcium carbonate) 50 A biodegradable resin composition for breathable films having a thickness greater than 2 μm and less than 8 μm.

4. In Paragraph 1, The span (D) of the above calcium carbonate 90 -D 10 / D 50 A biodegradable resin composition for breathable films in which ) is greater than 5 and less than 20.

5. In Paragraph 1, A biodegradable resin composition for a breathable film having a calcium oxide content of less than 0.01 volume % based on 100 volume % of the calcium carbonate.

6. In Paragraph 1, A biodegradable resin composition for a breathable film, wherein the surface free energy of the calcium carbonate is greater than 100 mN / m and less than 300 mN / m.

7. In Paragraph 1, A biodegradable resin composition for a breathable film, wherein the content of the above-mentioned inorganic filler is 40% by weight to 70% by weight based on the total weight of the biodegradable resin composition for a breathable film.

8. In Paragraph 1, A biodegradable resin composition for a breathable film, wherein the content of the inorganic filler is 80 to 200 parts by weight based on 100 parts by weight of the biodegradable resin.

9. In Paragraph 1, The above biodegradable resin composition for a breathable film comprises a lubricant containing calcium.

10. A biodegradable resin comprising an aliphatic-aromatic polyester resin; and It includes an inorganic filler containing calcium carbonate, The above biodegradable resin has a melt index of greater than 3 g / 10 min and less than 30 g / 10 min at 190 ℃ and 2.16 kg according to ASTM D1238, and A breathable film of the above calcium carbonate with a water contact angle of less than 90°.

11. In Paragraph 10, The above breathable film has a basis weight of 30 g / m² 2 Based on the standard Water vapor transmission rate (WVTR) is 200 g / m 2 · Breathable film exceeding 24 hours.

12. In Paragraph 10, The above breathable film has a basis weight of 30 g / m² 2 A breathable film having a longitudinal (MD) tensile strength exceeding 1,300 g / inch at the standard.

13. In Paragraph 10, The above breathable film has a basis weight of 30 g / m² 2 A breathable film having a longitudinal (MD) elongation of more than 120% at the standard.

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