WO2024112076A1 - Biodegradable composition and biodegradable film comprising same - Google Patents
Biodegradable composition and biodegradable film comprising same Download PDFInfo
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- WO2024112076A1 WO2024112076A1 PCT/KR2023/018806 KR2023018806W WO2024112076A1 WO 2024112076 A1 WO2024112076 A1 WO 2024112076A1 KR 2023018806 W KR2023018806 W KR 2023018806W WO 2024112076 A1 WO2024112076 A1 WO 2024112076A1
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- 229940116226 behenic acid Drugs 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- GDFPABMEKHDOGS-UHFFFAOYSA-N bis(2,4-ditert-butyl-5-methylphenoxy)-(2-phenylphenyl)phosphane Chemical group C1=C(C(C)(C)C)C(C)=CC(OP(OC=2C(=CC(=C(C)C=2)C(C)(C)C)C(C)(C)C)C=2C(=CC=CC=2)C=2C=CC=CC=2)=C1C(C)(C)C GDFPABMEKHDOGS-UHFFFAOYSA-N 0.000 description 1
- NMZURFAPYNEBQQ-UHFFFAOYSA-M bis(4-tert-butylphenyl) phosphate Chemical class C1=CC(C(C)(C)C)=CC=C1OP([O-])(=O)OC1=CC=C(C(C)(C)C)C=C1 NMZURFAPYNEBQQ-UHFFFAOYSA-M 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical class [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical class [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Definitions
- Examples relate to biodegradable compositions and biodegradable films containing the same.
- Biodegradable plastic refers to a material that is decomposed into low-molecular-weight substances by microorganisms existing in nature, and ultimately decomposes into water and carbon dioxide, or water and methane gas.
- Biodegradable plastics include, for example, polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), and polybutylene succinate (PBS). It is being used a lot.
- biodegradable resins meet the purpose of biodegrading waste products for a resource circulation structure, they have poor heat resistance and may have the problem of reduced durability due to decomposition by heat, ultraviolet rays, and bacteria.
- the heat deformation temperature is about 50°C to 60°C, so there are problems with processability and productivity due to heat deformation during the process, and product quality is affected. It may also have a negative impact.
- the biodegradable resins have limitations in processing, and in the case of biodegradable films and products manufactured using the biodegradable resins, they are limited to simply disposable products, which limits the expansion of their uses. there is.
- Patent Document 1 Korean Patent Publication No. 2012-0103158
- the present invention is designed to solve the problems of the prior art described above.
- it is biodegradable in both soil and the ocean, has excellent mechanical properties such as tensile strength and elongation, has improved durability, weather resistance, and heat resistance even in high temperature and high humidity environments, and is thermally stable in various processes.
- the aim is to provide a biodegradable composition that can improve processability and productivity.
- an object is to provide a biodegradable film formed from the biodegradable composition.
- it includes a copolymerized polyhydroxyalkanoate (PHA) resin, and the copolymerized polyhydroxyalkanoate (PHA) resin is 4-hydroxybutyrate (4-HB).
- PHA copolymerized polyhydroxyalkanoate
- PHA 4-hydroxybutyrate
- Tensile strength change rate (%) ((TS A - TS B )/TS A ) ⁇ 100
- TS A and TS B For TS A and TS B , according to ASTM D882, a specimen of the biodegradable film prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (UTM). The tensile strength (Mpa) measured at a tensile speed of 200 mm/min with as much installation as possible,
- TS A is the initial tensile strength of the biodegradable film at 25°C
- TS B is the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
- a biodegradable composition which has a decomposition rate of 50% or less, represented by Formula 2 below.
- Decomposition rate (%) ((Mw A - Mw B )/Mw A ) ⁇ 100
- Mw A and Mw B are the weight average molecular weight (g/mol) of the biodegradable film prepared from the biodegradable composition measured using gel permeation chromatography (GPC) after dissolving the biodegradable film in chloroform solvent,
- Mw A is the initial weight average molecular weight of the biodegradable film at 25°C
- Mw B is the weight average molecular weight of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
- a biodegradable composition which has an elongation change rate of 30% or less, represented by Equation 3 below.
- Elongation change rate (%) ((
- E A and E B cut a specimen of the biodegradable film made from the biodegradable composition into 10 cm in width and 1 cm in length, and used a universal testing machine (UTM) to measure the spacing between chucks at 20 mm. After mounting it as much as possible and measuring the maximum amount of deformation just before fracture at a speed of 200 mm/min, the elongation (%) is measured as the ratio of the maximum amount of deformation to the initial length,
- E A is the initial elongation of the biodegradable film at 25°C
- E B is the elongation of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
- a biodegradable composition wherein the dispersion index change rate represented by Equation 4 below is 50% or less.
- Dispersion index change rate (%) ((
- PDI A and PDI B are the number average molecular weight of the weight average molecular weight (Mw) of the biodegradable film measured using gel permeation chromatography (GPC) after dissolving the biodegradable film prepared from the biodegradable composition in chloroform solvent.
- GPC gel permeation chromatography
- PDI A is the initial dispersion index of the biodegradable film at 25°C
- PDI B is the dispersion index of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
- a biodegradable composition in which the copolymerized polyhydroxyalkanoate (PHA) resin satisfies one or more characteristics selected from the following characteristics: a glass transition temperature of -45°C to 80°C ( Tg), crystallization temperature (Tc) from 60°C to 120°C, and melting temperature (Tm) from 100°C to 170°C.
- PHA copolymerized polyhydroxyalkanoate
- the copolymerized polyhydroxyalkanoate (PHA) resin has a weight average molecular weight (Mw) of 200,000 g/mol to 900,000 g/mol, and a dispersion index (PDI) of more than 1.8 to 3.0 or less. ), providing a biodegradable composition.
- Mw weight average molecular weight
- PDI dispersion index
- the copolymerized polyhydroxyalkanoate (PHA) resin is 3-hydroxybutyrate (3-HB), 3-hydroxypropionate (3-HP), 3-hydroxyvalet late (3-HV), 3-hydroxyhexanoate (3-HH), 4-hydroxyvalerate (4-HV), 5-hydroxyvalerate (5-HV) and 6-hydroxyhexanoate
- a biodegradable composition is provided, further comprising at least one monomer selected from the group consisting of ate (6-HH).
- the copolymerized polyhydroxyalkanoate (PHA) resin includes a resin containing 3-hydroxybutyrate (3-HB) monomer and 4-hydroxybutyrate (4-HB) monomer. Provides a biodegradable composition.
- a biodegradable composition is provided, further comprising a lubricant.
- the biodegradable composition includes at least one selected from the group consisting of ester-based compounds, silicone-based compounds, and fatty acid amide-based compounds, and the content of the lubricant is 0.1 phr to 10 phr. provides.
- biodegradable film comprising the biodegradable composition.
- the tensile strength (MPa) of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH) is 10 MPa to 50 MPa, and the elongation is 10% to 40%.
- Phosphorus, biodegradable film is provided.
- the weight average molecular weight (g/mol) of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH) is 5,000 to 400,000 g/mol
- the biodegradable composition according to the above example includes a copolymerized polyhydroxyalkanoate (PHA) resin containing a specific content range of 4-hydroxybutyrate (4-HB) monomer, and has a tensile strength change rate below a specific range.
- PHA copolymerized polyhydroxyalkanoate
- 4-HB 4-hydroxybutyrate
- a biodegradable film containing a biodegradable composition is used not only for disposable packaging products used to maintain the packaging state for a short period of time, but also for food, medicine, sanitary products, and electronics used for long-term maintenance in a high-temperature and high-humidity environment. It can provide excellent physical properties such as thermal stability and mechanical properties even when applied to various products such as products, cosmetics, and industrial products, and is very thermally stable even in various processes such as heat curing, printing, and deposition for manufacturing final biodegradable products. As a result, there are no restrictions on the process, and moldability, processability, and productivity can be improved, allowing expansion of various uses.
- the copolymerized polyhydroxyalkanoate (PHA) resin includes a 4-hydroxybutyrate (4-HB) monomer.
- a biodegradable composition is provided, which contains 0.1% by weight or more and less than 30% by weight based on the total weight of alkanoate (PHA) resin, and has a tensile strength change rate of 5% or less, expressed by the following formula 1.
- Tensile strength change rate (%) ((TS A - TS B )/TS A ) ⁇ 100
- TS A and TS B For TS A and TS B , according to ASTM D882, a specimen of the biodegradable film prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (UTM). The tensile strength (Mpa) measured at a tensile speed of 200 mm/min with as much installation as possible,
- TS A is the initial tensile strength of the biodegradable film at 25°C
- TS B is the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
- the biodegradable composition includes a copolymerized polyhydroxyalkanoate (PHA) resin containing a specific content range of 4-hydroxybutyrate (4-HB) monomer, and has a tensile strength below a specific range.
- PHA copolymerized polyhydroxyalkanoate
- 4-HB 4-hydroxybutyrate
- biodegradable films and biodegradable products that are thermally stable even when stored for a long time in a high temperature and high humidity environment and have excellent mechanical properties can be provided.
- it is thermally very stable in various processes such as heat curing, printing, or deposition required for manufacturing final biodegradable products, so there are no process restrictions, and it has technical significance in that it not only improves processability and productivity, but also allows expansion of various uses. .
- the biodegradable composition is a biodegradable resin that uses the copolymerized polyhydroxyalkanoate (PHA) resin alone without mixing with other biodegradable resins other than the copolymerized polyhydroxyalkanoate (PHA) resin.
- PHA copolymerized polyhydroxyalkanoate
- the above characteristics can be satisfied even when used.
- the biodegradable composition includes a copolymerized polyhydroxyalkanoate (PHA) resin.
- PHA polyhydroxyalkanoate
- polyhydroxyalkanoate (PHA) resins include polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polybutylene succinate terephthalate (PBST), and It has similar physical properties to synthetic polymers such as polybutylene succinate adipate (PBSA), is completely biodegradable, and has excellent biocompatibility.
- PBAT polybutylene adipate terephthalate
- PBS polybutylene succinate
- PBST polybutylene succinate terephthalate
- PBSA polybutylene succinate adipate
- the polyhydroxyalkanoate (PHA) resin is a thermoplastic natural polyester polymer that accumulates in microbial cells, can be composted as a biodegradable material, and does not generate toxic waste, ultimately producing carbon dioxide, water, and organic waste. can be decomposed into
- the copolymerized polyhydroxyalkanoate (PHA) resin can be biodegraded in soil and the ocean, when the biodegradable composition contains the copolymerized polyhydroxyalkanoate (PHA) resin, it can be used in any area such as soil and ocean. It is biodegradable even under environmental conditions and has environmentally friendly characteristics.
- the copolymerized polyhydroxyalkanoate (PHA) resin may be a copolymer containing two or more different monomers in which the different monomers are randomly distributed in the polymer chain.
- the copolymerized polyhydroxyalkanoate (PHA) resin includes 4-hydroxybutyrate (hereinafter referred to as 4-HB).
- the content of the 4-HB monomer is important to improve the biodegradability of the desired soil and ocean, as well as to have excellent mechanical properties in a high temperature and high humidity environment, and to improve durability, weather resistance, and heat resistance. You can.
- the copolymerized polyhydroxyalkanoate (PHA) resin contains 4-hydroxybutyrate (4-HB) monomer in an amount of 0.1% by weight or more based on the total weight of the copolymerized polyhydroxyalkanoate (PHA) resin. Contains less than 30% by weight.
- the content of the 4-HB monomer is 0.1% by weight or more, 0.2% by weight or more, 0.5% by weight or more, or 1% by weight or more, based on the total weight of the copolymerized polyhydroxyalkanoate (PHA) resin. It may be at least 1.5 wt%, at least 2 wt%, at least 3 wt%, at least 5 wt%, or at least 6 wt%, and less than 30 wt%, at most 29 wt%, at most 28 wt%, at most 25 wt%, and at most 22 wt%. % or less, 20 weight% or less, 18 weight% or less, 15 weight% or less, 12 weight% or less, or 10 weight% or less.
- the content of the 4-HB monomer is 0.2% by weight or more and 29% by weight or less, 0.5% or more and 29% by weight or less, 0.5% by weight or more and 28% by weight or less, and 1% by weight or more and 28% by weight or less. , 1% by weight or more and 25% by weight or less, 1% by weight or more and 20% by weight or less, 1% by weight or more and 15% by weight or less, 1% by weight or more and 12% by weight or less, 1% by weight or more and 10% by weight or less.
- 3% by weight or more and 28% by weight or less 3% by weight or more and 25% by weight or less, 3% by weight or more and 20% by weight or less, 3% by weight or more and 15% by weight or less, 3% by weight or more and 12% by weight or less.
- 3% by weight or more and 10% by weight or less 5% by weight or more and 28% by weight or less, 5% by weight or more and 25% by weight or less, 5% by weight or more and 20% by weight or less, 5% by weight or more and 15% by weight or less.
- 5% by weight or more and 12% by weight or less or 5% by weight or more and 10% by weight or less.
- the copolymerized polyhydroxyalkanoate (PHA) resin includes the 4-HB monomer and further includes one monomer different from the 4-HB monomer, or 2, 3, or 4 different monomers. , may additionally include 5, 6 or more monomers.
- the copolymerized polyhydroxyalkanoate (PHA) resin is 3-hydroxybutyrate (3-HB), 3-hydroxypropionate (3-HP), and 3-hydroxyvalerate (3-HV).
- 3-hydroxyhexanoate (3-HH), 4-hydroxyvalerate (4-HV), 5-hydroxyvalerate (5-HV) and 6-hydroxyhexanoate (6-HH) may further include one or more monomers selected from the group consisting of
- the copolymerized polyhydroxyalkanoate (PHA) resin includes 4-HB monomer, 3-HB monomer, 3-HP monomer, 3-HV monomer, 3-HH monomer, 4-HV It may include a resin containing one or more monomers selected from the group consisting of monomers, 5-HV monomers, and 6-HH monomers.
- the copolymerized polyhydroxyalkanoate (PHA) resin may include a resin containing a 3-HB monomer and a 4-HB monomer, for example, poly 3-hydroxybutyrate-co-4- It may contain hydroxybutyrate (hereinafter referred to as 3HB-co-4HB) resin.
- the copolymerized polyhydroxyalkanoate (PHA) resin includes the 3-HB monomer and the 4-HB monomer, and the weight ratio of the 3-HB monomer and the 4-HB monomer is 71: 29 to 99.9:0.1, 71:29 to 99.8:0.2, 71:29 to 99.5:0.5, 71:29 to 99:1, 75:25 to 99:1, 77:23 to 99:1, 80:20 to 80:20 It can be 99:1, 85:15 to 99:1, 87:13 to 99:1, 88:12 to 99:1, 90:10 to 97:3, or 90:10 to 95:5.
- the content of the 4-HB monomer is 0.1% by weight or more, 0.2% by weight or more, 0.5% by weight or more, 1% by weight or more, 1.5% by weight, based on the total weight of the 3-HB monomer and the 4-HB monomer. It may be at least 30% by weight, at least 2% by weight, at least 3% by weight, at least 5% by weight, or at least 6% by weight, and less than 30% by weight, at most 29% by weight, at most 28% by weight, at most 25% by weight, and at least 22% by weight. It may be 20% by weight or less, 18% by weight or less, 15% by weight or less, 12% by weight or less, or 10% by weight or less.
- the content of the 4-HB monomer is 0.2% by weight to 29% by weight, 0.5% by weight to 29% by weight, based on the total weight of the 3-HB monomer and the 4-HB monomer. 0.5% by weight or more and 28% by weight or less, 1% by weight or more and 28% by weight or less, 1% by weight or more and 25% by weight or less, 1% by weight or more and 20% by weight or less, 1% by weight or more and 15% by weight or less, 1% by weight or more and 12% by weight or less, 1% by weight or more and 10% by weight or less, 3% by weight or more and 28% by weight or less, 3% by weight or more and 25% by weight or less, 3% by weight or more and 20% by weight or less, 3% by weight or more and 15% by weight or less, 3% by weight or more and 12% by weight or less, 3% by weight or more and 10% by weight or less, 5% by weight or more and 28% by weight or less, 5% by weight or more and 25% by weight or less, It may be
- the copolymerized polyhydroxyalkanoate (PHA) resin includes a PHA resin containing a resin containing at least one of the 4-HB monomers, and the copolymerized polyhydroxyalkanoate (PHA) resin is obtained by controlling the content of the 4-HB monomer.
- the crystallinity of phenoate (PHA) resin can be adjusted.
- the copolymerized polyhydroxyalkanoate (PHA) resin with controlled crystallinity may have its crystallinity adjusted by increasing irregularity in the molecular structure, and specifically, the type of monomer, the ratio of monomers, or the type of isomer, and /Or the content may be adjusted.
- the copolymerized polyhydroxyalkanoate (PHA) resin has a glass transition temperature (Tg) of, for example, -45°C to 80°C, -35°C to 80°C, -30°C to 80°C, -25°C.
- the copolymerized polyhydroxyalkanoate (PHA) resin may have a crystallization temperature (Tc), for example, which may not be measured, or may range from, for example, 60° C. to 120° C., 70° C. to 120° C., 75° C. to 120° C., It may be 75°C to 115°C, 75°C to 110°C, or 90°C to 110°C.
- Tc crystallization temperature
- the copolymerized polyhydroxyalkanoate (PHA) resin may have a melting temperature (Tm) that may not be measured, for example, from 100°C to 170°C, from 110°C to 150°C, or from 120°C to 140°C. It can be.
- Tm melting temperature
- the copolymerized polyhydroxyalkanoate (PHA) resin has a glass transition temperature (Tg) of -45°C to 80°C, a crystallization temperature (Tc) of 60°C to 120°C, and a melting temperature (Tm) of 100°C to 170°C. ) may satisfy one or more characteristics selected from among the characteristics.
- the copolymerized polyhydroxyalkanoate (PHA) resin has a glass transition temperature (Tg) of -20°C to 0°C, a crystallization temperature (Tc) of 75°C to 115°C, and a melting temperature of 110°C to 160°C.
- Tg glass transition temperature
- Tc crystallization temperature
- Tm melting temperature
- copolymerized polyhydroxyalkanoate (PHA) resin may be a copolymerized PHA resin with controlled crystallinity.
- the copolymerized polyhydroxyalkanoate (PHA) resin may include a semi-crystalline PHA resin (hereinafter referred to as scPHA resin).
- the scPHA resin may include, for example, 0.1% by weight or more to less than 30% by weight of 4-HB monomer based on the total weight of the copolymerized polyhydroxyalkanoate (PHA) resin.
- the glass transition temperature (Tg) of the scPHA resin may be -20°C to 0°C.
- the crystallization temperature (Tc) of the scPHA resin may be 75°C to 115°C.
- the melting temperature (Tm) of the scPHA resin may be, for example, 110°C to 160°C.
- the glass transition temperature (Tg), crystallization temperature (Tc), and melting temperature (Tm) of the copolymerized polyhydroxyalkanoate (PHA) resin respectively satisfy the above ranges, the optical properties, thermal properties, and mechanical properties are It can be further improved, and is more advantageous in improving the desired durability, weather resistance, and heat resistance, and can also improve formability, processability, and productivity when manufacturing biodegradable films.
- the copolymerized polyhydroxyalkanoate (PHA) resin may have a weight average molecular weight (Mw) of, for example, 10,000 g/mol to 1,200,000 g/mol.
- Mw weight average molecular weight
- the weight average molecular weight (Mw) of the copolymerized polyhydroxyalkanoate (PHA) resin is 50,000 g/mol to 1,200,000 g/mol, 100,000 g/mol to 1,200,000 g/mol, and 50,000 g/mol to 1,000,000.
- the copolymerized polyhydroxyalkanoate (PHA) resin may have a dispersion index (PDI) of 1.0 or more, 1.2 or more, 1.5 or more, 1.8 or more, more than 1.8, or 2.0 or more, 5.0 or less, 4.0 or less, 3.0 or less, It may be 2.9 or less, 2.8 or less, 2.7 or less, 2.6 or less, 2.5 or less, or 2.4 or less.
- the copolymerized polyhydroxyalkanoate (PHA) resin has a dispersion index (PDI) of 1.0 or more to 5.0 or less, 1.0 or more to 4.0 or less, 1.5 or more to 3.5 or less, 1.5 or more to 3.0 or less, and greater than 1.8. It may be from 3.0 to 3.0, from 1.8 to 2.8, from 2.0 to 3.0, or from 2.0 to 2.5.
- the weight average molecular weight (Mw) and dispersion index (PDI) of the copolymerized polyhydroxyalkanoate (PHA) resin are respectively the initial weight average molecular weight (Mw A ) and initial dispersion index of the biodegradable film at 25°C, which will be described later. It may be the same as (PDI A ).
- the copolymerized polyhydroxyalkanoate (PHA) resin may have a weight average molecular weight (Mw) of 200,000 g/mol to 900,000 g/mol and a dispersion index (PDI) of more than 1.8 to 3.0 or less. .
- Mw weight average molecular weight
- PDI dispersion index
- the weight average molecular weight (Mw) of the copolymerized polyhydroxyalkanoate (PHA) resin can be analyzed by gel permeation chromatography, and the dispersion index (PDI) of the copolymerized polyhydroxyalkanoate (PHA) resin can be analyzed by gel permeation chromatography. It may be a value calculated as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
- the weight average molecular weight (Mw) and dispersion index (PDI) of the copolymerized polyhydroxyalkanoate (PHA) resin respectively satisfy the above ranges, the optical properties, thermal properties, and mechanical properties can be further improved, It is more advantageous in improving the desired durability, weather resistance, and heat resistance, and can also improve formability, processability, and productivity when manufacturing biodegradable films.
- the biodegradable composition does not contain any other biodegradable resin other than the copolymerized polyhydroxyalkanoate (PHA) resin, and may contain only the copolymerized polyhydroxyalkanoate (PHA) resin.
- the biodegradable composition contains only the copolymerized polyhydroxyalkanoate (PHA) resin as a biodegradable resin, the desired durability, weather resistance, and heat resistance can be improved, even when stored for a long time in a high temperature and high humidity environment. It is possible to provide biodegradable films and biodegradable products that are thermally stable and have excellent mechanical properties, and can improve formability, processability, and productivity, as well as expand various uses.
- PHA copolymerized polyhydroxyalkanoate
- the biodegradable composition may optionally include polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene adipate (PBA), polybutylene succinate-adipate (PBSA), and polybutyl.
- PBAT polybutylene adipate terephthalate
- PLA polylactic acid
- PBA polybutylene adipate
- PBSA polybutylene succinate-adipate
- PBS polybutylene succinate-adipate
- TPS thermoplastic starch
- It may further include one or more biodegradable resins selected from.
- the biodegradable composition may further include one or more additives selected from the group consisting of lubricants, antioxidants, compatibilizers, weighting agents, nucleating agents, melt strength enhancers, and slip agents.
- the content of the additive may be 0.1 phr to 30 phr based on 100 parts by weight of the total resin included in the biodegradable composition.
- the phr (per hundred resin) refers to the unit of input amount of material per 100 parts by weight of the total polymer resin (1 phr: 1 g of input amount for 100 g of polymer resin).
- the additive may be at least 0.1 phr, at least 0.5 phr, at least 1 phr, at least 1.5 phr, at least 2 phr, or at least 3 phr.
- the additive may be 30 phr or less, 28 phr or less, 25 phr or less, 20 phr or less, 15 phr or less, 10 phr or less, 8 phr or less, or 5 phr or less.
- the lubricant can improve the flowability of the biodegradable composition, thereby improving processability, smoothing the surface of the final product, and preventing adhesion.
- the lubricant may include one or more selected from the group consisting of ester-based compounds, silicone-based compounds, and fatty acid amide-based compounds.
- the ester-based compound may include one or more selected from the group consisting of butyl stearate, glycerol monostearate, and montan-based wax.
- the montan-based wax may be a mixture of straight-chain saturated carboxylic acids having a chain length of 28 to 32 carbon atoms.
- the silicone-based compound may include one or more types selected from the group consisting of silicone oil and silicone wax.
- the fatty acid amide compound includes one or more selected from the group consisting of fatty acid amide, ethylene-bisstearamide, ethylene-bis-oleamide (Ethylenebis(oleamide)), and erucamide. can do.
- the lubricant is 0.1 phr to 10 phr, 0.5 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr. , or may be included in an amount of 3 phr to 6 phr.
- the lubricant satisfies the above range, the appearance, lubricity, and dispersibility are excellent, so processability can be improved.
- the biodegradable composition may include 0.1 phr to 10 phr, 3 phr to 7 phr, or 3 phr to 6 phr of a fatty acid amide-based compound.
- the antioxidant is an additive that prevents decomposition by ozone or oxygen, prevents oxidation during storage, and prevents deterioration of the physical properties of the biodegradable film or biodegradable product formed from the biodegradable composition.
- the antioxidant may be a commonly used antioxidant as long as it does not impede the desired effect.
- the antioxidant may include one or more selected from the group consisting of hindered phenol-based antioxidants and phosphite-based (phosphorus-based) antioxidants.
- the hindered phenolic antioxidant is, for example, 4,4'-methylene-bis(2,6-di-t-butylphenol), octadecyl-3-(3,5-di-t-butyl-4) -Hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), 3,9-bis[2-[3- (3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane. It may include one or more types.
- the phosphite-based (phosphorus-based) antioxidant is, for example, tris-(2,4-di-t-butylphenyl)phosphite, bis-(2,4-di-t-butylphenyl)pentaerythritol-dephosphite, Spite, bis-(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-diphosphite, distearyl-pentaerythritol-diphosphite, [bis(2,4-di-t-butyl- 5-methylphenoxy)phosphino]biphenyl, and N,N-bis[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1 ,3,2]deoxyphosphepin-6-yl]oxy]-ethyl]ethanamine.
- the antioxidant is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr.
- phr 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, It may be included at 0.1 to 1 phr, or 0.1 to 0.5 phr.
- the physical properties of the biodegradable film or biodegradable product formed from the biodegradable composition can be improved, and it can be more advantageous to achieve the desired effect.
- the compatibilizer is an additive for providing compatibility by removing the release property of the copolymerized polyhydroxyalkanoate (PHA) resin.
- the compatibilizer may be a commonly used compatibilizer as long as it does not impede the effect.
- the compatibilizer consists of polyvinyl acetate (PVAc)-based, isocyanate-based, polypropylene carbonate-based, glycidyl methacrylate, ethylene vinyl alcohol, polyvinyl alcohol (PVA), ethylene vinyl acetate, and maleic anhydride. It may include one or more types selected from the group.
- the compatibilizer is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr.
- phr 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, It may be included at 0.1 to 1 phr, or 0.1 to 0.5 phr.
- the compatibilizer satisfies the above content range, the physical properties of the biodegradable film or biodegradable product formed from the biodegradable composition can be improved by increasing the compatibility between the resin and additives used, and the desired effect can be achieved. may be more advantageous.
- the weighting agent is an inorganic material and is an additive added to increase moldability by speeding up the crystallization rate during the molding process and to reduce the problem of increased costs due to the use of biodegradable resin.
- the weighting agent may be a commonly used inorganic material as long as it does not impede the desired effect.
- the weighting agent is calcium carbonate, such as light or heavy calcium carbonate, silica, talc, kaolin, barium sulfate, clay, calcium oxide, magnesium hydroxide, titanium oxide, carbon black, and at least one selected from the group consisting of glass fiber. may include.
- the average particle size of the weighting agent may be 0.5 ⁇ m to 10 ⁇ m. If the average particle size of the weighting agent is less than 0.5 ⁇ m, it becomes difficult to disperse the particles, and if it is more than 10 ⁇ m, the particle size becomes too large, which may impede the effect.
- the weighting agent is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr.
- phr 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, It may be included at 0.1 to 1 phr, or 0.1 to 0.5 phr.
- weighting agent When the weighting agent satisfies the above content range, it may be more advantageous to achieve the desired effect.
- the nucleating agent is an additive that assists or changes the crystallization form of the polymer and improves solidification when the polymer melt is cooled.
- the copolymerized polyhydroxyalkanoate (PHA) resin used according to one embodiment has a low solidification rate, process suitability as a soft material may not be easy.
- the nucleating agent is used, the solidification speed can be improved to further improve processability, moldability, and productivity, and the desired physical properties can be efficiently achieved.
- the nucleating agent may be a commonly used nucleating agent as long as it does not impede the effect.
- the nucleating agent is a single element material (pure material), a metal compound containing a complex oxide, for example, carbon black, calcium carbonate, synthetic silicic acid and salt, silica, zinc white, clay, kaolin, basic Magnesium carbonate, mica, talc, quartz powder, diatomite, dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, calcium silicate, metal salts of organic phosphorus and boron nitride; Low molecular weight organic compounds with metal carboxylate groups, such as octylic acid, toluic acid, heptanoic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, Behenic acid, cerotic acid, montanic acid, melissic acid, benzenoic acid, p-tert-butylbenzene acid, terephthalic acid,
- Metal salts of each phthalic acid monomethyl ester Polymeric organic compounds with metal carboxylate groups, such as carboxyl group-containing polyethylene obtained by the oxidation reaction of polyethylene, carboxyl group-containing polypropylene obtained by the oxidation reaction of polypropylene, acrylic acid or methacrylic acid and olefin ( For example, copolymers of ethylene, propylene and butene-1), copolymers of acrylic acid or methacrylic acid and styrene, copolymers of olefin and maleic anhydride, and metal salts of each of the copolymers of styrene and maleic anhydride; Polymeric organic compounds, for example, alpha-olefins having 5 or more carbon atoms branched to the carbon atom in the 3rd position (e.g., 3,3 dimethylbutene-1,3-methylbutene-1,3-methylpentene-1) , 3-methylhexene-1 and 3,5,5-trimethylhex
- vinylcyclopentane, vinylcyclohexane and vinylnorbonane polyalkylene glycols (e.g. polyethylene glycol) and polypropylene glycol), poly(glycolic acid), cellulose, cellulose esters and cellulose ethers; Phosphoric acid or phosphorous acid and its metal salts, such as diphenyl phosphate, diphenyl phosphite, metal salts of bis(4-tert-butylphenyl)phosphate and methylene bis-(2,4-tert-butylphenyl).
- nucleating agents may be used alone or in combination with each other.
- the nucleating agent is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr.
- phr 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, It may be included at 0.1 to 1 phr, or 0.1 to 0.5 phr.
- the solidification rate is improved to improve moldability and, for example, when cutting for pellet production or during the manufacturing process, the solidification rate is improved to improve productivity and Processability can be further improved.
- the melt strength enhancer is an additive for improving reactive melt strength.
- the melt strength enhancer may be a commonly used melt strength enhancer as long as it does not impede the effect.
- melt strength enhancer is polyester, styrene-based polymers (such as acrylonitrile butadiene styrene and polystyrene), polysiloxane, organic modified siloxane polymer, polyester, and maleic anhydride grafted ethylene propylene diene monomer (MAH-g).
- -EPDM may include one or more selected from the group consisting of
- the melt strength enhancer is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr, 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr , 0.1 to 1 phr, or 0.1 to 0.5 phr.
- melt strength enhancer When the melt strength enhancer satisfies the above content range, it may be more advantageous to achieve the desired effect.
- the slip agent is an additive that improves slipperiness during extrusion and prevents the surfaces of sheets or films from sticking to each other during the process.
- the slip agent may be a commonly used slip agent as long as it does not impair the effect.
- the slip agent may be at least one selected from Erucamide, Oliamide, and Stearamide.
- the slip agent is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr.
- phr 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, It may be included at 0.1 to 1 phr, or 0.1 to 0.5 phr.
- the biodegradable composition may also include a crosslinking agent and/or stabilizer.
- the crosslinking agent is an additive for modifying the properties of the copolymerized polyhydroxyalkanoate (PHA) resin and increasing the molecular weight of the resin, and a commonly used crosslinking agent can be used as long as it does not impair the effect.
- the cross-linking agent may be fatty acid ester, natural oil containing an epoxy group (epoxidized), diallyl phthalate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythate.
- At least one selected from the group consisting of litol pentaacrylate, diethylene glycol dimethacrylate, and bis(2-methacryloxyethyl)phosphate may be used.
- the crosslinking agent is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr.
- the stabilizer is an additive that protects against oxidation and heat and prevents color change.
- the stabilizer may be a commonly used stabilizer as long as it does not impair the effect.
- the stabilizer may be one selected from the group consisting of trimethyl phosphate, triphenyl phosphate, trimethyl phosphine, phosphoric acid, and phosphorous acid.
- the stabilizer is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr.
- phr 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, It may be included at 0.1 to 1 phr, or 0.1 to 0.5 phr.
- the biodegradable composition not only has excellent biodegradability, optical properties, and mechanical properties when applied to a biodegradable film containing it, but also has a tensile strength change rate below a certain range even when stored for a long time in a high temperature and high humidity environment. , it satisfies elongation change rate, decomposition rate, and dispersion index change rate, and can improve durability, weather resistance, and heat resistance at the same time.
- the biodegradable composition according to one embodiment may have a tensile strength change rate of 5% or less, expressed by Equation 1 below.
- Tensile strength change rate (%) ((TS A - TS B )/TS A ) ⁇ 100
- TS A and TS B For TS A and TS B , according to ASTM D882, a specimen of the biodegradable film prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (UTM). The tensile strength (Mpa) measured at a tensile speed of 200 mm/min with as much installation as possible,
- TS A is the initial tensile strength of the biodegradable film at 25°C
- TS B is the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
- the rate of change in tensile strength is the initial tensile strength of the biodegradable film at 25°C (TS A ) and the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH) (TS B ).
- the difference is divided by the initial tensile strength (TS A ) of the biodegradable film at 25°C, converted into a percentage, and the rate of change in tensile strength is 4% or less, 3% or less, 2% or less, and less than 2%. , may be 1.9% or less, 1.8% or less, or 1.75% or less.
- TS A is the initial tensile strength (day 0) of the biodegradable film at 25°C, and is 10 Mpa to 50 Mpa, 15 Mpa to 45 Mpa, 15 Mpa to 40 Mpa, 20 Mpa to 40 Mpa, It may be 20 Mpa to 35 Mpa, or 20 Mpa to 30 Mpa.
- TS B is the tensile strength (5 days) of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH), 10 Mpa to 50 Mpa, 10 Mpa to 45 Mpa, 15 Mpa to 45 Mpa, 15 Mpa to 40 Mpa, 20 Mpa to 40 Mpa, 20 Mpa to 35 Mpa, or 20 Mpa to 30 Mpa.
- the tensile strength (1 day) of the biodegradable film after storage for 1 day at 85°C and 85% relative humidity (RH) is 10 Mpa to 50 Mpa, 10 Mpa to 45 Mpa, 15 Mpa to 45 Mpa, It may be 15 Mpa to 40 Mpa, 20 Mpa to 40 Mpa, 20 Mpa to 35 Mpa, or 20 Mpa to 30 Mpa.
- the tensile strength (2 days) of the biodegradable film after storage for 2 days at 85°C and 85% relative humidity (RH) is 10 Mpa to 50 Mpa, 10 Mpa to 45 Mpa, 15 Mpa to 45 Mpa, It may be 15 Mpa to 40 Mpa, 20 Mpa to 40 Mpa, 20 Mpa to 35 Mpa, or 20 Mpa to 30 Mpa.
- the mechanical strength, durability and weather resistance of the biodegradable film and biodegradable product can be further improved.
- the biodegradable composition according to another example may have a decomposition rate of 50% or less, expressed by Equation 2 below.
- Decomposition rate (%) ((Mw A - Mw B )/Mw A ) ⁇ 100
- Mw A and Mw B are the weight average molecular weight (g/mol) of the biodegradable film prepared from the biodegradable composition measured using gel permeation chromatography (GPC) after dissolving the biodegradable film in chloroform solvent,
- Mw A is the initial weight average molecular weight of the biodegradable film at 25°C
- Mw B is the weight average molecular weight of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
- the decomposition rate is the initial weight average molecular weight (Mw A ) of the biodegradable film at 25°C and the weight average molecular weight (Mw B ) of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH). The difference is divided by the initial weight average molecular weight (Mw A ) of the biodegradable film at 25°C, converted to a percentage, and the decomposition rate is less than 50%, 48% or less, 45% or less, 42% or less, It may be 40% or less, 39% or less, or 38% or less.
- Mw A is the initial weight average molecular weight (day 0) of the biodegradable film at 25°C, and may be the same as the molecular weight of the copolymerized polyhydroxyalkanoate (PHA) resin, specifically 100,000.
- Mw B is the weight average molecular weight (4 days) of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH), and is 100,000 g/mol to 900,000 g/mol. , 200,000 g/mol to 900,000 g/mol, 200,000 g/mol to 800,000 g/mol, 200,000 g/mol to 700,000 g/mol, 200,000 g/mol to 650,000 g/mol, 200,000 g/mol to 600,000 g/mol , 200,000 g/mol to 500,000 g/mol, 200,000 g/mol to 400,000 g/mol, or 200,000 g/mol to 300,000 g/mol.
- the weight average molecular weight (per day) of the biodegradable film after storage for 1 day at 85°C and 85% relative humidity (RH) is 100,000 g/mol to 900,000 g/mol, 190,000 g/mol to 900,000 g.
- the weight average molecular weight (2 days) of the biodegradable film after storage for 2 days at 85°C and 85% relative humidity (RH) is 100,000 g/mol to 900,000 g/mol, 180,000 g/mol to 900,000 g. /mol, 180,000 g/mol to 800,000 g/mol, 180,000 g/mol to 700,000 g/mol, 180,000 g/mol to 650,000 g/mol, 180,000 g/mol to 600,000 g/mol, 180,000 g/mol to 500,000 g /mol, 180,000 g/mol to 400,000 g/mol, or 180,000 g/mol to 300,000 g/mol.
- the decomposition rate after storage for 1 day which is a value calculated by dividing the difference by the initial weight average molecular weight (Mw A ) of the biodegradable film at 25°C and converting it into a percentage, is 30% or less, 20% or less, 18% or less, 15%. It may be less than, 14% or less, or less than or equal to 13%.
- the decomposition rate after storage for 2 days which is a value calculated by dividing the difference by the initial weight average molecular weight (Mw A ) of the biodegradable film at 25°C and converting it to a percentage, is 40% or less, 35% or less, 30% or less, 25%. It may be less than, 24% or less, or less than or equal to 22%.
- the molecular weight and decomposition rate of the biodegradable film manufactured from the biodegradable composition are controlled within the above range, the occurrence of thermal deformation during production of the biodegradable film can be minimized, and the heat resistance of the biodegradable film and biodegradable product can be improved. And mechanical strength can be further improved.
- the biodegradable composition according to another example may have an elongation change rate of 30% or less, expressed by Equation 3 below.
- Elongation change rate (%) ((
- E A and E B cut a specimen of the biodegradable film made from the biodegradable composition into 10 cm in width and 1 cm in length, and used a universal testing machine (UTM) to measure the spacing between chucks at 20 mm. After mounting it as much as possible and measuring the maximum amount of deformation just before fracture at a speed of 200 mm/min, the elongation (%) is measured as the ratio of the maximum amount of deformation to the initial length,
- E A is the initial elongation of the biodegradable film at 25°C
- E B is the elongation of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
- the rate of change in elongation is the difference between the initial elongation (E A ) of the biodegradable film at 25°C and the elongation (E B ) of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
- the absolute value is divided by the initial elongation (E A ) of the biodegradable film at 25°C, converted into a percentage, and the elongation change rate is less than 30%, 28% or less, 25% or less, 24% or less, 23 % or less, or 22% or less.
- E A is the initial elongation (day 0) of the biodegradable film at 25°C, which is 40% or less, 30% or less, 28% or less, 25% or less, 24% or less, 23% or less, 22 % or less, may be 20% or less, may be 10% or more, 12% or more, 15% or more, 16% or more, or 18% or more.
- E A may be 10% to 40%, 15% to 40%, 15% to 30%, or 15% to 25%.
- E B is the elongation (5 days) of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH), and is 40% or less, 35% or less, and 30% or less. , may be 28% or less, 25% or less, 24% or less, or 23% or less, and may be 10% or more, 12% or more, 15% or more, 16% or more, 18% or more, or 20% or more.
- E B may be 10% to 40%, 15% to 40%, 15% to 30%, or 15% to 25%.
- the elongation (per day) of the biodegradable film after storage for 1 day at 85°C and 85% relative humidity (RH) is 40% or less, 30% or less, 28% or less, 25% or less, and 24% or less. , may be 23% or less, 22% or less, or 20% or less, and may be 10% or more, 12% or more, 15% or more, 16% or more, or 18% or more.
- the elongation (2 days) of the biodegradable film after storage for 2 days at 85°C and 85% relative humidity (RH) is 40% or less, 30% or less, 28% or less, 25% or less, 24% or less. , may be 23% or less, 22% or less, 20% or less, or 19% or less, and may be 10% or more, 12% or more, 15% or more, 16% or more, or 18% or more.
- the mechanical strength, durability and weather resistance of the biodegradable film and biodegradable product can be further improved.
- the biodegradable composition according to another example may have a dispersion index change rate of 50% or less, expressed by Equation 4 below.
- Dispersion index change rate (%) ((
- PDI A and PDI B are the number average molecular weight of the weight average molecular weight (Mw) of the biodegradable film measured using gel permeation chromatography (GPC) after dissolving the biodegradable film prepared from the biodegradable composition in chloroform solvent.
- GPC gel permeation chromatography
- PDI A is the initial dispersion index of the biodegradable film at 25°C
- PDI B is the dispersion index of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
- the dispersion index change rate is the initial dispersion index (PDI A ) of the biodegradable film at 25°C and the dispersion index (PDI B ) of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
- the absolute value of the difference is divided by the initial dispersion index (PDI A ) of the biodegradable film at 25°C, converted into a percentage, and the rate of change in the dispersion index is less than 50%, less than 40%, less than 30%, It may be 20% or less, 18% or less, 15% or less, 12% or less, 10% or less, 10% or less, 9.5% or less, 9.2% or less, or 9.0% or less.
- PDI A is the initial dispersion index (day 0) of the biodegradable film at 25°C, and may be the same as the dispersion index of the copolymerized polyhydroxyalkanoate (PHA) resin, specifically 1.0. It may be from 1.0 to 5.0, 1.0 to 4.0, 1.5 to 3.5, 1.5 to 3.0, 1.8 to 3.0, 1.8 to 2.8, 2.0 to 3.0, or 2.0 to 2.5.
- PHA copolymerized polyhydroxyalkanoate
- PDI B is the dispersion index (4 days) of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH), and is 1.0 or more to 5.0 or less, 1.0 or more to 4.0.
- RH relative humidity
- PDI B is the dispersion index (4 days) of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH), and is 1.0 or more to 5.0 or less, 1.0 or more to 4.0.
- RH relative humidity
- the dispersion index (1 day) of the biodegradable film after storage for 1 day at 85°C and 85% relative humidity (RH) is 1.0 or more and 5.0 or less, 1.0 or more and 4.0 or less, 1.5 or more and 3.5 or less, It may be 1.5 or more and 3.0 or less, more than 1.8 and 3.0 or less, more than 1.8 and 2.8 or less, 2.0 or more and 3.0 or less, or 2.0 or more and 2.5 or less.
- the dispersion index (2 days) of the biodegradable film after storage for 2 days at 85°C and 85% relative humidity (RH) is 1.0 or more and 5.0 or less, 1.0 or more and 4.0 or less, 1.5 or more and 3.5 or less, It may be 1.5 or more and 3.0 or less, more than 1.8 and 3.0 or less, more than 1.8 and 2.8 or less, 2.0 or more and 3.0 or less, or 2.0 or more and 2.5 or less.
- the rate of change in the dispersion index is the initial dispersion index (PDI A ) of the biodegradable film at 25°C and the dispersion index (PDI) of the biodegradable film after storage for 1 day under conditions of 85°C and 85% relative humidity (RH).
- B The absolute value of the difference is divided by the initial dispersion index (PDI A ) of the biodegradable film at 25°C, converted into a percentage, and the dispersion index change rate after storage for 1 day is 40% or less, 30% or less, It may be 20% or less, 18% or less, 15% or less, 12% or less, 10% or less, 10% or less, 9% or less, 5% or less, or 4.5% or less.
- the dispersion index change rate is the initial dispersion index (PDI A ) of the biodegradable film at 25°C and the dispersion index (PDI) of the biodegradable film after storage for 2 days at 85°C and 85% relative humidity (RH).
- B The absolute value of the difference is divided by the initial dispersion index (PDI A ) of the biodegradable film at 25°C, converted into a percentage, and the dispersion index change rate after storage for 2 days is less than 50%, 40% or less, It may be 30% or less, 20% or less, 18% or less, 15% or less, 12% or less, 10% or less, less than 10%, 9.5% or less, 9.2% or less, or 9.0% or less.
- the dispersion index and dispersion index change rate over time of the biodegradable film manufactured from the biodegradable composition are controlled within the above range, the occurrence of thermal deformation during production of the biodegradable film can be minimized, and the biodegradable film and biodegradable film can be The heat resistance and mechanical strength of the product can be further improved.
- the biodegradable composition may have excellent physical properties suitable for various molding, such as extrusion molding, injection molding, compression molding, pressure molding, blowing or blow molding, and thermoforming.
- the biodegradable composition may be a biodegradable composition for extrusion used in extrusion molding.
- a biodegradable film comprising the biodegradable composition is provided.
- the biodegradable film can be prepared from the biodegradable composition.
- the biodegradable film includes a copolymerized polyhydroxyalkanoate (PHA) resin
- the copolymerized polyhydroxyalkanoate (PHA) resin is a copolymer of 4-hydroxybutyrate (4-HB) monomer. It contains polyhydroxyalkanoate (PHA) resin in an amount of 0.1% or more to less than 30% by weight based on the total weight, and the tensile strength change rate expressed by the following formula 1 is 5% or less.
- Tensile strength change rate (%) ((TS A - TS B )/TS A ) ⁇ 100
- TS A and TS B For TS A and TS B , according to ASTM D882, a specimen of the biodegradable film prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (UTM). The tensile strength (Mpa) measured at a tensile speed of 200 mm/min with as much installation as possible,
- TS A is the initial tensile strength of the biodegradable film at 25°C
- TS B is the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
- the biodegradable film can be biodegraded by any one of microorganisms, moisture, oxygen, light, and heat, and has excellent mechanical properties.
- the biodegradable film has excellent durability, weather resistance, and heat resistance, and is used not only for disposable products used to maintain packaging for a short period of time, but also for food, medicine, hygiene products, electronic products, cosmetics, and other products used for long-term storage in high-temperature and high-humidity environments. Even when applied to a variety of products such as industrial products, it can provide excellent physical properties such as thermal stability and mechanical properties, allowing expansion of various uses.
- the biodegradable film may have a tensile strength of 10 Mpa to 50 Mpa, 15 Mpa to 45 Mpa, 15 Mpa to 40 Mpa, 20 Mpa to 40 Mpa, 20 Mpa to 35 Mpa, or 20 Mpa to 30 Mpa.
- the tensile strength of the biodegradable film may be equal to the initial tensile strength (TS A ) of the biodegradable film at 25°C.
- the biodegradable film has a tensile strength of 10 Mpa to 50 Mpa, 10 Mpa to 45 Mpa, and 15 Mpa to 45 Mpa after being stored for 5 days at 85°C and 85% relative humidity (RH). It may be 15 Mpa to 40 Mpa, 20 Mpa to 40 Mpa, 20 Mpa to 35 Mpa, or 20 Mpa to 30 Mpa.
- the tensile strength of the biodegradable film after storage for 1 and 2 days at 85°C and 85% relative humidity (RH) is as described above.
- the tensile strength was determined by cutting a specimen of the biodegradable film into 10 cm width and 1 cm length, using a universal testing machine (UTM), and mounting it so that the spacing between chucks was 20 mm, using a tensile speed of 200 mm/mm, based on ASTM D882. After testing at a room temperature of 25°C at a speed of 100 min, the tensile strength was measured using a program built into the equipment. When the tensile strength satisfies the above range, the mechanical properties, productivity, processability, and formability of the biodegradable film can be improved simultaneously, and it can be more advantageous to achieve the desired effect.
- the biodegradable film may have an elongation of 40% or less, 30% or less, 28% or less, 25% or less, 24% or less, 23% or less, 22% or less, 20% or less, 10% or more, 12% or more. , may be 15% or more, 16% or more, or 18% or more.
- the elongation of the biodegradable film may be 10% to 40%, 15% to 40%, 15% to 30%, or 15% to 25%.
- the elongation rate of the biodegradable film may be equal to the initial elongation rate (E A ) of the biodegradable film at 25°C in Equation 3 above.
- biodegradable film can satisfy the range of elongation change rate represented by Equation 3 above.
- the elongation is determined by cutting the biodegradable film specimen into 10 cm width and 1 cm length, using a universal testing machine (UTM), and mounting it so that the spacing between chucks is 20 mm, at a speed of 200 mm/min, according to ASTM D882. After measuring the maximum strain just before fracture, the ratio of the maximum strain to the initial length was calculated as elongation.
- UTM universal testing machine
- the biodegradable film has a tensile strength (MPa) of 10 MPa to 50 MPa and an elongation of 10% after storage for 5 days at 85°C and 85% relative humidity (RH). It may be from 40% to 40%.
- the biodegradable film can satisfy the range of decomposition rate expressed by Equation 2 above.
- the range of weight average molecular weight (g/mol) of each of the biodegradable films after storage for 1 day, 2 days, and 4 days under the above-mentioned conditions of 85°C and 85% relative humidity (RH) is You can be satisfied.
- the biodegradable film can satisfy the range of dispersion index change rate expressed by Equation 4 above.
- the biodegradable film can satisfy the range of dispersion index (PDI) of each biodegradable film after being stored for 1 day, 2 days, and 4 days under the conditions of 85°C and 85% relative humidity (RH) described above. .
- PDI dispersion index
- the biodegradable film has a weight average molecular weight (g/mol) of 5,000 to 400,000 g/mol after being stored for 4 days at 85°C and 85% relative humidity (RH),
- the dispersion index (PDI) may be 1.5 to 3.5.
- the biodegradable film may have excellent optical properties.
- the biodegradable film may have a haze of 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, or 5% or less. If the haze exceeds the above-mentioned range, the transparency of the biodegradable film is significantly reduced, which may limit its use for packaging purposes where the contents inside are visible.
- the biodegradable film may have a light transmittance of 80% or more, 90% or more, 92% or more, or 93% or more.
- the biodegradable film has excellent mechanical properties and is characterized by a biodegradability of more than 90% in soil and ocean.
- the biodegradability indicates the rate of decomposition compared to a standard material (e.g., cellulose) during the same period, and the Ministry of Environment of the Republic of Korea defines a material as biodegradable when the biodegradability is 90% or more compared to the standard material. Specifically, the marine biodegradability measured according to the EL 724 standard is more than 90%.
- a standard material e.g., cellulose
- the biodegradable film may include a biodegradable extruded film manufactured by extrusion molding the biodegradable composition.
- a method for manufacturing a biodegradable film using the biodegradable composition is provided.
- the method for producing the biodegradable film includes a first step of preparing a biodegradable composition; And it may include a second step of molding the biodegradable composition.
- the method for producing the biodegradable film includes a first step of preparing a biodegradable composition.
- the biodegradable composition includes a copolymerized polyhydroxyalkanoate (PHA) resin
- the copolymerized polyhydroxyalkanoate (PHA) resin is the copolymerized 4-hydroxybutyrate (4-HB) monomer. It contains from 0.1% by weight to less than 30% by weight based on the total weight of polyhydroxyalkanoate (PHA) resin.
- biodegradable composition and the copolymerized polyhydroxyalkanoate (PHA) resin are as described above.
- the biodegradable composition can be prepared by using the copolymerized polyhydroxyalkanoate (PHA) resin alone, or by mixing the copolymerized polyhydroxyalkanoate (PHA) resin and the above-described additives. You can. At this time, the additive may be selected and applied in various ways depending on the application and desired effect, but is not limited thereto.
- the biodegradable composition can be prepared by mixing the copolymerized polyhydroxyalkanoate (PHA) resin and additives, wherein the additives include ester compounds, silicone compounds, and fatty acid amide compounds.
- PHA copolymerized polyhydroxyalkanoate
- the contents of the copolymerized polyhydroxyalkanoate (PHA) resin and additives are as described above.
- the method for producing the biodegradable film includes a second step of molding the biodegradable composition.
- the biodegradable composition according to one embodiment may be molded into a form suitable for the intended use.
- the biodegradable composition may be provided in the form of pellets and then molded to produce a biodegradable film, or the biodegradable composition may be directly molded to produce a biodegradable film.
- the molding may be performed by processing the biodegradable composition or a pellet obtained using the biodegradable composition into a desired shape and then cooling it to harden the shape and induce crystallization.
- the shapes include, but are not limited to, fibers, filaments, films, sheets, rods, or other shapes.
- the molding may be performed by extrusion molding, injection molding, compression molding, pressure molding, blowing or blow molding (e.g., blown film, blowing of foam), calendaring, rotational molding, casting (e.g., cast sheet, cast film), or It can be performed using any method known in the art, such as thermoforming.
- a method of manufacturing a biodegradable film according to an embodiment may include the step of extruding the biodegradable composition into an extruder.
- extruder a single-screw extruder or a twin-screw extruder can be used.
- the extruder may be a T-die twin screw extruder equipped with a screw.
- the extrusion molding conditions may vary depending on the purpose of the biodegradable film, and the extrusion may be performed by a commonly used process.
- the extrusion temperature may be 100°C to 250°C, 120°C to 200°C, 120°C to 180°C, 120°C to 170°C, 120°C to 166°C, or for example 120°C to 160°C. .
- the biodegradable film has excellent durability, weather resistance, and heat resistance, so it has thermal stability and mechanical properties when applied not only to disposable packaging products used to maintain the packaging state for a short period of time, but also to various products used to maintain the packaging state for a long period of time in a high temperature and high humidity environment. It can provide excellent physical properties such as, and is thermally very stable in various processes such as heat curing, printing, and deposition required for manufacturing final biodegradable products, so there are no process restrictions, and it not only improves formability, processability, and productivity, but also provides various Expansion of use is possible.
- a biodegradable product including the biodegradable composition or the biodegradable film can be provided.
- the biodegradable products include not only disposable packaging products used to maintain packaging for a short period of time, but also food, medicine, sanitary products, electronic products, cosmetics, and industrial products (industrial products) used to maintain the packaging for a long period of time in a high temperature and high humidity environment. It may include one or more types selected from the group consisting of packaging materials or containers for packaging various items, eating containers, straws, electronic product trays, fishing nets, adhesive products, adhesive tapes, window protection films, and cold cups. You can.
- the biodegradable composition is put into a T-die twin screw extruder (manufacturer: SM Platek), the temperature of the extruder barrel is set at a temperature gradient from about 120 °C to 166 °C, and T-die extrusion molding is performed.
- a biodegradable film was prepared.
- copolymerized polyhydroxyalkanoate (PHA) resin (3-HB-co-4-HB, aPHA, 4-HB content 34.6% by weight) (manufacturer: CJ) and polylactic acid (PLA) resin ( A mixed resin containing (product name: 2003D, manufacturer: Natureworks) at a weight ratio of 23:77, and 0.15 phr of a fatty acid amide compound (manufacturer: Kao) as an additive and 0.15 phr of primary antioxidant (product name: AO-60, manufacturer: Adeka) A biodegradable composition was prepared by mixing 0.15 phr of phr and secondary antioxidant (Product name: HP-10, Manufacturer: Adeka).
- the biodegradable composition is put into a T-die twin screw extruder (manufacturer: SM Platek), the temperature of the extruder barrel is set at a temperature gradient from about 100°C to 180°C, and T-die extrusion is performed to biodegrade. A film was prepared.
- the biodegradable film specimen prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (Product name: 4206-001, Manufacturer: UTM).
- the initial tensile strength (day 0) of the biodegradable film is measured using a program built into the equipment, and under conditions of 85°C and relative humidity (RH) of 85%.
- the tensile strength of the biodegradable film was measured after storage for 1 day, 2 days, and 5 days.
- Equation 1 the tensile strength change rate represented by Equation 1 below was calculated using the tensile strength of the biodegradable film measured above.
- Tensile strength change rate (%) ((TS A - TS B )/TS A ) ⁇ 100
- TS A and TS B For TS A and TS B , according to ASTM D882, a specimen of the biodegradable film prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (UTM). The tensile strength (Mpa) measured at a tensile speed of 200 mm/min with as much installation as possible,
- TS A is the initial tensile strength of the biodegradable film at 25°C
- TS B is the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
- the biodegradable film specimen prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (Product name: 4206-001, Manufacturer: UTM). After mounting it so that the maximum deformation amount just before fracture was measured at a speed of 200 mm/min, the ratio of the maximum deformation amount to the initial length was evaluated as elongation. Measure the initial elongation of the biodegradable film at 25°C (day 0) and the elongation of the biodegradable film after storage for 1, 2, and 5 days at 85°C and 85% relative humidity (RH), respectively. did.
- Equation 3 the elongation change rate represented by Equation 3 below was calculated using the measured elongation of the biodegradable film.
- Elongation change rate (%) ((
- E A and E B cut a specimen of the biodegradable film made from the biodegradable composition into 10 cm in width and 1 cm in length, and used a universal testing machine (UTM) to measure the spacing between chucks at 20 mm. After mounting it as much as possible and measuring the maximum amount of deformation just before fracture at a speed of 200 mm/min, the elongation (%) is measured as the ratio of the maximum amount of deformation to the initial length,
- E A is the initial elongation of the biodegradable film at 25°C
- E B is the elongation of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
- the biodegradable film prepared from the copolymerized polyhydroxyalkanoate (PHA) resin or the biodegradable composition was dissolved in chloroform solvent and analyzed by gel permeation chromatography (Product name: SIL-40, Manufacturer: Simadzu), and the dispersion index was calculated as the ratio of the weight average molecular weight to the measured number average molecular weight.
- the decomposition rate represented by the following equation 2 was calculated using the weight average molecular weight of the biodegradable film measured above.
- Decomposition rate (%) ((Mw A - Mw B )/Mw A ) ⁇ 100
- Mw A and Mw B are the weight average molecular weight (g/mol) of the biodegradable film prepared from the biodegradable composition measured using gel permeation chromatography (GPC) after dissolving the biodegradable film in chloroform solvent,
- Mw A is the initial weight average molecular weight of the biodegradable film at 25°C
- Mw B is the weight average molecular weight of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
- Dispersion index change rate (%) ((
- PDI A and PDI B are the number average molecular weight of the weight average molecular weight (Mw) of the biodegradable film measured using gel permeation chromatography (GPC) after dissolving the biodegradable film prepared from the biodegradable composition in chloroform solvent.
- GPC gel permeation chromatography
- PDI A is the initial dispersion index of the biodegradable film at 25°C
- PDI B is the dispersion index of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
- the biodegradable film prepared in Example 1 had a tensile strength change rate of 1.75% and an elongation change rate of 1.75% after 5 days under high temperature and high humidity conditions of 85°C and 85% relative humidity (RH). It was confirmed that the weather resistance was excellent as it was very low at 21.3%.
- the biodegradable film prepared in Example 1 was confirmed to have excellent heat resistance as the decomposition rate and dispersion index change rate were very low after 1, 2, and 4 days under the high temperature and high humidity conditions. .
- the decomposition rate and dispersion index change rate rapidly increased after 1 day under conditions of 85°C and 85% relative humidity (RH), and after 4 days, the decomposition rate was 98.2%.
- the decomposition rate was significantly higher than that of the biodegradable film prepared in Example 1, which had a decomposition rate of 37.9% under the same conditions.
- the dispersion index change rate was 50.0%, which was a sharp increase compared to the biodegradable film prepared in Example 1, which had a dispersion index change rate of 9.0%.
- the biodegradable film prepared in Example 1 had improved durability, weather resistance, and heat resistance simultaneously compared to the biodegradable film prepared in Comparative Example 1.
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Abstract
A biodegradable composition according to an embodiment comprises a copolymerized polyhydroxyalkanoate (PHA) resin comprising a certain content range of 4-hydroxybutyrate (4-HB) monomers, and satisfies a tensile strength change rate below a certain range and thus can provide biodegradable films and biodegradable products having excellent biodegradability and mechanical properties, and improved durability, weather resistance, and heat resistance.
Description
실시예는 생분해성 조성물 및 이를 포함하는 생분해성 필름에 관한 것이다.Examples relate to biodegradable compositions and biodegradable films containing the same.
현재 상용화된 범용 플라스틱은 그 물성이 뛰어나고, 안정적인 공급과 가격으로 인해 수요가 늘어나는 추세이다, 그러나, 이로 인한 폐 플라스틱 처리 문제가 생활 전반에 걸쳐 대두되고, 해양과 토양과 같은 자연상태에서 분해가 되지 않아 심각한 환경 오염 문제를 일으키는 요인이 되고 있다. 이러한 환경 오염 문제점을 해결하기 위하여 최근 생분해성 플라스틱에 대한 연구가 활발히 진행되고 있다. Currently commercialized general-purpose plastics have excellent physical properties, and demand is increasing due to stable supply and price. However, as a result, problems with waste plastic disposal are emerging throughout life, and it does not decompose in natural conditions such as the ocean and soil. As a result, it is becoming a factor causing serious environmental pollution problems. To solve these environmental pollution problems, research on biodegradable plastics has been actively conducted recently.
생분해성 플라스틱이란, 자연에 존재하는 미생물들에 의해 저분자 물질로 분해되고, 최종적으로 물과 이산화 탄소, 또는 물과 메탄가스로 분해되는 물질을 말한다. 생분해성 플라스틱으로는, 예를 들어 폴리락트산(poly lactic acid, PLA), 폴리부틸렌아디페이트 테레프탈레이트(polybutyleneadipate terephthalate, PBAT), 폴리부틸렌숙시네이트(polybutylene succinate, PBS)등의 생분해성 수지가 많이 사용되고 있다.Biodegradable plastic refers to a material that is decomposed into low-molecular-weight substances by microorganisms existing in nature, and ultimately decomposes into water and carbon dioxide, or water and methane gas. Biodegradable plastics include, for example, polylactic acid (PLA), polybutylene adipate terephthalate (PBAT), and polybutylene succinate (PBS). It is being used a lot.
이러한 생분해성 수지들은 자원 순환 구조를 위한 폐기 제품의 생분해 목적에는 부합하지만, 내열성이 약하고, 열, 자외선 및 균 등에 의한 분해로 인해 내구성이 저하되는 문제점이 있을 수 있다.Although these biodegradable resins meet the purpose of biodegrading waste products for a resource circulation structure, they have poor heat resistance and may have the problem of reduced durability due to decomposition by heat, ultraviolet rays, and bacteria.
또한, 상기 생분해성 수지를 이용하여 포장용 제품의 제조 시, 약 100℃ 이상의 고온에서 인쇄 및 증착 공정이 이루어지고, 접착용 제품 제조 시, 약 70℃ 이상에서 열경화 공정이 이루어진다. 이때, 상기 생분해성 수지, 예컨대 폴리락트산(poly lactic acid, PLA) 수지의 경우 열변형 온도가 약 50℃ 내지 60℃이므로, 상기 공정 시 열변형 등으로 가공성 및 생산성에 문제가 있고, 제품의 품질에도 악영향을 미칠 수 있다.In addition, when manufacturing packaging products using the biodegradable resin, printing and deposition processes are performed at a high temperature of approximately 100°C or higher, and when manufacturing adhesive products, a thermal curing process is performed at approximately 70°C or higher. At this time, in the case of the biodegradable resin, such as polylactic acid (PLA) resin, the heat deformation temperature is about 50°C to 60°C, so there are problems with processability and productivity due to heat deformation during the process, and product quality is affected. It may also have a negative impact.
이와 같이, 취약한 내열성 및 내구성으로 인해 상기 생분해성 수지들은 공정에 제약이 있고, 상기 생분해성 수지를 이용하여 제조된 생분해성 필름 및 제품의 경우, 단순히 일회용 제품에 한정되는 등, 용도 확장에도 한계가 있다.As such, due to their weak heat resistance and durability, the biodegradable resins have limitations in processing, and in the case of biodegradable films and products manufactured using the biodegradable resins, they are limited to simply disposable products, which limits the expansion of their uses. there is.
[선행기술문헌][Prior art literature]
[특허문헌][Patent Document]
(특허문헌 1) 한국 공개특허 제2012-0103158호(Patent Document 1) Korean Patent Publication No. 2012-0103158
본 발명은 상술한 종래 기술의 문제를 해결하기 위해 고안된 것이다.The present invention is designed to solve the problems of the prior art described above.
일 실시예에 따라, 토양 및 해양 모두에서 생분해가 가능하고, 인장강도, 연신율 등의 기계적 특성이 우수함은 물론, 고온고습한 환경에서도 내구성, 내후성 및 내열성이 향상되고, 다양한 공정에서도 열적으로 안정하여 가공성 및 생산성을 향상시킬 수 있는 생분해성 조성물을 제공하고자 한다.According to one embodiment, it is biodegradable in both soil and the ocean, has excellent mechanical properties such as tensile strength and elongation, has improved durability, weather resistance, and heat resistance even in high temperature and high humidity environments, and is thermally stable in various processes. The aim is to provide a biodegradable composition that can improve processability and productivity.
또 다른 실시예에 따라, 상기 생분해성 조성물로부터 형성되는 생분해성 필름을 제공하고자 한다.According to another embodiment, an object is to provide a biodegradable film formed from the biodegradable composition.
상기 목적을 달성하기 위해 일 실시예에 있어서, 공중합 폴리하이드록시알카노에이트(PHA) 수지를 포함하고, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가 4-하이드록시부티레이트(4-HB) 단량체를 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 총 중량을 기준으로 0.1 중량% 이상 내지 30 중량% 미만으로 포함하고, 하기 식 1로 표시되는 인장강도 변화율이 5% 이하인, 생분해성 조성물을 제공한다.In order to achieve the above object, in one embodiment, it includes a copolymerized polyhydroxyalkanoate (PHA) resin, and the copolymerized polyhydroxyalkanoate (PHA) resin is 4-hydroxybutyrate (4-HB). A biodegradable composition containing monomers in an amount of 0.1% or more to less than 30% by weight based on the total weight of the copolymerized polyhydroxyalkanoate (PHA) resin, and having a tensile strength change rate of 5% or less as expressed by the following formula 1. to provide.
[식 1][Equation 1]
인장강도 변화율(%) = ((TSA - TSB)/TSA) × 100Tensile strength change rate (%) = ((TS A - TS B )/TS A ) × 100
상기 식 1에서,In equation 1 above,
TSA및 TSB는 ASTM D882에 의거하여, 상기 생분해성 조성물로부터 제조된 생분해성 필름의 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 인장 속도 200 ㎜/분의 속도로 측정한 인장강도(Mpa)로서, For TS A and TS B , according to ASTM D882, a specimen of the biodegradable film prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (UTM). The tensile strength (Mpa) measured at a tensile speed of 200 mm/min with as much installation as possible,
TSA는 25℃에서의 상기 생분해성 필름의 초기 인장강도이고,TS A is the initial tensile strength of the biodegradable film at 25°C,
TSB는 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 인장강도이다.TS B is the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
또 다른 일 실시예에 있어서, 하기 식 2로 표시되는 분해율이 50% 이하인, 생분해성 조성물을 제공한다.In another embodiment, a biodegradable composition is provided, which has a decomposition rate of 50% or less, represented by Formula 2 below.
[식 2][Equation 2]
분해율(%) = ((MwA - MwB)/MwA) × 100Decomposition rate (%) = ((Mw A - Mw B )/Mw A ) × 100
상기 식 2에서,In equation 2 above,
MwA 및 MwB는 상기 생분해성 조성물로부터 제조된 생분해성 필름을 클로로포름 용매에 용해시킨 후 겔 투과 크로마토그래피(GPC)를 사용하여 측정한 상기 생분해성 필름의 중량평균분자량(g/mol)으로서,Mw A and Mw B are the weight average molecular weight (g/mol) of the biodegradable film prepared from the biodegradable composition measured using gel permeation chromatography (GPC) after dissolving the biodegradable film in chloroform solvent,
MwA는 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량이고,Mw A is the initial weight average molecular weight of the biodegradable film at 25°C,
MwB는 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 중량평균분자량이다.Mw B is the weight average molecular weight of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
또 다른 일 실시예에 있어서, 하기 식 3으로 표시되는 연신율 변화율이 30% 이하인, 생분해성 조성물을 제공한다.In another embodiment, a biodegradable composition is provided, which has an elongation change rate of 30% or less, represented by Equation 3 below.
[식 3][Equation 3]
연신율 변화율(%) = ((|EA - EB|)/EA) × 100Elongation change rate (%) = ((|E A - E B |)/E A ) × 100
상기 식 3에서,In equation 3 above,
EA 및 EB는 ASTM D882에 의거하여, 상기 생분해성 조성물로부터 제조된 생분해성 필름의 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 200 ㎜/분의 속도에서 파단 직전의 최대 변형량을 측정한 후, 최초 길이 대비 상기 최대 변형량의 비율을 측정한 연신율(%)로서, E A and E B , according to ASTM D882, cut a specimen of the biodegradable film made from the biodegradable composition into 10 cm in width and 1 cm in length, and used a universal testing machine (UTM) to measure the spacing between chucks at 20 mm. After mounting it as much as possible and measuring the maximum amount of deformation just before fracture at a speed of 200 mm/min, the elongation (%) is measured as the ratio of the maximum amount of deformation to the initial length,
EA는 25℃에서의 상기 생분해성 필름의 초기 연신율이고,E A is the initial elongation of the biodegradable film at 25°C,
EB는 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 연신율이다.E B is the elongation of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
또 다른 일 실시예에 있어서, 하기 식 4로 표시되는 분산지수 변화율이 50% 이하인, 생분해성 조성물을 제공한다.In another embodiment, a biodegradable composition is provided, wherein the dispersion index change rate represented by Equation 4 below is 50% or less.
[식 4][Equation 4]
분산지수 변화율(%) = ((|PDIA - PDIB|)/PDIA) × 100Dispersion index change rate (%) = ((|PDI A - PDI B |)/PDI A ) × 100
상기 식 4에서,In equation 4 above,
PDIA 및 PDIB는 상기 생분해성 조성물로부터 제조된 생분해성 필름을 클로로포름 용매에 용해시킨 후 겔 투과 크로마토그래피(GPC)를 사용하여 측정한 상기 생분해성 필름의 중량평균분자량(Mw)을 수평균분자량(Mn)으로 나눈 값(Mw/Mn)을 나타내는 분산지수로서,PDI A and PDI B are the number average molecular weight of the weight average molecular weight (Mw) of the biodegradable film measured using gel permeation chromatography (GPC) after dissolving the biodegradable film prepared from the biodegradable composition in chloroform solvent. As a dispersion index representing the value (Mw/Mn) divided by (Mn),
PDIA는 25℃에서의 상기 생분해성 필름의 초기 분산지수이고,PDI A is the initial dispersion index of the biodegradable film at 25°C,
PDIB는 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 분산지수이다.PDI B is the dispersion index of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
또 다른 일 실시예에 있어서, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가 하기 특성 중에서 선택된 하나 이상의 특성을 만족하는, 생분해성 조성물을 제공한다: -45℃ 내지 80℃의 유리전이 온도(Tg), 60℃ 내지 120℃의 결정화 온도(Tc), 및 100℃ 내지 170℃의 용융 온도(Tm).In another embodiment, a biodegradable composition is provided in which the copolymerized polyhydroxyalkanoate (PHA) resin satisfies one or more characteristics selected from the following characteristics: a glass transition temperature of -45°C to 80°C ( Tg), crystallization temperature (Tc) from 60°C to 120°C, and melting temperature (Tm) from 100°C to 170°C.
또 다른 일 실시예에 있어서, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가, 200,000 g/mol 내지 900,000 g/mol의 중량평균분자량(Mw), 및 1.8 초과 내지 3.0 이하의 분산지수(PDI)를 갖는, 생분해성 조성물을 제공한다.In another embodiment, the copolymerized polyhydroxyalkanoate (PHA) resin has a weight average molecular weight (Mw) of 200,000 g/mol to 900,000 g/mol, and a dispersion index (PDI) of more than 1.8 to 3.0 or less. ), providing a biodegradable composition.
또 다른 일 실시예에 있어서, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가 3-하이드록시부티레이트(3-HB), 3-하이드록시프로피오네이트(3-HP), 3-하이드록시발레레이트(3-HV), 3-하이드록시헥사노에이트(3-HH), 4-하이드록시발레레이트(4-HV), 5-하이드록시발레레이트(5-HV) 및 6-하이드록시헥사노에이트(6-HH)로 이루어진 군으로부터 선택된 1종 이상의 단량체를 더 포함하는, 생분해성 조성물을 제공한다.In another embodiment, the copolymerized polyhydroxyalkanoate (PHA) resin is 3-hydroxybutyrate (3-HB), 3-hydroxypropionate (3-HP), 3-hydroxyvalet late (3-HV), 3-hydroxyhexanoate (3-HH), 4-hydroxyvalerate (4-HV), 5-hydroxyvalerate (5-HV) and 6-hydroxyhexanoate A biodegradable composition is provided, further comprising at least one monomer selected from the group consisting of ate (6-HH).
또 다른 일 실시예에 있어서, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가 3-하이드록시부티레이트(3-HB) 단량체 및 4-하이드록시부티레이트(4-HB) 단량체를 포함하는 수지를 포함하는, 생분해성 조성물을 제공한다.In another embodiment, the copolymerized polyhydroxyalkanoate (PHA) resin includes a resin containing 3-hydroxybutyrate (3-HB) monomer and 4-hydroxybutyrate (4-HB) monomer. Provides a biodegradable composition.
또 다른 일 실시예에 있어서, 활제를 더 포함하는, 생분해성 조성물을 제공한다.In another embodiment, a biodegradable composition is provided, further comprising a lubricant.
또 다른 일 실시예에 있어서, 상기 활제가 에스테르계 화합물, 실리콘계 화합물, 및 지방산 아마이드계 화합물로 이루어진 군으로부터 선택된 1종 이상을 포함하고, 상기 활제의 함량은 0.1 phr 내지 10 phr인, 생분해성 조성물을 제공한다.In another embodiment, the biodegradable composition includes at least one selected from the group consisting of ester-based compounds, silicone-based compounds, and fatty acid amide-based compounds, and the content of the lubricant is 0.1 phr to 10 phr. provides.
또 다른 일 실시예에 있어서, 상기 생분해성 조성물을 포함하는, 생분해성 필름을 제공한다.In another embodiment, a biodegradable film comprising the biodegradable composition is provided.
또 다른 일 실시예에 있어서, 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 인장강도(MPa)가 10 MPa 내지 50 MPa이고, 연신율이 10% 내지 40%인, 생분해성 필름을 제공한다.In another embodiment, the tensile strength (MPa) of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH) is 10 MPa to 50 MPa, and the elongation is 10% to 40%. Phosphorus, biodegradable film is provided.
또 다른 일 실시예에 있어서, 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 중량평균분자량(g/mol)이 5,000 내지 400,000 g/mol이고, 분산지수(PDI)가 1.5 내지 3.5인, 생분해성 필름을 제공한다.In another example, the weight average molecular weight (g/mol) of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH) is 5,000 to 400,000 g/mol, and the dispersion index ( Provided is a biodegradable film having a PDI) of 1.5 to 3.5.
상기 실시예에 따른 생분해성 조성물은 특정 함량 범위의 4-하이드록시부티레이트(4-HB) 단량체를 포함하는 공중합 폴리하이드록시알카노에이트(PHA) 수지를 포함하고, 특정 범위 이하의 인장강도 변화율을 만족함으로써, 우수한 생분해성 및 기계적 특성을 가짐은 물론, 내구성, 내후성 및 내열성이 향상된 생분해성 필름 및 생분해성 제품을 제공할 수 있다.The biodegradable composition according to the above example includes a copolymerized polyhydroxyalkanoate (PHA) resin containing a specific content range of 4-hydroxybutyrate (4-HB) monomer, and has a tensile strength change rate below a specific range. By satisfying this, it is possible to provide biodegradable films and biodegradable products that not only have excellent biodegradability and mechanical properties, but also have improved durability, weather resistance, and heat resistance.
따라서, 또 다른 실시예에 따른 생분해성 조성물을 포함하는 생분해성 필름은 포장 상태를 단시간 유지하는데 사용되는 일회용 포장 제품뿐만 아니라, 고온고습한 환경에서 장기간 유지하는데 사용되는 식품, 의약품, 위생용품, 전자 제품, 화장품, 공산품 등의 다양한 제품에 적용 시에도 열 안정성 및 기계적 특성 등의 우수한 물성을 제공할 수 있고, 최종 생분해성 제품의 제조를 위한 열경화, 인쇄, 증착 등 다양한 공정에서도 열적으로 매우 안정하여 공정의 제약이 없고, 성형성, 가공성 및 생산성을 향상시킬 수 있어, 다양한 용도 확장이 가능하다.Therefore, a biodegradable film containing a biodegradable composition according to another embodiment is used not only for disposable packaging products used to maintain the packaging state for a short period of time, but also for food, medicine, sanitary products, and electronics used for long-term maintenance in a high-temperature and high-humidity environment. It can provide excellent physical properties such as thermal stability and mechanical properties even when applied to various products such as products, cosmetics, and industrial products, and is very thermally stable even in various processes such as heat curing, printing, and deposition for manufacturing final biodegradable products. As a result, there are no restrictions on the process, and moldability, processability, and productivity can be improved, allowing expansion of various uses.
이하, 실시예를 통해 발명을 상세하게 설명한다. 실시예는 이하에서 개시된 내용에 한정되는 것이 아니라 발명의 요지가 변경되지 않는 한, 다양한 형태로 변형될 수 있다.Hereinafter, the invention will be described in detail through examples. The embodiments are not limited to the content disclosed below and may be modified into various forms as long as the gist of the invention is not changed.
본 명세서에 있어서, 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한, 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.In this specification, when a part “includes” a certain component, this means that it may further include other components rather than excluding other components, unless specifically stated to the contrary.
또한, 본 명세서에 기재된 구성요소의 물성 값, 치수 등을 나타내는 모든 수치 범위는 특별한 기재가 없는 한 모든 경우에 "약"이라는 용어로 수식되는 것으로 이해하여야 한다.In addition, all numerical ranges representing physical property values, dimensions, etc. of components described in this specification should be understood as being modified by the term “about” in all cases unless otherwise specified.
본 명세서에서 제 1, 제 2 등의 용어는 다양한 구성요소를 설명하기 위해 사용되는 것이고, 상기 구성요소들은 상기 용어에 의해 한정되지 않는다. 상기 용어들은 하나의 구성요소를 다른 구성요소로 구별하는 목적으로만 사용된다.In this specification, terms such as first and second are used to describe various components, and the components are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another.
[생분해성 조성물][Biodegradable composition]
일 실시예에서, 공중합 폴리하이드록시알카노에이트(PHA) 수지를 포함하고, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가 4-하이드록시부티레이트(4-HB) 단량체를 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 총 중량을 기준으로 0.1 중량% 이상 내지 30 중량% 미만으로 포함하고, 하기 식 1로 표시되는 인장강도 변화율이 5% 이하인, 생분해성 조성물을 제공한다.In one embodiment, the copolymerized polyhydroxyalkanoate (PHA) resin includes a 4-hydroxybutyrate (4-HB) monomer. A biodegradable composition is provided, which contains 0.1% by weight or more and less than 30% by weight based on the total weight of alkanoate (PHA) resin, and has a tensile strength change rate of 5% or less, expressed by the following formula 1.
[식 1][Equation 1]
인장강도 변화율(%) = ((TSA - TSB)/TSA) × 100Tensile strength change rate (%) = ((TS A - TS B )/TS A ) × 100
상기 식 1에서,In equation 1 above,
TSA및 TSB는 ASTM D882에 의거하여, 상기 생분해성 조성물로부터 제조된 생분해성 필름의 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 인장 속도 200 ㎜/분의 속도로 측정한 인장강도(Mpa)로서, For TS A and TS B , according to ASTM D882, a specimen of the biodegradable film prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (UTM). The tensile strength (Mpa) measured at a tensile speed of 200 mm/min with as much installation as possible,
TSA는 25℃에서의 상기 생분해성 필름의 초기 인장강도이고,TS A is the initial tensile strength of the biodegradable film at 25°C,
TSB는 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 인장강도이다.TS B is the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
일 실시예에 따르면, 상기 생분해성 조성물은 특정 함량 범위의 4-하이드록시부티레이트(4-HB) 단량체를 포함하는 공중합 폴리하이드록시알카노에이트(PHA) 수지를 포함하고, 특정 범위 이하의 인장강도 변화율을 만족함으로써, 내구성, 내후성 및 내열성을 향상시킬 수 있어서, 고온고습한 환경에서 장시간 보관 시에도 열적으로 안정하고, 우수한 기계적 특성을 갖는 생분해성 필름 및 생분해성 제품을 제공할 수 있다. 또한, 최종 생분해성 제품의 제조에 필요한 열경화, 인쇄, 또는 증착 등 다양한 공정에서도 열적으로 매우 안정하여 공정의 제약이 없고, 가공성 및 생산성 향상은 물론, 다양한 용도 확장이 가능하다는 데 기술적 의의를 갖는다.According to one embodiment, the biodegradable composition includes a copolymerized polyhydroxyalkanoate (PHA) resin containing a specific content range of 4-hydroxybutyrate (4-HB) monomer, and has a tensile strength below a specific range. By satisfying the change rate, durability, weather resistance, and heat resistance can be improved, and biodegradable films and biodegradable products that are thermally stable even when stored for a long time in a high temperature and high humidity environment and have excellent mechanical properties can be provided. In addition, it is thermally very stable in various processes such as heat curing, printing, or deposition required for manufacturing final biodegradable products, so there are no process restrictions, and it has technical significance in that it not only improves processability and productivity, but also allows expansion of various uses. .
특히, 상기 생분해성 조성물은 생분해성 수지로서 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 이외의 다른 생분해성 수지와의 혼합 사용 없이, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지를 단독으로 사용하여도 상기 특성을 만족할 수 있다는 큰 이점이 있다.In particular, the biodegradable composition is a biodegradable resin that uses the copolymerized polyhydroxyalkanoate (PHA) resin alone without mixing with other biodegradable resins other than the copolymerized polyhydroxyalkanoate (PHA) resin. There is a great advantage that the above characteristics can be satisfied even when used.
이하, 상기 생분해성 조성물의 각 구성 성분을 구체적으로 설명한다.Hereinafter, each component of the biodegradable composition will be described in detail.
공중합 폴리하이드록시알카노에이트(PHA) 수지Copolymerized polyhydroxyalkanoate (PHA) resin
일 실시예에 따른 생분해성 조성물은 공중합 폴리하이드록시알카노에이트(PHA) 수지를 포함한다.The biodegradable composition according to one embodiment includes a copolymerized polyhydroxyalkanoate (PHA) resin.
일반적으로 폴리하이드록시알카노에이트(PHA) 수지는 기존의 석유로부터 유래된 폴리부틸렌아디페이트 테레프탈레이트(PBAT), 폴리부틸렌 숙시네이트(PBS), 폴리부틸렌 숙시네이트 테레프탈레이트(PBST), 폴리부틸렌 숙시네이트 아디페이트(PBSA)등과 같은 합성 고분자와 유사한 물성을 가지면서, 완전한 생분해성을 보이며, 생체 적합성 또한 우수하다. In general, polyhydroxyalkanoate (PHA) resins include polybutylene adipate terephthalate (PBAT), polybutylene succinate (PBS), polybutylene succinate terephthalate (PBST), and It has similar physical properties to synthetic polymers such as polybutylene succinate adipate (PBSA), is completely biodegradable, and has excellent biocompatibility.
구체적으로, 상기 폴리하이드록시알카노에이트(PHA) 수지는 미생물 세포 내에 축적되는 열가소성의 천연 폴리에스테르 고분자로서, 생분해성 소재로 퇴비화가 가능하고, 유독성 폐기물 발생도 없으면서 최종적으로 이산화탄소, 물, 유기 폐기물로 분해될 수 있다. 특히, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 토양 및 해양에서 생분해될 수 있으므로, 상기 생분해성 조성물이 공중합 폴리하이드록시알카노에이트(PHA) 수지를 포함하는 경우, 토양 및 해양 등 어떠한 환경 조건에서도 생분해 되어 환경 친화적인 특성을 갖는다.Specifically, the polyhydroxyalkanoate (PHA) resin is a thermoplastic natural polyester polymer that accumulates in microbial cells, can be composted as a biodegradable material, and does not generate toxic waste, ultimately producing carbon dioxide, water, and organic waste. can be decomposed into In particular, since the copolymerized polyhydroxyalkanoate (PHA) resin can be biodegraded in soil and the ocean, when the biodegradable composition contains the copolymerized polyhydroxyalkanoate (PHA) resin, it can be used in any area such as soil and ocean. It is biodegradable even under environmental conditions and has environmentally friendly characteristics.
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 중합체 사슬에 상이한 단량체들이 불규칙하게(randomly) 분포되어 있는 2개 이상의 상이한 단량체들을 함유하는 공중합체일 수 있다.The copolymerized polyhydroxyalkanoate (PHA) resin may be a copolymer containing two or more different monomers in which the different monomers are randomly distributed in the polymer chain.
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 4-하이드록시부티레이트(이하, 4-HB로 표기함)를 포함한다.The copolymerized polyhydroxyalkanoate (PHA) resin includes 4-hydroxybutyrate (hereinafter referred to as 4-HB).
일 실시예에 따르면, 목적하는 토양 및 해양의 생분해성을 증진시키는 것은 물론, 고온고습한 환경에서 우수한 기계적 특성을 갖고, 내구성, 내후성 및 내열성을 향상시키기 위해 상기 4-HB 단량체의 함량이 중요할 수 있다.According to one embodiment, the content of the 4-HB monomer is important to improve the biodegradability of the desired soil and ocean, as well as to have excellent mechanical properties in a high temperature and high humidity environment, and to improve durability, weather resistance, and heat resistance. You can.
구체적으로, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 4-하이드록시부티레이트(4-HB) 단량체를 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 총 중량을 기준으로 0.1 중량% 이상 내지 30 중량% 미만으로 포함한다.Specifically, the copolymerized polyhydroxyalkanoate (PHA) resin contains 4-hydroxybutyrate (4-HB) monomer in an amount of 0.1% by weight or more based on the total weight of the copolymerized polyhydroxyalkanoate (PHA) resin. Contains less than 30% by weight.
예를 들어, 상기 4-HB 단량체의 함량은 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지의 총 중량을 기준으로 0.1 중량% 이상, 0.2 중량% 이상, 0.5 중량% 이상, 1 중량% 이상, 1.5 중량% 이상, 2 중량% 이상, 3 중량% 이상, 5 중량% 이상, 또는 6 중량% 이상일 수 있고, 30 중량% 미만, 29 중량% 이하, 28 중량% 이하, 25 중량% 이하, 22 중량% 이하, 20 중량% 이하, 18 중량% 이하, 15 중량% 이하, 12 중량% 이하, 또는 10 중량% 이하일 수 있다.For example, the content of the 4-HB monomer is 0.1% by weight or more, 0.2% by weight or more, 0.5% by weight or more, or 1% by weight or more, based on the total weight of the copolymerized polyhydroxyalkanoate (PHA) resin. It may be at least 1.5 wt%, at least 2 wt%, at least 3 wt%, at least 5 wt%, or at least 6 wt%, and less than 30 wt%, at most 29 wt%, at most 28 wt%, at most 25 wt%, and at most 22 wt%. % or less, 20 weight% or less, 18 weight% or less, 15 weight% or less, 12 weight% or less, or 10 weight% or less.
구체적으로, 상기 4-HB 단량체의 함량은 0.2 중량% 이상 내지 29 중량% 이하, 0.5 중량% 이상 내지 29 중량% 이하, 0.5 중량% 이상 내지 28 중량% 이하, 1 중량% 이상 내지 28 중량% 이하, 1 중량% 이상 내지 25 중량% 이하, 1 중량% 이상 내지 20 중량% 이하, 1 중량% 이상 내지 15 중량% 이하, 1 중량% 이상 내지 12 중량% 이하, 1 중량% 이상 내지 10 중량% 이하, 3 중량% 이상 내지 28 중량% 이하, 3 중량% 이상 내지 25 중량% 이하, 3 중량% 이상 내지 20 중량% 이하, 3 중량% 이상 내지 15 중량% 이하, 3 중량% 이상 내지 12 중량% 이하, 3 중량% 이상 내지 10 중량% 이하, 5 중량% 이상 내지 28 중량% 이하, 5 중량% 이상 내지 25 중량% 이하, 5 중량% 이상 내지 20 중량% 이하, 5 중량% 이상 내지 15 중량% 이하, 5 중량% 이상 내지 12 중량% 이하, 또는 5 중량% 이상 내지 10 중량% 이하일 수 있다.Specifically, the content of the 4-HB monomer is 0.2% by weight or more and 29% by weight or less, 0.5% or more and 29% by weight or less, 0.5% by weight or more and 28% by weight or less, and 1% by weight or more and 28% by weight or less. , 1% by weight or more and 25% by weight or less, 1% by weight or more and 20% by weight or less, 1% by weight or more and 15% by weight or less, 1% by weight or more and 12% by weight or less, 1% by weight or more and 10% by weight or less. , 3% by weight or more and 28% by weight or less, 3% by weight or more and 25% by weight or less, 3% by weight or more and 20% by weight or less, 3% by weight or more and 15% by weight or less, 3% by weight or more and 12% by weight or less. , 3% by weight or more and 10% by weight or less, 5% by weight or more and 28% by weight or less, 5% by weight or more and 25% by weight or less, 5% by weight or more and 20% by weight or less, 5% by weight or more and 15% by weight or less. , 5% by weight or more and 12% by weight or less, or 5% by weight or more and 10% by weight or less.
상기 4-HB 단량체의 함량이 상기 범위를 만족하는 경우, 상기 생분해성 조성물을 포함하는 생분해성 필름 및 생분해성 제품의 내구성, 내후성 및 내열성을 향상시킬 수 있어, 예컨대 85℃ 이상 및 상대습도(RH) 85% 이상의 고온고습한 환경에서도 우수한 열적 특성 및 기계적 특성을 제공할 수 있다. When the content of the 4-HB monomer satisfies the above range, durability, weather resistance, and heat resistance of biodegradable films and biodegradable products containing the biodegradable composition can be improved, for example, at temperatures above 85°C and relative humidity (RH). ) It can provide excellent thermal and mechanical properties even in a high temperature and high humidity environment of 85% or more.
또한, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 상기 4-HB 단량체를 포함하면서, 상기 4-HB 단량체와 상이한 1개의 단량체를 추가로 포함하거나, 서로 상이한 2개, 3개, 4개, 5개, 6개 또는 그 이상의 단량체를 추가로 포함할 수 있다.In addition, the copolymerized polyhydroxyalkanoate (PHA) resin includes the 4-HB monomer and further includes one monomer different from the 4-HB monomer, or 2, 3, or 4 different monomers. , may additionally include 5, 6 or more monomers.
구체적으로, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 3-하이드록시부티레이트(3-HB), 3-하이드록시프로피오네이트(3-HP), 3-하이드록시발레레이트(3-HV), 3-하이드록시헥사노에이트(3-HH), 4-하이드록시발레레이트(4-HV), 5-하이드록시발레레이트(5-HV) 및 6-하이드록시헥사노에이트(6-HH)로 이루어진 군으로부터 선택된 1종 이상의 단량체를 더 포함할 수 있다. Specifically, the copolymerized polyhydroxyalkanoate (PHA) resin is 3-hydroxybutyrate (3-HB), 3-hydroxypropionate (3-HP), and 3-hydroxyvalerate (3-HV). ), 3-hydroxyhexanoate (3-HH), 4-hydroxyvalerate (4-HV), 5-hydroxyvalerate (5-HV) and 6-hydroxyhexanoate (6-HH) ) may further include one or more monomers selected from the group consisting of
일 실시예에 따르면, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 4-HB 단량체를 포함하면서, 3-HB 단량체, 3-HP 단량체, 3-HV 단량체, 3-HH 단량체, 4-HV 단량체, 5-HV 단량체 및 6-HH 단량체로 이루어진 군으로부터 선택된 1종 이상의 단량체를 포함하는 수지를 포함할 수 있다.According to one embodiment, the copolymerized polyhydroxyalkanoate (PHA) resin includes 4-HB monomer, 3-HB monomer, 3-HP monomer, 3-HV monomer, 3-HH monomer, 4-HV It may include a resin containing one or more monomers selected from the group consisting of monomers, 5-HV monomers, and 6-HH monomers.
더욱 구체적으로, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 3-HB 단량체 및 4-HB 단량체를 포함하는 수지를 포함할 수 있으며, 예를 들어 폴리 3-하이드록시부티레이트-co-4-하이드록시부티레이트(이하, 3HB-co-4HB로 표기함) 수지를 포함할 수 있다.More specifically, the copolymerized polyhydroxyalkanoate (PHA) resin may include a resin containing a 3-HB monomer and a 4-HB monomer, for example, poly 3-hydroxybutyrate-co-4- It may contain hydroxybutyrate (hereinafter referred to as 3HB-co-4HB) resin.
일 실시예에 따르면, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 상기 3-HB 단량체 및 상기 4-HB 단량체를 포함하고, 상기 3-HB 단량체 및 상기 4-HB 단량체의 중량비가 71:29 내지 99.9:0.1, 71:29 내지 99.8:0.2, 71:29 내지 99.5:0.5, 71:29 내지 99:1, 75:25 내지 99:1, 77:23 내지 99:1, 80:20 내지 99:1, 85:15 내지 99:1, 87:13 내지 99:1, 88:12 내지 99:1, 90:10 내지 97:3, 또는 90:10 내지 95:5일 수 있다.According to one embodiment, the copolymerized polyhydroxyalkanoate (PHA) resin includes the 3-HB monomer and the 4-HB monomer, and the weight ratio of the 3-HB monomer and the 4-HB monomer is 71: 29 to 99.9:0.1, 71:29 to 99.8:0.2, 71:29 to 99.5:0.5, 71:29 to 99:1, 75:25 to 99:1, 77:23 to 99:1, 80:20 to 80:20 It can be 99:1, 85:15 to 99:1, 87:13 to 99:1, 88:12 to 99:1, 90:10 to 97:3, or 90:10 to 95:5.
상기 3-HB 단량체 및 상기 4-HB 단량체의 중량비가 상기 범위를 만족하는 경우, 목적하는 효과를 구현하는 데에 더욱 유리할 수 있다.When the weight ratio of the 3-HB monomer and the 4-HB monomer satisfies the above range, it may be more advantageous to achieve the desired effect.
구체적으로, 상기 4-HB 단량체의 함량은 상기 3-HB 단량체 및 상기 4-HB 단량체의 총 중량을 기준으로, 0.1 중량% 이상, 0.2 중량% 이상, 0.5 중량% 이상, 1 중량% 이상, 1.5 중량% 이상, 2 중량% 이상, 3 중량% 이상, 5 중량% 이상, 또는 6 중량% 이상일 수 있고, 30 중량% 미만, 29 중량% 이하, 28 중량% 이하, 25 중량% 이하, 22 중량% 이하, 20 중량% 이하, 18 중량% 이하, 15 중량% 이하, 12 중량% 이하, 또는 10 중량% 이하일 수 있다.Specifically, the content of the 4-HB monomer is 0.1% by weight or more, 0.2% by weight or more, 0.5% by weight or more, 1% by weight or more, 1.5% by weight, based on the total weight of the 3-HB monomer and the 4-HB monomer. It may be at least 30% by weight, at least 2% by weight, at least 3% by weight, at least 5% by weight, or at least 6% by weight, and less than 30% by weight, at most 29% by weight, at most 28% by weight, at most 25% by weight, and at least 22% by weight. It may be 20% by weight or less, 18% by weight or less, 15% by weight or less, 12% by weight or less, or 10% by weight or less.
예를 들어, 상기 4-HB 단량체의 함량은 상기 3-HB 단량체 및 상기 4-HB 단량체의 총 중량을 기준으로, 0.2 중량% 이상 내지 29 중량% 이하, 0.5 중량% 이상 내지 29 중량% 이하, 0.5 중량% 이상 내지 28 중량% 이하, 1 중량% 이상 내지 28 중량% 이하, 1 중량% 이상 내지 25 중량% 이하, 1 중량% 이상 내지 20 중량% 이하, 1 중량% 이상 내지 15 중량% 이하, 1 중량% 이상 내지 12 중량% 이하, 1 중량% 이상 내지 10 중량% 이하, 3 중량% 이상 내지 28 중량% 이하, 3 중량% 이상 내지 25 중량% 이하, 3 중량% 이상 내지 20 중량% 이하, 3 중량% 이상 내지 15 중량% 이하, 3 중량% 이상 내지 12 중량% 이하, 3 중량% 이상 내지 10 중량% 이하, 5 중량% 이상 내지 28 중량% 이하, 5 중량% 이상 내지 25 중량% 이하, 5 중량% 이상 내지 20 중량% 이하, 5 중량% 이상 내지 15 중량% 이하, 5 중량% 이상 내지 12 중량% 이하, 또는 5 중량% 이상 내지 10 중량% 이하일 수 있다.For example, the content of the 4-HB monomer is 0.2% by weight to 29% by weight, 0.5% by weight to 29% by weight, based on the total weight of the 3-HB monomer and the 4-HB monomer. 0.5% by weight or more and 28% by weight or less, 1% by weight or more and 28% by weight or less, 1% by weight or more and 25% by weight or less, 1% by weight or more and 20% by weight or less, 1% by weight or more and 15% by weight or less, 1% by weight or more and 12% by weight or less, 1% by weight or more and 10% by weight or less, 3% by weight or more and 28% by weight or less, 3% by weight or more and 25% by weight or less, 3% by weight or more and 20% by weight or less, 3% by weight or more and 15% by weight or less, 3% by weight or more and 12% by weight or less, 3% by weight or more and 10% by weight or less, 5% by weight or more and 28% by weight or less, 5% by weight or more and 25% by weight or less, It may be 5 wt% or more and 20 wt% or less, 5 wt% or more and 15 wt% or less, 5 wt% or more and 12 wt% or less, or 5 wt% or more and 10 wt% or less.
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 상기 4-HB 단량체를 적어도 하나 이상 포함하는 수지를 포함하는 PHA 수지를 포함하고, 상기 4-HB 단량체의 함량을 제어함으로써 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지의 결정성을 조절할 수 있다. The copolymerized polyhydroxyalkanoate (PHA) resin includes a PHA resin containing a resin containing at least one of the 4-HB monomers, and the copolymerized polyhydroxyalkanoate (PHA) resin is obtained by controlling the content of the 4-HB monomer. The crystallinity of phenoate (PHA) resin can be adjusted.
상기 결정성이 조절된 공중합 폴리하이드록시알카노에이트(PHA) 수지는 분자 구조상 비규칙성을 증가시킴으로써 결정성이 조절된 것일 수 있으며, 구체적으로는 단량체의 종류, 단량체의 비율 또는 이성질체의 종류 및/또는 함량을 조절한 것일 수 있다.The copolymerized polyhydroxyalkanoate (PHA) resin with controlled crystallinity may have its crystallinity adjusted by increasing irregularity in the molecular structure, and specifically, the type of monomer, the ratio of monomers, or the type of isomer, and /Or the content may be adjusted.
한편, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는, 유리전이 온도(Tg)가 예를 들면 -45℃ 내지 80℃, -35℃ 내지 80℃, -30℃ 내지 80℃, -25℃ 내지 75℃, -20℃ 내지 70℃, -35℃ 내지 5℃, -25℃ 내지 5℃, -35℃ 내지 0℃, -25℃ 내지 0℃, -30℃ 내지 -10℃, -35℃ 내지 -15℃, -35℃ 내지 -20℃, -20℃ 내지 0℃, -15℃ 내지 0℃, 또는 -15℃ 내지 -5℃일 수 있다.On the other hand, the copolymerized polyhydroxyalkanoate (PHA) resin has a glass transition temperature (Tg) of, for example, -45°C to 80°C, -35°C to 80°C, -30°C to 80°C, -25°C. to 75℃, -20℃ to 70℃, -35℃ to 5℃, -25℃ to 5℃, -35℃ to 0℃, -25℃ to 0℃, -30℃ to -10℃, -35℃ It may be -15°C to -15°C, -35°C to -20°C, -20°C to 0°C, -15°C to 0°C, or -15°C to -5°C.
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는, 결정화 온도(Tc)가 예를 들어 측정되지 않을 수 있거나, 예를 들어 60℃ 내지 120℃, 70℃ 내지 120℃, 75℃ 내지 120℃, 75℃ 내지 115℃, 75℃ 내지 110℃, 또는 90℃ 내지 110℃일 수 있다.The copolymerized polyhydroxyalkanoate (PHA) resin may have a crystallization temperature (Tc), for example, which may not be measured, or may range from, for example, 60° C. to 120° C., 70° C. to 120° C., 75° C. to 120° C., It may be 75°C to 115°C, 75°C to 110°C, or 90°C to 110°C.
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는, 용융 온도(Tm)가 예를 들면 측정되지 않을 수 있거나, 예를 들면 100℃ 내지 170℃, 110℃ 내지 150℃, 또는 120℃ 내지 140℃일 수 있다. The copolymerized polyhydroxyalkanoate (PHA) resin may have a melting temperature (Tm) that may not be measured, for example, from 100°C to 170°C, from 110°C to 150°C, or from 120°C to 140°C. It can be.
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 -45℃ 내지 80℃의 유리전이 온도(Tg), 60℃ 내지 120℃의 결정화 온도(Tc), 및 100℃ 내지 170℃의 용융 온도(Tm)의 특성 중에서 선택된 하나 이상의 특성을 만족할 수 있다.The copolymerized polyhydroxyalkanoate (PHA) resin has a glass transition temperature (Tg) of -45°C to 80°C, a crystallization temperature (Tc) of 60°C to 120°C, and a melting temperature (Tm) of 100°C to 170°C. ) may satisfy one or more characteristics selected from among the characteristics.
구체적으로, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 -20℃ 내지 0℃의 유리전이 온도(Tg), 75℃ 내지 115℃의 결정화 온도(Tc), 및 110℃ 내지 160℃의 용융 온도(Tm)의 특성 중에서 선택된 하나 이상의 특성을 만족할 수 있다.Specifically, the copolymerized polyhydroxyalkanoate (PHA) resin has a glass transition temperature (Tg) of -20°C to 0°C, a crystallization temperature (Tc) of 75°C to 115°C, and a melting temperature of 110°C to 160°C. One or more characteristics selected from the characteristics of temperature (Tm) may be satisfied.
또한, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 결정화도(결정성)가 조절된 공중합 PHA 수지일 수 있다. Additionally, the copolymerized polyhydroxyalkanoate (PHA) resin may be a copolymerized PHA resin with controlled crystallinity.
예를 들어, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 반결정형 PHA 수지(이하, scPHA 수지로 표기함)를 포함할 수 있다.For example, the copolymerized polyhydroxyalkanoate (PHA) resin may include a semi-crystalline PHA resin (hereinafter referred to as scPHA resin).
상기 scPHA 수지는 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 총 중량을 기준으로 4-HB 단량체를 예를 들어 0.1 중량% 이상 내지 30 중량% 미만으로 포함할 수 있다. The scPHA resin may include, for example, 0.1% by weight or more to less than 30% by weight of 4-HB monomer based on the total weight of the copolymerized polyhydroxyalkanoate (PHA) resin.
상기 scPHA 수지의 유리전이 온도(Tg)는 -20℃내지 0℃일 수 있다.The glass transition temperature (Tg) of the scPHA resin may be -20°C to 0°C.
상기 scPHA 수지의 결정화 온도(Tc)는 75℃내지 115℃일 수 있다.The crystallization temperature (Tc) of the scPHA resin may be 75°C to 115°C.
상기 scPHA 수지의 용융 온도(Tm)는 예를 들어 110℃ 내지 160℃일 수 있다.The melting temperature (Tm) of the scPHA resin may be, for example, 110°C to 160°C.
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지의 유리전이 온도(Tg), 결정화 온도(Tc) 및 용융 온도(Tm)가 각각 상기 범위로 만족하는 경우, 광학적 특성, 열적 특성, 및 기계적 특성을 더욱 향상시킬 수 있고, 목적하는 내구성, 내후성 및 내열성을 향상시키는 데에 더욱 유리하며, 생분해성 필름 제조 시, 성형성, 가공성, 및 생산성도 향상시킬 수 있다.When the glass transition temperature (Tg), crystallization temperature (Tc), and melting temperature (Tm) of the copolymerized polyhydroxyalkanoate (PHA) resin respectively satisfy the above ranges, the optical properties, thermal properties, and mechanical properties are It can be further improved, and is more advantageous in improving the desired durability, weather resistance, and heat resistance, and can also improve formability, processability, and productivity when manufacturing biodegradable films.
한편, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는, 중량평균분자량(Mw)이 예를 들면 10,000 g/mol 내지 1,200,000 g/mol일 수 있다. 예를 들어, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지의 중량평균분자량(Mw)은 50,000 g/mol 내지 1,200,000 g/mol, 100,000 g/mol 내지 1,200,000 g/mol, 50,000 g/mol 내지 1,000,000 g/mol, 100,000 g/mol 내지 1,000,000 g/mol, 200,000 g/mol 내지 1,200,000 g/mol, 250,000 g/mol 내지 1,150,000 g/mol, 300,000 g/mol 내지 1,100,000 g/mol, 350,000 g/mol 내지 1,000,000 g/mol, 350,000 g/mol 내지 950,000 g/mol, 100,000 g/mol 내지 900,000 g/mol, 200,000 g/mol 내지 900,000 g/mol, 200,000 g/mol 내지 800,000 g/mol, 200,000 g/mol 내지 700,000 g/mol, 200,000 g/mol 내지 650,000 g/mol, 200,000 g/mol 내지 600,000 g/mol, 200,000 g/mol 내지 500,000 g/mol, 200,000 g/mol 내지 400,000 g/mol, 200,000 g/mol 내지 300,000 g/mol, 300,000 g/mol 내지 800,000 g/mol, 300,000 g/mol 내지 600,000 g/mol, 500,000 g/mol 내지 1,200,000 g/mol, 500,000 g/mol 내지 1,000,000 g/mol 550,000 g/mol 내지 1,050,000 g/mol, 550,000 g/mol 내지 900,000 g/mol, 또는 600,000 g/mol 내지 900,000 g/mol일 수 있다.Meanwhile, the copolymerized polyhydroxyalkanoate (PHA) resin may have a weight average molecular weight (Mw) of, for example, 10,000 g/mol to 1,200,000 g/mol. For example, the weight average molecular weight (Mw) of the copolymerized polyhydroxyalkanoate (PHA) resin is 50,000 g/mol to 1,200,000 g/mol, 100,000 g/mol to 1,200,000 g/mol, and 50,000 g/mol to 1,000,000. g/mol, 100,000 g/mol to 1,000,000 g/mol, 200,000 g/mol to 1,200,000 g/mol, 250,000 g/mol to 1,150,000 g/mol, 300,000 g/mol to 1,100,000 g/mol, 350,000 g/mol to 1, 000,000 g/mol, 350,000 g/mol to 950,000 g/mol, 100,000 g/mol to 900,000 g/mol, 200,000 g/mol to 900,000 g/mol, 200,000 g/mol to 800,000 g/mol, 200,000 g/mol to 700,000 g/mol, 200,000 g/mol to 650,000 g/mol, 200,000 g/mol to 600,000 g/mol, 200,000 g/mol to 500,000 g/mol, 200,000 g/mol to 400,000 g/mol, 200,000 g/mol to 300,000 g/mol, 300,000 g/mol to 800,000 g/mol, 300,000 g/mol to 600,000 g/mol, 500,000 g/mol to 1,200,000 g/mol, 500,000 g/mol to 1,000,000 g/mol 550,000 g/mol to 1,050,0 00g /mol, 550,000 g/mol to 900,000 g/mol, or 600,000 g/mol to 900,000 g/mol.
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는, 분산지수(PDI)가 1.0 이상, 1.2 이상, 1.5 이상, 1.8 이상, 1.8 초과, 또는 2.0 이상일 수 있고, 5.0 이하, 4.0 이하, 3.0 이하, 2.9 이하, 2.8 이하, 2.7 이하, 2.6 이하, 2.5 이하, 또는 2.4 이하일 수 있다. 예를 들어, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는, 분산지수(PDI)가 1.0 이상 내지 5.0 이하, 1.0 이상 내지 4.0 이하, 1.5 이상 내지 3.5 이하, 1.5 이상 내지 3.0 이하, 1.8 초과 내지 3.0 이하, 1.8 초과 내지 2.8 이하, 2.0 이상 내지 3.0 이하, 또는 2.0 이상 내지 2.5 이하일 수 있다.The copolymerized polyhydroxyalkanoate (PHA) resin may have a dispersion index (PDI) of 1.0 or more, 1.2 or more, 1.5 or more, 1.8 or more, more than 1.8, or 2.0 or more, 5.0 or less, 4.0 or less, 3.0 or less, It may be 2.9 or less, 2.8 or less, 2.7 or less, 2.6 or less, 2.5 or less, or 2.4 or less. For example, the copolymerized polyhydroxyalkanoate (PHA) resin has a dispersion index (PDI) of 1.0 or more to 5.0 or less, 1.0 or more to 4.0 or less, 1.5 or more to 3.5 or less, 1.5 or more to 3.0 or less, and greater than 1.8. It may be from 3.0 to 3.0, from 1.8 to 2.8, from 2.0 to 3.0, or from 2.0 to 2.5.
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지의 중량평균분자량(Mw) 및 분산지수(PDI)는 각각 후술하는 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량(MwA) 및 초기 분산지수(PDIA)와 동일할 수 있다.The weight average molecular weight (Mw) and dispersion index (PDI) of the copolymerized polyhydroxyalkanoate (PHA) resin are respectively the initial weight average molecular weight (Mw A ) and initial dispersion index of the biodegradable film at 25°C, which will be described later. It may be the same as (PDI A ).
일 실시예에 따르면, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 중량평균분자량(Mw)이 200,000 g/mol 내지 900,000 g/mol이고, 분산지수(PDI)가 1.8 초과 내지 3.0 이하일 수 있다.According to one embodiment, the copolymerized polyhydroxyalkanoate (PHA) resin may have a weight average molecular weight (Mw) of 200,000 g/mol to 900,000 g/mol and a dispersion index (PDI) of more than 1.8 to 3.0 or less. .
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지의 중량평균분자량(Mw)은 겔 투과 크로마토그래피로 분석할 수 있으며, 상기 분산지수(PDI)는 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지의 수평균분자량(Mn)에 대한 중량평균분자량(Mw)의 비로 계산된 값일 수 있다.The weight average molecular weight (Mw) of the copolymerized polyhydroxyalkanoate (PHA) resin can be analyzed by gel permeation chromatography, and the dispersion index (PDI) of the copolymerized polyhydroxyalkanoate (PHA) resin can be analyzed by gel permeation chromatography. It may be a value calculated as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지의 중량평균분자량(Mw) 및 분산지수(PDI)가 각각 상기 범위를 만족하는 경우, 광학적 특성, 열적 특성, 및 기계적 특성을 더욱 향상시킬 수 있고, 목적하는 내구성, 내후성 및 내열성을 향상시키는 데에 더욱 유리하며, 생분해성 필름 제조 시, 성형성, 가공성, 및 생산성도 향상시킬 수 있다.When the weight average molecular weight (Mw) and dispersion index (PDI) of the copolymerized polyhydroxyalkanoate (PHA) resin respectively satisfy the above ranges, the optical properties, thermal properties, and mechanical properties can be further improved, It is more advantageous in improving the desired durability, weather resistance, and heat resistance, and can also improve formability, processability, and productivity when manufacturing biodegradable films.
한편, 상기 생분해성 조성물은 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 이외의 다른 생분해성 수지를 포함하지 않고, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지만을 포함할 수 있다.Meanwhile, the biodegradable composition does not contain any other biodegradable resin other than the copolymerized polyhydroxyalkanoate (PHA) resin, and may contain only the copolymerized polyhydroxyalkanoate (PHA) resin.
상기 생분해성 조성물은 생분해성 수지로서 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지만을 포함하는 경우에도, 목적하는 내구성, 내후성 및 내열성을 향상시킬 수 있어서, 고온고습한 환경에서 장시간 보관 시에도 열적으로 안정하고, 우수한 기계적 특성을 갖는 생분해성 필름 및 생분해성 제품을 제공할 수 있으며, 성형성, 가공성 및 생산성 향상은 물론, 다양한 용도 확장이 가능하다.Even when the biodegradable composition contains only the copolymerized polyhydroxyalkanoate (PHA) resin as a biodegradable resin, the desired durability, weather resistance, and heat resistance can be improved, even when stored for a long time in a high temperature and high humidity environment. It is possible to provide biodegradable films and biodegradable products that are thermally stable and have excellent mechanical properties, and can improve formability, processability, and productivity, as well as expand various uses.
또한, 상기 생분해성 조성물은 필요에 따라 폴리부틸렌아디페이트 테레프탈레이트(PBAT), 폴리락트산(PLA), 폴리부틸렌아디페이트(PBA), 폴리부틸렌숙시네이트-아디페이트(PBSA), 폴리부틸렌숙시네이트-테레프탈레이트(PBST), 폴리히드록시부틸레이트-발레레이트(PHBV), 폴리카프로락톤(PCL), 폴리부틸렌 숙시네이트 아디페이트 테레프탈레이트(PBSAT) 및 열가소성 전분(TPS)으로 이루어진 군으로부터 선택된 1종 이상의 생분해성 수지를 더 포함할 수 있다.In addition, the biodegradable composition may optionally include polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene adipate (PBA), polybutylene succinate-adipate (PBSA), and polybutyl. A group consisting of rensuccinate-terephthalate (PBST), polyhydroxybutyrate-valerate (PHBV), polycaprolactone (PCL), polybutylene succinate adipate terephthalate (PBSAT), and thermoplastic starch (TPS). It may further include one or more biodegradable resins selected from.
첨가제additive
상기 생분해성 조성물은 활제, 산화방지제, 상용화제, 중량제, 기핵제, 용융강도 증강제, 및 슬립제로 구성된 군으로부터 선택된 1종 이상의 첨가제를 더 포함할 수 있다.The biodegradable composition may further include one or more additives selected from the group consisting of lubricants, antioxidants, compatibilizers, weighting agents, nucleating agents, melt strength enhancers, and slip agents.
상기 첨가제의 함량은 상기 생분해성 조성물에 포함되는 전체 수지 100 중량부를 기준으로 0.1 phr 내지 30 phr일 수 있다. 상기 phr(per hundred resin)은 전체 고분자 수지 100 중량부당 투입되는 물질의 투입량 단위를 의미한다(1 phr: 고분자 수지가 100 g일 때 투입량 1 g).The content of the additive may be 0.1 phr to 30 phr based on 100 parts by weight of the total resin included in the biodegradable composition. The phr (per hundred resin) refers to the unit of input amount of material per 100 parts by weight of the total polymer resin (1 phr: 1 g of input amount for 100 g of polymer resin).
예를 들어, 상기 첨가제는 0.1 phr 이상, 0.5 phr 이상, 1 phr 이상, 1.5 phr 이상, 2 phr 이상, 또는 3 phr 이상일 수 있다. 상기 첨가제는 30 phr 이하, 28 phr 이하, 25 phr 이하, 20 phr 이하, 15 phr 이하, 10 phr 이하, 8 phr 이하, 또는 5 phr 이하일 수 있다.For example, the additive may be at least 0.1 phr, at least 0.5 phr, at least 1 phr, at least 1.5 phr, at least 2 phr, or at least 3 phr. The additive may be 30 phr or less, 28 phr or less, 25 phr or less, 20 phr or less, 15 phr or less, 10 phr or less, 8 phr or less, or 5 phr or less.
상기 활제는 상기 생분해성 조성물의 흐름성을 향상시켜 가공성 향상에 바람직하게 작용할 수 있으며, 최종 생산 제품의 표면을 매끄럽게 하며, 유착을 방지할 수 있는 역할을 할 수 있다. The lubricant can improve the flowability of the biodegradable composition, thereby improving processability, smoothing the surface of the final product, and preventing adhesion.
상기 활제는 에스테르계 화합물, 실리콘계 화합물, 및 지방산 아마이드계 화합물로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The lubricant may include one or more selected from the group consisting of ester-based compounds, silicone-based compounds, and fatty acid amide-based compounds.
상기 에스테르계 화합물은 부틸스테아레이트, 글리세롤 모노 스테아레이트 및 몬탄계 왁스로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. 상기 몬탄계 왁스는 탄소수 28 내지 32개의 사슬 길이를 갖는 직쇄 포화 카르복실산의 혼합물일 수 있다.The ester-based compound may include one or more selected from the group consisting of butyl stearate, glycerol monostearate, and montan-based wax. The montan-based wax may be a mixture of straight-chain saturated carboxylic acids having a chain length of 28 to 32 carbon atoms.
상기 실리콘계 화합물은 실리콘 오일 및 실리콘 왁스로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The silicone-based compound may include one or more types selected from the group consisting of silicone oil and silicone wax.
상기 지방산 아마이드계 화합물은 지방산 아마이드, 에틸렌-비스-스테아르아미드(Ethylene-bisstearamide), 에틸렌-비스-올레아미드(Ethylenebis(oleamide)) 및 에루카아미드(erucamide)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. The fatty acid amide compound includes one or more selected from the group consisting of fatty acid amide, ethylene-bisstearamide, ethylene-bis-oleamide (Ethylenebis(oleamide)), and erucamide. can do.
상기 활제는 0.1 phr 내지 10 phr, 0.5 phr 내지 10 phr, 1 phr 내지 10 phr, 1 phr 내지 8 phr, 1 phr 내지 7 phr, 1 phr 내지 6 phr, 2 phr 내지 7 phr, 3 phr 내지 7 phr, 또는 3 phr 내지 6 phr의 양으로 포함될 수 있다. 상기 활제가 상기 범위를 만족하는 경우, 외관성, 윤활성이 우수하고, 분산성이 우수하여 가공성이 향상될 수 있다.The lubricant is 0.1 phr to 10 phr, 0.5 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr. , or may be included in an amount of 3 phr to 6 phr. When the lubricant satisfies the above range, the appearance, lubricity, and dispersibility are excellent, so processability can be improved.
일 실시예에 따르면, 상기 생분해성 조성물은 지방산 아마이드계 화합물을 0.1 phr 내지 10 phr, 3 phr 내지 7 phr, 또는 3 phr 내지 6 phr 포함할 수 있다. According to one embodiment, the biodegradable composition may include 0.1 phr to 10 phr, 3 phr to 7 phr, or 3 phr to 6 phr of a fatty acid amide-based compound.
상기 산화방지제는 오존이나 산소에 분해되는 것을 방지하거나 보관 시 산화를 방지하고, 상기 생분해성 조성물로부터 형성된 생분해성 필름 또는 생분해성 제품의 물성 저하를 방지하기 위한 첨가제이다. The antioxidant is an additive that prevents decomposition by ozone or oxygen, prevents oxidation during storage, and prevents deterioration of the physical properties of the biodegradable film or biodegradable product formed from the biodegradable composition.
상기 산화방지제는 목적하는 효과를 저해하지 않는 한, 통상적으로 사용되는 산화방지제를 사용할 수 있다.The antioxidant may be a commonly used antioxidant as long as it does not impede the desired effect.
구체적으로, 상기 산화 방지제는 힌더드 페놀계 산화 방지제 및 포스파이트계(인계) 산화 방지제로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. Specifically, the antioxidant may include one or more selected from the group consisting of hindered phenol-based antioxidants and phosphite-based (phosphorus-based) antioxidants.
상기 힌더드 페놀계 산화 방지제는 예를 들면, 4,4'-메틸렌-비스(2,6-디-t-부틸페놀), 옥타데실-3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트, 펜타에리트리톨 테트라키스[3-(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트), 3,9-비스[2-[3-(3-tert-부틸-4-히드록시-5-메틸페닐)프로피오닐옥시]-1,1-디메틸에틸]-2,4,8,10-테트라옥사스피로[5.5]운데칸으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. The hindered phenolic antioxidant is, for example, 4,4'-methylene-bis(2,6-di-t-butylphenol), octadecyl-3-(3,5-di-t-butyl-4) -Hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), 3,9-bis[2-[3- (3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane. It may include one or more types.
상기 포스파이트계(인계) 산화 방지제는 예를 들면, 트리스-(2,4-디-t-부틸페닐)포스파이트, 비스-(2,4-디-t-부틸페닐)펜타에리트리톨-디포스파이트, 비스-(2,6-디-t-부틸-4-메틸페닐)펜타에리트리톨-디포스파이트, 디스테아릴-펜타에리트리톨-디포스파이트, [비스(2,4-디-t-부틸-5-메틸페녹시)포스피노]비페닐, 및 N,N-비스[2-[[2,4,8,10-테트라키스(1,1-디메틸에틸)디벤 조[d,f][1,3,2]디옥시포스페핀-6-일]옥시]-에틸]에탄아민으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The phosphite-based (phosphorus-based) antioxidant is, for example, tris-(2,4-di-t-butylphenyl)phosphite, bis-(2,4-di-t-butylphenyl)pentaerythritol-dephosphite, Spite, bis-(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-diphosphite, distearyl-pentaerythritol-diphosphite, [bis(2,4-di-t-butyl- 5-methylphenoxy)phosphino]biphenyl, and N,N-bis[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1 ,3,2]deoxyphosphepin-6-yl]oxy]-ethyl]ethanamine.
상기 산화방지제는 0.01 phr 내지 10 phr, 0.1 phr 내지 10 phr, 1 phr 내지 10 phr, 1 phr 내지 8 phr, 1 phr 내지 7 phr, 1 phr 내지 6 phr, 2 phr 내지 7 phr, 3 phr 내지 7 phr, 1 phr 내지 5 phr, 1 phr 내지 3 phr, 1 phr 내지 2 phr, 0.01 phr 내지 3 phr, 0.05 phr 내지 3 phr, 0.05 phr 내지 2.5 phr, 0.05 phr 내지 1.5 phr, 0.05 phr 내지 1 phr, 0.1 내지 1 phr, 또는 0.1 내지 0.5 phr로 포함될 수 있다.The antioxidant is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr. phr, 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, It may be included at 0.1 to 1 phr, or 0.1 to 0.5 phr.
상기 산화방지제가 상기 함량 범위를 만족하는 경우, 상기 생분해성 조성물로부터 형성된 생분해성 필름 또는 생분해성 제품의 물성을 향상시킬 수 있고, 목적하는 효과를 달성하는 데에 더욱 유리할 수 있다.When the antioxidant satisfies the above content range, the physical properties of the biodegradable film or biodegradable product formed from the biodegradable composition can be improved, and it can be more advantageous to achieve the desired effect.
상기 상용화제(compatibilizer)는 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지의 이형성을 제거하여 상용성을 부여하기 위한 첨가제이다.The compatibilizer is an additive for providing compatibility by removing the release property of the copolymerized polyhydroxyalkanoate (PHA) resin.
상기 상용화제는 효과를 저해하지 않는 한, 통상적으로 사용되는 상용화제를 사용할 수 있다.The compatibilizer may be a commonly used compatibilizer as long as it does not impede the effect.
구체적으로, 상기 상용화제는 폴리비닐아세테이트(PVAc)계, 이소시아네이트계, 폴리프로필렌카보네이트계, 글리시딜메타크릴레이트, 에틸렌비닐알콜, 폴리 비닐알코올(PVA), 에틸렌비닐아세테이트, 및 무수말레인산으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.Specifically, the compatibilizer consists of polyvinyl acetate (PVAc)-based, isocyanate-based, polypropylene carbonate-based, glycidyl methacrylate, ethylene vinyl alcohol, polyvinyl alcohol (PVA), ethylene vinyl acetate, and maleic anhydride. It may include one or more types selected from the group.
상기 상용화제는 0.01 phr 내지 10 phr, 0.1 phr 내지 10 phr, 1 phr 내지 10 phr, 1 phr 내지 8 phr, 1 phr 내지 7 phr, 1 phr 내지 6 phr, 2 phr 내지 7 phr, 3 phr 내지 7 phr, 1 phr 내지 5 phr, 1 phr 내지 3 phr, 1 phr 내지 2 phr, 0.01 phr 내지 3 phr, 0.05 phr 내지 3 phr, 0.05 phr 내지 2.5 phr, 0.05 phr 내지 1.5 phr, 0.05 phr 내지 1 phr, 0.1 내지 1 phr, 또는 0.1 내지 0.5 phr로 포함될 수 있다.The compatibilizer is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr. phr, 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, It may be included at 0.1 to 1 phr, or 0.1 to 0.5 phr.
상기 상용화제가 상기 함량 범위를 만족하는 경우, 사용되는 수지 및 첨가제간의 상용성을 증가시켜 상기 생분해성 조성물로부터 형성된 생분해성 필름 또는 생분해성 제품의 물성을 향상시킬 수 있고, 목적하는 효과를 달성하는 데에 더욱 유리할 수 있다.When the compatibilizer satisfies the above content range, the physical properties of the biodegradable film or biodegradable product formed from the biodegradable composition can be improved by increasing the compatibility between the resin and additives used, and the desired effect can be achieved. may be more advantageous.
상기 중량제는 무기물로서, 성형 과정에서 결정화 속도를 빠르게 하여 성형성을 증가시키고, 생분해성 수지의 사용으로 인해 원가 상승의 문제를 줄이기 위해 첨가되는 첨가제이다. The weighting agent is an inorganic material and is an additive added to increase moldability by speeding up the crystallization rate during the molding process and to reduce the problem of increased costs due to the use of biodegradable resin.
상기 중량제는 목적하는 효과를 저해하지 않는 한, 통상적으로 사용되는 무기물을 사용할 수 있다.The weighting agent may be a commonly used inorganic material as long as it does not impede the desired effect.
구체적으로, 상기 중량제는 탄산칼슘, 예컨대 경질 또는 중질 탄산칼슘, 실리카, 탈크, 카올린, 황산바륨, 클레이, 산화칼슘, 수산화마그네슘, 산화티탄, 카본블랙 및 유리섬유로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. Specifically, the weighting agent is calcium carbonate, such as light or heavy calcium carbonate, silica, talc, kaolin, barium sulfate, clay, calcium oxide, magnesium hydroxide, titanium oxide, carbon black, and at least one selected from the group consisting of glass fiber. may include.
상기 중량제의 평균 입도가 0.5 ㎛ 내지 10 ㎛일 수 있다. 상기 중량제의 평균입도가 0.5 ㎛ 미만이면 입자의 분산이 곤란해지며, 10 ㎛ 초과이면 입자의 크기가 지나치게 커져, 효과를 저해할 수 있다.The average particle size of the weighting agent may be 0.5 ㎛ to 10 ㎛. If the average particle size of the weighting agent is less than 0.5 ㎛, it becomes difficult to disperse the particles, and if it is more than 10 ㎛, the particle size becomes too large, which may impede the effect.
상기 중량제는 0.01 phr 내지 10 phr, 0.1 phr 내지 10 phr, 1 phr 내지 10 phr, 1 phr 내지 8 phr, 1 phr 내지 7 phr, 1 phr 내지 6 phr, 2 phr 내지 7 phr, 3 phr 내지 7 phr, 1 phr 내지 5 phr, 1 phr 내지 3 phr, 1 phr 내지 2 phr, 0.01 phr 내지 3 phr, 0.05 phr 내지 3 phr, 0.05 phr 내지 2.5 phr, 0.05 phr 내지 1.5 phr, 0.05 phr 내지 1 phr, 0.1 내지 1 phr, 또는 0.1 내지 0.5 phr로 포함될 수 있다.The weighting agent is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr. phr, 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, It may be included at 0.1 to 1 phr, or 0.1 to 0.5 phr.
상기 중량제가 상기 함량 범위를 만족하는 경우, 목적하는 효과를 달성하는 데에 더욱 유리할 수 있다.When the weighting agent satisfies the above content range, it may be more advantageous to achieve the desired effect.
상기 기핵제는 중합체 용융물이 냉각될 때 중합체의 결정화 형태를 보조하거나 변화시키고 고화 속도(Solidification)를 향상시키기 위한 첨가제이다. 특히, 일 실시예에 따라 사용되는 공중합 폴리하이드록시알카노에이트(PHA) 수지는 고화 속도가 낮기 때문에, 연질의 재료로서 공정 적합성이 용이하지 않을 수 있다. 상기 기핵제를 사용하는 경우 고화 속도를 향상시켜 가공성, 성형성 및 생산성을 더욱 향상시킬 수 있고, 목적하는 물성을 효율적으로 달성할 수 있다.The nucleating agent is an additive that assists or changes the crystallization form of the polymer and improves solidification when the polymer melt is cooled. In particular, since the copolymerized polyhydroxyalkanoate (PHA) resin used according to one embodiment has a low solidification rate, process suitability as a soft material may not be easy. When the nucleating agent is used, the solidification speed can be improved to further improve processability, moldability, and productivity, and the desired physical properties can be efficiently achieved.
상기 기핵제는 효과를 저해하지 않는 한, 통상적으로 사용되는 기핵제를 사용할 수 있다. The nucleating agent may be a commonly used nucleating agent as long as it does not impede the effect.
구체적으로, 상기 기핵제는 홑원소 물질(순물질), 복합 산화물을 포함하는 금속 화합물, 예를 들면, 카본블랙, 탄산칼슘, 합성규산 및 염, 실리카, 아연 화이트(zinc white), 점토, 고령토, 염기성 탄산마그네슘, 미카, 탈크, 석영분말, 규조암(diatomite), 백운석(dolomite) 분말, 산화티타늄, 산화아연, 산화안티몬, 황산바륨, 황산칼슘, 알루미나, 규산칼슘, 유기인의 금속염 및 질화붕소; 금속 카복실레이트기를 가진 저분자 유기화합물, 예를 들면, 옥틸산, 톨루엔산, 헵탄산, 펠라르곤산(pelargonic acid), 라우르산, 미리스트산(myristic acid), 팔미틴산(palmitic acid), 스테아린산, 베헨산(behenic acid), 세로트산(cerotic acid), 몬타닌산(montanic acid), 멜리스산(melissic acid), 벤젠산, p-tert-부틸벤젠산, 테레프탈산, 테레프탈산 모노메틸 에스테르, 이소프탈산 및 이소프탈산 모노메틸 에스테르 각각의 금속염; 금속 카복실레이트기를 가진 중합체 유기화합물, 예를 들면, 폴리에틸렌의 산화반응에 의해 수득되는 카복실기-함유 폴리에틸렌, 폴리프로필렌의 산화반응에 의해 수득되는 카복실기-함유 폴리프로필렌, 아크릴산 또는 메타크릴산과 올레핀(예컨대, 에틸렌, 프로필렌 및 부텐-1)의 공중합체, 아크릴산 또는 메타크릴산과 스티렌의 공중합체, 올레핀과 말레산 무수물의 공중합체 및 스티렌과 말레산 무수물의 공중합체 각각의 금속염; 중합체 유기화합물, 예를 들면, 제3위치 탄소원자에 분기결합되며 5개 이상의 탄소원자를 갖는 알파-올레핀(예컨대, 3,3 디메틸부텐-1,3-메틸부텐-1,3-메틸펜텐-1,3-메틸헥센-1 및 3,5,5-트리메틸헥센-1), 비닐사이클로알칸의 중합체(예컨대, 비닐사이클로펜탄, 비닐사이클로헥산 및 비닐노르보난), 폴리알킬렌 글리콜(예컨대, 폴리에틸렌 글리콜 및 폴리프로필렌 글리콜), 폴리(글리콜산), 셀룰로오스, 셀룰로오스에스테르 및 셀룰로오스 에테르; 인산 또는 아인산 및 그의 금속염, 예를 들면, 디페닐 포스페이트, 디페닐 포스파이트(diphenyl phosphite), 비스(4-tert-부틸페닐)포스페이트의 금속염 및 메틸렌 비스-(2,4-tert-부틸페닐)포스페이트; 소르비톨 유도체, 예를 들면, 비스(p-메틸벤질리덴) 소르비톨 및 비스(p-에틸벤질리덴) 소르비톨; 및 무수 티오글리콜산, p-톨루엔술폰산 및 그의 금속염이다. 상기 기핵제들은 단독으로 또는 서로 조합되어 사용될 수 있다.Specifically, the nucleating agent is a single element material (pure material), a metal compound containing a complex oxide, for example, carbon black, calcium carbonate, synthetic silicic acid and salt, silica, zinc white, clay, kaolin, basic Magnesium carbonate, mica, talc, quartz powder, diatomite, dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, calcium silicate, metal salts of organic phosphorus and boron nitride; Low molecular weight organic compounds with metal carboxylate groups, such as octylic acid, toluic acid, heptanoic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, stearic acid, Behenic acid, cerotic acid, montanic acid, melissic acid, benzenoic acid, p-tert-butylbenzene acid, terephthalic acid, terephthalic acid monomethyl ester, isophthalic acid and isophthalic acid. Metal salts of each phthalic acid monomethyl ester; Polymeric organic compounds with metal carboxylate groups, such as carboxyl group-containing polyethylene obtained by the oxidation reaction of polyethylene, carboxyl group-containing polypropylene obtained by the oxidation reaction of polypropylene, acrylic acid or methacrylic acid and olefin ( For example, copolymers of ethylene, propylene and butene-1), copolymers of acrylic acid or methacrylic acid and styrene, copolymers of olefin and maleic anhydride, and metal salts of each of the copolymers of styrene and maleic anhydride; Polymeric organic compounds, for example, alpha-olefins having 5 or more carbon atoms branched to the carbon atom in the 3rd position (e.g., 3,3 dimethylbutene-1,3-methylbutene-1,3-methylpentene-1) , 3-methylhexene-1 and 3,5,5-trimethylhexene-1), polymers of vinylcycloalkanes (e.g. vinylcyclopentane, vinylcyclohexane and vinylnorbonane), polyalkylene glycols (e.g. polyethylene glycol) and polypropylene glycol), poly(glycolic acid), cellulose, cellulose esters and cellulose ethers; Phosphoric acid or phosphorous acid and its metal salts, such as diphenyl phosphate, diphenyl phosphite, metal salts of bis(4-tert-butylphenyl)phosphate and methylene bis-(2,4-tert-butylphenyl). phosphate; Sorbitol derivatives such as bis(p-methylbenzylidene)sorbitol and bis(p-ethylbenzylidene)sorbitol; and thioglycolic anhydride, p-toluenesulfonic acid, and metal salts thereof. The nucleating agents may be used alone or in combination with each other.
상기 기핵제는 0.01 phr 내지 10 phr, 0.1 phr 내지 10 phr, 1 phr 내지 10 phr, 1 phr 내지 8 phr, 1 phr 내지 7 phr, 1 phr 내지 6 phr, 2 phr 내지 7 phr, 3 phr 내지 7 phr, 1 phr 내지 5 phr, 1 phr 내지 3 phr, 1 phr 내지 2 phr, 0.01 phr 내지 3 phr, 0.05 phr 내지 3 phr, 0.05 phr 내지 2.5 phr, 0.05 phr 내지 1.5 phr, 0.05 phr 내지 1 phr, 0.1 내지 1 phr, 또는 0.1 내지 0.5 phr로 포함될 수 있다.The nucleating agent is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr. phr, 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, It may be included at 0.1 to 1 phr, or 0.1 to 0.5 phr.
상기 기핵제가 상기 함량 범위를 만족하는 경우, 고화 속도(Solidification)를 향상시켜 성형성을 좋게 하고, 예를 들어 펠렛 제조를 위한 커팅 시, 또는 제조 공정에 있어서 고화 속도(Solidification)를 향상시켜 생산성 및 가공성을 더욱 향상시킬 수 있다.When the nucleating agent satisfies the above content range, the solidification rate is improved to improve moldability and, for example, when cutting for pellet production or during the manufacturing process, the solidification rate is improved to improve productivity and Processability can be further improved.
상기 용융강도 증강제는 반응성의 용융 강도를 향상시키기 위한 첨가제이다. The melt strength enhancer is an additive for improving reactive melt strength.
상기 용융강도 증강제는 효과를 저해하지 않는 한, 통상적으로 사용되는 용융강도 증강제를 사용할 수 있다. The melt strength enhancer may be a commonly used melt strength enhancer as long as it does not impede the effect.
구체적으로, 상기 용융강도 증강제는 폴리에스테르, 스티렌계 폴리머(예컨대 아크릴로니트릴 부타디엔 스티렌 및 폴리스티렌), 폴리실록산, 유기변성 실록산 폴리머, 폴리에스테르, 및 말레산 무수물 그라프팅된 에틸렌 프로필렌 디엔 모노머(MAH-g-EPDM)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. Specifically, the melt strength enhancer is polyester, styrene-based polymers (such as acrylonitrile butadiene styrene and polystyrene), polysiloxane, organic modified siloxane polymer, polyester, and maleic anhydride grafted ethylene propylene diene monomer (MAH-g). -EPDM) may include one or more selected from the group consisting of
상기 용융강도 증강제는 0.01 phr 내지 10 phr, 0.1 phr 내지 10 phr, 1 phr 내지 10 phr, 1 phr 내지 8 phr, 1 phr 내지 7 phr, 1 phr 내지 6 phr, 2 phr 내지 7 phr, 3 phr 내지 7 phr, 1 phr 내지 5 phr, 1 phr 내지 3 phr, 1 phr 내지 2 phr, 0.01 phr 내지 3 phr, 0.05 phr 내지 3 phr, 0.05 phr 내지 2.5 phr, 0.05 phr 내지 1.5 phr, 0.05 phr 내지 1 phr, 0.1 내지 1 phr, 또는 0.1 내지 0.5 phr로 포함될 수 있다.The melt strength enhancer is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr, 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr , 0.1 to 1 phr, or 0.1 to 0.5 phr.
상기 용융강도 증강제가 상기 함량 범위를 만족하는 경우, 목적하는 효과를 달성하는 데에 더욱 유리할 수 있다.When the melt strength enhancer satisfies the above content range, it may be more advantageous to achieve the desired effect.
상기 슬립제는 압출 시 슬립성(미끄러움성)을 향상시키고, 공정 시 시트 또는 필름 표면끼리 달라붙는 현상을 방지하기 위한 첨가제이다. The slip agent is an additive that improves slipperiness during extrusion and prevents the surfaces of sheets or films from sticking to each other during the process.
상기 슬립제는 효과를 저해하지 않는 한, 통상적으로 사용되는 슬립제를 사용할 수 있다. 예를 들면 상기 슬립제는 에루카미드(Erucamide), 올리아미드(Oliamide) 및 스테아라미드(Stearamide)에서 선택된 적어도 하나 이상을 사용할 수 있다. The slip agent may be a commonly used slip agent as long as it does not impair the effect. For example, the slip agent may be at least one selected from Erucamide, Oliamide, and Stearamide.
상기 슬립제는 0.01 phr 내지 10 phr, 0.1 phr 내지 10 phr, 1 phr 내지 10 phr, 1 phr 내지 8 phr, 1 phr 내지 7 phr, 1 phr 내지 6 phr, 2 phr 내지 7 phr, 3 phr 내지 7 phr, 1 phr 내지 5 phr, 1 phr 내지 3 phr, 1 phr 내지 2 phr, 0.01 phr 내지 3 phr, 0.05 phr 내지 3 phr, 0.05 phr 내지 2.5 phr, 0.05 phr 내지 1.5 phr, 0.05 phr 내지 1 phr, 0.1 내지 1 phr, 또는 0.1 내지 0.5 phr로 포함될 수 있다.The slip agent is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr. phr, 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, It may be included at 0.1 to 1 phr, or 0.1 to 0.5 phr.
상기 슬립제가 상기 함량 범위를 만족하는 경우, 가공성, 생산성 및 성형성을 더욱 향상시킬 수 있고, 목적하는 효과를 달성하는 데에 더욱 유리할 수 있다.When the slip agent satisfies the above content range, processability, productivity, and moldability can be further improved, and it can be more advantageous to achieve the desired effect.
그밖에 첨가제로서, 상기 생분해성 조성물은 가교제 및/또는 안정화제도 포함할 수 있다.As other additives, the biodegradable composition may also include a crosslinking agent and/or stabilizer.
상기 가교제는 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지의 특성을 개질하고, 수지의 분자량을 증가시키기 위한 첨가제로서, 효과를 저해하지 않는 한, 통상적으로 사용되는 가교제를 사용할 수 있다. The crosslinking agent is an additive for modifying the properties of the copolymerized polyhydroxyalkanoate (PHA) resin and increasing the molecular weight of the resin, and a commonly used crosslinking agent can be used as long as it does not impair the effect.
예를 들면 상기 가교제는 지방산 에스테르, 또는 에폭시기를 함유한(에폭시화) 천연유래 오일, 디알릴프탈레이트, 펜타에리트리톨 테트라아크릴레이트, 트리메틸올프로판 트리아크릴레이트, 펜타에리트리톨 트리아크릴레이트, 디펜타에리트리톨 펜타아크릴레이트, 디에틸렌 글리콜 디메타크릴레이트, 및 비스(2-메트아크릴옥시에틸)포스페이트로 이루어진 군으로부터 선택된 적어도 하나 이상을 사용할 수 있다.For example, the cross-linking agent may be fatty acid ester, natural oil containing an epoxy group (epoxidized), diallyl phthalate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythate. At least one selected from the group consisting of litol pentaacrylate, diethylene glycol dimethacrylate, and bis(2-methacryloxyethyl)phosphate may be used.
상기 가교제는 0.01 phr 내지 10 phr, 0.1 phr 내지 10 phr, 1 phr 내지 10 phr, 1 phr 내지 8 phr, 1 phr 내지 7 phr, 1 phr 내지 6 phr, 2 phr 내지 7 phr, 3 phr 내지 7 phr, 1 phr 내지 5 phr, 1 phr 내지 3 phr, 1 phr 내지 2 phr, 0.01 phr 내지 3 phr, 0.05 phr 내지 3 phr, 0.05 phr 내지 2.5 phr, 0.05 phr 내지 1.5 phr, 0.05 phr 내지 1 phr, 0.1 내지 1 phr, 또는 0.1 내지 0.5 phr로 포함될 수 있다.The crosslinking agent is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr. , 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, 0.1 phr to 1 phr, or 0.1 to 0.5 phr.
상기 안정화제는 산화 및 열로부터 보호하고, 색상 변화를 방지하기 위한 첨가제이다. 상기 안정화제는 효과를 저해하지 않는 한, 통상적으로 사용되는 안정화제를 사용할 수 있다.The stabilizer is an additive that protects against oxidation and heat and prevents color change. The stabilizer may be a commonly used stabilizer as long as it does not impair the effect.
구체적으로, 상기 안정화제는 트리메틸포스페이트, 트리페닐포스페이트, 트리메틸포스핀, 인산 및 아인산으로 이루어진 군으로부터 선택된 1종 일 수 있다. Specifically, the stabilizer may be one selected from the group consisting of trimethyl phosphate, triphenyl phosphate, trimethyl phosphine, phosphoric acid, and phosphorous acid.
상기 안정화제는 0.01 phr 내지 10 phr, 0.1 phr 내지 10 phr, 1 phr 내지 10 phr, 1 phr 내지 8 phr, 1 phr 내지 7 phr, 1 phr 내지 6 phr, 2 phr 내지 7 phr, 3 phr 내지 7 phr, 1 phr 내지 5 phr, 1 phr 내지 3 phr, 1 phr 내지 2 phr, 0.01 phr 내지 3 phr, 0.05 phr 내지 3 phr, 0.05 phr 내지 2.5 phr, 0.05 phr 내지 1.5 phr, 0.05 phr 내지 1 phr, 0.1 내지 1 phr, 또는 0.1 내지 0.5 phr로 포함될 수 있다.The stabilizer is 0.01 phr to 10 phr, 0.1 phr to 10 phr, 1 phr to 10 phr, 1 phr to 8 phr, 1 phr to 7 phr, 1 phr to 6 phr, 2 phr to 7 phr, 3 phr to 7 phr. phr, 1 phr to 5 phr, 1 phr to 3 phr, 1 phr to 2 phr, 0.01 phr to 3 phr, 0.05 phr to 3 phr, 0.05 phr to 2.5 phr, 0.05 phr to 1.5 phr, 0.05 phr to 1 phr, It may be included at 0.1 to 1 phr, or 0.1 to 0.5 phr.
생분해성 조성물의 물성Physical properties of biodegradable compositions
실시예에 따르면, 상기 생분해성 조성물은 이를 포함하는 생분해성 필름에 적용 시, 우수한 생분해성, 광학적 특성, 및 기계적 특성을 가짐은 물론, 고온고습 환경에서 장시간 보관 시에도 특정 범위 이하의 인장강도 변화율, 연신율 변화율, 분해율, 분산지수 변화율 등을 만족하고, 내구성, 내후성 및 내열성을 동시에 향상시킬 수 있다.According to an example, the biodegradable composition not only has excellent biodegradability, optical properties, and mechanical properties when applied to a biodegradable film containing it, but also has a tensile strength change rate below a certain range even when stored for a long time in a high temperature and high humidity environment. , it satisfies elongation change rate, decomposition rate, and dispersion index change rate, and can improve durability, weather resistance, and heat resistance at the same time.
일 실시예에 따른 생분해성 조성물은 하기 식 1로 표시되는 인장강도 변화율이 5% 이하일 수 있다.The biodegradable composition according to one embodiment may have a tensile strength change rate of 5% or less, expressed by Equation 1 below.
[식 1][Equation 1]
인장강도 변화율(%) = ((TSA - TSB)/TSA) × 100Tensile strength change rate (%) = ((TS A - TS B )/TS A ) × 100
상기 식 1에서,In equation 1 above,
TSA및 TSB는 ASTM D882에 의거하여, 상기 생분해성 조성물로부터 제조된 생분해성 필름의 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 인장 속도 200 ㎜/분의 속도로 측정한 인장강도(Mpa)로서, For TS A and TS B , according to ASTM D882, a specimen of the biodegradable film prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (UTM). The tensile strength (Mpa) measured at a tensile speed of 200 mm/min with as much installation as possible,
TSA는 25℃에서의 상기 생분해성 필름의 초기 인장강도이고,TS A is the initial tensile strength of the biodegradable film at 25°C,
TSB는 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 인장강도이다.TS B is the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
상기 인장강도 변화율은 25℃에서의 상기 생분해성 필름의 초기 인장강도(TSA)와 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 인장강도(TSB)의 차를 25℃에서의 상기 생분해성 필름의 초기 인장강도(TSA)로 나눈 값을 백분율로 환산한 값으로서, 상기 인장강도 변화율은 4% 이하, 3% 이하, 2% 이하, 2% 미만, 1.9% 이하, 1.8% 이하, 또는 1.75% 이하일 수 있다.The rate of change in tensile strength is the initial tensile strength of the biodegradable film at 25°C (TS A ) and the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH) (TS B ). The difference is divided by the initial tensile strength (TS A ) of the biodegradable film at 25°C, converted into a percentage, and the rate of change in tensile strength is 4% or less, 3% or less, 2% or less, and less than 2%. , may be 1.9% or less, 1.8% or less, or 1.75% or less.
상기 식 1에서, TSA는 25℃에서의 상기 생분해성 필름의 초기 인장강도(0일)로서, 10 Mpa 내지 50 Mpa, 15 Mpa 내지 45 Mpa, 15 Mpa 내지 40 Mpa, 20 Mpa 내지 40 Mpa, 20 Mpa 내지 35 Mpa, 또는 20 Mpa 내지 30 Mpa일 수 있다.In Equation 1, TS A is the initial tensile strength (day 0) of the biodegradable film at 25°C, and is 10 Mpa to 50 Mpa, 15 Mpa to 45 Mpa, 15 Mpa to 40 Mpa, 20 Mpa to 40 Mpa, It may be 20 Mpa to 35 Mpa, or 20 Mpa to 30 Mpa.
또한, 상기 식 1에서, TSB는 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 인장강도(5일)로서, 10 Mpa 내지 50 Mpa, 10 Mpa 내지 45 Mpa, 15 Mpa 내지 45 Mpa, 15 Mpa 내지 40 Mpa, 20 Mpa 내지 40 Mpa, 20 Mpa 내지 35 Mpa, 또는 20 Mpa 내지 30 Mpa일 수 있다. In addition, in Equation 1, TS B is the tensile strength (5 days) of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH), 10 Mpa to 50 Mpa, 10 Mpa to 45 Mpa, 15 Mpa to 45 Mpa, 15 Mpa to 40 Mpa, 20 Mpa to 40 Mpa, 20 Mpa to 35 Mpa, or 20 Mpa to 30 Mpa.
또한, 85℃ 및 상대습도(RH) 85%의 조건에서 1일간 보관 후의 상기 생분해성 필름의 인장강도(1일)는, 10 Mpa 내지 50 Mpa, 10 Mpa 내지 45 Mpa, 15 Mpa 내지 45 Mpa, 15 Mpa 내지 40 Mpa, 20 Mpa 내지 40 Mpa, 20 Mpa 내지 35 Mpa, 또는 20 Mpa 내지 30 Mpa일 수 있다. In addition, the tensile strength (1 day) of the biodegradable film after storage for 1 day at 85°C and 85% relative humidity (RH) is 10 Mpa to 50 Mpa, 10 Mpa to 45 Mpa, 15 Mpa to 45 Mpa, It may be 15 Mpa to 40 Mpa, 20 Mpa to 40 Mpa, 20 Mpa to 35 Mpa, or 20 Mpa to 30 Mpa.
또한, 85℃ 및 상대습도(RH) 85%의 조건에서 2일간 보관 후의 상기 생분해성 필름의 인장강도(2일)는, 10 Mpa 내지 50 Mpa, 10 Mpa 내지 45 Mpa, 15 Mpa 내지 45 Mpa, 15 Mpa 내지 40 Mpa, 20 Mpa 내지 40 Mpa, 20 Mpa 내지 35 Mpa, 또는 20 Mpa 내지 30 Mpa일 수 있다. In addition, the tensile strength (2 days) of the biodegradable film after storage for 2 days at 85°C and 85% relative humidity (RH) is 10 Mpa to 50 Mpa, 10 Mpa to 45 Mpa, 15 Mpa to 45 Mpa, It may be 15 Mpa to 40 Mpa, 20 Mpa to 40 Mpa, 20 Mpa to 35 Mpa, or 20 Mpa to 30 Mpa.
상기 생분해성 조성물로부터 제조된 생분해성 필름의 상기 시간에 따른 인장강도 및 인장강도 변화율을 상기 범위로 제어하는 경우, 상기 생분해성 필름 및 생분해성 제품의 기계적 강도, 내구성 및 내후성을 더욱 향상시킬 수 있다.When the tensile strength and tensile strength change rate over time of the biodegradable film manufactured from the biodegradable composition are controlled within the above range, the mechanical strength, durability and weather resistance of the biodegradable film and biodegradable product can be further improved. .
또 다른 실시예에 따른 생분해성 조성물은 하기 식 2로 표시되는 분해율이 50% 이하일 수 있다.The biodegradable composition according to another example may have a decomposition rate of 50% or less, expressed by Equation 2 below.
[식 2][Equation 2]
분해율(%) = ((MwA - MwB)/MwA) × 100Decomposition rate (%) = ((Mw A - Mw B )/Mw A ) × 100
상기 식 2에서,In equation 2 above,
MwA 및 MwB는 상기 생분해성 조성물로부터 제조된 생분해성 필름을 클로로포름 용매에 용해시킨 후 겔 투과 크로마토그래피(GPC)를 사용하여 측정한 상기 생분해성 필름의 중량평균분자량(g/mol)으로서,Mw A and Mw B are the weight average molecular weight (g/mol) of the biodegradable film prepared from the biodegradable composition measured using gel permeation chromatography (GPC) after dissolving the biodegradable film in chloroform solvent,
MwA는 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량이고,Mw A is the initial weight average molecular weight of the biodegradable film at 25°C,
MwB는 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 중량평균분자량이다.Mw B is the weight average molecular weight of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
상기 분해율은 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량(MwA)과 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 중량평균분자량(MwB)의 차를 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량(MwA)으로 나눈 값을 백분율로 환산한 값으로서, 상기 분해율은 50% 미만, 48% 이하, 45% 이하, 42% 이하, 40% 이하, 39% 이하, 또는 38% 이하일 수 있다.The decomposition rate is the initial weight average molecular weight (Mw A ) of the biodegradable film at 25°C and the weight average molecular weight (Mw B ) of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH). The difference is divided by the initial weight average molecular weight (Mw A ) of the biodegradable film at 25°C, converted to a percentage, and the decomposition rate is less than 50%, 48% or less, 45% or less, 42% or less, It may be 40% or less, 39% or less, or 38% or less.
상기 식 2에서, MwA는 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량(0일)으로서, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지의 분자량과 동일할 수 있으며, 구체적으로 100,000 g/mol 내지 900,000 g/mol, 200,000 g/mol 내지 900,000 g/mol, 200,000 g/mol 내지 800,000 g/mol, 200,000 g/mol 내지 700,000 g/mol, 200,000 g/mol 내지 650,000 g/mol, 200,000 g/mol 내지 600,000 g/mol, 200,000 g/mol 내지 500,000 g/mol, 200,000 g/mol 내지 400,000 g/mol, 또는 200,000 g/mol 내지 300,000 g/mol일 수 있다.In Equation 2, Mw A is the initial weight average molecular weight (day 0) of the biodegradable film at 25°C, and may be the same as the molecular weight of the copolymerized polyhydroxyalkanoate (PHA) resin, specifically 100,000. g/mol to 900,000 g/mol, 200,000 g/mol to 900,000 g/mol, 200,000 g/mol to 800,000 g/mol, 200,000 g/mol to 700,000 g/mol, 200,000 g/mol to 650,000 g/mol, 200,000 g/mol to 600,000 g/mol, 200,000 g/mol to 500,000 g/mol, 200,000 g/mol to 400,000 g/mol, or 200,000 g/mol to 300,000 g/mol.
또한, 상기 식 2에서, MwB는 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 중량평균분자량(4일)로서, 100,000 g/mol 내지 900,000 g/mol, 200,000 g/mol 내지 900,000 g/mol, 200,000 g/mol 내지 800,000 g/mol, 200,000 g/mol 내지 700,000 g/mol, 200,000 g/mol 내지 650,000 g/mol, 200,000 g/mol 내지 600,000 g/mol, 200,000 g/mol 내지 500,000 g/mol, 200,000 g/mol 내지 400,000 g/mol, 또는 200,000 g/mol 내지 300,000 g/mol일 수 있다.In addition, in Equation 2, Mw B is the weight average molecular weight (4 days) of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH), and is 100,000 g/mol to 900,000 g/mol. , 200,000 g/mol to 900,000 g/mol, 200,000 g/mol to 800,000 g/mol, 200,000 g/mol to 700,000 g/mol, 200,000 g/mol to 650,000 g/mol, 200,000 g/mol to 600,000 g/mol , 200,000 g/mol to 500,000 g/mol, 200,000 g/mol to 400,000 g/mol, or 200,000 g/mol to 300,000 g/mol.
또한, 85℃ 및 상대습도(RH) 85%의 조건에서 1일간 보관 후의 상기 생분해성 필름의 중량평균분자량(1일)은, 100,000 g/mol 내지 900,000 g/mol, 190,000 g/mol 내지 900,000 g/mol, 190,000 g/mol 내지 800,000 g/mol, 190,000 g/mol 내지 700,000 g/mol, 190,000 g/mol 내지 650,000 g/mol, 190,000 g/mol 내지 600,000 g/mol, 190,000 g/mol 내지 500,000 g/mol, 190,000 g/mol 내지 400,000 g/mol, 또는 190,000 g/mol 내지 300,000 g/mol일 수 있다.In addition, the weight average molecular weight (per day) of the biodegradable film after storage for 1 day at 85°C and 85% relative humidity (RH) is 100,000 g/mol to 900,000 g/mol, 190,000 g/mol to 900,000 g. /mol, 190,000 g/mol to 800,000 g/mol, 190,000 g/mol to 700,000 g/mol, 190,000 g/mol to 650,000 g/mol, 190,000 g/mol to 600,000 g/mol, 190,000 g/mol to 500,000 g /mol, 190,000 g/mol to 400,000 g/mol, or 190,000 g/mol to 300,000 g/mol.
또한, 85℃ 및 상대습도(RH) 85%의 조건에서 2일간 보관 후의 상기 생분해성 필름의 중량평균분자량(2일)은, 100,000 g/mol 내지 900,000 g/mol, 180,000 g/mol 내지 900,000 g/mol, 180,000 g/mol 내지 800,000 g/mol, 180,000 g/mol 내지 700,000 g/mol, 180,000 g/mol 내지 650,000 g/mol, 180,000 g/mol 내지 600,000 g/mol, 180,000 g/mol 내지 500,000 g/mol, 180,000 g/mol 내지 400,000 g/mol, 또는 180,000 g/mol 내지 300,000 g/mol일 수 있다.In addition, the weight average molecular weight (2 days) of the biodegradable film after storage for 2 days at 85°C and 85% relative humidity (RH) is 100,000 g/mol to 900,000 g/mol, 180,000 g/mol to 900,000 g. /mol, 180,000 g/mol to 800,000 g/mol, 180,000 g/mol to 700,000 g/mol, 180,000 g/mol to 650,000 g/mol, 180,000 g/mol to 600,000 g/mol, 180,000 g/mol to 500,000 g /mol, 180,000 g/mol to 400,000 g/mol, or 180,000 g/mol to 300,000 g/mol.
또한, 상기 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량(MwA)과 85℃ 및 상대습도(RH) 85%의 조건에서 1일간 보관 후의 상기 생분해성 필름의 중량평균분자량(MwB)의 차를 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량(MwA)으로 나눈 값을 백분율로 환산한 값인, 1일간 보관 후의 분해율은 30% 이하, 20% 이하, 18% 이하, 15% 이하, 14% 이하, 또는 13% 이하일 수 있다.In addition, the initial weight average molecular weight (Mw A ) of the biodegradable film at 25°C and the weight average molecular weight (Mw B ) of the biodegradable film after storage for 1 day under conditions of 85°C and 85% relative humidity (RH). The decomposition rate after storage for 1 day, which is a value calculated by dividing the difference by the initial weight average molecular weight (Mw A ) of the biodegradable film at 25°C and converting it into a percentage, is 30% or less, 20% or less, 18% or less, 15%. It may be less than, 14% or less, or less than or equal to 13%.
또한, 상기 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량(MwA)과 85℃ 및 상대습도(RH) 85%의 조건에서 2일간 보관 후의 상기 생분해성 필름의 중량평균분자량(MwB)의 차를 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량(MwA)으로 나눈 값을 백분율로 환산한 값인, 2일간 보관 후의 분해율은 40% 이하, 35% 이하, 30% 이하, 25% 이하, 24% 이하, 또는 22% 이하일 수 있다.In addition, the initial weight average molecular weight (Mw A ) of the biodegradable film at 25°C and the weight average molecular weight (Mw B ) of the biodegradable film after storage for 2 days at 85°C and 85% relative humidity (RH). The decomposition rate after storage for 2 days, which is a value calculated by dividing the difference by the initial weight average molecular weight (Mw A ) of the biodegradable film at 25°C and converting it to a percentage, is 40% or less, 35% or less, 30% or less, 25%. It may be less than, 24% or less, or less than or equal to 22%.
상기 생분해성 조성물로부터 제조된 생분해성 필름의 상기 시간에 따른 분자량 및 분해율을 상기 범위로 제어하는 경우, 상기 생분해성 필름 제조 시 열변형 발생을 최소화할 수 있고, 생분해성 필름 및 생분해성 제품의 내열성 및 기계적 강도를 더욱 향상시킬 수 있다.When the molecular weight and decomposition rate of the biodegradable film manufactured from the biodegradable composition are controlled within the above range, the occurrence of thermal deformation during production of the biodegradable film can be minimized, and the heat resistance of the biodegradable film and biodegradable product can be improved. And mechanical strength can be further improved.
또 다른 실시예에 따른 생분해성 조성물은 하기 식 3으로 표시되는 연신율 변화율이 30% 이하일 수 있다.The biodegradable composition according to another example may have an elongation change rate of 30% or less, expressed by Equation 3 below.
[식 3][Equation 3]
연신율 변화율(%) = ((|EA - EB|)/EA) × 100Elongation change rate (%) = ((|E A - E B |)/E A ) × 100
상기 식 3에서,In equation 3 above,
EA 및 EB는 ASTM D882에 의거하여, 상기 생분해성 조성물로부터 제조된 생분해성 필름의 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 200 ㎜/분의 속도에서 파단 직전의 최대 변형량을 측정한 후, 최초 길이 대비 상기 최대 변형량의 비율을 측정한 연신율(%)로서, E A and E B , according to ASTM D882, cut a specimen of the biodegradable film made from the biodegradable composition into 10 cm in width and 1 cm in length, and used a universal testing machine (UTM) to measure the spacing between chucks at 20 mm. After mounting it as much as possible and measuring the maximum amount of deformation just before fracture at a speed of 200 mm/min, the elongation (%) is measured as the ratio of the maximum amount of deformation to the initial length,
EA는 25℃에서의 상기 생분해성 필름의 초기 연신율이고,E A is the initial elongation of the biodegradable film at 25°C,
EB는 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 연신율이다.E B is the elongation of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
상기 연신율 변화율은 25℃에서의 상기 생분해성 필름의 초기 연신율(EA)와 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 연신율(EB)의 차의 절대값을 25℃에서의 상기 생분해성 필름의 초기 연신율(EA)로 나눈 값을 백분율로 환산한 값으로서, 상기 연신율 변화율은 30% 미만, 28% 이하, 25% 이하, 24% 이하, 23% 이하, 또는 22% 이하일 수 있다.The rate of change in elongation is the difference between the initial elongation (E A ) of the biodegradable film at 25°C and the elongation (E B ) of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH). The absolute value is divided by the initial elongation (E A ) of the biodegradable film at 25°C, converted into a percentage, and the elongation change rate is less than 30%, 28% or less, 25% or less, 24% or less, 23 % or less, or 22% or less.
상기 식 3에서, EA는 25℃에서의 상기 생분해성 필름의 초기 연신율(0일)로서, 40% 이하, 30% 이하, 28% 이하, 25% 이하, 24% 이하, 23% 이하, 22% 이하, 20% 이하일 수 있고, 10% 이상, 12% 이상, 15% 이상, 16% 이상, 또는 18% 이상일 수 있다. 예를 들어, 상기 EA는 10% 내지 40%, 15% 내지 40%, 15% 내지 30%, 또는 15% 내지 25%일 수 있다.In Equation 3, E A is the initial elongation (day 0) of the biodegradable film at 25°C, which is 40% or less, 30% or less, 28% or less, 25% or less, 24% or less, 23% or less, 22 % or less, may be 20% or less, may be 10% or more, 12% or more, 15% or more, 16% or more, or 18% or more. For example, E A may be 10% to 40%, 15% to 40%, 15% to 30%, or 15% to 25%.
또한, 상기 식 3에서, EB는 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 연신율(5일)로서, 40% 이하, 35% 이하, 30% 이하, 28% 이하, 25% 이하, 24% 이하, 또는 23% 이하일 수 있고, 10% 이상, 12% 이상, 15% 이상, 16% 이상, 18% 이상, 또는 20% 이상일 수 있다. 예를 들어, 상기 EB는 10% 내지 40%, 15% 내지 40%, 15% 내지 30%, 또는 15% 내지 25%일 수 있다. In addition, in Equation 3, E B is the elongation (5 days) of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH), and is 40% or less, 35% or less, and 30% or less. , may be 28% or less, 25% or less, 24% or less, or 23% or less, and may be 10% or more, 12% or more, 15% or more, 16% or more, 18% or more, or 20% or more. For example, E B may be 10% to 40%, 15% to 40%, 15% to 30%, or 15% to 25%.
또한, 85℃ 및 상대습도(RH) 85%의 조건에서 1일간 보관 후의 상기 생분해성 필름의 연신율(1일)은, 40% 이하, 30% 이하, 28% 이하, 25% 이하, 24% 이하, 23% 이하, 22% 이하, 또는 20% 이하일 수 있고, 10% 이상, 12% 이상, 15% 이상, 16% 이상, 또는 18% 이상일 수 있다. In addition, the elongation (per day) of the biodegradable film after storage for 1 day at 85°C and 85% relative humidity (RH) is 40% or less, 30% or less, 28% or less, 25% or less, and 24% or less. , may be 23% or less, 22% or less, or 20% or less, and may be 10% or more, 12% or more, 15% or more, 16% or more, or 18% or more.
또한, 85℃ 및 상대습도(RH) 85%의 조건에서 2일간 보관 후의 상기 생분해성 필름의 연신율(2일)은, 40% 이하, 30% 이하, 28% 이하, 25% 이하, 24% 이하, 23% 이하, 22% 이하, 20% 이하, 또는 19% 이하일 수 있고, 10% 이상, 12% 이상, 15% 이상, 16% 이상, 또는 18% 이상일 수 있다.In addition, the elongation (2 days) of the biodegradable film after storage for 2 days at 85°C and 85% relative humidity (RH) is 40% or less, 30% or less, 28% or less, 25% or less, 24% or less. , may be 23% or less, 22% or less, 20% or less, or 19% or less, and may be 10% or more, 12% or more, 15% or more, 16% or more, or 18% or more.
상기 생분해성 조성물로부터 제조된 생분해성 필름의 상기 시간에 따른 연신율 및 연신율 변화율을 상기 범위로 제어하는 경우, 상기 생분해성 필름 및 생분해성 제품의 기계적 강도, 내구성 및 내후성을 더욱 향상시킬 수 있다.When the elongation and elongation rate change rate over time of the biodegradable film manufactured from the biodegradable composition are controlled within the above range, the mechanical strength, durability and weather resistance of the biodegradable film and biodegradable product can be further improved.
또 다른 실시예에 따른 생분해성 조성물은, 하기 식 4로 표시되는 분산지수 변화율이 50% 이하일 수 있다.The biodegradable composition according to another example may have a dispersion index change rate of 50% or less, expressed by Equation 4 below.
[식 4][Equation 4]
분산지수 변화율(%) = ((|PDIA - PDIB|)/PDIA) × 100Dispersion index change rate (%) = ((|PDI A - PDI B |)/PDI A ) × 100
상기 식 4에서,In equation 4 above,
PDIA 및 PDIB는 상기 생분해성 조성물로부터 제조된 생분해성 필름을 클로로포름 용매에 용해시킨 후 겔 투과 크로마토그래피(GPC)를 사용하여 측정한 상기 생분해성 필름의 중량평균분자량(Mw)을 수평균분자량(Mn)으로 나눈 값(Mw/Mn)을 나타내는 분산지수로서,PDI A and PDI B are the number average molecular weight of the weight average molecular weight (Mw) of the biodegradable film measured using gel permeation chromatography (GPC) after dissolving the biodegradable film prepared from the biodegradable composition in chloroform solvent. As a dispersion index representing the value (Mw/Mn) divided by (Mn),
PDIA는 25℃에서의 상기 생분해성 필름의 초기 분산지수이고,PDI A is the initial dispersion index of the biodegradable film at 25°C,
PDIB는 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 분산지수이다.PDI B is the dispersion index of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
상기 분산지수 변화율은 25℃에서의 상기 생분해성 필름의 초기 분산지수(PDIA)와 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 분산지수(PDIB)의 차의 절대값을 25℃에서의 상기 생분해성 필름의 초기 분산지수(PDIA)로 나눈 값을 백분율로 환산한 값으로서, 상기 분산지수 변화율은 50% 미만, 40% 이하, 30% 이하, 20% 이하, 18% 이하, 15% 이하, 12% 이하, 10% 이하, 10% 미만, 9.5% 이하, 9.2% 이하, 또는 9.0% 이하일 수 있다.The dispersion index change rate is the initial dispersion index (PDI A ) of the biodegradable film at 25°C and the dispersion index (PDI B ) of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH). The absolute value of the difference is divided by the initial dispersion index (PDI A ) of the biodegradable film at 25°C, converted into a percentage, and the rate of change in the dispersion index is less than 50%, less than 40%, less than 30%, It may be 20% or less, 18% or less, 15% or less, 12% or less, 10% or less, 10% or less, 9.5% or less, 9.2% or less, or 9.0% or less.
상기 식 4에서, PDIA는 25℃에서의 상기 생분해성 필름의 초기 분산지수(0일)으로서, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지의 분산지수와 동일할 수 있으며, 구체적으로 1.0 이상 내지 5.0 이하, 1.0 이상 내지 4.0 이하, 1.5 이상 내지 3.5 이하, 1.5 이상 내지 3.0 이하, 1.8 초과 내지 3.0 이하, 1.8 초과 내지 2.8 이하, 2.0 이상 내지 3.0 이하, 또는 2.0 이상 내지 2.5 이하일 수 있다. In Equation 4, PDI A is the initial dispersion index (day 0) of the biodegradable film at 25°C, and may be the same as the dispersion index of the copolymerized polyhydroxyalkanoate (PHA) resin, specifically 1.0. It may be from 1.0 to 5.0, 1.0 to 4.0, 1.5 to 3.5, 1.5 to 3.0, 1.8 to 3.0, 1.8 to 2.8, 2.0 to 3.0, or 2.0 to 2.5.
또한, 상기 식 4에서, PDIB는 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 분산지수(4일)로서, 1.0 이상 내지 5.0 이하, 1.0 이상 내지 4.0 이하, 1.5 이상 내지 3.5 이하, 1.5 이상 내지 3.0 이하, 1.8 초과 내지 3.0 이하, 1.8 초과 내지 2.8 이하, 2.0 이상 내지 3.0 이하, 또는 2.0 이상 내지 2.5 이하일 수 있다.In addition, in Equation 4, PDI B is the dispersion index (4 days) of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH), and is 1.0 or more to 5.0 or less, 1.0 or more to 4.0. Hereinafter, it may be 1.5 or more and 3.5 or less, 1.5 or more and 3.0 or less, 1.8 or more and 3.0 or less, more than 1.8 and 2.8 or less, 2.0 or more and 3.0 or less, or 2.0 or more and 2.5 or less.
또한, 85℃ 및 상대습도(RH) 85%의 조건에서 1일간 보관 후의 상기 생분해성 필름의 분산지수(1일)은, 1.0 이상 내지 5.0 이하, 1.0 이상 내지 4.0 이하, 1.5 이상 내지 3.5 이하, 1.5 이상 내지 3.0 이하, 1.8 초과 내지 3.0 이하, 1.8 초과 내지 2.8 이하, 2.0 이상 내지 3.0 이하, 또는 2.0 이상 내지 2.5 이하일 수 있다. In addition, the dispersion index (1 day) of the biodegradable film after storage for 1 day at 85°C and 85% relative humidity (RH) is 1.0 or more and 5.0 or less, 1.0 or more and 4.0 or less, 1.5 or more and 3.5 or less, It may be 1.5 or more and 3.0 or less, more than 1.8 and 3.0 or less, more than 1.8 and 2.8 or less, 2.0 or more and 3.0 or less, or 2.0 or more and 2.5 or less.
또한, 85℃ 및 상대습도(RH) 85%의 조건에서 2일간 보관 후의 상기 생분해성 필름의 분산지수(2일)은, 1.0 이상 내지 5.0 이하, 1.0 이상 내지 4.0 이하, 1.5 이상 내지 3.5 이하, 1.5 이상 내지 3.0 이하, 1.8 초과 내지 3.0 이하, 1.8 초과 내지 2.8 이하, 2.0 이상 내지 3.0 이하, 또는 2.0 이상 내지 2.5 이하일 수 있다. In addition, the dispersion index (2 days) of the biodegradable film after storage for 2 days at 85°C and 85% relative humidity (RH) is 1.0 or more and 5.0 or less, 1.0 or more and 4.0 or less, 1.5 or more and 3.5 or less, It may be 1.5 or more and 3.0 or less, more than 1.8 and 3.0 or less, more than 1.8 and 2.8 or less, 2.0 or more and 3.0 or less, or 2.0 or more and 2.5 or less.
또한, 상기 분산지수 변화율은 25℃에서의 상기 생분해성 필름의 초기 분산지수(PDIA)와 85℃ 및 상대습도(RH) 85%의 조건에서 1일간 보관 후의 상기 생분해성 필름의 분산지수(PDIB)의 차의 절대값을 25℃에서의 상기 생분해성 필름의 초기 분산지수(PDIA)로 나눈 값을 백분율로 환산한 값인, 1일간 보관 후의 분산지수 변화율은 40% 이하, 30% 이하, 20% 이하, 18% 이하, 15% 이하, 12% 이하, 10% 이하, 10% 미만, 9% 이하, 5% 이하, 또는 4.5% 이하일 수 있다.In addition, the rate of change in the dispersion index is the initial dispersion index (PDI A ) of the biodegradable film at 25°C and the dispersion index (PDI) of the biodegradable film after storage for 1 day under conditions of 85°C and 85% relative humidity (RH). B ) The absolute value of the difference is divided by the initial dispersion index (PDI A ) of the biodegradable film at 25°C, converted into a percentage, and the dispersion index change rate after storage for 1 day is 40% or less, 30% or less, It may be 20% or less, 18% or less, 15% or less, 12% or less, 10% or less, 10% or less, 9% or less, 5% or less, or 4.5% or less.
또한, 상기 분산지수 변화율은 25℃에서의 상기 생분해성 필름의 초기 분산지수(PDIA)와 85℃ 및 상대습도(RH) 85%의 조건에서 2일간 보관 후의 상기 생분해성 필름의 분산지수(PDIB)의 차의 절대값을 25℃에서의 상기 생분해성 필름의 초기 분산지수(PDIA)로 나눈 값을 백분율로 환산한 값인, 2일간 보관 후의 분산지수 변화율은 50% 미만, 40% 이하, 30% 이하, 20% 이하, 18% 이하, 15% 이하, 12% 이하, 10% 이하, 10% 미만, 9.5% 이하, 9.2% 이하, 또는 9.0% 이하일 수 있다.In addition, the dispersion index change rate is the initial dispersion index (PDI A ) of the biodegradable film at 25°C and the dispersion index (PDI) of the biodegradable film after storage for 2 days at 85°C and 85% relative humidity (RH). B ) The absolute value of the difference is divided by the initial dispersion index (PDI A ) of the biodegradable film at 25°C, converted into a percentage, and the dispersion index change rate after storage for 2 days is less than 50%, 40% or less, It may be 30% or less, 20% or less, 18% or less, 15% or less, 12% or less, 10% or less, less than 10%, 9.5% or less, 9.2% or less, or 9.0% or less.
상기 생분해성 조성물로부터 제조된 생분해성 필름의 상기 시간에 따른 분산지수 및 분산지수 변화율을 상기 범위로 제어하는 경우, 상기 생분해성 필름 제조 시 열변형 발생을 최소화할 수 있고, 생분해성 필름 및 생분해성 제품의 내열성 및 기계적 강도를 더욱 향상시킬 수 있다.When the dispersion index and dispersion index change rate over time of the biodegradable film manufactured from the biodegradable composition are controlled within the above range, the occurrence of thermal deformation during production of the biodegradable film can be minimized, and the biodegradable film and biodegradable film can be The heat resistance and mechanical strength of the product can be further improved.
또한, 일 실시예에 있어서 상기 생분해성 조성물은 예컨대, 압출 성형, 사출 성형, 압축 성형, 압공 성형, 블로잉 또는 블로우 성형, 열성형(thermoforming) 등의 다양한 성형에 적합한 우수한 물성을 가질 수 있다.Additionally, in one embodiment, the biodegradable composition may have excellent physical properties suitable for various molding, such as extrusion molding, injection molding, compression molding, pressure molding, blowing or blow molding, and thermoforming.
예를 들어, 상기 생분해성 조성물은 압출 성형에 사용되는 압출용 생분해성 조성물일 수 있다.For example, the biodegradable composition may be a biodegradable composition for extrusion used in extrusion molding.
[생분해성 필름][Biodegradable film]
일 실시예에서, 상기 생분해성 조성물을 포함하는, 생분해성 필름을 제공한다.In one embodiment, a biodegradable film comprising the biodegradable composition is provided.
다른 구현예에서, 상기 생분해성 필름은 상기 생분해성 조성물로부터 제조될 수 있다.In another embodiment, the biodegradable film can be prepared from the biodegradable composition.
구체적으로, 상기 생분해성 필름은 공중합 폴리하이드록시알카노에이트(PHA) 수지를 포함하고, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가 4-하이드록시부티레이트(4-HB) 단량체를 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 총 중량을 기준으로 0.1 중량% 이상 내지 30 중량% 미만으로 포함하고 하기 식 1로 표시되는 인장강도 변화율이 5% 이하이다.Specifically, the biodegradable film includes a copolymerized polyhydroxyalkanoate (PHA) resin, and the copolymerized polyhydroxyalkanoate (PHA) resin is a copolymer of 4-hydroxybutyrate (4-HB) monomer. It contains polyhydroxyalkanoate (PHA) resin in an amount of 0.1% or more to less than 30% by weight based on the total weight, and the tensile strength change rate expressed by the following formula 1 is 5% or less.
[식 1][Equation 1]
인장강도 변화율(%) = ((TSA - TSB)/TSA) × 100Tensile strength change rate (%) = ((TS A - TS B )/TS A ) × 100
상기 식 1에서,In equation 1 above,
TSA및 TSB는 ASTM D882에 의거하여, 상기 생분해성 조성물로부터 제조된 생분해성 필름의 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 인장 속도 200 ㎜/분의 속도로 측정한 인장강도(Mpa)로서, For TS A and TS B , according to ASTM D882, a specimen of the biodegradable film prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (UTM). The tensile strength (Mpa) measured at a tensile speed of 200 mm/min with as much installation as possible,
TSA는 25℃에서의 상기 생분해성 필름의 초기 인장강도이고,TS A is the initial tensile strength of the biodegradable film at 25°C,
TSB는 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 인장강도이다.TS B is the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
상기 생분해성 필름은 미생물, 수분, 산소, 빛, 열 중 어느 하나에 의하여 생분해가 가능하며, 기계적 물성이 우수하다. 특히 상기 생분해성 필름은 우수한 내구성, 내후성 및 내열성을 가져, 포장 상태를 단시간 유지하는데 사용되는 일회용 제품뿐만 아니라, 고온고습한 환경에서 장기간 유지하는데 사용되는 식품, 의약품, 위생용품, 전자 제품, 화장품, 공산품 등의 다양한 제품에 적용 시에도, 열 안정성 및 기계적 특성 등의 우수한 물성을 제공할 수 있어서, 다양한 용도 확장이 가능하다.The biodegradable film can be biodegraded by any one of microorganisms, moisture, oxygen, light, and heat, and has excellent mechanical properties. In particular, the biodegradable film has excellent durability, weather resistance, and heat resistance, and is used not only for disposable products used to maintain packaging for a short period of time, but also for food, medicine, hygiene products, electronic products, cosmetics, and other products used for long-term storage in high-temperature and high-humidity environments. Even when applied to a variety of products such as industrial products, it can provide excellent physical properties such as thermal stability and mechanical properties, allowing expansion of various uses.
구체적으로, 상기 생분해성 필름은 인장강도가 10 Mpa 내지 50 Mpa, 15 Mpa 내지 45 Mpa, 15 Mpa 내지 40 Mpa, 20 Mpa 내지 40 Mpa, 20 Mpa 내지 35 Mpa, 또는 20 Mpa 내지 30 Mpa일 수 있다. 상기 생분해성 필름의 인장강도는 상기 식 1에서, 25℃에서의 상기 생분해성 필름의 초기 인장강도(TSA)와 동일할 수 있다. Specifically, the biodegradable film may have a tensile strength of 10 Mpa to 50 Mpa, 15 Mpa to 45 Mpa, 15 Mpa to 40 Mpa, 20 Mpa to 40 Mpa, 20 Mpa to 35 Mpa, or 20 Mpa to 30 Mpa. . In Equation 1, the tensile strength of the biodegradable film may be equal to the initial tensile strength (TS A ) of the biodegradable film at 25°C.
또한, 상기 생분해성 필름은 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 인장강도가 10 Mpa 내지 50 Mpa, 10 Mpa 내지 45 Mpa, 15 Mpa 내지 45 Mpa, 15 Mpa 내지 40 Mpa, 20 Mpa 내지 40 Mpa, 20 Mpa 내지 35 Mpa, 또는 20 Mpa 내지 30 Mpa일 수 있다. In addition, the biodegradable film has a tensile strength of 10 Mpa to 50 Mpa, 10 Mpa to 45 Mpa, and 15 Mpa to 45 Mpa after being stored for 5 days at 85°C and 85% relative humidity (RH). It may be 15 Mpa to 40 Mpa, 20 Mpa to 40 Mpa, 20 Mpa to 35 Mpa, or 20 Mpa to 30 Mpa.
또한, 85℃ 및 상대습도(RH) 85%의 조건에서 1일 및 2일간 보관 후의 상기 생분해성 필름의 인장강도는 각각 상술한 바와 같다.In addition, the tensile strength of the biodegradable film after storage for 1 and 2 days at 85°C and 85% relative humidity (RH) is as described above.
상기 인장강도는 ASTM D882에 의거하여, 상기 생분해성 필름의 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 인장 속도 200 ㎜/분의 속도로 25℃의 상온에서 실험한 후, 설비에 내장된 프로그램으로 인장강도를 측정하였다. 상기 인장강도가 상기 범위를 만족하는 경우, 상기 생분해성 필름의 기계적 특성, 생산성, 가공성 및 성형성을 동시에 향상시킬 수 있고, 목적하는 효과를 달성하는 데에 더욱 유리할 수 있다.The tensile strength was determined by cutting a specimen of the biodegradable film into 10 cm width and 1 cm length, using a universal testing machine (UTM), and mounting it so that the spacing between chucks was 20 mm, using a tensile speed of 200 mm/mm, based on ASTM D882. After testing at a room temperature of 25°C at a speed of 100 min, the tensile strength was measured using a program built into the equipment. When the tensile strength satisfies the above range, the mechanical properties, productivity, processability, and formability of the biodegradable film can be improved simultaneously, and it can be more advantageous to achieve the desired effect.
또한, 상기 생분해성 필름은 연신율이 40% 이하, 30% 이하, 28% 이하, 25% 이하, 24% 이하, 23% 이하, 22% 이하, 20% 이하일 수 있고, 10% 이상, 12% 이상, 15% 이상, 16% 이상, 또는 18% 이상일 수 있다. 예를 들어, 상기 생분해성 필름의 연신율은 10% 내지 40%, 15% 내지 40%, 15% 내지 30%, 또는 15% 내지 25%일 수 있다. 상기 생분해성 필름의 연신율은 상기 식 3에서, 25℃에서의 상기 생분해성 필름의 초기 연신율(EA)과 동일할 수 있다.In addition, the biodegradable film may have an elongation of 40% or less, 30% or less, 28% or less, 25% or less, 24% or less, 23% or less, 22% or less, 20% or less, 10% or more, 12% or more. , may be 15% or more, 16% or more, or 18% or more. For example, the elongation of the biodegradable film may be 10% to 40%, 15% to 40%, 15% to 30%, or 15% to 25%. The elongation rate of the biodegradable film may be equal to the initial elongation rate (E A ) of the biodegradable film at 25°C in Equation 3 above.
또한, 상기 생분해성 필름은 상기 식 3으로 표시되는 연신율 변화율의 범위를 만족할 수 있다.Additionally, the biodegradable film can satisfy the range of elongation change rate represented by Equation 3 above.
상기 연신율은 ASTM D882에 의거하여, 상기 생분해성 필름 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 200 ㎜/분의 속도에서 파단 직전의 최대 변형량을 측정한 후, 최초 길이 대비 상기 최대 변형량의 비율을 연신율로 계산하였다.The elongation is determined by cutting the biodegradable film specimen into 10 cm width and 1 cm length, using a universal testing machine (UTM), and mounting it so that the spacing between chucks is 20 mm, at a speed of 200 mm/min, according to ASTM D882. After measuring the maximum strain just before fracture, the ratio of the maximum strain to the initial length was calculated as elongation.
일 실시예에 따르면, 상기 생분해성 필름은 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 인장강도(MPa)가 10 MPa 내지 50 MPa이고, 연신율이 10% 내지 40%일 수 있다.According to one embodiment, the biodegradable film has a tensile strength (MPa) of 10 MPa to 50 MPa and an elongation of 10% after storage for 5 days at 85°C and 85% relative humidity (RH). It may be from 40% to 40%.
또한, 상기 생분해성 필름은 상기 식 2으로 표시되는 분해율의 범위를 만족할 수 있다. 또한, 상기 생분해성 필름은 상술한 85℃ 및 상대습도(RH) 85%의 조건에서 1일, 2일, 및 4일간 보관 후의 상기 생분해성 필름 각각의 중량평균분자량(g/mol)의 범위를 만족할 수 있다.Additionally, the biodegradable film can satisfy the range of decomposition rate expressed by Equation 2 above. In addition, the range of weight average molecular weight (g/mol) of each of the biodegradable films after storage for 1 day, 2 days, and 4 days under the above-mentioned conditions of 85°C and 85% relative humidity (RH) is You can be satisfied.
또한, 상기 생분해성 필름은 상기 식 4로 표시되는 분산지수 변화율의 범위를 만족할 수 있다. 또한, 상기 생분해성 필름은 상술한 85℃ 및 상대습도(RH) 85%의 조건에서 1일, 2일, 및 4일간 보관 후의 상기 생분해성 필름 각각의 분산지수(PDI)의 범위를 만족할 수 있다.In addition, the biodegradable film can satisfy the range of dispersion index change rate expressed by Equation 4 above. In addition, the biodegradable film can satisfy the range of dispersion index (PDI) of each biodegradable film after being stored for 1 day, 2 days, and 4 days under the conditions of 85°C and 85% relative humidity (RH) described above. .
일 실시예에 따르면, 상기 생분해성 필름은 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 중량평균분자량(g/mol)이 5,000 내지 400,000 g/mol이고, 분산지수(PDI)가 1.5 내지 3.5일 수 있다.According to one embodiment, the biodegradable film has a weight average molecular weight (g/mol) of 5,000 to 400,000 g/mol after being stored for 4 days at 85°C and 85% relative humidity (RH), The dispersion index (PDI) may be 1.5 to 3.5.
한편, 상기 생분해성 필름은 광학적 특성이 우수할 수 있다.Meanwhile, the biodegradable film may have excellent optical properties.
구체적으로, 상기 생분해성 필름은 헤이즈가 10% 이하, 9% 이하, 8% 이하, 7% 이하, 6% 이하, 또는 5% 이하일 수 있다. 헤이즈가 상술한 범위를 초과하는 경우 생분해성 필름의 투명도가 현저히 감소하여 안의 내용물이 보이는 포장용도로 사용하는데 제한이 있을 수 있다.Specifically, the biodegradable film may have a haze of 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, or 5% or less. If the haze exceeds the above-mentioned range, the transparency of the biodegradable film is significantly reduced, which may limit its use for packaging purposes where the contents inside are visible.
또한, 상기 생분해성 필름은 광투과율이 80% 이상, 90% 이상, 92% 이상, 또는 93% 이상일 수 있다.Additionally, the biodegradable film may have a light transmittance of 80% or more, 90% or more, 92% or more, or 93% or more.
상기 생분해성 필름은 기계적 물성이 우수하고, 토양 및 해양에 대한 생분해도가 90% 이상임을 특징으로 한다. The biodegradable film has excellent mechanical properties and is characterized by a biodegradability of more than 90% in soil and ocean.
상기 생분해도는 동일 기간에 표준물질(예컨대, 셀룰로오즈) 대비 분해된 비율을 나타낸 것으로서, 대한민국 환경부에서는 생분해도가 표준물질 대비 90% 이상일 때 생분해성 물질로 규정하고 있다. 구체적으로, EL 724 규격에 따라 측정한 해양 생분해도가 90% 이상이다.The biodegradability indicates the rate of decomposition compared to a standard material (e.g., cellulose) during the same period, and the Ministry of Environment of the Republic of Korea defines a material as biodegradable when the biodegradability is 90% or more compared to the standard material. Specifically, the marine biodegradability measured according to the EL 724 standard is more than 90%.
상기 생분해성 필름은 상기 생분해성 조성물을 압출 성형하여 제조된 생분해성 압출 필름을 포함할 수 있다.The biodegradable film may include a biodegradable extruded film manufactured by extrusion molding the biodegradable composition.
[생분해성 필름의 제조방법][Method for manufacturing biodegradable film]
일 실시예에서, 상기 생분해성 조성물을 이용한 생분해성 필름의 제조방법을 제공한다.In one embodiment, a method for manufacturing a biodegradable film using the biodegradable composition is provided.
구체적으로, 상기 생분해성 필름의 제조방법은 생분해성 조성물을 준비하는 제 1 단계; 및 상기 생분해성 조성물을 성형하는 제 2 단계를 포함할 수 있다.Specifically, the method for producing the biodegradable film includes a first step of preparing a biodegradable composition; And it may include a second step of molding the biodegradable composition.
상기 생분해성 필름의 제조방법을 이하 구체적으로 설명한다.The manufacturing method of the biodegradable film will be described in detail below.
우선, 상기 생분해성 필름의 제조방법은 생분해성 조성물을 준비하는 제 1 단계를 포함한다.First, the method for producing the biodegradable film includes a first step of preparing a biodegradable composition.
구체적으로, 상기 생분해성 조성물은 공중합 폴리하이드록시알카노에이트(PHA) 수지를 포함하고, 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가 4-하이드록시부티레이트(4-HB) 단량체를 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 총 중량을 기준으로 0.1 중량% 이상 내지 30 중량% 미만으로 포함한다.Specifically, the biodegradable composition includes a copolymerized polyhydroxyalkanoate (PHA) resin, and the copolymerized polyhydroxyalkanoate (PHA) resin is the copolymerized 4-hydroxybutyrate (4-HB) monomer. It contains from 0.1% by weight to less than 30% by weight based on the total weight of polyhydroxyalkanoate (PHA) resin.
상기 생분해성 조성물 및 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지는 상술한 바와 같다.The biodegradable composition and the copolymerized polyhydroxyalkanoate (PHA) resin are as described above.
상기 생분해성 조성물은 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지를 단독으로 이용하거나, 또는 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 및 상술한 첨가제를 혼합하여 상기 생분해성 조성물을 제조할 수 있다. 이때, 상기 첨가제는 적용되는 용도 및 목적하는 효과에 따라 다양하게 선택하여 적용될 수 있으며, 이에 한정되는 것은 아니다.The biodegradable composition can be prepared by using the copolymerized polyhydroxyalkanoate (PHA) resin alone, or by mixing the copolymerized polyhydroxyalkanoate (PHA) resin and the above-described additives. You can. At this time, the additive may be selected and applied in various ways depending on the application and desired effect, but is not limited thereto.
예를 들어, 상기 생분해성 조성물은 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 및 첨가제를 혼합하여 제조될 수 있고, 이때, 상기 첨가제로서 에스테르계 화합물, 실리콘계 화합물, 및 지방산 아마이드계 화합물로 이루어진 군으로부터 선택된 1종 이상을 포함하는 활제, 구체적으로 지방산 아마이드계 화합물을 포함하는 활제를 사용할 수 있다. For example, the biodegradable composition can be prepared by mixing the copolymerized polyhydroxyalkanoate (PHA) resin and additives, wherein the additives include ester compounds, silicone compounds, and fatty acid amide compounds. A lubricant containing one or more types selected from the group, specifically a lubricant containing a fatty acid amide-based compound, may be used.
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 및 첨가제의 함량은 상술한 바와 같다.The contents of the copolymerized polyhydroxyalkanoate (PHA) resin and additives are as described above.
한편, 상기 생분해성 필름의 제조방법은 상기 생분해성 조성물을 성형하는 제 2 단계를 포함한다.Meanwhile, the method for producing the biodegradable film includes a second step of molding the biodegradable composition.
일 실시예에 따른 생분해성 조성물을 목적하는 용도에 적합한 형태로 성형을 수행할 수 있다. 예를 들면, 상기 생분해성 조성물을 펠렛(pellet) 형태로 제공한 후에 성형하여 생분해성 필름을 제조하거나, 또는 상기 생분해성 조성물을 바로 성형하여 생분해성 필름을 제조할 수 있다.The biodegradable composition according to one embodiment may be molded into a form suitable for the intended use. For example, the biodegradable composition may be provided in the form of pellets and then molded to produce a biodegradable film, or the biodegradable composition may be directly molded to produce a biodegradable film.
상기 성형은 상기 생분해성 조성물, 또는 상기 생분해성 조성물을 이용하여 얻은 펠렛을 원하는 형상으로 가공한 후 냉각시켜, 상기 형상이 굳어지도록 하고 결정화를 유도하여 수행될 수 있다. 상기 형상으로는, 섬유, 필라멘트, 필름, 시트, 로드(rod), 또는 기타 형상이 포함되나, 이에 한정되는 것은 아니다. The molding may be performed by processing the biodegradable composition or a pellet obtained using the biodegradable composition into a desired shape and then cooling it to harden the shape and induce crystallization. The shapes include, but are not limited to, fibers, filaments, films, sheets, rods, or other shapes.
또한, 상기 성형은 압출 성형, 사출 성형, 압축 성형, 압공 성형, 블로잉 또는 블로우 성형(예컨대, 블로운 필름, 발포체의 블로잉), 캘린더링, 회전성형, 주조(예컨대, 주조 시트, 주조 필름) 또는 열 성형(thermoforming)과 같이 당해 기술분야에 공지된 임의의 방법을 이용하여 수행될 수 있다.In addition, the molding may be performed by extrusion molding, injection molding, compression molding, pressure molding, blowing or blow molding (e.g., blown film, blowing of foam), calendaring, rotational molding, casting (e.g., cast sheet, cast film), or It can be performed using any method known in the art, such as thermoforming.
일 실시예에 따른 생분해성 필름의 제조방법은 상기 생분해성 조성물을 압출기에 투입하여 압출 성형하는 단계를 포함할 수 있다.A method of manufacturing a biodegradable film according to an embodiment may include the step of extruding the biodegradable composition into an extruder.
상기 압출기로는 일축 압출기, 또는 이축 압출기를 사용할 수 있다. As the extruder, a single-screw extruder or a twin-screw extruder can be used.
구체적으로, 상기 압출기는 스크류가 장착된 T-다이 이축 압출기(Twin screw extruder)일 수 있다.Specifically, the extruder may be a T-die twin screw extruder equipped with a screw.
상기 압출 성형 조건은 생분해성 필름의 용도에 따라 다양할 수 있으며, 상기 압출은 통상적으로 사용되는 공정에 의해 수행될 수 있다.The extrusion molding conditions may vary depending on the purpose of the biodegradable film, and the extrusion may be performed by a commonly used process.
예를 들어, 상기 압출 온도는 100℃ 내지 250℃, 120℃ 내지 200℃, 120℃ 내지 180℃, 120℃ 내지 170℃, 120℃ 내지 166℃, 또는 예를 들어 120℃ 내지 160℃일 수 있다.For example, the extrusion temperature may be 100°C to 250°C, 120°C to 200°C, 120°C to 180°C, 120°C to 170°C, 120°C to 166°C, or for example 120°C to 160°C. .
상기 생분해성 필름은 내구성, 내후성 및 내열성이 우수하여, 포장 상태를 단시간 유지하는데 사용되는 일회용 포장 제품뿐만 아니라, 고온고습한 환경에서 장기간 유지하는데 사용되는 다양한 제품에 적용 시에도, 열 안정성 및 기계적 특성 등의 우수한 물성을 제공할 수 있고, 최종 생분해성 제품의 제조에 필요한 열경화, 인쇄, 증착 등 다양한 공정에서도 열적으로 매우 안정하여 공정의 제약이 없고, 성형성, 가공성 및 생산성 향상은 물론, 다양한 용도 확장이 가능하다.The biodegradable film has excellent durability, weather resistance, and heat resistance, so it has thermal stability and mechanical properties when applied not only to disposable packaging products used to maintain the packaging state for a short period of time, but also to various products used to maintain the packaging state for a long period of time in a high temperature and high humidity environment. It can provide excellent physical properties such as, and is thermally very stable in various processes such as heat curing, printing, and deposition required for manufacturing final biodegradable products, so there are no process restrictions, and it not only improves formability, processability, and productivity, but also provides various Expansion of use is possible.
따라서, 일 실시예에 따르면 상기 생분해성 조성물, 또는 상기 생분해성 필름을 포함하는 생분해성 제품을 제공할 수 있다.Therefore, according to one embodiment, a biodegradable product including the biodegradable composition or the biodegradable film can be provided.
상기 생분해성 제품은 포장 상태를 단시간 유지하는데 사용되는 일회용 포장 제품뿐만 아니라, 예를 들면 고온고습한 환경에서 장기간 유지하는데 사용되는 식품, 의약품, 위생용품, 전자 제품, 화장품, 공산품(산업 제품) 등의 다양한 물품을 포장하는 포장재 또는 용기, 취식용 용기, 빨대, 전자제품 트레이, 어망, 접착용 제품, 점착 테이프, 윈도우(window) 보호 필름, 및 콜드컵으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The biodegradable products include not only disposable packaging products used to maintain packaging for a short period of time, but also food, medicine, sanitary products, electronic products, cosmetics, and industrial products (industrial products) used to maintain the packaging for a long period of time in a high temperature and high humidity environment. It may include one or more types selected from the group consisting of packaging materials or containers for packaging various items, eating containers, straws, electronic product trays, fishing nets, adhesive products, adhesive tapes, window protection films, and cold cups. You can.
상기 내용을 하기 실시예에 의하여 더욱 상세하게 설명한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 실시예의 범위가 이들만으로 한정되는 것은 아니다.The above will be explained in more detail by the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples is not limited to these only.
<실시예><Example>
실시예 1Example 1
하기 표 1과 같이 공중합 폴리하이드록시알카노에이트(PHA) 수지(3-HB-co-4-HB, scPHA, 4-HB 함량 8.7 중량%)(제조사: CJ) 100 중량부, 및 활제로서 지방산 아마이드계 화합물(제조사: Kao) 5 phr를 혼합하여 생분해성 조성물을 제조하였다.As shown in Table 1 below, 100 parts by weight of copolymerized polyhydroxyalkanoate (PHA) resin (3-HB-co-4-HB, scPHA, 4-HB content 8.7% by weight) (manufacturer: CJ), and fatty acid as a lubricant A biodegradable composition was prepared by mixing 5 phr of an amide-based compound (manufacturer: Kao).
상기 생분해성 조성물을 T-다이 이축 압출기(Twin screw extruder, 제조사: SM Platek)에 투입하고, 압출기 배럴의 온도를 약 120℃에서 166℃까지 온도 구배를 주어 설정하고 T-다이 압출 성형을 진행하여 생분해성 필름을 제조하였다.The biodegradable composition is put into a T-die twin screw extruder (manufacturer: SM Platek), the temperature of the extruder barrel is set at a temperature gradient from about 120 ℃ to 166 ℃, and T-die extrusion molding is performed. A biodegradable film was prepared.
비교예 1Comparative Example 1
하기 표 1과 같이 공중합 폴리하이드록시알카노에이트(PHA) 수지(3-HB-co-4-HB, aPHA, 4-HB 함량 34.6 중량%)(제조사: CJ) 및 폴리락트산(PLA) 수지(상품명: 2003D, 제조사: Natureworks)를 23:77 중량비로 포함하는 혼합 수지, 및 첨가제로서 지방산 아마이드계 화합물(제조사: Kao) 0.15 phr와 1차 산화방지제(상품명: AO-60, 제조사: Adeka) 0.15 phr, 및 2차 산화방지제(상품명: HP-10, 제조사: Adeka) 0.15 phr을 혼합하여 생분해성 조성물을 제조하였다.As shown in Table 1 below, copolymerized polyhydroxyalkanoate (PHA) resin (3-HB-co-4-HB, aPHA, 4-HB content 34.6% by weight) (manufacturer: CJ) and polylactic acid (PLA) resin ( A mixed resin containing (product name: 2003D, manufacturer: Natureworks) at a weight ratio of 23:77, and 0.15 phr of a fatty acid amide compound (manufacturer: Kao) as an additive and 0.15 phr of primary antioxidant (product name: AO-60, manufacturer: Adeka) A biodegradable composition was prepared by mixing 0.15 phr of phr and secondary antioxidant (Product name: HP-10, Manufacturer: Adeka).
상기 생분해성 조성물을 T-다이 이축 압출기(twin screw extruder, 제조사: SM Platek)에 투입하고, 압출기 배럴의 온도 약 100℃에서 180℃까지 온도 구배를 주어 설정하고 T-다이 압출 성형을 진행하여 생분해성 필름을 제조하였다.The biodegradable composition is put into a T-die twin screw extruder (manufacturer: SM Platek), the temperature of the extruder barrel is set at a temperature gradient from about 100°C to 180°C, and T-die extrusion is performed to biodegrade. A film was prepared.
<평가예><Evaluation example>
평가예 1: 인장강도Evaluation Example 1: Tensile Strength
ASTM D882에 의거하여, 상기 생분해성 조성물로부터 제조된 생분해성 필름 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(상품명: 4206-001, 제조사: UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 인장 속도 200 ㎜/분의 속도로 25℃에서, 설비에 내장된 프로그램으로 상기 생분해성 필름의 초기 인장강도(0일), 및 85℃ 및 상대습도(RH) 85%의 조건에서 1일, 2일, 및 5일간 보관 후의 상기 생분해성 필름의 인장강도를 각각 측정하였다. In accordance with ASTM D882, the biodegradable film specimen prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (Product name: 4206-001, Manufacturer: UTM). At 25°C at a tensile speed of 200 mm/min, the initial tensile strength (day 0) of the biodegradable film is measured using a program built into the equipment, and under conditions of 85°C and relative humidity (RH) of 85%. The tensile strength of the biodegradable film was measured after storage for 1 day, 2 days, and 5 days.
또한, 상기 측정된 생분해성 필름의 인장강도를 이용하여 하기 식 1로 표시되는 인장강도 변화율을 산출하였다.In addition, the tensile strength change rate represented by Equation 1 below was calculated using the tensile strength of the biodegradable film measured above.
[식 1][Equation 1]
인장강도 변화율(%) = ((TSA - TSB)/TSA) × 100Tensile strength change rate (%) = ((TS A - TS B )/TS A ) × 100
상기 식 1에서,In equation 1 above,
TSA및 TSB는 ASTM D882에 의거하여, 상기 생분해성 조성물로부터 제조된 생분해성 필름의 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 인장 속도 200 ㎜/분의 속도로 측정한 인장강도(Mpa)로서, For TS A and TS B , according to ASTM D882, a specimen of the biodegradable film prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (UTM). The tensile strength (Mpa) measured at a tensile speed of 200 mm/min with as much installation as possible,
TSA는 25℃에서의 상기 생분해성 필름의 초기 인장강도이고,TS A is the initial tensile strength of the biodegradable film at 25°C,
TSB는 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 인장강도이다.TS B is the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
평가예 2: 연신율 Evaluation Example 2: Elongation
ASTM D882에 의거하여, 상기 생분해성 조성물로부터 제조된 생분해성 필름 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(상품명: 4206-001, 제조사: UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 200 ㎜/분의 속도에서 파단 직전의 최대 변형량을 측정한 후, 최초 길이 대비 상기 최대 변형량의 비율을 연신율로 평가하였다. 25℃에서의 상기 생분해성 필름의 초기 연신율(0일), 및 85℃ 및 상대습도(RH) 85%의 조건에서 1일, 2일, 및 5일간 보관 후의 상기 생분해성 필름의 연신율을 각각 측정하였다. In accordance with ASTM D882, the biodegradable film specimen prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (Product name: 4206-001, Manufacturer: UTM). After mounting it so that the maximum deformation amount just before fracture was measured at a speed of 200 mm/min, the ratio of the maximum deformation amount to the initial length was evaluated as elongation. Measure the initial elongation of the biodegradable film at 25°C (day 0) and the elongation of the biodegradable film after storage for 1, 2, and 5 days at 85°C and 85% relative humidity (RH), respectively. did.
또한, 상기 측정된 생분해성 필름의 연신율을 이용하여 하기 식 3으로 표시되는 연신율 변화율을 산출하였다.In addition, the elongation change rate represented by Equation 3 below was calculated using the measured elongation of the biodegradable film.
[식 3][Equation 3]
연신율 변화율(%) = ((|EA - EB|)/EA) × 100Elongation change rate (%) = ((|E A - E B |)/E A ) × 100
상기 식 3에서,In equation 3 above,
EA 및 EB는 ASTM D882에 의거하여, 상기 생분해성 조성물로부터 제조된 생분해성 필름의 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 200 ㎜/분의 속도에서 파단 직전의 최대 변형량을 측정한 후, 최초 길이 대비 상기 최대 변형량의 비율을 측정한 연신율(%)로서, E A and E B , according to ASTM D882, cut a specimen of the biodegradable film made from the biodegradable composition into 10 cm in width and 1 cm in length, and used a universal testing machine (UTM) to measure the spacing between chucks at 20 mm. After mounting it as much as possible and measuring the maximum amount of deformation just before fracture at a speed of 200 mm/min, the elongation (%) is measured as the ratio of the maximum amount of deformation to the initial length,
EA는 25℃에서의 상기 생분해성 필름의 초기 연신율이고,E A is the initial elongation of the biodegradable film at 25°C,
EB는 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 연신율이다.E B is the elongation of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
평가예 3: 분자량 및 분산지수Evaluation Example 3: Molecular weight and dispersion index
상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 또는 상기 생분해성 조성물로부터 제조된 생분해성 필름을 클로로포름 용매에 용해시켜 겔 투과 크로마토그래피(상품명: SIL-40, 제조사: Simadzu)로 분석하였고, 분산 지수는 측정된 수평균 분자량에 대한 중량평균분자량의 비로 계산되었다. The biodegradable film prepared from the copolymerized polyhydroxyalkanoate (PHA) resin or the biodegradable composition was dissolved in chloroform solvent and analyzed by gel permeation chromatography (Product name: SIL-40, Manufacturer: Simadzu), and the dispersion index was calculated as the ratio of the weight average molecular weight to the measured number average molecular weight.
한편, 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량(0일), 및 85℃ 및 상대습도(RH) 85%의 조건에서 1일, 2일 및 4일간 보관 후의 상기 생분해성 필름의 중량평균분자량을 각각 측정하였다.Meanwhile, the initial weight average molecular weight of the biodegradable film at 25°C (day 0), and the weight of the biodegradable film after storage for 1, 2, and 4 days under conditions of 85°C and relative humidity (RH) of 85%. The average molecular weight was measured for each.
또한, 상기 측정된 생분해성 필름의 중량평균분자량을 이용하여 하기 식 2로 표시되는 분해율을 산출하였다.In addition, the decomposition rate represented by the following equation 2 was calculated using the weight average molecular weight of the biodegradable film measured above.
[식 2][Equation 2]
분해율(%) = ((MwA - MwB)/MwA) × 100Decomposition rate (%) = ((Mw A - Mw B )/Mw A ) × 100
상기 식 2에서,In equation 2 above,
MwA 및 MwB는 상기 생분해성 조성물로부터 제조된 생분해성 필름을 클로로포름 용매에 용해시킨 후 겔 투과 크로마토그래피(GPC)를 사용하여 측정한 상기 생분해성 필름의 중량평균분자량(g/mol)으로서,Mw A and Mw B are the weight average molecular weight (g/mol) of the biodegradable film prepared from the biodegradable composition measured using gel permeation chromatography (GPC) after dissolving the biodegradable film in chloroform solvent,
MwA는 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량이고,Mw A is the initial weight average molecular weight of the biodegradable film at 25°C,
MwB는 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 중량평균분자량이다.Mw B is the weight average molecular weight of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
또한, 25℃에서의 상기 생분해성 필름의 초기 분산지수(0일), 및 85℃ 및 상대습도(RH) 85%의 조건에서 1일, 2일 및 4일간 보관 후의 상기 생분해성 필름의 분산지수를 구하였다.In addition, the initial dispersion index of the biodegradable film at 25°C (day 0), and the dispersion index of the biodegradable film after storage for 1, 2, and 4 days at 85°C and 85% relative humidity (RH). was obtained.
또한, 상기 계산된 생분해성 필름의 분산지수를 이용하여, 하기 식 4로 표시되는 분산지수 변화율을 산출하였다:In addition, using the dispersion index of the biodegradable film calculated above, the dispersion index change rate represented by the following equation 4 was calculated:
[식 4][Equation 4]
분산지수 변화율(%) = ((|PDIA - PDIB|)/PDIA) × 100Dispersion index change rate (%) = ((|PDI A - PDI B |)/PDI A ) × 100
상기 식 4에서,In equation 4 above,
PDIA 및 PDIB는 상기 생분해성 조성물로부터 제조된 생분해성 필름을 클로로포름 용매에 용해시킨 후 겔 투과 크로마토그래피(GPC)를 사용하여 측정한 상기 생분해성 필름의 중량평균분자량(Mw)을 수평균분자량(Mn)으로 나눈 값(Mw/Mn)을 나타내는 분산지수로서,PDI A and PDI B are the number average molecular weight of the weight average molecular weight (Mw) of the biodegradable film measured using gel permeation chromatography (GPC) after dissolving the biodegradable film prepared from the biodegradable composition in chloroform solvent. As a dispersion index representing the value (Mw/Mn) divided by (Mn),
PDIA는 25℃에서의 상기 생분해성 필름의 초기 분산지수이고,PDI A is the initial dispersion index of the biodegradable film at 25°C,
PDIB는 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 분산지수이다.PDI B is the dispersion index of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
상기 실시예 및 비교예에서 얻은 생분해성 조성물의 구체적인 조성을 하기 표 1에 정리하였고, 상기 평가예에 의해 얻은 결과를 하기 표 2 및 3에 정리하였다.The specific compositions of the biodegradable compositions obtained in the examples and comparative examples are summarized in Table 1 below, and the results obtained by the evaluation examples are summarized in Tables 2 and 3 below.
상기 표 2에서 볼 수 있듯이, 실시예 1에서 제조된 생분해성 필름은 상기 85℃ 및 상대습도(RH) 85%의 고온고습 조건에서 5일 경과 시, 인장강도 변화율이 1.75%이고, 연신율 변화율이 21.3%로 매우 낮아 내후성이 우수함을 확인하였다As can be seen in Table 2, the biodegradable film prepared in Example 1 had a tensile strength change rate of 1.75% and an elongation change rate of 1.75% after 5 days under high temperature and high humidity conditions of 85°C and 85% relative humidity (RH). It was confirmed that the weather resistance was excellent as it was very low at 21.3%.
이에 반해, 비교예 1에서 제조된 생분해성 필름의 경우 상기 고온고습 조건에서 2일 경과 시부터 생분해성 필름의 취성이 급격히 상승하여 기계적 물성 측정이 불가하였다.On the other hand, in the case of the biodegradable film prepared in Comparative Example 1, the brittleness of the biodegradable film rapidly increased after 2 days under the high temperature and high humidity conditions, making it impossible to measure mechanical properties.
또한, 표 3에서 볼 수 있듯이, 실시예 1에서 제조된 생분해성 필름은 상기 고온고습 조건에서 1일, 2일, 및 4일 경과 시, 분해율 및 분산지수 변화율이 매우 낮아 내열성이 우수함을 확인하였다.In addition, as can be seen in Table 3, the biodegradable film prepared in Example 1 was confirmed to have excellent heat resistance as the decomposition rate and dispersion index change rate were very low after 1, 2, and 4 days under the high temperature and high humidity conditions. .
반면, 비교예 1에서 제조된 생분해성 필름의 경우, 85℃ 및 상대습도(RH) 85%의 조건에서 1일 경과 시부터 분해율 및 분산지수 변화율이 급격히 상승하였고, 4일 경과 시 분해율이 98.2%로, 동일 조건에서 분해율이 37.9%인 실시예 1에서 제조된 생분해성 필름에 비해 현저히 상승하였다. 또한, 상기 고온고습 조건에서 4일 경과 시 분산지수 변화율이 50.0%로, 분산지수 변화율이 9.0%인 실시예 1에서 제조된 생분해성 필름에 비해 급격히 증가하였다.On the other hand, in the case of the biodegradable film prepared in Comparative Example 1, the decomposition rate and dispersion index change rate rapidly increased after 1 day under conditions of 85°C and 85% relative humidity (RH), and after 4 days, the decomposition rate was 98.2%. As a result, the decomposition rate was significantly higher than that of the biodegradable film prepared in Example 1, which had a decomposition rate of 37.9% under the same conditions. In addition, after 4 days under the high temperature and high humidity conditions, the dispersion index change rate was 50.0%, which was a sharp increase compared to the biodegradable film prepared in Example 1, which had a dispersion index change rate of 9.0%.
결과적으로, 실시예 1에서 제조된 생분해성 필름은 비교예 1에서 제조된 생분해성 필름에 비해 내구성, 내후성 및 내열성이 동시에 향상되었음을 확인하였다.As a result, it was confirmed that the biodegradable film prepared in Example 1 had improved durability, weather resistance, and heat resistance simultaneously compared to the biodegradable film prepared in Comparative Example 1.
Claims (13)
- 공중합 폴리하이드록시알카노에이트(PHA) 수지를 포함하고,Contains a copolymerized polyhydroxyalkanoate (PHA) resin,상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가 4-하이드록시부티레이트(4-HB) 단량체를 상기 공중합 폴리하이드록시알카노에이트(PHA) 수지 총 중량을 기준으로 0.1 중량% 이상 내지 30 중량% 미만으로 포함하고,The copolymerized polyhydroxyalkanoate (PHA) resin contains 4-hydroxybutyrate (4-HB) monomer in an amount of 0.1% by weight or more to 30% by weight based on the total weight of the copolymerized polyhydroxyalkanoate (PHA) resin. Contains less than,하기 식 1로 표시되는 인장강도 변화율이 5% 이하인, 생분해성 조성물:A biodegradable composition having a tensile strength change rate of 5% or less, expressed by the following formula 1:[식 1][Equation 1]인장강도 변화율(%) = ((TSA - TSB)/TSA) × 100Tensile strength change rate (%) = ((TS A - TS B )/TS A ) × 100상기 식 1에서,In equation 1 above,TSA및 TSB는 ASTM D882에 의거하여, 상기 생분해성 조성물로부터 제조된 생분해성 필름의 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 인장 속도 200 ㎜/분의 속도로 측정한 인장강도(Mpa)로서, For TS A and TS B , according to ASTM D882, a specimen of the biodegradable film prepared from the biodegradable composition was cut to 10 cm in width and 1 cm in length, and the spacing between chucks was 20 mm using a universal testing machine (UTM). The tensile strength (Mpa) measured at a tensile speed of 200 mm/min with as much installation as possible,TSA는 25℃에서의 상기 생분해성 필름의 초기 인장강도이고,TS A is the initial tensile strength of the biodegradable film at 25°C,TSB는 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 인장강도이다.TS B is the tensile strength of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
- 제 1 항에 있어서,According to claim 1,하기 식 2로 표시되는 분해율이 50% 이하인, 생분해성 조성물:A biodegradable composition having a decomposition rate of 50% or less, represented by the following formula 2:[식 2][Equation 2]분해율(%) = ((MwA - MwB)/MwA) × 100Decomposition rate (%) = ((Mw A - Mw B )/Mw A ) × 100상기 식 2에서,In equation 2 above,MwA 및 MwB는 상기 생분해성 조성물로부터 제조된 생분해성 필름을 클로로포름 용매에 용해시킨 후 겔 투과 크로마토그래피(GPC)를 사용하여 측정한 상기 생분해성 필름의 중량평균분자량(g/mol)으로서,Mw A and Mw B are the weight average molecular weight (g/mol) of the biodegradable film prepared from the biodegradable composition measured using gel permeation chromatography (GPC) after dissolving the biodegradable film in chloroform solvent,MwA는 25℃에서의 상기 생분해성 필름의 초기 중량평균분자량이고,Mw A is the initial weight average molecular weight of the biodegradable film at 25°C,MwB는 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 중량평균분자량이다.Mw B is the weight average molecular weight of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
- 제 1 항에 있어서,According to claim 1,하기 식 3으로 표시되는 연신율 변화율이 30% 이하인, 생분해성 조성물:A biodegradable composition having an elongation change rate of 30% or less, represented by the following formula 3:[식 3][Equation 3]연신율 변화율(%) = ((|EA - EB|)/EA) × 100Elongation change rate (%) = ((|E A - E B |)/E A ) × 100상기 식 3에서,In equation 3 above,EA 및 EB는 ASTM D882에 의거하여, 상기 생분해성 조성물로부터 제조된 생분해성 필름의 시편을 가로 10 cm 및 세로 1 cm로 절단하고, 만능시험기(UTM)를 이용하여 척간 간격이 20 mm가 되도록 장착하여 200 ㎜/분의 속도에서 파단 직전의 최대 변형량을 측정한 후, 최초 길이 대비 상기 최대 변형량의 비율을 측정한 연신율(%)로서, E A and E B , according to ASTM D882, cut a specimen of the biodegradable film made from the biodegradable composition into 10 cm in width and 1 cm in length, and used a universal testing machine (UTM) to measure the spacing between chucks at 20 mm. After mounting it as much as possible and measuring the maximum amount of deformation just before fracture at a speed of 200 mm/min, the elongation (%) is measured as the ratio of the maximum amount of deformation to the initial length,EA는 25℃에서의 상기 생분해성 필름의 초기 연신율이고,E A is the initial elongation of the biodegradable film at 25°C,EB는 85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 연신율이다.E B is the elongation of the biodegradable film after storage for 5 days at 85°C and 85% relative humidity (RH).
- 제 1 항에 있어서,According to claim 1,하기 식 4로 표시되는 분산지수 변화율이 50% 이하인, 생분해성 조성물:A biodegradable composition having a dispersion index change rate of 50% or less, represented by the following formula 4:[식 4][Equation 4]분산지수 변화율(%) = ((|PDIA - PDIB|)/PDIA) × 100Dispersion index change rate (%) = ((|PDI A - PDI B |)/PDI A ) × 100상기 식 4에서,In equation 4 above,PDIA 및 PDIB는 상기 생분해성 조성물로부터 제조된 생분해성 필름을 클로로포름 용매에 용해시킨 후 겔 투과 크로마토그래피(GPC)를 사용하여 측정한 상기 생분해성 필름의 중량평균분자량(Mw)을 수평균분자량(Mn)으로 나눈 값(Mw/Mn)을 나타내는 분산지수로서,PDI A and PDI B are the number average molecular weight of the weight average molecular weight (Mw) of the biodegradable film measured using gel permeation chromatography (GPC) after dissolving the biodegradable film prepared from the biodegradable composition in chloroform solvent. As a dispersion index representing the value (Mw/Mn) divided by (Mn),PDIA는 25℃에서의 상기 생분해성 필름의 초기 분산지수이고,PDI A is the initial dispersion index of the biodegradable film at 25°C,PDIB는 85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 분산지수이다.PDI B is the dispersion index of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH).
- 제 1 항에 있어서,According to claim 1,상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가 하기 특성 중에서 선택된 하나 이상의 특성을 만족하는, 생분해성 조성물:A biodegradable composition wherein the copolymerized polyhydroxyalkanoate (PHA) resin satisfies one or more characteristics selected from the following characteristics:-45℃ 내지 80℃의 유리전이 온도(Tg),Glass transition temperature (Tg) of -45°C to 80°C,60℃ 내지 120℃의 결정화 온도(Tc), 및a crystallization temperature (Tc) of 60°C to 120°C, and100℃ 내지 170℃의 용융 온도(Tm).Melting temperature (Tm) between 100°C and 170°C.
- 제 1 항에 있어서,According to claim 1,상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가,The copolymerized polyhydroxyalkanoate (PHA) resin,200,000 g/mol 내지 900,000 g/mol의 중량평균분자량(Mw), 및a weight average molecular weight (Mw) of 200,000 g/mol to 900,000 g/mol, and1.8 초과 내지 3.0 이하의 분산지수(PDI)를 갖는, 생분해성 조성물.A biodegradable composition having a dispersion index (PDI) of greater than 1.8 and less than or equal to 3.0.
- 제 1 항에 있어서,According to claim 1,상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가 3-하이드록시부티레이트(3-HB), 3-하이드록시프로피오네이트(3-HP), 3-하이드록시발레레이트(3-HV), 3-하이드록시헥사노에이트(3-HH), 4-하이드록시발레레이트(4-HV), 5-하이드록시발레레이트(5-HV) 및 6-하이드록시헥사노에이트(6-HH)로 이루어진 군으로부터 선택된 1종 이상의 단량체를 더 포함하는, 생분해성 조성물.The copolymerized polyhydroxyalkanoate (PHA) resin is 3-hydroxybutyrate (3-HB), 3-hydroxypropionate (3-HP), 3-hydroxyvalerate (3-HV), 3 -consisting of hydroxyhexanoate (3-HH), 4-hydroxyvalerate (4-HV), 5-hydroxyvalerate (5-HV) and 6-hydroxyhexanoate (6-HH) A biodegradable composition further comprising one or more monomers selected from the group.
- 제 7 항에 있어서,According to claim 7,상기 공중합 폴리하이드록시알카노에이트(PHA) 수지가 3-하이드록시부티레이트(3-HB) 단량체 및 4-하이드록시부티레이트(4-HB) 단량체를 포함하는 수지를 포함하는, 생분해성 조성물.A biodegradable composition, wherein the copolymerized polyhydroxyalkanoate (PHA) resin includes a resin containing 3-hydroxybutyrate (3-HB) monomer and 4-hydroxybutyrate (4-HB) monomer.
- 제 1 항에 있어서,According to claim 1,활제를 더 포함하는, 생분해성 조성물.A biodegradable composition further comprising a lubricant.
- 제 9 항에 있어서,According to clause 9,상기 활제가 에스테르계 화합물, 실리콘계 화합물, 및 지방산 아마이드계 화합물로 이루어진 군으로부터 선택된 1종 이상을 포함하고,The lubricant includes at least one selected from the group consisting of ester-based compounds, silicone-based compounds, and fatty acid amide-based compounds,상기 활제의 함량은 0.1 phr 내지 10 phr인, 생분해성 조성물.A biodegradable composition wherein the content of the lubricant is 0.1 phr to 10 phr.
- 제 1 항의 생분해성 조성물을 포함하는, 생분해성 필름.A biodegradable film comprising the biodegradable composition of claim 1.
- 제 11 항에 있어서, According to claim 11,85℃ 및 상대습도(RH) 85%의 조건에서 5일간 보관 후의 상기 생분해성 필름의 인장강도(MPa)가 10 MPa 내지 50 MPa이고, 연신율이 10% 내지 40%인, 생분해성 필름.A biodegradable film having a tensile strength (MPa) of 10 MPa to 50 MPa and an elongation of 10% to 40% after storage for 5 days at 85°C and relative humidity (RH) of 85%.
- 제 11 항에 있어서, According to claim 11,85℃ 및 상대습도(RH) 85%의 조건에서 4일간 보관 후의 상기 생분해성 필름의 중량평균분자량(g/mol)이 5,000 내지 400,000 g/mol이고, 분산지수(PDI)가 1.5 내지 3.5인, 생분해성 필름.The weight average molecular weight (g/mol) of the biodegradable film after storage for 4 days at 85°C and 85% relative humidity (RH) is 5,000 to 400,000 g/mol, and the dispersion index (PDI) is 1.5 to 3.5, Biodegradable film.
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| KR1020220157006A KR20240075226A (en) | 2022-11-22 | 2022-11-22 | Biodegradable composition and biodegradable film comprising the same |
| KR10-2022-0157006 | 2022-11-22 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120107917A (en) * | 2009-06-26 | 2012-10-04 | 메타볼릭스 인코포레이티드 | Pha compositions comprising pbs and pbsa and methods for their production |
| KR20150120810A (en) * | 2014-04-18 | 2015-10-28 | (주)엘지하우시스 | A resin composition comprising polylactide resin and polyhydroxyalkanoate resin, a film and a floor material prepared by using the resin composition |
| CN106751625A (en) * | 2017-01-13 | 2017-05-31 | 江苏南方包装有限公司 | A kind of biodegradable high-barrier shape material products and preparation method thereof |
| KR20200046051A (en) * | 2017-08-29 | 2020-05-06 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyester comprising 4-hydroxybutyrate units |
| KR20210111186A (en) * | 2021-07-30 | 2021-09-10 | 씨제이제일제당 (주) | Biodegradable resin composition, biodegradable film and biodegradable articles using same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120103158A (en) | 2011-03-10 | 2012-09-19 | (주)한국벤처그린산업 | Composition for biodegradable plastic and biodegradable plastic goods molded by the composition |
-
2022
- 2022-11-22 KR KR1020220157006A patent/KR20240075226A/en unknown
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2023
- 2023-11-21 WO PCT/KR2023/018806 patent/WO2024112076A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120107917A (en) * | 2009-06-26 | 2012-10-04 | 메타볼릭스 인코포레이티드 | Pha compositions comprising pbs and pbsa and methods for their production |
| KR20150120810A (en) * | 2014-04-18 | 2015-10-28 | (주)엘지하우시스 | A resin composition comprising polylactide resin and polyhydroxyalkanoate resin, a film and a floor material prepared by using the resin composition |
| CN106751625A (en) * | 2017-01-13 | 2017-05-31 | 江苏南方包装有限公司 | A kind of biodegradable high-barrier shape material products and preparation method thereof |
| KR20200046051A (en) * | 2017-08-29 | 2020-05-06 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyester comprising 4-hydroxybutyrate units |
| KR20210111186A (en) * | 2021-07-30 | 2021-09-10 | 씨제이제일제당 (주) | Biodegradable resin composition, biodegradable film and biodegradable articles using same |
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