WO2024117626A1 - Composition de résine biodégradable et produit moulé biodégradable la comprenant - Google Patents

Composition de résine biodégradable et produit moulé biodégradable la comprenant Download PDF

Info

Publication number
WO2024117626A1
WO2024117626A1 PCT/KR2023/018501 KR2023018501W WO2024117626A1 WO 2024117626 A1 WO2024117626 A1 WO 2024117626A1 KR 2023018501 W KR2023018501 W KR 2023018501W WO 2024117626 A1 WO2024117626 A1 WO 2024117626A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
biodegradable resin
sample
less
resin composition
Prior art date
Application number
PCT/KR2023/018501
Other languages
English (en)
Korean (ko)
Inventor
최유진
김상민
이득영
Original Assignee
에스케이티비엠지오스톤 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020220163328A external-priority patent/KR20240079913A/ko
Priority claimed from KR1020220163327A external-priority patent/KR20240079912A/ko
Application filed by 에스케이티비엠지오스톤 주식회사 filed Critical 에스케이티비엠지오스톤 주식회사
Publication of WO2024117626A1 publication Critical patent/WO2024117626A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a biodegradable resin composition and a biodegradable molded article containing the same.
  • PLA polylactic acid
  • PBAT polybutylene adipate terephthalate
  • PBS polybutylene succinate
  • the present invention provides a biodegradable resin composition that has excellent water resistance, improves durability, and improves solvent resistance to provide dimensional stability in solvents, and a biodegradable molded article containing the same.
  • the biodegradable resin composition according to the present invention contains a biodegradable resin and an inorganic filler, and has a weight loss rate A (%) of 1% or less as measured by Measurement Method 1 below.
  • a biodegradable resin sheet with an average thickness of 0.9mm is manufactured under the conditions of 180°C temperature and 20Mpa pressure.
  • Weight reduction rate A(%) ( ⁇ Wi - Wa ⁇ / Wi) ⁇ 100
  • the biodegradable resin composition may have a weight loss rate B (%) of 1% or less as measured by Measurement Method 2 below.
  • step 2 After maintaining the sample prepared in step 2) for 3 weeks at a temperature of 85°C and relative humidity of 85%, the weight (Wb) of the sample is measured, and the weight reduction rate B (%) is calculated using the following calculation formula 2. .
  • Weight reduction rate B(%) ( ⁇ Wi - Wb ⁇ / Wi) ⁇ 100
  • the biodegradable resin composition may have a weight loss rate deviation of 0.8% or less calculated by the following calculation equation 3.
  • Weight reduction rate deviation ⁇ Weight reduction rate A(%) - Weight loss rate B(%) ⁇
  • the biodegradable resin composition may have a change rate C (%) in the number of carboxyl terminal groups measured by Measurement Method 4 below of 25% or less.
  • the biodegradable resin composition may have a change rate D (%) in the number of carboxyl terminal groups measured by Measurement Method 5 below of 50% or less.
  • the biodegradable resin composition according to the present invention contains a biodegradable resin and an inorganic filler, and has a weight swelling ratio of less than 4% as measured by Measurement Method 6 below.
  • a biodegradable resin sheet with an average thickness of 0.9mm is manufactured under the conditions of 180°C temperature and 20Mpa pressure.
  • Weight swelling ratio (%) [Weight of sample (B) - Weight of sample (A)] / Weight of sample (A) ⁇ 100
  • the biodegradable resin composition may have a volumetric swelling ratio of less than 2.5% as measured by Measurement Method 7 below.
  • Volume swelling rate (%) [Volume of sample (Y) - Volume of sample (X)] / Volume of sample (X) ⁇ 100
  • the weight swelling ratio of the biodegradable resin composition may be less than 3%.
  • the volumetric swelling ratio of the biodegradable resin composition may be less than 2%.
  • the inorganic filler may include calcium carbonate.
  • the calcium carbonate may be surface treated with an organic acid.
  • the content of the inorganic filler may be 30% by weight or more based on the total weight of the biodegradable resin composition.
  • the biodegradable molded article according to the present invention includes a biodegradable resin and an inorganic filler, and includes a biodegradable resin composition with a weight loss rate A (%) of 1% or less as measured by Measurement Method 1 below.
  • a biodegradable resin sheet with an average thickness of 0.9mm is manufactured under the conditions of 180°C temperature and 20Mpa pressure.
  • Weight reduction rate A(%) ( ⁇ Wi - Wa ⁇ / Wi) ⁇ 100
  • the biodegradable molded article according to the present invention includes a biodegradable resin and an inorganic filler, and includes a biodegradable resin composition having a weight swelling ratio of less than 4% as measured by Measurement Method 6 below.
  • a biodegradable resin sheet with an average thickness of 0.9mm is manufactured under the conditions of 180°C temperature and 20Mpa pressure.
  • Weight swelling ratio (%) [Weight of sample (B) - Weight of sample (A)] / Weight of sample (A) ⁇ 100
  • the biodegradable molded article may be disposable gloves, food packaging material, fabric, knitted fabric, non-woven fabric, rope, or food packaging container.
  • the biodegradable resin composition according to the present invention contains a high content of inorganic filler, thereby improving the mechanical properties of the biodegradable molded article manufactured from the biodegradable resin composition.
  • the biodegradable resin composition according to the present invention has a low weight change rate not only in a mild environment but also in a high temperature and high humidity environment, and thus water resistance can be significantly improved without deteriorating mechanical properties. Accordingly, it has the effect of being able to be commercialized in a wider range of fields than conventional biodegradable resin compositions.
  • biodegradable resin composition according to the present invention satisfies a weight swelling ratio within a specific numerical range, thereby significantly improving solvent resistance without deteriorating mechanical properties, making it possible to commercialize it in a wider range of fields than conventional biodegradable resin compositions.
  • biodegradable resin composition according to the present invention and the biodegradable molded article containing the same will be described.
  • the biodegradable resin composition according to the present invention contains a biodegradable resin and an inorganic filler, and has a weight loss rate A (%) of 1% or less as measured by Measurement Method 1 below.
  • a biodegradable resin sheet with an average thickness of 0.9mm is manufactured under the conditions of 180°C temperature and 20Mpa pressure.
  • Weight reduction rate A(%) ( ⁇ Wi - Wa ⁇ / Wi) ⁇ 100
  • the biodegradable resin composition includes a biodegradable resin.
  • the biodegradable resin may be a resin that can be easily decomposed by microorganisms in soil.
  • the biodegradable resin may include a biodegradable polyester resin.
  • the biodegradable polyester resin may include a diol component and a dicarboxylic acid component.
  • the biodegradable resin may include a first repeating unit and a second repeating unit, the first repeating unit may include a diol component and an aromatic dicarboxylic acid component, and the second repeating unit may include It may contain a diol component and an aliphatic dicarboxylic acid component.
  • the diol component may include 1,4-butanediol or a derivative thereof.
  • the diol component may include 95 mol% or more, 97 mol% or more, 98 mol% or more, 99 mol% or more, or 100 mol% of 1,4-butanediol or a derivative thereof based on the total number of moles of the diol component.
  • the diol component can improve biodegradability, flexibility, and strength by containing 1,4-butanediol or a derivative thereof, and when the diol component consists only of 1,4-butanediol, the effect of improving biodegradability and strength is can be maximized.
  • the diol component may further include a second diol that is different from the first diol, which is 1,4-butanediol or a derivative thereof.
  • the second diol may be one or more selected from the group consisting of propanediol, hexanediol, cyclohexanedimethanol, and ethylene glycol.
  • the second diol is 1,3-propanediol, 1,2-propanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 2,6-hexanediol, 3,4-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexane It may be one or more selected from the group consisting of dimethanol, 1,4-cyclohexanedimethanol, and ethylene glycol.
  • the diol component may include 5 mol% or less, 3 mol% or less, 2 mol% or less, or 1 mol% or less of the second diol based on the total number of moles of the diol component.
  • the aromatic dicarboxylic acid component may be one or more selected from the group consisting of terephthalic acid, dimethyl terephthalic acid, and derivatives thereof. Specifically, the aromatic dicarboxylic acid component may be terephthalic acid or dimethyl terephthalic acid.
  • the dicarboxylic acid component is 15 mol% or more, 30 mol% or more, 45 mol% or more, 50 mol% or more, or 75 moles of the aromatic dicarboxylic acid component based on the total number of moles of the dicarboxylic acid component. % or more, and may include 30 mol% to 90 mol%, 35 mol% to 80 mol%, 40 mol% to 75 mol%, 45 mol% to 65 mol%, or 45 mol% to 55 mol%. can do.
  • the aliphatic dicarboxylic acid component may be one or more selected from the group consisting of adipic acid, succinic acid, and derivatives thereof. Specifically, the aliphatic dicarboxylic acid component may be adipic acid or succinic acid.
  • the dicarboxylic acid component is 15 mol% or more, 30 mol% or more, 45 mol% or more, 50 mol% or more, or 75 moles of the aliphatic dicarboxylic acid component based on the total number of moles of the dicarboxylic acid component. % or more, and may include 30 mol% to 90 mol%, 35 mol% to 80 mol%, 40 mol% to 75 mol%, 45 mol% to 65 mol%, or 45 mol% to 55 mol%. You can.
  • the molar ratio of the aromatic dicarboxylic acid component and the aliphatic dicarboxylic acid component may be 0.5 to 1.5:1, 0.7 to 1.3:1, or 0.8 to 1.2:1.
  • the molar ratio of the diol component and the dicarboxylic acid component may be 0.5 to 2:1, 0.5 to 1.8:1, 0.7 to 1.5:1, or 0.9 to 1.2:1.
  • the biodegradable resin composition can improve biodegradability, strength, and processability without discoloration such as yellowing.
  • the biodegradable resin is polybutylene adipate terephthalate (polybutylene adipate), wherein the first repeating unit may include a diol component and an aromatic dicarboxylic acid component, and the second repeating unit may include a diol component and an aliphatic dicarboxylic acid component.
  • PBAT polybutylene adipate terephthalate
  • the polybutylene adipate terephthalate may include a unit represented by the following formula (1).
  • m may be 1 to 20, and n may be 1 to 20.
  • the biodegradable resin composition may include a different type of biodegradable resin other than polybutylene adipate terephthalate.
  • the heterogeneous biodegradable resins include polybutylene azelate terephthalate (PBAzT), polybutylene sebacate terephthalate (PBSeT), polybutylene succinate terephthalate (PBST), and polyhydroxyalkanoate. (PHA), and polylactic acid (PLA).
  • PBAzT polybutylene azelate terephthalate
  • PBSeT polybutylene sebacate terephthalate
  • PBST polybutylene succinate terephthalate
  • PHA polyhydroxyalkanoate
  • PDA polylactic acid
  • the heterogeneous biodegradable resin can complement the mechanical properties of polybutylene adipate terephthalate.
  • the polylactic acid may be a high melting point polylactic acid having stereo complex crystals. Additionally, the polylactic acid may be formed by solution mixing or melt mixing of poly L-lactic acid and poly D-lactic acid.
  • the polylactic acid may include a unit represented by the following formula (2).
  • the polylactic acid may be a polymer containing L-lactic acid units and/or D-lactic acid units.
  • the polylactic acid may include poly L-lactic acid and/or poly D-lactic acid.
  • the poly L-lactic acid may be a polymer mainly containing L-lactic acid units.
  • the poly L-lactic acid may include L-lactic acid units in an amount of about 90 mol% to about 100 mol%, about 95 mol% to about 100 mol%, or about 97 mol% to about 100 mol%.
  • the poly L-lactic acid may include D-lactic acid units and/or units other than lactic acid.
  • the poly L-lactic acid contains the D-lactic acid units and/or units other than lactic acid in an amount of about 0 mol% to about 10 mol%, about 0 mol% to about 5 mol%, or about 0 mol% to about 3 mol%. It can be included.
  • the poly D-lactic acid may be a polymer mainly containing D-lactic acid units.
  • the poly D-lactic acid may include the D-lactic acid unit in an amount of about 90 mol% to about 100 mol%, about 95 mol% to about 100 mol%, or about 97 mol% to about 100 mol%.
  • the poly D-lactic acid may include units other than the L-lactic acid unit and/or lactic acid.
  • the poly D-lactic acid contains the L-lactic acid units and/or units other than lactic acid in an amount of about 0 mol% to about 10 mol%, about 0 mol% to about 5 mol%, or about 0 mol% to about 3 mol%. It can be included.
  • Units other than the lactic acid include units derived from dicarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, etc., which have a functional group capable of forming two or more ester bonds, and various polyesters and various polyesters composed of these various components. It may be a unit derived from ether, various polycarbonates, etc.
  • dicarboxylic acid examples include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, and isophthalic acid.
  • the polyhydric alcohols include aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. and aromatic polyhydric alcohols such as those obtained by adding ethylene oxide to bisphenol.
  • hydroxycarboxylic acid examples include glycolic acid and hydroxybutyric acid.
  • Lactones include, for example, glycolide, ⁇ -caprolactone glycolide, ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ - or ⁇ -butyrolactone, pivalolactone, ⁇ - Valerolactone, etc. can be mentioned.
  • the polylactic acid can be commercially available from Biomer, Inc. under the name BIOMERTM L9000. Additionally, the polylactic acid may be commercially available from Natureworks LLC (NATUREWORKS®) or Mitsui Chemical (LACEATM). Additionally, the polylactic acid may be described in U.S. Patent Nos. 4,797,468, 5,470,944, 5,770,682, 5,821,327, 5,880,254 and 6,326,458, which are hereby incorporated by reference in their entirety for all purposes.
  • the polyhydroxyalkanoate may include a unit represented by the following formula (3).
  • R is independently selected from the group consisting of hydrogen atoms, hydrocarbon groups, heteroatoms, and combinations thereof, n is the number of repeating units from 1 to 35,000, and x may represent an integer from 1 to 5. .
  • the polyhydroxyalkanoate is 3-hydroxypropionate, 3-hydroxybutyrate, 3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyheptanoate, 3-hydroxyocta
  • at least one moiety selected from the group consisting of noate, 3-hydroxynonanoate, 3-hydroxydecanoate, 3-hydroxyundecanoate, 3-hydroxydodecanoate, and combinations thereof. It may be a homopolymer or copolymer. Additionally, the at least one moiety may have the same or different numbers of repeat units.
  • the polyhydroxyalkanoate may be a copolymer containing 3-hydroxybutyrate units and 3-hydroxyhexanoate units as main structural units.
  • the polyhydroxyalkanoate may contain 80 mol% or more of 3-hydroxybutyrate units as a component.
  • the polyhydroxyalkanoate may include 3-hydroxybutyrate units in an amount of about 85 mol% or more.
  • the polyhydroxyalkanoate is poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) copolymer resin or poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co- 3-hydroxyhexanoate) copolymer resin.
  • the polyhydroxyalkanoate is, for example, Alcaligenes eutrophus AC 32 strain (International Depositary based on the Budapest Treaty, International Depository Authority: Independent Administration), which introduced the PHA synthase gene from Aeromonas caviae into Alcaligenes eutrophus.
  • Patent Organism Deposit Center Industrial Technology Research Institute (1 Central No. 6, 1-1-chome, Tsukuba-shi, Ibaraki Prefecture, Japan), original deposit date: August 12, 1996, transferred and deposited on August 7, 1997 It can be produced by microorganisms such as number FERM BP-6038 (transferred from original deposit FERM P-15786) (J. Bacteriol., 179, 4821 (1997)).
  • the polyhydroxyalkanoate can be obtained as a commercial product.
  • Commercially available products of the polyhydroxyalkanoate include Danimer's "NODAX”, Tianan biopolymer's “ENMAT”, CJ CheilJedang's “PHACT”, Kaneka's “Aonilex (registered trademark) ”, “Aonilex (registered trademark) 151A”, “Aonilex (registered trademark) 151C”, “PHBH (registered trademark) Registered trademark) 151C”, etc.
  • the content of the biodegradable resin is less than 90% by weight, less than 85% by weight, more than 10% by weight and less than 85% by weight, more than 10% by weight and less than 80% by weight, and 10% by weight, based on the total weight of the biodegradable resin composition. It may be more than 70% by weight, more than 20% by weight and less than 70% by weight, more than 25% by weight and less than 70% by weight, more than 26.8% by weight and less than 70% by weight, or more than 26.8% by weight and less than 68.8% by weight. When the above range is satisfied, water resistance can be significantly improved without deteriorating mechanical properties.
  • the biodegradable resin composition includes an inorganic filler.
  • the content of the inorganic filler is 30% by weight or more, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight or more, 60% by weight or more based on the total weight of the biodegradable resin composition. , 65% by weight or more, 70% by weight or more, 75% by weight or more, 80% by weight or more, 30% by weight or more and 85% by weight or less, 30% by weight or more and 80% by weight or less, 30% by weight or more and 75% by weight or less.
  • 30% by weight or more and 70% by weight or less 35% by weight or more and 85% by weight or less, 35% by weight or more and 80% by weight or less, 35% by weight or more and 75% by weight or less, 35% by weight or more and 70% by weight or less.
  • 40% by weight or more and 85% by weight or less 40% by weight or more and 80% by weight or less, 40% by weight or more and 75% by weight or less, 40% by weight or more and 70% by weight or less, 45% by weight or more and 85% by weight or less.
  • the specific surface area of the inorganic filler is 0.1 m 2 /g to 10.0 m 2 /g, 0.1 m 2 /g to 9.0 m 2 /g, 0.1 m 2 /g to 8.0 m 2 /g, 0.1 m 2 /g to 7.0. m 2 /g, 0.1 m 2 /g to 6.0 m 2 /g, 0.1 m 2 /g to 5.0 m 2 /g, 0.1 m 2 /g to 4.0 m 2 /g, or 0.1 m 2 /g to 3.0 m It may be 2 /g.
  • the specific surface area can be measured by a nitrogen gas adsorption method. If the above range is satisfied, it can be easily dispersed in a biodegradable resin, thereby promoting biodegradability of the biodegradable resin and improving processability.
  • the average particle diameter of the inorganic filler is 0.1 ⁇ m to 10.0 ⁇ m, 0.1 ⁇ m to 9.0 ⁇ m, 0.1 ⁇ m to 8.0 ⁇ m, 0.1 ⁇ m to 7.0 ⁇ m, 0.1 ⁇ m to 6.0 ⁇ m, 0.1 ⁇ m to 5.0 ⁇ m, 0.1 ⁇ m ⁇ m to 4.0 ⁇ m, It may be 0.1 ⁇ m to 3.0 ⁇ m, 1.0 ⁇ m to 5.0 ⁇ m, 1.0 ⁇ m to 4.0 ⁇ m, or 1.0 ⁇ m to 3.0 ⁇ m.
  • the average particle diameter can be calculated from the results of measuring the specific surface area by the air permeation method using a specific surface area measuring device. If the above range is satisfied, the viscosity may not increase when mixing the biodegradable resin and the inorganic filler, and the uniformity of particle size may be improved.
  • the sphericity of the inorganic filler 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. If the above range is satisfied, a large number of fine pores generated at the interface between the biodegradable resin and the inorganic filler can be included, so biodegradability can be improved, and the strength and molding processability of the molded product can be increased.
  • the inorganic filler may include calcium carbonate (CaCO 3 ).
  • CaCO 3 calcium carbonate
  • molded articles made from biodegradable resin compositions may generate acid components when biodegraded. Since the acid component and the calcium carbonate can react to generate CO 2 and H 2 O, the biodegradation rate of the molded product on a molecular basis can be further improved. Additionally, the calcium carbonate can neutralize the acid component to reduce environmental load and prevent acidification of the soil.
  • the calcium carbonate may be heavy calcium carbonate obtained by mechanically crushing or classifying natural calcium carbonate containing CaCO 3 as a main component, such as limestone, chalk, marble, shell, and coral.
  • the calcium carbonate may be surface treated with an organic acid.
  • an organic acid By surface-treating the calcium carbonate with the organic acid, dispersibility in the biodegradable resin composition can be increased and reactivity with the biodegradable resin can be improved.
  • the surface treatment can be performed by physical methods such as plasma treatment or corona treatment, or by chemical methods such as silane coupling agents, titanium coupling agents, or surfactants.
  • the organic acid may include higher fatty acids, higher fatty acid esters, higher fatty acid amides, and higher fatty acids, and may be, for example, calcium stearate.
  • the surface-treated calcium carbonate can be produced by the following method.
  • calcium carbonate powder is produced by a grinding process. Thereafter, the calcium carbonate powder is classified to obtain calcium carbonate of the desired particle size.
  • the calcium carbonate is then heat treated at about 200° C. to about 800° C. by a heating device selected from a kiln, electric furnace or microwave furnace.
  • the heat treatment time may be about 5 minutes to about 30 minutes, about 7 minutes to about 15 minutes, or about 7 minutes to about 14 minutes.
  • the heat treatment temperature may be about 250°C to about 700°C or about 300°C to about 600°C.
  • an organic acid may be added to the heat-treated calcium carbonate to perform a process to treat the surface of the calcium carbonate.
  • the process temperature may be from 70°C to about 130°C.
  • the amount of the organic acid added is 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, and about 0.5 parts by weight to about 0.5 parts by weight, based on 100 parts by weight of the calcium carbonate.
  • the 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.
  • the surface-treated calcium carbonate may undergo an additional process of crushing and classifying the aggregates aggregated in the surface treatment process.
  • the content of the organic acid is about 0.1% by weight to about 3% by weight, about 0.1% by weight to about 2% by weight, about 0.1% by weight to about 1% by weight, based on the total 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.
  • Calcium carbonate surface-treated with the organic acid may be partially oxidized.
  • the surface-treated calcium carbonate may partially include calcium oxide (CaO).
  • the proportion of calcium oxide is 5 vol% or less, 4 vol% or less, 3 vol% or less, 2 vol% or less, 1 vol% or less, 0.01 vol% or more to 5 vol% based on 100 vol% of the surface-treated calcium carbonate particles. It may be 0.01 volume% or more and 4 volume% or less, 0.01 volume% or more and 3 volume% or less, 0.01 volume% or more and 2 volume% or less, or 0.01 volume% or more and 1 volume% or less.
  • the ratio of calcium oxide can be measured by EDTA (Ethylene diamine tetra acetic acid) titrimetry according to JIS R 9011. When the above range is satisfied, the uniformity of the surface of the calcium carbonate can be improved, the phenomenon of organic acids eluting from the surface of the calcium carbonate can be minimized, and water resistance can be improved.
  • the biodegradable resin composition may include reinforcing materials.
  • the reinforcing material may be a fiber derived from biomass.
  • the reinforcing material may include nanocellulose.
  • the nanocellulose may be a natural nanocellulose in the form of a gel or dry powder, and the dispersion stability, strength, and processability of a biodegradable resin composition containing the nanocellulose can all be improved.
  • 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 ⁇ m, 5 nm to 1 ⁇ m, 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. there is.
  • 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 is 1 ⁇ m to 50 ⁇ m, 2 ⁇ m to 45 ⁇ m, Or it may be 5 ⁇ m to 50 ⁇ m.
  • the nanocellulose may be in the form of a freeze-dried powder to reduce its volume for easy storage and transportation.
  • 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. When the above range is satisfied, the dispersibility and durability of the nanocellulose can be improved.
  • the nanocellulose functions as a crystal nucleating agent and can improve the crystallization rate of the biodegradable resin composition and increase the crystallization temperature of the biodegradable resin composition.
  • the nanocellulose may be one or more types selected from the group consisting of cellulose nanocrystals, cellulose nanofibers, and microfibrillated cellulose. In terms of strength and thermal properties, the cellulose nanocrystals or the cellulose nanofibers are more preferable.
  • the nanocellulose performs UV resistance and can provide appropriate UV resistance, biodegradation rate, and hydrolysis rate to the biodegradable resin.
  • the nanocellulose includes 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. It may be one or more types selected from the group consisting of.
  • the nanocellulose may be bead mill pretreated or ultrasonic pretreated.
  • the nanocellulose may be water-dispersed nanocellulose pretreated with a bead mill or pretreated with ultrasonic waves.
  • the nanocellulose may be obtained by dispersing cellulose nanocrystals in the form of dry powder or gel having a particle size of 1 ⁇ m to 50 ⁇ m in water, followed by pre-treatment with a bead mill or ultrasonic pre-treatment.
  • a bead mill or ultrasonic pre-treatment When the water-dispersed nanocellulose is bead mill pretreated or ultrasonic pretreated, the number of nanocellulose particles can increase and dispersibility can be maximized.
  • the nanocellulose is pretreated with 0.01 to 10% by weight, 0.05 to 8% by weight, 0.1 to 8% by weight, 0.5 to 6% by weight, or 0.7 to 6% by weight based on the total weight of the nanocellulose. You can. When the above range is satisfied, interfacial adhesion, dispersibility, and compatibility can be maximized, and thus the mechanical properties, durability, and hydrolysis resistance of the biodegradable resin composition containing it can be further improved.
  • the biodegradable resin composition may include oligomers.
  • the weight average molecular weight of the oligomer may be about 400 g/mol to about 1,300 g/mol.
  • the oligomer may be included in the biodegradable resin composition in an amount of about 3,000 ppm to about 30,000 ppm, about 5,000 ppm to about 20,000 ppm, or about 5,000 ppm to about 15,000 ppm, based on the weight of the biodegradable resin.
  • the oligomer may be a reaction product of at least two of the diol, the aromatic dicarboxylic acid, and the aliphatic dicarboxylic acid.
  • the oligomer may be a reaction product of 1,4-butanediol, terephthalic acid, and adipic acid.
  • the biodegradable resin composition may include a plasticizer.
  • the plasticizer can provide processability or flexibility to the molded product being manufactured.
  • the plasticizer may be glycerol, acrylate, glycerin, glycerol monostearate (GMS), sorbitol, or mixtures thereof.
  • the plasticizer may be 0.1% by weight to 15% by weight, 0.1% by weight to 10% by weight, or 0.1% by weight to 5% by weight based on the total weight of the biodegradable resin composition. When the above range is satisfied, the elongation and tear properties of molded products manufactured from the biodegradable resin composition can be improved.
  • the biodegradable resin composition 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.
  • the phosphorus-based antioxidants include triesters, diesters, monoesters, trimethyl phosphate, and triethyl of phosphorous acid such as triphenyl phosphite, trisnonylphenyl phosphite, and tris(2,4-di-t-butylphenyl)phosphite. It may be one or more selected from the group consisting of phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl)phosphate, and 2-ethylphenyl diphenyl phosphate.
  • the phenol-based antioxidants include ⁇ -tocopherol, butylhydroxytoluene, cinaphil alcohol, vitamin E, and n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate.
  • the antioxidants include BHT, ascorbic acid, catechin, quercetin, dodecyl gallate, TBHQ, Ralox, Irganox 1135, Irganox 1076, nordihydroguaiaretic acid, epicatechin gall. gallate, epigallocatechin gallate, epigallocatein, propyl gallate, 2,3,5-trihydroxybutyrophenone, butylated hydroxyanisole, 4-hydroxymethyl-2,6-di. It may further include one or more selected from the group consisting of -tert-butylphenol, ⁇ -tocopherol, resveratrol, rutin, astasatin, lycopene, beta-carotene, and melatonin.
  • the antioxidant is present in an amount of 5% by weight or less, 3% by weight or less, 2% by weight or less, 1.5% by weight or less, 1% by weight or less, 0.5% by weight or less, 0.3% by weight or less, 0 It may be from 5% by weight, 0.01 to 4% by weight, 0.1 to 3% by weight, 1 to 3% by weight, 1 to 2% by weight, 0.01 to 0.5% by weight, or 0.1 to 0.5% by weight.
  • the antioxidant may include both the phosphorus-based antioxidant and the phenol-based antioxidant.
  • the weight ratio of the phosphorus-based antioxidant and the phenolic antioxidant is 1:10 to 10:1, 1:5 to 5:1, and 1:1. to 5:1, 2:1 to 4:1, 2.5:1 to 3.5:1, 1:5 to 1:1, 1:2 to 1:4, or 1:2.5 to 1:3.5.
  • the biodegradable resin composition may include a heat stabilizer.
  • the heat stabilizer may be a phosphorus-based heat stabilizer.
  • the heat stabilizer is selected from the group consisting of amine-based high temperature heat stabilizers such as tetraethylenepentamine, triethylphosphonoacetate, phosphoric acid, phosphorous acid, polyphosphoric acid, trimethylphosphate, triethylphosphate, trimethylphosphine, and triphenylphosphine. It may include one or more types.
  • the heat stabilizer may be an antioxidant that has an oxidation prevention function.
  • the content of the heat stabilizer may be 3,000 ppm or less, 10 ppm to 3,000 ppm, 20 ppm to 2,000 ppm, 20 ppm to 1,500 ppm, or 20 ppm to 1,000 ppm, based on the total weight of the biodegradable resin.
  • the biodegradable resin composition may include a lubricant.
  • the lubricant is a fatty acid-based lubricant containing stearic acid, an aliphatic alcohol-based lubricant, an aliphatic amide-based lubricant containing stearamide, n-butyl stearate, methyl hydroxystearate, polyhydric alcohol fatty acid ester, saturated fatty acid ester, It may include one or more types selected from the group consisting of aliphatic ester-based lubricants such as ester-based waxes, and fatty acid metal soap-based lubricants.
  • the lubricant may be a stearate-based lubricant and may include one or more selected from the group consisting of calcium stearate, zinc stearate, barium stearate, magnesium stearate, glycerin stearate, and butyl stearate.
  • the stearate-based lubricant reduces heat generation due to friction during mixing, melting, and processing of raw materials, has an excellent dispersion effect for biodegradable resins relative to the price, and has an excellent lubricating effect, which can improve manufacturing efficiency.
  • the content of the lubricant is 5% by weight or less, 1% by weight or less, less than 1% by weight, 0.9% by weight or less, 0.8% by weight or less, 0.7% by weight or less, 0.5% by weight or less, based on the total weight of the biodegradable resin composition. It may be 0.3% by weight or less, or 0.1% by weight or less. If the above range is satisfied, manufacturing efficiency can be improved without deteriorating the physical properties of the biodegradable resin composition.
  • the biodegradable resin composition may include a flame retardant.
  • the flame retardant may include at least one selected from the group consisting of halogen-based flame retardants, phosphorus-based flame retardants, and non-phosphorus-based halogen-based flame retardants such as metal hydrates.
  • the halogenated flame retardants include halogenated bisphenol-based compounds such as halogenated bisphenyl alkane, halogenated bisphenyl ether, halogenated bisphenyl thioether, and halogenated bisphenyl sulfone, brominated bisphenol A, brominated bisphenol S, chlorinated bisphenol A, and chlorinated bisphenol S. It may include one or more types selected from the group consisting of bisphenol-bis (alkyl ether) compounds.
  • the phosphorus-based flame retardant is from the group consisting of tris(diethyl phosphinic acid) aluminum, bisphenol A bis(diphenyl phosphate), triaryl phosphate isopropylate, cresyl di2, 6-xylenyl phosphate, and aromatic condensed phosphoric acid ester. It may include one or more selected types.
  • the metal hydrate may include aluminum trihydrate, magnesium dihydroxide, or a combination thereof.
  • the flame retardant is a flame retardant aid to improve the flame retardant effect, and is one 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. It may include more.
  • the biodegradable resin composition may include a foaming agent.
  • the foaming agent may be mixed with the biodegradable resin composition in a molten state or injected under pressure to change phase from solid to gas, liquid to gas, or the gas itself, and may be used to change the foaming ratio (foaming density) of the foam sheet. Can be used for control.
  • the blowing agent may include one or more selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, inorganic gases, and water.
  • the biodegradable resin composition may include a dispersant.
  • the dispersant can improve the dispersibility of solvents and solutes.
  • the dispersant may include one or more selected from the group consisting of aliphatic polyester, polylactic acid, polyglycolic acid, polycaprolactone, and polyhydroxyalkanoate.
  • the dispersant is present in an amount of 1 to 20% by weight, 1 to 15% by weight, 1 to 13% by weight, 1 to 11% by weight, 2 to 10% by weight, 5 to 15% by weight, based on the total weight of the biodegradable resin composition. It may contain 7 to 12% by weight, 2 to 8% by weight, 5 to 8% by weight, or 2 to 5% by weight.
  • the biodegradable resin composition may include a chain extender.
  • the chain extender may include one or more selected from the group consisting of aromatic diisocyanate, aliphatic diisocyanate, isocyanurate, bisoxazoline, carboxylic acid anhydride, and epoxide.
  • the aromatic diisocyanate is tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'- It may include at least one member selected from the group consisting of diphenylmethane diisocyanate, naphthylene 1,5-diisocyanate, and xylylene diisocyanate.
  • the aliphatic diisocyanate may include one or more selected from the group consisting of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and methylenebis(4-isocyanatocyclohexane).
  • the isocyanurate may include isophorone diisocyanate or methylenebis(4-isocyanatocyclohexane).
  • the bisoxazoline is 2,2'-bis(2-oxazoline), bis(2-oxazolinyl)methane, 1,2-bis(2-oxazolinyl)ethane, 1,3-bis(2- It may include at least one member selected from the group consisting of oxazolinyl)propane, and 1,4-bis(2-oxazolinyl)butane.
  • the epoxide refers to an epoxy-containing copolymer based on at least one of styrene, acrylic acid ester, and methacrylic acid ester, and the copolymer content with glycidyl (meth)acrylate is greater than 20, greater than 30, or greater than 50. Weight percent copolymers are preferred.
  • the chain extender may be 1.5% by weight or less, 1% by weight or less, 0.5% by weight or less, 0.3% by weight or less, and 0 to 1.5% by weight, 0.01 to 1% by weight, 0.1% by weight, based on the total weight of the biodegradable resin composition. It can be from 1 weight %, 0.01 to 0.5 weight %, 0.01 to 0.3 weight %, or 0.1 to 0.5 weight %.
  • the biodegradable resin composition may include a hydrolysis-resistant agent.
  • the hydrolysis resistant agent may be selected from at least one silicon-based compound such as silane, silazane, or siloxane.
  • the biodegradable resin composition has a weight loss rate A (%) of 1% or less as measured by Measurement Method 1 below.
  • a biodegradable resin sheet with an average thickness of 0.9mm is manufactured under the conditions of 180°C temperature and 20Mpa pressure.
  • Weight reduction rate A(%) ( ⁇ Wi - Wa ⁇ / Wi) ⁇ 100
  • the weight loss rate A is 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.1% or more and 0.9% or less, 0.1% or more and 0.8% or less, 0.1% or more and 0.7% or less, 0.1% or less. % or more and 0.6% or less, or 0.1% or more and 0.5% or less.
  • the biodegradable resin composition may have a weight loss rate B (%) of 1% or less as measured by Measurement Method 2 below.
  • step 2 After maintaining the sample prepared in step 2) for 3 weeks at a temperature of 85°C and relative humidity of 85%, the weight (Wb) of the sample is measured, and the weight reduction rate B (%) is calculated using the following calculation formula 2. .
  • Weight reduction rate B(%) ( ⁇ Wi - Wb ⁇ / Wi) ⁇ 100
  • the weight loss rate B is 0.95% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.1% or more and 0.95% or less, 0.1% or more and 0.9% or less, 0.1% or more and 0.8% or less, 0.1% or less. % or more and 0.7% or less, or 0.1% or more and 0.6% or less.
  • the biodegradable resin composition may have a weight loss rate deviation of 0.8% or less as calculated by the following calculation equation 3.
  • Weight reduction rate deviation ⁇ Weight reduction rate A(%) - Weight loss rate B(%) ⁇
  • the weight loss rate deviation is 0.95% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.1% or more and 0.95% or less, 0.1% or more and 0.9% or less, 0.1% or more and 0.8% or less, 0.1% or less. % or more and 0.7% or less, or 0.1% or more and 0.6% or less.
  • the weight loss rate A, weight loss rate B, and weight loss rate deviation may be indicators of the water resistance of the biodegradable resin composition under various temperature conditions. Additionally, the weight loss rate A, weight loss rate B, and weight loss rate deviation may vary depending on the content of the inorganic filler included in the biodegradable resin composition.
  • the biodegradable resin composition according to the present invention can improve water resistance, prevent a rapid increase in biodegradability, and maintain elongation and strength by appropriately controlling the content of the inorganic filler contained in the biodegradable resin composition. This ensures product reliability.
  • the biodegradable resin composition has a weight loss rate B of 1% or less, so the water resistance can be improved not only in a mild environment but also in a high temperature and high humidity environment.
  • the biodegradable resin composition has a weight loss rate deviation of 0.8% or less, and its water resistance does not deteriorate not only in mild environments but also in high-temperature and high-humidity environments, making it possible to commercialize it in a wider range of fields.
  • the biodegradable resin composition may have a change rate C (%) in the number of carboxyl terminal groups measured by Measurement Method 4 below of 25% or less.
  • the rate of change C in the number of carboxyl group terminal groups is 24.7% or less, 24.5% or less, 24.2% or less, 22% or less, 20% or less, 12% or less, 10% or less, 5% or less, 1% or more to 24.7% or less, 1% or greater than or equal to 24.5%, greater than or equal to 1% and less than or equal to 24.2%, greater than or equal to 1% and less than or equal to 22%, greater than or equal to 1% and less than or equal to 20%, greater than or equal to 1% and less than or equal to 12%, greater than or equal to 1% and less than or equal to 10%, or greater than or equal to 1%. It may be 5% or less.
  • the biodegradable resin composition may have a change rate D (%) in the number of carboxyl terminal groups measured by Measurement Method 5 below of 50% or less.
  • the rate of change D in the number of carboxyl terminal groups is 49.9% or less, 49.8% or less, 40% or less, 30% or less, 25% or less, 20% or less, 5% or more to 49.9% or less, 5% or more to 49.8% or less, 5% It may be 5% or more and 40% or less, 5% or more and 30% or less, 5% or more and 25% or less, or 5% or more and 20% or less.
  • the rate of change in the number of carboxyl end groups C and the rate of change in the number of carboxyl end groups D may be indicators of the water resistance of the biodegradable resin composition under various temperature conditions.
  • the weight of the biodegradable resin composition may be reduced by hydrolysis, and the smaller the value of the rate of change in the number of carboxyl end groups C or the rate of change in the number of carboxyl end groups D, the rate of change in the number of carboxyl end groups due to hydrolysis is. As it decreases, it may mean that the water resistance of the biodegradable resin composition is improved.
  • the biodegradable resin composition has a weight swelling ratio of less than 4% as measured by Measurement Method 6 below.
  • a biodegradable resin sheet with an average thickness of 0.9mm is manufactured under the conditions of 180°C temperature and 20Mpa pressure.
  • Weight swelling ratio (%) [Weight of sample (B) - Weight of sample (A)] / Weight of sample (A) ⁇ 100
  • the weight swelling ratio may be an indicator of the solvent resistance of the biodegradable resin composition. For example, as the weight swelling ratio increases, it may mean that the weight of the solvent absorbed into the biodegradable resin composition increases, which may mean that the solvent resistance of the biodegradable resin composition decreases.
  • the weight swelling ratio may vary depending on the content of the inorganic filler contained in the biodegradable resin composition.
  • the biodegradable resin included in the biodegradable resin composition exhibits a high solvent absorption rate compared to the inorganic filler.
  • the weight swelling ratio may decrease, and conversely, if the ratio of the inorganic filler to the biodegradable resin decreases, the weight swelling rate may decrease. The rate may increase.
  • the biodegradable resin composition has a weight swelling ratio measured by Measurement Method 6 of less than 3.7%, less than 3.5%, less than 3.3%, less than 3%, less than 2.7%, less than 2.5%, less than 2%, less than 1.5%, Less than 1%, 0.01% to less than 4%, 0.01% to less than 3.7%, 0.01% to less than 3.5%, 0.01% to less than 3.3%, 0.01% to less than 3%, 0.01% to 2.7% It may be less than 0.01% to less than 2.5%, more than 0.01% to less than 2%, more than 0.01% to less than 1.5%, more than 0.01% to less than 1%, or more than 0.02% to less than 2.7%.
  • the present invention provides that when the weight swelling ratio of the biodegradable resin composition measured by the above measurement method satisfies the above range, resistance to solvents can be improved without deteriorating mechanical properties, and can be used in product fields requiring long-term durability. You can. In addition, it does not cause a decrease in the dispersibility of the inorganic filler, the physical properties of the manufactured molded article can be improved, a rapid increase in biodegradability can be prevented, and elongation and strength can be maintained, thereby ensuring product reliability.
  • the biodegradable resin composition may have a volumetric swelling ratio of less than 2.5% as measured by Measurement Method 7 below.
  • Volume swelling rate (%) [Volume of sample (Y) - Volume of sample (X)] / Volume of sample (X) ⁇ 100
  • the volumetric swelling ratio may be another indicator indicating the solvent resistance of the biodegradable resin composition.
  • a larger volumetric swelling ratio may mean that the volume of solvent absorbed into the biodegradable resin composition increases, which may mean that the solvent resistance of the biodegradable resin composition decreases.
  • the volumetric swelling ratio may vary depending on the content of the inorganic filler contained in the biodegradable resin composition.
  • the biodegradable resin included in the biodegradable resin composition exhibits a high solvent absorption rate compared to the inorganic filler.
  • the volumetric swelling rate may decrease, and conversely, if the ratio of the inorganic filler to the biodegradable resin decreases, the volumetric swelling may decrease. The rate may increase.
  • the biodegradable resin composition has a volumetric swelling ratio measured by Measurement Method 7 of less than 2.0%, less than 1.99%, less than 1.98%, less than 1.9%, less than 1.5%, less than 1%, less than 0.9%, less than 0.8%, Less than 0.7%, less than 0.6%, less than 0.5%, less than 0.4%, less than 0.3%, less than 0.2%, less than 0.1%, more than 0.01% to less than 2.0%, more than 0.01% to less than 1.99%, more than 0.01% to less than 1.98% less than 0.01% to less than 1.9%, more than 0.01% to less than 1.5%, more than 0.01% to less than 1%, more than 0.01% to less than 0.9%, more than 0.01% to less than 0.8%, more than 0.01% to less than 0.7%, 0.01% or more and less than 0.6%, 0.01% or more and less than 0.5%, 0.01% or more and less than 0.4%, 0.01% or more and less than 0.3%, 0.01% or more and less than 0.2%, 0.0
  • the volumetric swelling ratio of the biodegradable resin composition measured by the above measurement method satisfies the above range, resistance to solvents can be improved without deteriorating mechanical properties, and it can be used in product fields that require long-term durability. In addition, it does not cause a decrease in the dispersibility of the inorganic filler, the physical properties of the manufactured molded article can be improved, a rapid increase in biodegradability can be prevented, and elongation and strength can be maintained, thereby ensuring product reliability.
  • the biodegradable molded article according to the present invention can be manufactured from the biodegradable resin composition.
  • the biodegradable molded product may be manufactured by molding the biodegradable resin composition by methods known in the art, such as extrusion and injection.
  • the molded product may be an injection molded product, an extrusion molded product, a thin film molded product, or a blow molded product. It is not limited to this.
  • the biodegradable molded article may be agricultural mulching film, disposable gloves, food packaging, fabric, knitted fabric, non-woven fabric, rope, or food packaging container. Since the biodegradable molded product can be manufactured from a biodegradable resin composition with excellent water resistance, it can exhibit excellent properties when applied to packaging materials and mulching films that require dimensional stability in an outdoor environment.
  • the biodegradable molded article contains a biodegradable resin and an inorganic filler, and has a weight loss rate A (%) of 1% or less as measured by Measurement Method 1 below.
  • a biodegradable resin sheet with an average thickness of 0.9mm is manufactured under the conditions of 180°C temperature and 20Mpa pressure.
  • Weight reduction rate A(%) ( ⁇ Wi - Wa ⁇ / Wi) ⁇ 100
  • the weight loss rate A is 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.1% or more and 0.9% or less, 0.1% or more and 0.8% or less, 0.1% or more and 0.7% or less, 0.1% or less. % or more and 0.6% or less, or 0.1% or more and 0.5% or less.
  • the biodegradable molded article may include a biodegradable resin composition that satisfies the values of the above-described weight loss rate B, weight loss rate deviation, carboxyl end group number change rate C, or carboxyl end group number change rate D.
  • the biodegradable resin and the inorganic filler may be the same as the biodegradable resin and the inorganic filler in the biodegradable resin composition described above.
  • the biodegradable molded article includes a biodegradable resin and an inorganic filler, and includes a biodegradable resin composition having a weight swelling ratio of less than 4% as measured by Measurement Method 6 below.
  • the biodegradable resin and the inorganic filler may be the same as the biodegradable resin and the inorganic filler in the biodegradable resin composition described above.
  • a biodegradable resin sheet with an average thickness of 0.9mm is manufactured under the conditions of 180°C temperature and 20Mpa pressure.
  • Weight swelling ratio (%) [Weight of sample (B) - Weight of sample (A)] / Weight of sample (A) ⁇ 100
  • the weight swelling ratio may be an indicator of the solvent resistance of the biodegradable molded article.
  • a higher weight swelling ratio may mean that the weight of solvent absorbed into the biodegradable molded article increases, which may mean that the solvent resistance of the biodegradable molded article decreases.
  • the biodegradable molded product has a weight swelling ratio measured by Measurement Method 6 of less than 3.7%, less than 3.5%, less than 3.3%, less than 3%, less than 2.7%, less than 2.5%, less than 2%, less than 1.5%, 1 % or more, 0.01% or more to less than 4%, 0.01% or more to less than 3.7%, 0.01% or more to less than 3.5%, 0.01% or more to less than 3.3%, 0.01% or more to less than 3%, 0.01% or more to less than 2.7% , 0.01% to less than 2.5%, 0.01% to less than 2%, 0.01% to less than 1.5%, 0.01% to less than 1%, or 0.02% to less than 2.7%.
  • the biodegradable molded article may have a volumetric swelling ratio of less than 2.5% as measured by Measurement Method 7 below.
  • Volume swelling rate (%) [Volume of sample (Y) - Volume of sample (X)] / Volume of sample (X) ⁇ 100
  • the volumetric swelling ratio may be an indicator of the solvent resistance of the biodegradable molded article.
  • a higher volumetric swelling ratio may mean that the volume of solvent absorbed into the biodegradable molded article increases, which may mean that the solvent resistance of the biodegradable molded article decreases.
  • the biodegradable molded product has a volume swelling ratio measured by Measurement Method 7 of less than 2.0%, less than 1.99%, less than 1.98%, less than 1.9%, less than 1.5%, less than 1%, less than 0.9%, less than 0.8%, less than 0.7 less than %, less than 0.6%, less than 0.5%, less than 0.4%, less than 0.3%, less than 0.2%, less than 0.1%, more than 0.01% to less than 2.0%, more than 0.01% to less than 1.99%, more than 0.01% to less than 1.98% , 0.01% or more and less than 1.9%, 0.01% or more and less than 1.5%, 0.01% or more and less than 1%, 0.01% or more and less than 0.9%, 0.01% or more and less than 0.8%, 0.01% or more and less than 0.7%, 0.01 % or more and less than 0.6%, 0.01% or more and less than 0.5%, 0.01% or more and less than 0.4%, 0.01% or more and less than 0.3%, 0.01% or more and less
  • the volumetric swelling ratio of the biodegradable molded product measured by Measurement Method 4 satisfies the above range, resistance to solvents can be improved without deteriorating mechanical properties, and it can be used in product fields requiring long-term durability. In addition, it does not cause a decrease in the dispersibility of the inorganic filler, the physical properties of the manufactured molded article can be improved, a rapid increase in biodegradability can be prevented, and elongation and strength can be maintained, thereby ensuring product reliability.
  • the biodegradable molded article may be a biodegradable film.
  • the thickness of the biodegradable film is 5 ⁇ m to 200 ⁇ m, 5 ⁇ m to 180 ⁇ m, 5 ⁇ m to 160 ⁇ m, 10 ⁇ m to 150 ⁇ m, 15 ⁇ m to 130 ⁇ m, 20 ⁇ m to 100 ⁇ m, 25 ⁇ m to 80 ⁇ m, 10 It may be ⁇ m to 50 ⁇ m, 10 ⁇ m to 30 ⁇ m, or 25 ⁇ m to 60 ⁇ m.
  • the tensile strength of the biodegradable film may be 5 MPa or more, 7 MPa or more, 9 MPa or more, 10 MPa or more, 11 MPa or more, 30 MPa or less, 27 MPa or less, 25 MPa or less, 23 MPa or less, or 21 MPa or less. When the above range is satisfied, excellent mechanical properties are achieved.
  • the tear strength of the biodegradable film is 75 N/mm or more, 80 N/mm or more, 85 N/mm or more, 90 N/mm or more, 200 N/mm or less, 180 N/mm or less, 150 N/mm or less. , or may be 135 N/mm or less. If the above range is satisfied, the film is not easily torn, and the biodegradation rate can be further improved after biodegradation begins.
  • the elongation of the biodegradable film may be 85% or more, 90% or more, 95% or more, 700% or less, 650% or less, 600% or less, or 550% or less. If the above range is satisfied, elasticity can be secured and a certain load can be withstood.
  • the biodegradable molded article may be a biodegradable sheet.
  • the thickness of the biodegradable sheet is 5 ⁇ m to 180 ⁇ m, 5 ⁇ m to 160 ⁇ m, 10 ⁇ m to 150 ⁇ m, 15 ⁇ m to 130 ⁇ m, 20 ⁇ m to 100 ⁇ m, 25 ⁇ m to 80 ⁇ m, 10 ⁇ m to 50 ⁇ m, or It may be 10 ⁇ m to 30 ⁇ m.
  • the tensile strength of the biodegradable sheet is 5 MPa or more, 6 MPa or more, 9 MPa or more, 10 MPa or more, 11 MPa or more, 12 MPa or more, 40 MPa or less, 35 MPa or less, 30 MPa or less, 27 MPa or less, 25 MPa. It may be less than or equal to 23 MPa, or less than or equal to 21 MPa. If the above range is satisfied, the sheet is not easily torn, and the biodegradation rate can be further improved after biodegradation begins.
  • the elongation of the biodegradable sheet may be 10% or more, 15% or more, 20% or less, 50% or less, 70% or more, 700% or less, 650% or less, 550% or less, 500% or less, or 450% or less. If the above range is satisfied, elasticity can be secured and a certain load can be withstood.
  • the method for producing a biodegradable molded article according to the present invention includes the steps of (a) producing a prepolymer by esterifying a diol component and a dicarboxylic acid component, (b) polycondensing the prepolymer to produce a biodegradable resin. (c) preparing a biodegradable resin composition by mixing the biodegradable resin and an inorganic filler, (d) preparing a pellet from the biodegradable resin composition, and (e) preparing the pellet. It may include drying and melt extrusion steps.
  • the manufacturing method may include the step of (a) preparing a prepolymer by esterifying a diol component and a dicarboxylic acid component.
  • the diol component and the dicarboxylic acid component may be the same as the diol component and dicarboxylic acid component in the biodegradable resin composition described above.
  • step (a) the composition containing the diol component, the dicarboxylic acid component, and optionally the nanocellulose is prepared through a one-step esterification reaction or a first esterification reaction and a second esterification reaction. It can be manufactured through a two-step esterification reaction.
  • the two-step esterification reaction includes (a-1) performing a first esterification reaction of the diol component and the dicarboxylic acid component, and (a-2) adding the above to the reaction product of step (a-1). It may include the step of adding a diol component and the dicarboxylic acid component and performing a secondary esterification reaction.
  • the binding force of the nanocellulose can be improved by adding the nanocellulose in the second esterification reaction step.
  • the binding force of the nanocellulose can be further improved by adding water-dispersed nanocellulose in the second esterification reaction step.
  • the nanocellulose can be added under temperature conditions of 100°C to 160°C, 110°C to 140°C, or 110°C to 150°C. If the above range is satisfied, water resistance can be improved.
  • the nanocellulose may be added at a rate of 2 kg/min to 10 kg/min, 2.5 kg/min to 9.5 kg/min, or 3 kg/min to 8 kg/min. If the above range is satisfied, the efficiency of the manufacturing process can be improved without causing re-agglomeration of nanocellulose.
  • a titanium-based catalyst, a germanium-based catalyst, an antimony-based catalyst, additives, and stabilizers may be added before the esterification reaction.
  • the esterification reaction is carried out for 0.5 hours to 5 hours and 0.5 hours to 4.5 hours at a temperature range of 250°C or less, 240°C or less, 235°C or less, 180°C to 250°C, 185°C to 240°C, or 200°C to 240°C, respectively. hours, 0.5 hours to 3.5 hours, or 1 hour to 3 hours.
  • the esterification reaction can be performed at normal pressure until the by-products of water and methanol theoretically reach 90%.
  • the number average molecular weight of the prepolymer is 500 g/mol to 10,000 g/mol, 500 g/mol to 8,500 g/mol, 500 g/mol to 7,000 g/mol, 1,000 g/mol to 6,000 g/mol, or 2,500 g/mol. It can be g/mol to 5,500 g/mol.
  • the number average molecular weight can be measured by gel permeation chromatography (GPC). When the above range is satisfied, the molecular weight of the prepolymer can be efficiently increased in the polycondensation reaction, thereby improving strength characteristics.
  • the manufacturing method may include the step of (b) polycondensing the prepolymer to produce a biodegradable resin.
  • the polycondensation reaction is performed at a temperature range of 180°C to 280°C, 190°C to 270°C, 210°C to 260°C, or 230°C to 255°C, 1. Torr or less, 0.9 Torr or less, 0.7 Torr or less, 0.2 Torr or less. It may be performed for 1 hour to 6 hours, 1.5 hours to 5.5 hours, 2 hours to 5 hours, or 3.5 hours to 4.5 hours, at a pressure range of 1.0 Torr, 0.3 Torr to 0.9 Torr, or 0.5 Torr to 0.9 Torr.
  • the intrinsic viscosity of the biodegradable resin prepared in step (b) may be 0.05 to 10 dL/gr.
  • the melt viscosity of the biodegradable resin is measured with a rheometrics dynamic spectrometer (RDS) under 100 s -1 conditions, it may be 1,000 to 30,000 poise.
  • the number average molecular weight (Mn) of the biodegradable resin may be 40,000 g/mol or more, 43,000 g/mol or more, 45,000 g/mol or more, or 40,000 g/mol to 70,000 g/mol.
  • the weight average molecular weight (MW) of the biodegradable resin may be 60,000 g/mol or more, 65,000 g/mol or more, 75,000 g/mol or more, 80,000 g/mol or more, or 85,000 g/mol to 100,000 g/mol.
  • the polydispersity index (PDI) of the biodegradable resin may be 1.2 to 2.0, 1.5 to 1.9, or 1.6 to 1.8.
  • the acid value of the biodegradable resin may be 1.8 mgKOH/g or less, 1.5 mgKOH/g or less, 1.3 mgKOH/g or less, or 1.25 mgKOH/g or less. If the above range is satisfied, water resistance can be improved.
  • the manufacturing method may include the step of (c) mixing the biodegradable resin and an inorganic filler to prepare a biodegradable resin composition.
  • the mixing can be appropriately set depending on the molding method.
  • the biodegradable resin and the inorganic filler can be kneaded and melted before being introduced from the hopper into the molding machine, and the biodegradable resin and the inorganic filler can also be kneaded and melted simultaneously with molding by being integrated with the molding machine.
  • the kneading is preferably performed by uniformly dispersing the inorganic filler in the biodegradable resin and at the same time applying high shear stress.
  • step (c) may additionally add one or more of the plasticizer or the additive.
  • Step (c) may include one or more mixing steps.
  • the inorganic filler is added in an amount of 60 to 80% by weight, 61 to 80% by weight, 62 to 80% by weight, 63 to 80% by weight, and 64 to 80% by weight based on the total weight of the biodegradable resin composition. , 65 to 80% by weight, 60 to 75% by weight, 61 to 75% by weight, 62 to 75% by weight, 63 to 75% by weight, 64 to 75% by weight, 65 to 75% by weight, or 65 to 72% by weight. It may be a single mixing step to prepare a biodegradable resin composition.
  • the inorganic filler is added in an amount of 60 to 80% by weight, 61 to 80% by weight, 62 to 80% by weight, 63 to 80% by weight, 64 to 80% by weight, based on the total weight of the biodegradable resin composition.
  • the inorganic filler is added in an amount of 30 to 85% by weight, 30 to 80% by weight, 30 to 75% by weight, and 30 to 70% by weight. %, 35 to 85% by weight, 35 to 80% by weight, 35 to 75% by weight, 35 to 70% by weight, 40 to 85% by weight, 40 to 80% by weight, 40 to 75% by weight, 40 to 70% by weight, 45 to 85% by weight, 45 to 80% by weight, 45 to 75% by weight, 45 to 70% by weight, 50 to 85% by weight, 50 to 80% by weight, 50 to 75% by weight, or 50 to 70% by weight. It may include a second mixing step to prepare a biodegradable resin composition.
  • the one or more mixing steps may be a tandem continuous process.
  • the temperature of the mixing step may be 150 to 190°C, 150 to 180°C, or 160 to 180°C. When the above range is satisfied, the phenomenon of increased torque in the mixing step and the phenomenon of thermal decomposition of the mixed biodegradable resin composition can be reduced.
  • the manufacturing method may include the step of (d) manufacturing pellets from the biodegradable resin composition.
  • step (d) the biodegradable resin composition is put into an extrusion molding machine equipped with a single screw or an extrusion molding machine equipped with a twin screw and extruded at a temperature of 150 °C to 180 °C, and cut with a hot-cut pellet cutting machine.
  • pellets can be manufactured by cooling at 30°C or lower, 25°C or lower, 5 to 50°C, 10 to 30°C, 15 to 25°C, or 20 to 25°C.
  • the cutting step is not particularly limited as long as it is a pellet cutting machine used in the industry, and the shape of the produced pellets is not particularly limited.
  • the manufacturing method may include the step of (e) drying and melt-extruding the pellet.
  • the drying is performed at a temperature range of 60°C to 100°C, 65°C to 95°C, 70°C to 90°C, or 75°C to 85°C for 2 hours to 12 hours, 3 hours to 12 hours, or 4 hours to 10 hours. It can be performed during When the above conditions are met, the appearance, mechanical properties, and chemical properties of the manufactured biodegradable molded product can be further improved.
  • the melt extrusion is performed at 270°C or lower, 265°C or lower, 260°C or lower, 255°C or lower, 130°C to 270°C, 130°C to 250°C, 140°C to 230°C, 150°C to 200°C, or 150°C to 180°C. It can be performed in The melt extrusion may be performed by a blown film process or a press process, but is not particularly limited.
  • the torque during melt extrusion may be 100 N ⁇ m to 300 N ⁇ m, or 150 N ⁇ m to 250 N ⁇ m.
  • Glycerol monostearate (GMS) Glycerol monostearate
  • Biodegradable resin #1 calcium carbonate #1: plasticizer: antioxidant #1: antioxidant #2 was added to the kneader reactor at a weight ratio of 68.7:30:1:0.1:0.2 and kneaded at a temperature of 175°C. Afterwards, it was extruded with an extrusion molding machine equipped with a single screw, cut and cooled with a hot-cut pellet cutting machine to prepare a pelletized biodegradable resin composition.
  • a flat stainless steel (SUS) plate with a width of 12 cm and a height of 12 cm was placed on one of the Teflon sheets, and then the pelletized biodegradable resin composition was placed on the stainless steel plate. placed on a plate. Afterwards, it was covered with another Teflon sheet among the Teflon sheets, and a biodegradable resin sheet with an average thickness of 0.9 mm was manufactured under the conditions of 180°C temperature and 20Mpa pressure.
  • a biodegradable resin sheet was manufactured through the same process as Example 1-1, except that a pelletized biodegradable resin composition was prepared with the composition shown in Table 1 below.
  • Samples of the biodegradable resin sheets were prepared by cutting each of the biodegradable resin sheets prepared in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-3 into 10 cm in width and 3 cm in length.
  • Examples 1-1 to 1-4 have a weight loss rate of 1% or less after aging for 3 weeks at a temperature of 50°C and a relative humidity of 50%, and a temperature of 85°C and a relative humidity of 85%.
  • the weight loss rate after aging for 3 weeks under conditions of relative humidity was less than 1%, confirming that the phenomenon of sample weight loss due to hydrolysis was minimized not only in a mild environment but also in a relatively high temperature and high humidity environment.
  • Examples 1-1 to 1-4 have a weight loss rate deviation of 1% or less under the conditions of a temperature of 50°C and a relative humidity of 50% and a temperature of 85°C and a relative humidity of 85%, indicating a mild environment.
  • water resistance can be maintained even in relatively high temperature and humidity environments, making it possible to commercialize it in a variety of environments.
  • the sample was dissolved in benzyl alcohol and dispersed in a chloroform solvent, and then the color change was confirmed using phenol red to measure the number of carboxyl terminal groups in each sample. Thereafter, the samples were aged for 3 weeks in a chamber with a temperature of 50°C and a relative humidity of 50%, and then the number of carboxyl terminal groups in each sample was measured, and the results are shown in Table 3 below.
  • the sample was dissolved in benzyl alcohol and dispersed in a chloroform solvent, and then the color change was confirmed using phenol red to measure the number of carboxyl terminal groups in each sample. Thereafter, the samples were aged for 3 weeks in a chamber at a temperature of 85°C and a relative humidity of 85%, and then the number of carboxyl terminal groups in each sample was measured, and the results are shown in Table 3 below.
  • Examples 1-1 to 1-4 have a rate of change in the number of carboxyl (COOH) terminal groups of 25% or less after aging for 3 weeks at a temperature of 50°C and a relative humidity of 50%, and at 85°C.
  • the rate of change in the number of carboxyl end groups after aging for 3 weeks at a temperature and relative humidity of 85% is less than 50%, indicating that the number of carboxyl end groups is reduced by hydrolysis not only in mild environments but also in relatively high temperature and humidity environments. It was confirmed that the phenomenon was minimized.
  • the initial number average molecular weight of each of the samples was measured using gel permeation chromatography (GPC). Afterwards, the samples were immersed in water (100% RH) at 70°C for 10 days, and then the number average molecular weight of each sample was measured. The ratio of the number average molecular weight after immersion to the initial number average molecular weight is shown in the table below. It is shown in 4.
  • Examples 1-1 to 1-4 which contain calcium carbonate in the biodegradable resin composition and have a weight loss rate of 1% or less under the conditions of a temperature of 50 ° C. and a relative humidity of 50%, are compared. It was confirmed that the weight loss rate, number of carboxyl terminal groups, and number average molecular weight change rate were all reduced compared to Examples 1-1 to 1-2.
  • Examples 1-1 to 1-4 in which the calcium carbonate content is 30% by weight or more have a weight loss rate of 1% or less under the conditions of a temperature of 50°C and a relative humidity of 50%, and a temperature of 85°C and a relative humidity of 85%.
  • Biodegradable resin #1 calcium carbonate #2: plasticizer: antioxidant #1: antioxidant #2 was added to the kneader reactor at a weight ratio of 69.55:30:0.3:0.05:0.10 and kneaded at a temperature of 175°C. Afterwards, it was extruded with an extrusion molding machine equipped with a single screw, cut and cooled with a hot-cut pellet cutting machine to prepare a pelletized biodegradable resin composition.
  • a pelletized biodegradable resin composition was prepared by the same process as Example 2-1, except that the pelletized biodegradable resin composition was prepared with the composition shown in Table 5 below.
  • Example 2-1 69.55 Not included 30 0.30 0.05 0.10
  • Example 2-2 59.55 Not included 40 0.30 0.05 0.10
  • Example 2-3 50.55 Not included 49 0.30 0.05 0.10
  • Example 2-4 29.20 Not included 70 0.60 0.10 0.10 Comparative Example 2-1 99.55 Not included Not included 0.30 0.05 0.10 Comparative Example 2-2 Not included 99.55 Not included 0.30 0.05 0.10
  • Each of the pelletized biodegradable resin compositions prepared in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2 was placed on a flat stainless steel (SUS) plate with a width of 12 cm and a length of 12 cm.
  • a biodegradable resin sheet with an average thickness of 0.9 mm was manufactured under conditions of 180°C temperature and 20Mpa pressure. Thereafter, the sheet was cut into 2 cm in width and 2 cm in length to prepare a sample of the biodegradable resin sheet.
  • Each of the pelletized biodegradable resin compositions prepared in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-2 was dried at a temperature of 80°C for 5 hours and then extruded using a blown film extruder.
  • Biodegradable films with a thickness of 15 ⁇ m were manufactured by melt extrusion at a temperature of 160°C using Line, Manufacturer: Eugene Engineering.
  • the volume (X) of each sample was measured. Thereafter, the sample was placed in 50 ml of ethanol solvent and stored at room temperature for 24 hours. The surface of the sample was wiped twice using gauze, and the volume (Y) of each sample was measured. The results are shown in Table 6 below. indicated.
  • the decomposed surface area is less than 10% compared to the total surface area of the film.
  • the decomposed surface area is more than 10% and less than 30% compared to the total surface area of the film.
  • the decomposed surface area is more than 30% and less than 60% of the total surface area of the film.
  • Example 2-1 30 395.2 405.8 2.68 18.83 19.53 0.81 297.88 18.98 19.76 0.81 303.79 1.98 B
  • Example 2-2 40 349.0 354.5 1.58 19.58 20.93 0.63 258.18 21.04 19.73 0.63 261.53 1.30
  • Example 2-3 49 352.0 355.8 1.08 19.62 20.36 0.61 243.67 19.64 20.51 0.61 245.72 0.84
  • a Example 2-4 70 548.3 548.4 0.02 19.69 20.16 0.81 321.53 19.70 20.16 0.81 321.69 0.05
  • Comparative Example 2-1 - 2) 301.1 315.9 4.92 19.96 20.17 0.67 269.74 20.
  • Examples 2-1 to 2-4 which have a weight swelling ratio of less than 4% as measured by the measurement method of the present invention, have significantly improved solvent resistance compared to Comparative Examples 2-1 to 2-2. could be confirmed. Therefore, it was confirmed that the biodegradable resin compositions according to Examples 2-1 to 2-4 can be commercialized in a wider range of fields than conventional biodegradable resin compositions.
  • Examples may be applied to biodegradable resin compositions and biodegradable molded articles containing the same.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

La présente invention concerne : une composition de résine biodégradable comprenant une résine biodégradable et une charge inorganique ; et un produit moulé biodégradable la comprenant. Dans la composition de résine biodégradable, le taux de réduction de poids, A (%), est inférieur ou égal à 1%. Dans la composition de résine biodégradable, le taux d'expansion pondérale est inférieur à 4%.
PCT/KR2023/018501 2022-11-29 2023-11-16 Composition de résine biodégradable et produit moulé biodégradable la comprenant WO2024117626A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2022-0163327 2022-11-29
KR10-2022-0163328 2022-11-29
KR1020220163328A KR20240079913A (ko) 2022-11-29 2022-11-29 생분해성 수지 조성물 및 이를 포함하는 생분해성 성형품
KR1020220163327A KR20240079912A (ko) 2022-11-29 2022-11-29 생분해성 수지 조성물 및 이를 포함하는 생분해성 성형품

Publications (1)

Publication Number Publication Date
WO2024117626A1 true WO2024117626A1 (fr) 2024-06-06

Family

ID=91324226

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2023/018501 WO2024117626A1 (fr) 2022-11-29 2023-11-16 Composition de résine biodégradable et produit moulé biodégradable la comprenant

Country Status (2)

Country Link
TW (1) TW202428784A (fr)
WO (1) WO2024117626A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017119850A (ja) * 2015-12-24 2017-07-06 アキレス株式会社 耐引裂伝播性を有する生分解性フィルム
KR101823409B1 (ko) * 2017-05-12 2018-01-31 (주)세진바이오 생분해성 농업용 멀칭필름
KR101999919B1 (ko) * 2018-02-21 2019-07-12 서울대학교산학협력단 생분해성 고분자 복합재
KR20210005735A (ko) * 2018-10-26 2021-01-14 가부시키가이샤 티비엠 생분해성 수지 성형품 및 그 제조 방법, 및 이에 이용되는 펠렛체
KR20220116678A (ko) * 2021-02-15 2022-08-23 대상 주식회사 열가소성 전분 조성물, 이의 제조방법 및 이의 용도

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017119850A (ja) * 2015-12-24 2017-07-06 アキレス株式会社 耐引裂伝播性を有する生分解性フィルム
KR101823409B1 (ko) * 2017-05-12 2018-01-31 (주)세진바이오 생분해성 농업용 멀칭필름
KR101999919B1 (ko) * 2018-02-21 2019-07-12 서울대학교산학협력단 생분해성 고분자 복합재
KR20210005735A (ko) * 2018-10-26 2021-01-14 가부시키가이샤 티비엠 생분해성 수지 성형품 및 그 제조 방법, 및 이에 이용되는 펠렛체
KR20220116678A (ko) * 2021-02-15 2022-08-23 대상 주식회사 열가소성 전분 조성물, 이의 제조방법 및 이의 용도

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TING ZHANG; CAILI ZHANG; YANG YANG; FAN YANG; MIN ZHAO; YUNXUAN WENG: "Improved properties of poly(butylene adipate‐co‐terephthalate)/calcium carbonate films through silane modification", JOURNAL OF APPLIED POLYMER SCIENCE, JOHN WILEY & SONS, INC., US, vol. 138, no. 38, 7 May 2021 (2021-05-07), US , pages n/a - n/a, XP071322623, ISSN: 0021-8995, DOI: 10.1002/app.50970 *

Also Published As

Publication number Publication date
TW202428784A (zh) 2024-07-16

Similar Documents

Publication Publication Date Title
WO2021241931A1 (fr) Composition de résine de polyester biodégradable, tissu non tissé et film, et leur procédé de fabrication
WO2023080496A1 (fr) Composition de résine biodégradable ayant une teneur élevée en carbonate de calcium
WO2023008903A1 (fr) Composition de résine biodégradable, et film biodégradable et film de paillage biodégradable utilisant chacun celle-ci
WO2023008902A1 (fr) Composition de résine biodégradable, et film biodégradable et produit biodégradable l'utilisant
WO2023033547A1 (fr) Composition moussante, mousse biodégradable et son procédé de préparation
WO2022102902A1 (fr) Film stratifié biodégradable et son procédé de fabrication
WO2024117626A1 (fr) Composition de résine biodégradable et produit moulé biodégradable la comprenant
WO2024029818A1 (fr) Composition de résine biodégradable et article moulé biodégradable la comprenant
WO2021141236A1 (fr) Composition de résine biodégradable ayant des propriétés mécaniques, une aptitude au moulage et une résistance aux intempéries améliorées, et son procédé de préparation
WO2014142590A1 (fr) Modificateur d'acide polylactique, procédé de préparation d'un modificateur d'acide polylactique, procédé pour modifier l'acide lactique l'employant, composition de mousse biodégradable employant le modificateur d'acide polylactique et mousse pour chaussures employant la composition de mousse biodégradable
WO2024029811A1 (fr) Procédé de préparation d'une composition de résine biodégradable, composition de résine biodégradable ainsi préparée et produit moulé biodégradable la comprenant
WO2024117627A1 (fr) Composition de résine biodégradable et article moulé biodégradable la comprenant
WO2023033518A1 (fr) Composition pour fibre biodégradable et fibre biodégradable fabriquée à l'aide de celle-ci
WO2023008959A1 (fr) Dispersion de polyhydroxyalcanoate (pha) et son procédé de préparation
WO2024122974A1 (fr) Composition de résine biodégradable, film biodégradable la comprenant et article moulé biodégradable la comprenant
WO2024112154A1 (fr) Procédé de préparation de composition de résine de polyester biodégradable et procédé de production de film de polyester biodégradable l'utilisant
WO2023068594A1 (fr) Résine de polyester biodégradable, et film de polyester biodégradable et stratifié la comprenant
WO2023229216A1 (fr) Article moulé biodégradable et composition de résine de polyester biodégradable
WO2023229235A1 (fr) Composition de résine de polyester biodégradable, son procédé de préparation et article moulé biodégradable la comprenant
WO2023229311A1 (fr) Résine de polyester biodégradable, son procédé de préparation et film de polyester biodégradable comprenant ladite résine
WO2023239039A1 (fr) Composition de résine de polyester biodégradable, film de polyester biodégradable la comprenant, et article moulé biodégradable la comprenant
WO2023229310A1 (fr) Composition de polymère de polyester biodégradable, résine de polyester biodégradable faisant appel à celle-ci, et son procédé de préparation
WO2023234644A1 (fr) Résine de polyester biodégradable, son procédé de préparation et film de polyester biodégradable la comprenant
WO2023229212A1 (fr) Composition de résine de polyester biodégradable et article moulé en polyester biodégradable la comprenant
WO2022260363A1 (fr) Mousse de polyuréthane et son procédé de fabrication

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23898157

Country of ref document: EP

Kind code of ref document: A1