Biodegradable resin composition for printing and printing sheet comprising same

Abstract

The present invention provides a biodegradable resin composition for printing and a printing sheet comprising same, the biodegradable resin composition comprising: a biodegradable resin comprising an aliphatic-aromatic polyester resin and an aliphatic polyester resin; an inorganic filler comprising calcium carbonate; and an opacifying agent, wherein the biodegradable resin composition has a melt index of greater than 3 g / 10 min and less than 20 g / 10 min at 190°C and 2.16 kg according to ASTM D1238, and has a haze of greater than 1% and less than 30%, as measured on a 1-mm thick specimen according to ASTM D1003.

Description

Biodegradable resin composition for printing and printing sheet comprising the same

[0001] The present invention relates to a biodegradable resin composition for printing and a printing sheet 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, the applications of PLA and PBAT were limited due to their lack of flexibility and poor mechanical properties, respectively. In particular, when the aforementioned biodegradable resins were used as printing sheets, there was a problem where the readability of text and images printed on the sheet was reduced due to high light transmittance. Furthermore, due to the characteristics of the biodegradable resins, it was difficult to ensure smooth flowability, making it difficult to manufacture sheets of uniform size and consequently leading to reduced production efficiency. Additionally, when inorganic materials were included to reduce light transmittance, there were problems with degraded printability and mechanical properties.

[0006]

[0007] The present invention provides a biodegradable resin composition for printing with improved opacity and improved processability, printability, and mechanical properties, and a printing sheet comprising the same.

[0008]

[0009] The biodegradable resin composition for printing according to the present invention comprises an aliphatic-aromatic polyester resin and a biodegradable resin including the aliphatic polyester resin, an inorganic filler including calcium carbonate, and an opacifying agent, wherein the melt index at 190°C and 2.16 kg according to ASTM D1238 is greater than 3 g / 10 min and less than 20 g / 10 min, and the haze of a 1 mm thick specimen according to ASTM D1003 is greater than 1% and less than 30%.

[0010] In one embodiment of the present invention, the weight ratio of the aliphatic-aromatic polyester resin to the aliphatic polyester resin may be 1:1 to 2:1.

[0011] In one embodiment of the present invention, the content of the inorganic filler may be greater than 30 weight % and less than 60 weight % based on the total weight of the biodegradable resin composition for printing.

[0012] In one embodiment of the present invention, the content of the opacifying agent may be greater than 3 weight % and less than 10 weight % based on the total weight of the printing biodegradable resin composition.

[0013] In one embodiment of the present invention, the opacifying agent may include titanium dioxide (TiO2) surface-treated with an organic acid.

[0014] In one embodiment of the present invention, the average particle size (D) of the titanium dioxide 50 ) may be greater than 0.1 μm to less than 0.5 μm.

[0015] In one embodiment of the present invention, the oil absorption of the titanium dioxide may be greater than 10 g / 100g and less than 30 g / 100g.

[0016] In one embodiment of the present invention, the moisture content of the titanium dioxide may be less than 4,000 ppm based on the total weight of the titanium dioxide.

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

[0018] The printing sheet according to the present invention comprises a printing biodegradable resin composition comprising an aliphatic-aromatic polyester resin and a biodegradable resin including an aliphatic polyester resin, an inorganic filler including calcium carbonate, and an opacifying agent, wherein the printing biodegradable resin composition has a melt index at 190°C and 2.16 kg according to ASTM D1238 greater than 3 g / 10 min and less than 20 g / 10 min, and a haze of a 1 mm thick specimen according to ASTM D1003 greater than 1% and less than 30%.

[0019] In one embodiment of the present invention, the printing sheet may have a contact angle with water greater than 50° and less than 90°.

[0020] In one embodiment of the present invention, when the printing sheet is measured with a three-dimensional roughness measuring instrument, the average surface roughness (Sa) according to ISO 25178 may be greater than 0.8 μm and less than 0.9 μm.

[0021] In one embodiment of the present invention, the printing sheet may have a surface energy according to ISO 8296 of greater than 34 mN / m and less than 45 mN / m.

[0022] In one embodiment of the present invention, the printing sheet may be for business cards.

[0023]

[0024] The resin composition according to the present invention comprises a biodegradable resin. As a result, a printing sheet produced from the resin composition can be easily decomposed after disposal. Furthermore, the biodegradable resin comprises an aliphatic-aromatic polyester resin and an aliphatic polyester resin having mutually complementary properties. As a result, the printing sheet comprising the biodegradable resin exhibits flexibility, and printability and mechanical properties can be improved.

[0025] The resin composition according to the present invention comprises an inorganic filler containing calcium carbonate. As a result, the relative proportion of the biodegradable resin can be reduced, thereby improving economic efficiency, and the flowability of the biodegradable resin can be improved, allowing for the production of a uniform sheet and improved production efficiency.

[0026] The resin composition according to the present invention includes an opacifying agent, and the haze and melt index are controlled within a specific range. As a result, light transmittance can be reduced, thereby improving the readability of printed characters and images. In addition, printability and mechanical properties are improved, allowing patterns to be printed cleanly, suppressing peeling of the printed ink, and enhancing durability.

[0027]

[0028] 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.

[0029] 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.

[0030] In this specification or application, 'ppm' refers to a weight basis.

[0031] In this specification or application, the description of "A and / or B" means "A, B, or A and B".

[0032]

[0033] The biodegradable resin composition for printing according to the present invention comprises an aliphatic-aromatic polyester resin and a biodegradable resin comprising an aliphatic polyester resin.

[0034] By including the above-mentioned aliphatic-aromatic polyester resin, the brittleness of the aliphatic polyester resin can be compensated for, and the flexibility of the printed sheet being manufactured can be improved. The above-mentioned aliphatic-aromatic polyester resin may include a diol-derived unit, an aliphatic dicarboxylic acid-derived unit, and an aromatic dicarboxylic acid-derived unit.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] When the aliphatic-aromatic polyester resin comprises the first block and the second block within the above range, the printing sheet comprising the aliphatic-aromatic polyester resin can have appropriate mechanical strength while improving biodegradability.

[0050] The above aliphatic-aromatic polyester resin may include the following bonding structures 1 to 3.

[0051] [Coupling Structure 1]

[0052] - Aromatic dicarboxylic acid - Diol - Aliphatic dicarboxylic acid -

[0053] [Combination Structure 2]

[0054] - Aromatic dicarboxylic acid - Diol - Aromatic dicarboxylic acid -

[0055] [Combination Structure 3]

[0056] - Aliphatic dicarboxylic acid - Diol - Aliphatic dicarboxylic acid -

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] The above-mentioned alternation ratio can be calculated using the following formula 1.

[0063] [Formula 1]

[0064]

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] The above hard segment ratio can be expressed by the following formula 2.

[0070] [Equation 2]

[0071]

[0072] 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.

[0073] 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.

[0074] The above aliphatic-aromatic polyester resin may include soft segments.

[0075] 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.

[0076] 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.

[0077] The above soft segment ratio can be expressed by the following formula 3.

[0078] [Equation 3]

[0079]

[0080] 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.

[0081] 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.

[0082] The above soft segment ratio may be larger than the above hard segment ratio.

[0083] 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.

[0084] 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.

[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 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] The above alternating ratio can be derived using the following Equation 4 or Equation 5.

[0096] [Equation 4]

[0097]

[0098] 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.

[0099] [Formula 5]

[0100]

[0101] 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.

[0102] The above hard segment ratio can be derived using the following formula 6 or the following formula 7.

[0103] [Equation 6]

[0104]

[0105] 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.

[0106] [Equation 7]

[0107]

[0108] 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.

[0109] The above soft segment ratio can be derived using the following formula 8 or formula 9.

[0110] [Equation 8]

[0111]

[0112] 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.

[0113] [Formula 9]

[0114]

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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).

[0119] 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.

[0120] 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 ).

[0121] Specifically, it can be calculated according to the following formula.

[0122] [Calculation Formula]

[0123] 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

[0124] 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 printed sheet being manufactured may be secured.

[0125] The content of the aliphatic-aromatic polyester resin may be 20% to 50% by weight, 25% to 50% by weight, 25% to 45% by weight, or 28% to 45% by weight based on the total weight of the biodegradable resin composition for printing. When the above range is satisfied, processability may be improved, and mechanical properties that allow for functionality as a printing sheet may be satisfied.

[0126] The above biodegradable resin includes an aliphatic polyester resin. By including the above aliphatic polyester resin, the strength and stiffness of the above aliphatic-aromatic polyester resin can be supplemented, and the surface smoothness and ink adhesion of the manufactured printing sheet can be improved.

[0127] 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 for printing, thereby minimizing changes in volume during the extrusion process of the biodegradable resin composition for printing.

[0128] The content of the aliphatic polyester resin may be greater than 10% by weight and less than 40% by weight, 15% by weight and less than 40% by weight, 15% by weight and 35% by weight, or 15% by weight and 30% by weight, based on the total weight of the biodegradable resin composition for printing. When the above range is satisfied, the mechanical properties, surface smoothness, and ink adhesion of the printing sheet produced may be improved.

[0129] The above aliphatic polyester resin may contain polylactic acid.

[0130] The above polylactic acid may include a unit represented by the following chemical formula 1.

[0131] [Chemical Formula 1]

[0132]

[0133] 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.

[0134] 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.

[0135] 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 properties of the printed sheet being manufactured may be improved.

[0136] The weight ratio of the aliphatic-aromatic polyester resin to the aliphatic polyester resin may be 1:1 to 2:1, 1:1 to 1.9:1, 1:1 to 1.8:1, or 1:1 to 1.5:1. When the above range is satisfied, the printing sheet produced may have appropriate flexibility and mechanical properties, and surface smoothness and ink adhesion may be improved.

[0137] The number average molecular weight of the above-described biodegradable resin composition for printing may vary depending on the content ratio of the aliphatic-aromatic polyester resin and the aliphatic polyester resin. Additionally, the melt index of the above-described biodegradable resin composition for printing may vary depending on the number average molecular weight and / or the degree of bonding between the aliphatic-aromatic polyester resin and the aliphatic polyester resin.

[0138] The above aliphatic polyester resin can be modified by a surface treatment agent.

[0139] 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 compatibility with an aliphatic-aromatic polyester resin can be improved, and the bleeding phenomenon in which the aliphatic polyester resin flows out onto the surface of the printed sheet product can be suppressed.

[0140] The above surface treatment agent may include an amide group. The above 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, so that compatibility with the aliphatic-aromatic polyester resin can be improved and bleeding phenomena can be more suppressed.

[0141] The above surface-modified aliphatic polyester resin can be manufactured by the following method.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] The above 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 biodegradable resin containing the nanocellulose may all be improved.

[0146] 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 for printing may be further improved.

[0147] 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.

[0148] 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.

[0149] The nanocellulose above performs the function of a crystal nucleating agent, thereby increasing the crystallization rate and crystallization temperature of the biodegradable resin composition for printing. 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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 for printing containing the same.

[0154] The above 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 above biodegradable resin. When the above range is satisfied, the biodegradability and mechanical strength of the printing biodegradable resin composition may be further improved.

[0155] The biodegradable resin composition for printing according to the present invention comprises an inorganic filler comprising calcium carbonate. By including the inorganic filler comprising calcium carbonate in the biodegradable resin composition for printing, the relative proportion of the biodegradable resin can be reduced, thereby improving economic efficiency. Additionally, the flowability of the biodegradable resin can be improved, thereby improving the uniformity of the manufactured sheet.

[0156] The content of the inorganic filler may be greater than 30 weight % and less than 60 weight %, 35 weight % and less than 60 weight %, 40 weight % and less than 60 weight %, or 40 weight % and 50 weight % based on the total weight of the biodegradable resin composition for printing. When the above range is satisfied, the flowability of the biodegradable resin can be improved without degrading the mechanical properties of the printing sheet due to the extrusion process. In addition, dimensional stability is improved, so that changes in the volume of the printing sheet due to changes over time after the extrusion process can be minimized. Furthermore, the surface gloss of the printing sheet can be increased, thereby improving the appearance quality.

[0157] The above-mentioned 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 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. The calcium carbonate 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.

[0158] When the above-mentioned inorganic filler includes calcium carbonate having the above-mentioned average particle size range, dispersibility within the above-mentioned biodegradable resin composition for printing can be improved, and an excessive increase in viscosity of the above-mentioned biodegradable resin composition for printing can be suppressed. Furthermore, the above-mentioned heavy calcium carbonate may have increased tensile strength compared to light calcium carbonate, thereby improving the mechanical properties of the above-mentioned biodegradable resin composition for printing. Additionally, damage to the surface properties and mechanical strength of the above-mentioned printing sheet can be suppressed by preventing the above-mentioned inorganic filler from protruding or detaching from the surface of the printing sheet due to the extrusion process. Moreover, the above-mentioned heavy calcium carbonate may react with acidic components that may be generated during the biodegradation of the printing sheet to produce CO2 and H2O, thereby further enhancing the biodegradation rate of the printing sheet at the molecular level. Furthermore, the above-mentioned heavy calcium carbonate can neutralize the acidic components, thereby reducing the environmental burden and preventing soil acidification.

[0159] 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 2 It 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 a biodegradable resin, thereby promoting biodegradability.

[0160] The sphericity of the heavy calcium carbonate above 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 satisfying the above range, it may contain a large number of fine pores generated at the interface between the biodegradable resin and the inorganic filler, thereby improving biodegradability.

[0161] 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 for printing may be increased, and the reactivity with the 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.

[0162] The above-mentioned surface-treated heavy calcium carbonate can be manufactured by the following method.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] The biodegradable resin composition for printing according to the present invention includes an opacifying agent, and has a melt index at 190°C and 2.16 kg according to ASTM D1238 greater than 3 g / 10 min and less than 20 g / 10 min, and a haze of a 1 mm thick specimen according to ASTM D1003 greater than 1% and less than 30%.

[0169] Conventionally, when biodegradable resin compositions for printing included biodegradable resin, there was a problem where the readability of text and images was reduced due to high light transmittance. Furthermore, due to the characteristics of the biodegradable resin, it was difficult to ensure smooth resin flowability, making it difficult to manufacture sheets of uniform size and consequently leading to reduced production efficiency. Additionally, when inorganic materials were included to reduce light transmittance, there was a problem of degraded printability and mechanical properties. The inventors confirmed that by including an opacifying agent in the biodegradable resin composition for printing and controlling the melt index and haze to a specific range, light transmittance is reduced, thereby improving the readability of printed text and images. Furthermore, it was confirmed that production efficiency is improved because the resin exhibits smooth flowability, allowing for the manufacture of sheets of uniform size. Additionally, it was confirmed that printability and mechanical properties are improved, resulting in clean pattern printing, the absence of ink peeling, and enhanced durability of the sheet.

[0170] The content of the opacifying agent may be greater than 3 weight % and less than 10 weight %, greater than 3 weight % and 9 weight %, greater than 3 weight % and 8 weight %, or greater than 3 weight % and 7 weight % based on the total weight of the printing biodegradable resin composition. When the above range is satisfied, the haze of the printing sheet produced may be increased, thereby improving the readability of characters and images. In addition, the printing biodegradable resin composition may have an appropriate melt index, thereby improving production efficiency, printability, and mechanical properties.

[0171] The above opacifying agent may include inorganic materials. The above opacifying agent may be selected from one or more of the group consisting of titanium dioxide (TiO2), alumina (Al2O3), zirconia (ZrO2), zinc oxide (ZnO), tin oxide (SnO2), and iron oxide. In terms of UV blocking effect, improvement of whiteness and color clarity, and improvement of chemical resistance, it is preferable for the above opacifying agent to include titanium dioxide.

[0172] The above-mentioned opacifying agent may include titanium dioxide (TiO2) surface-treated with an organic acid. The surface treatment can improve the dispersibility, water resistance, and chemical resistance of the titanium dioxide. Additionally, the optical properties of the titanium dioxide can be improved, allowing the haze-increasing effect to appear uniformly. Furthermore, the surface energy of the titanium dioxide can be controlled, thereby suppressing printability and the peeling of the printed ink.

[0173] The above 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. The above organic acid may include higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acids, etc., and may be, for example, calcium stearate.

[0174] Average particle size (D of the above titanium dioxide) 50 ) may be greater than 0.1 μm to less than 0.5 μm, 0.15 μm to less than 0.5 μm, 0.15 μm to 0.4 μm, 0.2 μm to 0.4 μm, or 0.25 μm to 0.35 μm.

[0175] The oil absorption of the titanium dioxide may be greater than 10 g / 100g and less than 30 g / 100g, 15 g / 100g and 25 g / 100g, 15 g / 100g and 22 g / 100g, or 17 g / 100g and 22 g / 100g.

[0176] If the above range is satisfied, the kneading ability with the biodegradable resin and the printability in the manufactured printing sheet can be improved.

[0177] The moisture content of the titanium dioxide may be less than 4,000 ppm, less than 3,800 ppm, less than 3,600 ppm, or less than 3,000 ppm based on the total weight of the titanium dioxide. When the above range is satisfied, the aggregation phenomenon of the titanium dioxide can be minimized, and the printability of the printed sheet being manufactured can be improved.

[0178] The above-mentioned biodegradable resin composition for printing may include a heat stabilizer.

[0179] The above heat stabilizer may be selected from one or more of the group consisting of metal salt stabilizers, organotin stabilizers, phosphate esters, phenolic antioxidants, phosphate stabilizers, polymeric stabilizers, and basic magnesium oxide.

[0180] The above heat stabilizer may include the above phosphate ester system.

[0181] The above phosphate ester system has excellent thermal stability, so discoloration of the biodegradable resin at high temperatures can be minimized. In addition, it has excellent compatibility with the above biodegradable resins, does not easily evaporate under high temperature conditions, is environmentally friendly, and can improve plasticizing properties. Specifically, the above phosphate ester system may be a phosphate octadecyl ester.

[0182] The content of the heat stabilizer may be 0.1% to 3% by weight, 0.1% to 2% by weight, 0.1% to 1% by weight, or 0.1% to 0.5% by weight based on the total weight of the biodegradable resin composition for printing. When the above range is satisfied, the degradation of the biodegradable resin under high temperature conditions can be controlled, so that the color is maintained stably and weight change is minimized.

[0183] The above-degradable resin composition for printing 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 20 g / 10 min, greater than 3 g / 10 min to 15 g / 10 min, greater than 3 g / 10 min to 10 g / 10 min, or greater than 3 g / 10 min to 5 g / 10 min. The melt index may be adjusted according to the content of the aliphatic-aromatic polyester resin, the melt index of the aliphatic-aromatic polyester resin, the content of the aliphatic polyester resin, the melt index of the aliphatic polyester resin, the content of the inorganic filler, and / or the content of the opacifying agent. When the above range is satisfied, the production efficiency, printability, and mechanical properties of the printed sheet produced may be improved.

[0184] The above-degradable resin composition for printing may have a haze of more than 1% to less than 30%, more than 1% to 20%, more than 1% to 15%, or 5% to 10% in a 1 mm thick specimen according to ASTM D1003. The haze may be controlled according to the content of the inorganic filler and / or the type and content of the opacifying agent. When the above range is satisfied, the readability of text and images on the printed sheet produced may be improved.

[0185] The above-degradable resin composition for printing may include an antioxidant. The antioxidant may include one or more selected from the group consisting of phosphorus-based antioxidants, phenol-based antioxidants, and pentaerythritol-based antioxidants.

[0186] 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.

[0187] 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.

[0188] Preferably, the above-mentioned biodegradable resin composition for printing may include a phosphate ester-based (Phosphite) antioxidant. The phosphate ester-based antioxidant has excellent high-temperature stability and excellent radical capture and peroxide decomposition performance, so the thermal stability and long-term storage stability of the printing sheet produced by the extrusion process can be improved.

[0189] 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, greater than 0 wt% to 5 wt%, 0.01 wt% to 4 wt%, 0.1 wt% to 3 wt%, 1 wt% to 3 wt%, 1 wt% to 2 wt%, 0.01 wt% to 0.3 wt%, 0.05 wt% to 0.3 wt%, 0.15 wt% to 0.3 wt%, or 0.2 wt% to 0.3 wt%, based on the total weight of the biodegradable resin composition for printing.

[0190] The above-mentioned biodegradable resin composition for printing may further include a lubricant.

[0191] 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 stearoamide, aliphatic ester-based lubricants such as stearate-n-butyl, methyl hydroxystearate, polyhydric alcohol fatty acid esters, saturated fatty acid esters, and ester-based waxes, and fatty acid metal soap-based lubricants. Specifically, the above lubricant may be a stearate-based lubricant.

[0192] Preferably, the above-mentioned biodegradable resin composition for printing may further include a lubricant containing calcium. Specifically, the lubricant may be calcium stearate. The calcium stearate-based lubricant has the same calcium component as the calcium carbonate, thereby having excellent compatibility, reducing heat generation due to friction during raw material mixing, melting, and processing, providing excellent dispersion effect on the biodegradable resin relative to cost, and having a superior lubricating effect, which can improve manufacturing efficiency.

[0193] More preferably, the above-degradable resin composition for printing may further include a calcium-containing lubricant and a stearyl stearate-based lubricant. The weight ratio of the calcium-containing lubricant to the stearyl stearate-based lubricant may be 1:3 to 3:1, 1:2.5 to 2.5:1, 1:2 to 2:1, or 1:1.5 to 1.5:1. When the above ranges are satisfied, the compatibility between the calcium-containing lubricant and the calcium carbonate is improved, and due to the excellent lubricity of the stearyl stearate-based lubricant, the production speed of the printing sheet according to the extrusion process may be improved.

[0194] 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 above-mentioned biodegradable resin composition for printing. When the above range is satisfied, manufacturing efficiency can be improved without deteriorating the mechanical properties of the above-mentioned biodegradable resin composition for printing.

[0195] The above-degradable resin composition for printing 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.

[0196] 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.

[0197] 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.

[0198] The above metal hydrate may include aluminum trihydrate, magnesium dihydrate, or a combination thereof.

[0199] 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.

[0200] The above-degradable resin composition for printing 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.

[0201] 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 printing biodegradable resin composition.

[0202] The above-degradable resin composition for printing may include a chain extender. The chain extender may include one or more selected from the group consisting of aromatic diisocyanates, aliphatic diisocyanates, isocyanurates, bisoxazoline, carboxylic acid anhydrides, and epoxides.

[0203] 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.

[0204] 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).

[0205] The above isocyanurate may include isophorone diisocyanate or methylenebis(4-isocyanatocyclohexane).

[0206] 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.

[0207] 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.

[0208] 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 for printing, and may be 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 %.

[0209] The above-described biodegradable resin composition for printing may include a hydrolysis inhibitor. If the weight-average molecular weight (Mw) of the hydrolysis inhibitor is high, volatility may be low and water resistance may be improved, and if the weight-average molecular weight (Mw) of the hydrolysis inhibitor is low, compatibility with the biodegradable resin may be increased.

[0210] The above hydrolysis inhibitor may use two types of hydrolysis inhibitors with different weight-average molecular weights. To increase compatibility with the biodegradable resin, one type of hydrolysis inhibitor with a weight-average molecular weight (Mw) of 10,000 g / mol or less, 9,000 g / mol or less, 8,000 g / mol or less, 7,000 g / mol or less, 6,000 g / mol or less, or 5,000 g / mol or less may be used, and to improve low volatility and water resistance, one type of hydrolysis inhibitor with a weight-average molecular weight of 10,000 g / mol or more, 20,000 g / mol or more, 30,000 g / mol or more, 40,000 g / mol or more, or 50,000 g / mol or more may be used. The weight-average molecular weight can be measured as a relative value to a standard PS (standard polystyrene) sample via GPC using THF as the eluent. If the above range is satisfied, the mechanical properties and water resistance of the printing biodegradable resin composition can be improved.

[0211] The above hydrolysis inhibitor may include a carbodiimide-based compound. The carbodiimide-based compound reacts with moisture and acid to convert into a urea structure, thereby reducing the reactivity between moisture and acid and the ester groups contained in the biodegradable resin. Consequently, the phenomenon of hydrolysis of the biodegradable resin by moisture and acid can be reduced, and consequently, the water resistance of the printing biodegradable resin composition can be improved.

[0212] The above carbodiimide-based compound may include a compound represented by the following chemical formula 2.

[0213] [Chemical Formula 2]

[0214]

[0215] In the above chemical formula 2, n is an integer from 1 to 20.

[0216] 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.

[0217] The weight-average molecular weight (Mw) 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.

[0218] 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, compatibility with the above biodegradable resin is not reduced, and the water resistance of the above printing biodegradable resin composition may be improved.

[0219] Based on the total weight of the above-mentioned biodegradable resin composition for printing, 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. When the above range is satisfied, the water resistance and odor reduction effect of the above-mentioned biodegradable resin composition for printing may be improved.

[0220] The above-degradable resin composition for printing may contain a compound containing urea groups in an amount of 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 above-degradable resin composition for printing. When the above range is satisfied, the proportion of ester groups included in the biodegradable resin that can react with moisture or acid is reduced, and water resistance may be improved.

[0221] The printing sheet according to the present invention comprises a printing biodegradable resin composition comprising an aliphatic-aromatic polyester resin and a biodegradable resin including an aliphatic polyester resin, an inorganic filler including calcium carbonate, and an opacifying agent, wherein the printing biodegradable resin composition has a melt index at 190°C and 2.16 kg according to ASTM D1238 greater than 3 g / 10 min and less than 20 g / 10 min, and a haze of a 1 mm thick specimen according to ASTM D1003 greater than 1% and less than 30%.

[0222] The above-mentioned biodegradable resin composition for printing may be the same as the aforementioned biodegradable resin composition for printing.

[0223] The above printing sheet may have a contact angle with water of greater than 50° to less than 90°, 55° to 85°, 55° to 80°, or 65° to 80°. The contact angle can be measured by filling a cylinder with water, dropping about 2 μl onto the surface of the printing sheet, and then using a DMe-210 (KYOWA). If the above range is satisfied, ink bleeding during printing is suppressed, and ink adhesion can be improved.

[0224] When measuring the above printing sheet with a 3D roughness measuring instrument, the average surface roughness (Sa) according to ISO 25178 may be greater than 0.8 μm and less than 0.9 μm, 0.805 μm to 0.88 μm, 0.805 μm to 0.87 μm, or 0.81 μm to 0.87 μm. The above average surface roughness may mean extracting only the reference length in the direction of the average line from the roughness curve, measuring the distance between the curve line and the curve line of this extracted portion in the direction of the vertical scale of the roughness curve, and expressing this value in micrometers (μm). If the above range is satisfied, ink adsorption is improved, ink bleeding is suppressed, and ink drying time and print quality may be improved.

[0225] The printing sheet above may have a surface energy according to ISO 8296 of greater than 34 mN / m and less than 45 mN / m, 35 mN / m and 44 mN / m, 36 mN / m and 44 mN / m, or 40 mN / m and 44 mN / m. When satisfying the above range, it may have a relatively high surface tension compared to the surface tension of the ink, so that the printing quality can be improved.

[0226] The above printing sheet may have a transmissive light (TT) of less than 99%, less than 98%, less than 97%, less than 96.8%, or between 96% and less than 96.8% on a 1 mm thick specimen according to ASTM D1003. If the above range is satisfied, the readability of printed text and images may be improved.

[0227] The above-mentioned printing sheet can be used for conveying information and visual representation.

[0228] The above printing sheet can be used for banners, posters, placards, food packaging materials, industrial packaging materials, brochures, pamphlets, catalogs, labels, etc.

[0229] Preferably, the printing sheet can be used for business cards. When the printing sheet is used for business cards, clear images and high-resolution text required for business cards can be realized. In addition, due to its excellent flexibility and durability, the business card can be prevented from being easily crumpled or damaged. Furthermore, as a biodegradable material, it is recyclable and can be used as an eco-friendly business card to emphasize eco-brands or sustainability.

[0230] The above printing sheet may have a biodegradability of 90% to 100%, 91% to 100%, 91% to 99%, or 92% to 99% according to the following evaluation method. If the above range is satisfied, the printing sheet can be easily decomposed after disposal.

[0231] [Biodegradability Evaluation Method]

[0232] 1) A sample is prepared by grinding a biodegradable resin composition for printing.

[0233] 2) Prepare an inoculum container containing only compost (Manufacturer: Taeheung F&G, Product Name: Jisengto (Grade 1 By-product Fertilizer Compost)). Separately, prepare a test container in which the compost and the sample are mixed in a weight ratio of 6:1 based on the dry weight of the compost.

[0234] 3) The above inoculum container and test container are 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.

[0235] 4) After capturing the CO2 generated in each container, the amount of CO2 generated in each container is measured by titrating with an aqueous phenolphthalein solution. The biodegradability of a reference (cellulose), which serves as the evaluation standard for biodegradability, is calculated according to the following formula. The biodegradability of the above samples is calculated according to the following formula, and then a relative biodegradability value is calculated based on 100% biodegradability of the above reference.

[0236] [ceremony]

[0237] Biodegradability (%) = [(CO2 emissions from test container) - (CO2 emissions from inoculum container)] / (Theoretical CO2 emissions from test container) × 100

[0238]

[0239] 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.

[0240]

[0241] Examples

[0242] - Aliphatic-aromatic polyester resin: PBAT (SK Livio)

[0243] - Aliphatic polyester resin: PLA (NatureWorks 3251D)

[0244] - Inorganic filler: Calcium carbonate (AMC, NSS-500C)

[0245] - Opaqueant: TiO2 (D2) surface-treated with organic acid 50 0.3 µm, Oil Absorption 19.6 g / 100g, Moisture 0.3 wt%

[0246] - Chain extender: BASF's Joncryl

[0247] - Lubricant #1: Calcium Stearate

[0248] - Lubricant #2: Stearyl Stearate

[0249] - Antioxidant #1: Phenolic antioxidant (Adeka, AO-80)

[0250] - Antioxidant #2: Phosphorus-based antioxidant (Adeka 2112)

[0251]

[0252] Example 1

[0253] A resin composition mixed with 31.6 wt% aliphatic-aromatic polyester resin, 20 wt% aliphatic polyester resin, 42 wt% inorganic filler, 5 wt% opacifying agent, 0.2 wt% chain extender, 0.5 wt% lubricant #1, 0.5 wt% lubricant #2, 0.1 wt% antioxidant #1, and 0.1 wt% antioxidant #2 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.

[0254] Subsequently, the extruded resin composition was cut and cooled using a hot-cut pellet cutter to produce a pelletized resin composition.

[0255]

[0256] Examples 2 to 3 and Comparative Examples 1 to 4

[0257] A resin composition was prepared by the same process as in Example 1, except that the composition and content listed in Table 1 below were applied.

[0258]

[0259] Classification Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Aliphatic-aromatic polyester resin 31.6 wt% 33.6 wt% 31.6 wt% 31.6 wt% 75.6 wt% 28.6 wt% 28.6 wt% Aliphatic polyester resin 20 wt% 20 wt% 20 wt% 20 wt% --- Inorganic filler 42 wt% 40 wt% 41.5 wt% 42 wt% 18 wt% 70 wt% 60 wt% Opaquer 5 wt% 5 wt% 5.5 wt% - 5 wt% - 10 wt% Chain extender 0.2 wt% 0.2 wt% 0.2 wt% 0.2 wt% 0.2 wt% 0.2 wt% Lubricant # 10.5 wt% 0.5 wt% 0.5 wt% 0.5 wt% 0.5 wt% 0.5 wt% 0.5 wt% Lubricant #20.5 wt% 0.5 wt% 0.5 wt% 0.5 wt% 0.5 wt% 0.5 wt% 0.5 wt% Antioxidant #10.1 wt% 0.1 wt% 0.1 wt% 0.1 wt% 0.1 wt% 0.1 wt% 0.1 wt% Antioxidant #20.1 wt% 0.1 wt% 0.1 wt% 0.1 wt% 0.1 wt% 0.1 wt% 0.1 wt% 0.1 wt%

[0260]

[0261] Experimental Example

[0262] Each of the pelletized resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was placed on a flat stainless steel (SUS) plate with a width of 12 cm and a length of 12 cm, and then a specimen of a printing sheet having an average thickness of about 1 mm was prepared under conditions of a temperature of about 180 ℃ and a pressure of about 20 Mpa.

[0263]

[0264] Experimental Example 1 - Melt Index

[0265] For the resin compositions used in Examples 1 to 3 and Comparative Examples 1 to 4 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.

[0266]

[0267] Experimental Example 2 - Haze

[0268] For each specimen prepared in Examples 1 to 3 and Comparative Examples 1 to 4 above, haze according to ASTM D1003 was measured using a standard colorimeter, and the results are shown in Table 2 below.

[0269]

[0270] Experimental Example 3 - Average Surface Roughness (Sa)

[0271] For each specimen prepared in Examples 1 to 3 and Comparative Examples 1 to 4 above, the average surface roughness according to ISO 25178 was measured using a 3D roughness measuring instrument, and the results are shown in Table 2 below.

[0272]

[0273] Experimental Example 4 - Contact Angle

[0274] For each specimen prepared in Examples 1 to 3 and Comparative Examples 1 to 4 above, water was filled into a cylinder, and then about 2 μl of the water was dropped onto the surface of the specimen. The contact angle with water was then measured using a DMe-210 (KYOWA). The results are shown in Table 2 below.

[0275]

[0276] Experimental Example 5 - Surface Energy

[0277] For each specimen prepared in Examples 1 to 3 and Comparative Examples 1 to 4 above, the surface energy of the specimen was measured in accordance with ISO 8296, and the results are shown in Table 2 below.

[0278]

[0279] Experimental Example 6 - Fairness

[0280] Each specimen prepared in Examples 1 to 3 and Comparative Examples 1 to 4 was evaluated according to the following criteria, and the results are shown in Table 2 below.

[0281] - ○: Excellent extrusion process, uniform specimen size

[0282] - △: Extrusion process good, thickness of manufactured specimen is partially non-uniform

[0283] - ×: Inadequate extrusion process, non-uniformity in thickness and size of manufactured specimens

[0284]

[0285] Experimental Example 7 - Printability

[0286] For each specimen prepared in Examples 1 to 3 and Comparative Examples 1 to 4 above, a test pattern was printed using oil-based offset ink. After visual inspection of the results after printing, they were evaluated according to the following criteria, and the results are shown in Table 2 below.

[0287] - ○: Patterns are printed cleanly, and there is no ink peeling.

[0288] - △: The pattern was printed well, but slight ink peeling occurred.

[0289] - ×: Poor pattern printing and significant ink peeling

[0290]

[0291] Experimental Example 8 - Mechanical Properties

[0292] For each specimen prepared in Examples 1 to 3 and Comparative Examples 1 to 4 above, tensile strength and elongation at break were measured according to ASTM D638 using an INSTRON Universal Testing Machine (UTM, 4206-001), and evaluated according to the following criteria. The results are shown in Table 2 below.

[0293] - Excellent: Tensile strength exceeding 40 MPa and elongation at break exceeding 300%

[0294] - Good: Tensile strength exceeding 40 MPa or elongation at break exceeding 300%

[0295] - Insufficient: Tensile strength 40 MPa or less and elongation at break 300% or less

[0296]

[0297] Classification Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Melt Index 4g / 10min 3.5g / 10min 3.5g / 10min 6g / 10min 2.5g / 10min 35g / 10min 25g / 10min Haze 7% 6.5% 7% 1% 5% 1% 30% Average Surface Roughness (Sa) 0.825 µm 0.814 µm 0.821 µm 0.637 µm 0.582 µm 2.255 µm 2.138 µm Contact Angle 74° 76° 75° 90° 92° 45° 50° Surface Energy 42 mN / m 41 mN / m 41 mN / m 32 mN / m 33 mN / m 25 mN / m 28 mN / m Processability ○○○○×△△ Printability ○○○△△×× Mechanical Properties Excellent Excellent Excellent Excellent Excellent Poor Poor

[0298]

[0299] As can be seen in Tables 1 to 2 above, the biodegradable resin compositions for printing used in Examples 1 to 3 and the printing sheets prepared therefrom satisfy a certain range of haze compared to Comparative Examples 1 to 4, thereby improving the readability of printed characters and images. In addition, by satisfying a melt index greater than 3 g / 10 min and less than 20 g / 10 min, the resin has smooth flowability, allowing for the production of uniform sheets and improving production efficiency.

[0300] In addition, compared to Comparative Examples 1 to 4, the printability and mechanical properties of Examples 1 to 3 are improved, so that the pattern is printed cleanly, there is no ink peeling, and the durability of the sheet can be improved.

[0301]

[0302] The examples can be applied to a biodegradable resin composition for printing and a printing sheet containing the same.

Claims

1. Aliphatic-aromatic polyester resin and a biodegradable resin comprising an aliphatic polyester resin; Inorganic filler containing calcium carbonate; and It contains an opacifying agent, A biodegradable resin composition for printing having a melt index of greater than 3 g / 10 min and less than 20 g / 10 min at 190 ℃ and 2.16 kg according to ASTM D1238, and a haze of greater than 1% and less than 30% of a 1 mm thick specimen according to ASTM D1003.

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

1.

3. In Paragraph 1, A printing biodegradable resin composition having a content of the above-mentioned inorganic filler of more than 30 weight % and less than 60 weight % based on the total weight of the printing biodegradable resin composition.

4. In Paragraph 1, A printing biodegradable resin composition having a content of the opacifying agent of more than 3 weight % and less than 10 weight % based on the total weight of the printing biodegradable resin composition.

5. In Paragraph 1, The above-mentioned opacifying agent is a biodegradable resin composition for printing comprising titanium dioxide (TiO2) surface-treated with an organic acid.

6. In Paragraph 5, Average particle size (D of the above titanium dioxide) 50 A biodegradable resin composition for printing in which ) is greater than 0.1 μm and less than 0.5 μm.

7. In Paragraph 5, A biodegradable resin composition for printing in which the oil absorption of the titanium dioxide is greater than 10 g / 100g and less than 30 g / 100g.

8. In Paragraph 5, A biodegradable resin composition for printing in which the moisture content of the titanium dioxide is less than 4,000 ppm based on the total weight of the titanium dioxide.

9. In Paragraph 1, The above-mentioned biodegradable resin composition for printing comprises a lubricant containing calcium.

10. Aliphatic-aromatic polyester resin and a biodegradable resin comprising an aliphatic polyester resin; Inorganic filler containing calcium carbonate; and A biodegradable resin composition for printing comprising an opacifying agent, and The above-mentioned biodegradable resin composition for printing is a printing sheet having a melt index of greater than 3 g / 10 min and less than 20 g / 10 min at 190 ℃ and 2.16 kg according to ASTM D1238, and a haze of greater than 1% and less than 30% of a 1 mm thick specimen according to ASTM D1003.

11. In Paragraph 10, The above printing sheet is a printing sheet having a contact angle with water of more than 50° and less than 90°.

12. In Paragraph 10, A printing sheet having an average surface roughness (Sa) according to ISO 25178 that is greater than 0.8 μm and less than 0.9 μm when the above printing sheet is measured with a 3D roughness measuring instrument.

13. In Paragraph 10, The above printing sheet is a printing sheet having a surface energy of more than 34 mN / m and less than 45 mN / m in accordance with ISO 8296.

14. In Paragraph 10, The above printing sheet is a printing sheet intended for business cards.

Images