WO2018056539A1 - Biodegradable resin composition and biodegradable article manufactured therefrom - Google Patents

Biodegradable resin composition and biodegradable article manufactured therefrom Download PDF

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Publication number
WO2018056539A1
WO2018056539A1 PCT/KR2017/003780 KR2017003780W WO2018056539A1 WO 2018056539 A1 WO2018056539 A1 WO 2018056539A1 KR 2017003780 W KR2017003780 W KR 2017003780W WO 2018056539 A1 WO2018056539 A1 WO 2018056539A1
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biodegradable
resin composition
weight
group
pla
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PCT/KR2017/003780
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French (fr)
Korean (ko)
Inventor
김희수
강경돈
김예진
천종필
윤기철
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롯데정밀화학 주식회사
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Publication of WO2018056539A1 publication Critical patent/WO2018056539A1/en

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    • 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
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/018—Additives for biodegradable polymeric composition
    • 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

  • the present invention relates to a biodegradable resin composition and a biodegradable article prepared therefrom, and more particularly, to a biodegradable resin composition capable of producing a biodegradable article having excellent mechanical properties, improved whiteness and hiding power, and low gloss.
  • a biodegradable bag such as a biodegradable film made therefrom or a shopping bag made from the film.
  • Synthetic resins such as polyethylene, polystyrene, polypropylene, and polyvinyl chloride have been widely used in trash bags, rollbacks, shopping bags, food packaging, building materials and home appliances in various fields throughout the industry, and are indispensable in everyday life. Occupies. Although these synthetic resins are very durable, there is a problem in that degradability in the natural state adversely affects the ecosystem and causes environmental destruction upon disposal after use. Among these, the proportion of disposable products using the resins is increasing, which is a big social problem and also causes an increase in economic cost.
  • biodegradable resin polylactic acid (PLA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate-co-terephthalate (PBAT), etc. are commercially available. . These resins can be biodegraded due to the action of the enzymes produced by environmentally existing microorganisms to break down into low molecular weight materials and finally to water and carbon dioxide.
  • PLA has the advantage of excellent rigidity and good transparency in addition to biodegradability, but brittle is strong, brittle, brittle, heat deformation temperature is low as low as 60 °C low thermal stability, very low flexibility and tear characteristics film If manufactured with a disadvantage that is easily torn.
  • Patent Document 1 Korean Unexamined Patent Publication No. 10-2001-0032052
  • Patent Document 1 Korean Unexamined Patent Publication No. 10-2001-0032052
  • a polylactic acid-family polymer and other aliphatic polyester in a weight ratio of 80:20 to 20:80. It discloses about a film and it is described that according to the said method, a brittleness improves and the biodegradable film excellent in sealing property is obtained.
  • the tensile strength of the film produced is poor due to lack of compatibility between the polylactic acid polymer and other aliphatic polyester.
  • Patent Document 2 Korean Patent Publication No. 10-2012-0131961 uses the montmorillonite-based nanoclay together with PLA to manufacture a PBSA blend to improve the compatibility between the resins.
  • Patent Document 2 although the tensile strength and elongation of the produced film was slightly improved, it did not show an improvement effect on the tear strength.
  • biodegradable film prepared according to the prior documents may be insufficiently limited to the application of products such as shopping bags or garbage bags for mart due to insufficient whiteness, hiding power, glossiness, and the like.
  • Patent Document 1 KR1020010032052 A
  • Patent Document 2 KR1020120131961 A
  • the problem to be solved by the present invention is a biodegradable resin composition
  • a biodegradable resin composition comprising PLA and an inorganic material capable of producing a biodegradable article having excellent tensile strength, tensile elongation and tear strength and improved whiteness and hiding power and low gloss To provide.
  • Another object of the present invention is to provide a biodegradable article prepared from the biodegradable resin composition.
  • the present invention (a) 20 to 30% by weight of poly lactic acid (PLA), (b) made of an aliphatic polyester resin and aliphatic / aromatic polyester resin other than the PLA 60 to 70% by weight of at least one biodegradable polyester resin selected from the group, (c) 3 to 10% by weight of calcium carbonate (CaCO 3 ) and (d) 3 to 10% by weight of titanium dioxide (TiO 2 ), ( e) a basic resin composition having a total content of calcium carbonate and titanium dioxide in an amount of 10 to 20% by weight; Plasticizers; And it provides a biodegradable resin composition comprising a compatibilizer.
  • PVA poly lactic acid
  • b made of an aliphatic polyester resin and aliphatic / aromatic polyester resin other than the PLA 60 to 70% by weight of at least one biodegradable polyester resin selected from the group, (c) 3 to 10% by weight of calcium carbonate (CaCO 3 ) and (d) 3 to 10% by weight of titanium dioxide (TiO 2 ),
  • the content ratio of titanium dioxide: calcium carbonate is preferably 1: 1 to 1: 2 (by weight).
  • the (b) biodegradable polyester resin is poly butylene adipate-co-terephthalate (PBAT), poly butylenes succinate (PBS), polybutylene succinate It may include at least one selected from the group consisting of poly butylene succinate-co-adipate (PBSA) and poly hydroxyl alkanoate (PHA).
  • PBAT poly butylene adipate-co-terephthalate
  • PBS poly butylenes succinate
  • PHA poly hydroxyl alkanoate
  • the amount of the plasticizer may be 0.1 to 1.0 parts by weight based on 100 parts by weight of the base resin composition, the plasticizer in the group consisting of dioctyl adipate (DOA), citric acid ester and fatty acid ester It may include at least one selected from the group consisting of at least one ester plasticizer, citric acid (citric acid), polyethylene glycol (PEG) and polypropylene glycol (PPG).
  • DOA dioctyl adipate
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • the content of the compatibilizer may be 0.1 to 0.5 parts by weight based on 100 parts by weight of the base resin composition, the compatibilizer is a polyisocyanate, a styrene-acrylate copolymer having an epoxy functional group and a carbodiimide It may include one or more selected from the group consisting of.
  • the present invention also provides a biodegradable article prepared from the biodegradable resin composition.
  • the biodegradable article may be a biodegradable film, or may be a biodegradable envelope prepared from the biodegradable film.
  • the biodegradable resin composition comprising polylactic acid according to the present invention comprises calcium carbonate (CaCO 3 ) and titanium dioxide (TiO 2 ) in an appropriate content and ratio to provide a biodegradable article having excellent whiteness and hiding power and reduced gloss. It can manufacture.
  • the biodegradable resin composition may include a suitable plasticizer and a compatibilizer to prepare a biodegradable article having excellent mechanical properties such as tensile strength, tensile elongation and tear strength.
  • the present invention (a) 20 to 30% by weight of poly lactic acid (PLA), (b) at least one biodegradable polyester selected from the group consisting of aliphatic polyester resins and aliphatic / aromatic polyester resins other than the PLA Resin 60 to 70% by weight, (c) 3 to 10% by weight of calcium carbonate (CaCO 3 ) and (d) 3 to 10% by weight of titanium dioxide (TiO 2 ), (e) of the calcium carbonate and titanium dioxide A basic resin composition having a total content of 10 to 20% by weight; Plasticizers; And a biodegradable resin composition comprising a compatibilizer and a biodegradable article prepared therefrom.
  • PLA poly lactic acid
  • biodegradable polyester selected from the group consisting of aliphatic polyester resins and aliphatic / aromatic polyester resins other than the PLA Resin 60 to 70% by weight, (c) 3 to 10% by weight of calcium carbonate (CaCO 3 ) and (d) 3 to 10% by weight of titanium dioxide (TiO 2 ), (
  • PLA is obtained by polymerizing lactic acid or ring-opening polymerization of lactide, which is relatively inexpensive and has advantages as a raw material for biodegradable resins.
  • Such PLA may be at least one selected from the group consisting of poly L-lactic acid, poly D-lactic acid and poly L, D-lactic acid.
  • the content of PLA is 20 to 30% by weight based on the weight of the base resin composition.
  • the content of PLA is less than 20% by weight, the mechanical properties such as tensile strength of the finally produced biodegradable article are lowered, and the content of relatively expensive biodegradable polyester resin is increased, thereby reducing economic efficiency.
  • the content of PLA exceeds 30% by weight, brittleness of the biodegradable article is increased, resulting in a problem in that tensile elongation, tear strength and impact strength are lowered.
  • the content of such biodegradable polyester resin is 60 to 70% by weight based on the weight of the base resin composition.
  • the content of the biodegradable polyester resin composition is less than 60% by weight, the effect of improving the brittleness of the PLA is insignificant, resulting in a problem that the tensile elongation and tear strength of the biodegradable article are lowered.
  • the mechanical properties such as tensile strength of the article is poor and has the disadvantage of low economic efficiency.
  • the biodegradable polyester resin is poly butylene adipate-co-terephthalate (PBAT), poly butylenes succinate (PBS), polybutylene succinate-co- It may include at least one selected from the group consisting of adipate (poly butylene succinate-co-adipate (PBSA) and poly hydroxyl alkanoate (PHA), preferably PBAT.
  • PBAT poly butylene adipate-co-terephthalate
  • PBS poly butylenes succinate
  • PHA poly hydroxyl alkanoate
  • the biodegradable resin composition according to the present invention is titrated with two inorganic additives consisting of calcium carbonate (CaCO 3 ) and titanium dioxide (TiO 2 ) for the purpose of simultaneously obtaining the hiding power, the whiteness improvement and the gloss reduction effect of the biodegradable article. Include in content.
  • the content of (c) calcium carbonate (CaCO 3 ) is 3 to 10% by weight based on the weight of the base resin composition.
  • the content of the calcium carbonate (CaCO 3 ) is less than 3% by weight, there is a problem that the hiding power of the biodegradable article is lowered, whereas when the content of more than 10% by weight, the b value of the chromaticity value is lowered and the whiteness is lowered. .
  • the content of the (d) titanium dioxide (TiO 2 ) is 3 to 10% by weight based on the weight of the base resin composition.
  • the content of the titanium dioxide (TiO 2 ) is less than 3% by weight, a problem arises in that the whiteness of the biodegradable article is lowered.
  • the content of the titanium dioxide (TiO 2 ) is more than 10% by weight is not well stretched, there is a difficulty in producing a biodegradable article in the form of a film, for example.
  • the total content of the calcium carbonate and titanium dioxide is 10 to 20% by weight, and in particular, the content ratio of the titanium dioxide: calcium carbonate is 1: 1 to 1: It is more preferable that it is 2 (weight basis).
  • the plasticizer is an additive that is added to the polymer to modify the properties and functions, such as processability, flexibility
  • the content of the plasticizer is preferably 0.1 to 1.0 parts by weight based on 100 parts by weight of the base resin composition. If the content of the plasticizer is less than 0.1 parts by weight, there is a concern that the improvement of physical properties may be insignificant. On the other hand, if the content of the plasticizer exceeds 1.0 parts by weight, the plasticizer may be included in an excessive amount to migrate to the surface after the biodegradable article is manufactured. The sealing strength of the shopping bag may be gradually weakened, which may cause a problem of degrading the quality of the biodegradable final product.
  • the plasticizer may be at least one ester plasticizer selected from the group consisting of dioctyl adipate (DOA), citric acid ester and fatty acid ester, citric acid, polyethylene glycol (PEG) and It may include one or more selected from the group consisting of polypropylene glycol (PPG).
  • DOA dioctyl adipate
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • the compatibilizer is added to ensure compatibility of PLA and biodegradable polyester resins other than PLA, and serves to improve mechanical properties such as tensile strength and tear strength of biodegradable articles.
  • the content of the compatibilizer is preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of the base resin composition. When the content of the compatibilizer is less than 0.1 parts by weight, the compatibility between the resins may be lowered, whereas mechanical properties may be lowered. On the other hand, when the content of the compatibilizer exceeds 0.5 parts by weight, the melt index (MI) may be excessively low, resulting in a biodegradable article. There is a fear that the workability is poor.
  • the compatibilizer may include at least one selected from the group consisting of polyisocyanate, styrene-acrylate copolymer having an epoxy functional group, and carbodiimide.
  • styrene-acrylate copolymer having an epoxy functional group for example, the "JONCRYL” (registered trademark) series of BASF can be used.
  • polyisocyanate may be used as the compatibilizer, and more preferably trifunctional polyisocyanate, such as trifunctional polyisocyanate represented by Formula 1 below, may be used.
  • biodegradable resin composition according to the present invention may further include an antioxidant.
  • the antioxidant prevents crosslinking of the polymer that may occur during the process of processing, and serves to prevent discoloration as well as to maintain long-term physical properties of the finished product.
  • the content of the antioxidant is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the base resin composition. When the content of the antioxidant is less than 0.1 parts by weight, the antioxidant effect is insignificant, which may lower the durability of the biodegradable article. On the other hand, if the content of the antioxidant is more than 5 parts by weight, the effect of the content may be insufficient, rather, the excessive amount of the antioxidant may be transferred to the surface may not look good.
  • the antioxidant may include a primary antioxidant and a secondary antioxidant.
  • the primary antioxidant is to inhibit the generation of unstable free radicals generated by the oxidation action or to make the free radicals in a stable form, phenolic or aromatic amine-based antioxidants are typical .
  • the secondary antioxidant serves to inhibit the production of another unstable free radical that may be caused by the oxidation of hydroperoxides formed by the combination of unstable free radicals with oxygen, and phosphorus or thio-based antioxidants Can be used.
  • the present invention also provides a biodegradable article prepared from the biodegradable resin composition.
  • the biodegradable article may be a biodegradable film prepared from the biodegradable resin composition.
  • the biodegradable film can be produced using a film maker according to a conventional method.
  • calcium carbonate (CaCO 3 ) and titanium dioxide (TiO 2 ) may be used for film production in the form of a master batch (M / B) chip to improve dispersibility.
  • biodegradable film is excellent in tensile strength, tensile elongation and tear strength can be used to replace the existing synthetic resin.
  • the biodegradable article may be a biodegradable bag made from the biodegradable film, and may be used, for example, in a garbage bag, a roll bag, a shopping bag, or the like.
  • the biodegradable article may be widely commercialized in fields such as food packaging materials.
  • the biodegradable film prepared according to the present invention is excellent in whiteness, hiding power and low glossiness, when used as a shopping bag for mart, it is more preferable to satisfy the needs of consumers.
  • a plasticizer dioctyl adipate, Aekyung emulsification
  • a twin-screw extruder manufactured by Changsung P & R, L / D: 36/1, diameter: 24.2 mm
  • a compatibilizer trifunctional polyisocyanate, Aekyung Chemical
  • the pellets were melt kneaded at a processing temperature of 170 ° C. using a Eugene Engineering Co., Ltd. YJF-2 (diameter: 60 mm) film molding machine to prepare a biodegradable film having a width of 400 mm and a thickness of 50 ⁇ m, 300 m.
  • Biodegradable film was prepared in the same manner as in Example 1 except that the content of PBAT, PLA, TiO 2 , CaCO 3 , plasticizer and compatibilizer were adjusted as described in Table 1 below.
  • MI Melt index
  • the melt index of the biodegradable resin composition (pellet state) prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 was measured according to ASTM D1238. Specifically, the amount (g) flowing through an orifice (radius: 2 mm, length: 8 mm) for 10 minutes under a temperature of 190 ° C. and a 2.16 kg load was measured as a melt index (MI).
  • the chromaticities L *, a * and b * of the biodegradable films prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 were obtained using a CIE-L * a * b * (CIE 1976) colorimeter using a Konica Minolta colorimeter. Measured at The " L * ", " a * " values and " b * " values are indices of color tone displayed in the CIE-L * a * b * (CIE1976) colorimeter.
  • the value "L *” represents brightness, and the larger this value, the brighter it is.
  • the value "a *” indicates the degree of redness, and the larger this value, the higher the degree of redness.
  • the value "b *” indicates the degree of yellowness, and the larger this value, the higher the yellowness and the lower the whiteness.
  • the tensile strength and tensile elongation in the longitudinal direction (MD) and the transverse direction (TD) of the biodegradable films prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 were measured based on JIS K6251-1.
  • the hiding power of the biodegradable films prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 was measured using a hiding rate measuring instrument (NOVO-SHOADE DUO, Rhopoint Instrument).
  • the glossiness of the biodegradable film was measured using a gloss meter (Micro-TRI-Gloss, BKY).
  • Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 PBAT (% by weight) 67 67 62 62 74 74 70 PLA (% by weight) 23 23 25 25 19 19 23 TiO 2 (% by weight) 7 5 9 4.5 5 5 5 CaCO 3 (% by weight) 3 5 4 8.5 2 2 2 Total (% by weight) 100 100 100 100 100 100 100 100 100 Plasticizer (parts by weight) 0.30 0.30 0.30 - 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 Compatibilizer (parts by weight) 0.25 0.25 0.25 0.25 - 0.25 0.25 MI (g / 10min) 3.5 3.6 3.4 3.8 4.7 4.0 3.9 Film chromaticity L 96 96 97 96 96 96 96 a -0.5 -0.5 -0.3 -0.4 -0.7 -0.4 -0.5 b 1.1 1.0 0.8 1.0 1.3 1.2 1.3 Tear strength (gf) MD 49 49 48 48
  • the content units of the plasticizer and the compatibilizer in Table 1 are parts by weight based on 100 parts by weight of the total amount of PBAT, PLA, TiO 2 and CaCO 3 .
  • the biodegradable film prepared according to Examples 1 to 4 is excellent in whiteness and hiding power and low glossiness as compared to the biodegradable film prepared according to Comparative Examples 1 to 3.
  • the hiding power is markedly high and the gloss is also low. It may be more preferably used for the use of biodegradable bags such as shopping bags for marts and the like.
  • the melt index is lower than that of the resin pellets prepared according to Comparative Examples 1 to 3, and thus the biodegradable resin compositions having excellent processability are It can be confirmed that the manufacturing.
  • biodegradable films according to Comparative Examples 2 and 3 prepared by adding a plasticizer and a compatibilizer may be confirmed to exhibit higher tensile strength, tensile elongation and tear strength than the biodegradable films of Comparative Example 1.
  • the biodegradable films of Examples 1 to 4 were prepared by applying the same plasticizer and compatibilizer content as in Comparative Examples 2 and 3, and a biodegradable film showing excellent physical properties could be prepared.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a biodegradable resin composition and a biodegradable article manufactured therefrom, the biodegradable resin composition comprising: a base resin composition; a plasticizer; and a compatibilizer, the base resin composition comprising (a) 20-30 wt% of poly lactic acid (PLA), (b) 60-70 wt% of at least one biodegradable polyester resin selected from the group consisting of aliphatic polyester resins, excluding the PLA, and aliphatic/aromatic polyester resins, (c) 3-10 wt% of calcium carbonate (CaCO3), and (d) 3-10 wt% of titanium dioxide (TiO2), wherein (e) the sum of the contents of calcium carbonate and titanium dioxide is 10-20 wt%. The biodegradable resin composition comprising polylactic acid according to the present invention can produce a biodegradable article which has improved whiteness and hiding power and reduced gloss while having excellent tensile strength, tensile elongation, and tearing strength.

Description

생분해성 수지 조성물 및 이로부터 제조된 생분해성 물품Biodegradable Resin Compositions and Biodegradable Articles Made Therefrom
본 발명은 생분해성 수지 조성물 및 이로부터 제조된 생분해성 물품에 관한 것으로서, 더욱 상세하게는 기계적 물성이 우수하면서도 백색도 및 은폐력이 향상되고 광택도가 낮아진 생분해성 물품을 제조할 수 있는 생분해성 수지 조성물 및 이로부터 제조된 생분해성 필름 또는 상기 필름으로부터 제조된 쇼핑백 등과 같은 생분해성 봉투를 포함하는 생분해성 물품에 관한 것이다.The present invention relates to a biodegradable resin composition and a biodegradable article prepared therefrom, and more particularly, to a biodegradable resin composition capable of producing a biodegradable article having excellent mechanical properties, improved whiteness and hiding power, and low gloss. And a biodegradable bag such as a biodegradable film made therefrom or a shopping bag made from the film.
폴리에틸렌, 폴리스티렌, 폴리프로필렌 및 폴리염화비닐과 같은 합성수지는 산업 전반의 다양한 분야에서 쓰레기봉투, 롤백, 쇼핑백, 식품포장, 건축자재 및 가전제품 등에서 폭넓게 사용되어 왔으며, 일상생활에서 없어서는 안 될 정도의 위치를 차지하고 있다. 이러한 합성수지들은 내구성이 매우 우수하지만, 자연상태에서의 분해성이 떨어져 사용 후 폐기 시 생태계에 악영향을 끼치고 환경파괴를 야기하는 문제점이 있다. 이러한 가운데 상기 수지들을 이용한 일회용 제품의 비중이 높아지고 있어 사회적으로 큰 문제가 되고 있고 경제적 비용 상승도 초래하고 있다.Synthetic resins such as polyethylene, polystyrene, polypropylene, and polyvinyl chloride have been widely used in trash bags, rollbacks, shopping bags, food packaging, building materials and home appliances in various fields throughout the industry, and are indispensable in everyday life. Occupies. Although these synthetic resins are very durable, there is a problem in that degradability in the natural state adversely affects the ecosystem and causes environmental destruction upon disposal after use. Among these, the proportion of disposable products using the resins is increasing, which is a big social problem and also causes an increase in economic cost.
상기와 같은 문제점을 해결하기 위한 방안으로 제시된 것이 생분해성 수지를 이용하는 것이다. 상기 생분해성 수지로는 폴리락트산(PLA), 폴리부틸렌 숙시네이트(PBS), 폴리부틸렌 숙시네이트 아디페이트(PBSA), 폴리부틸렌 아디페이트-코-테레프탈레이트(PBAT) 등이 상용화되어 있다. 이러한 수지는 환경적으로 존재하는 미생물이 생산하는 효소들의 작용으로 인해 생분해되어 저분자 물질로 분해되고 최종적으로 물과 이산화탄소로 분해될 수 있다.What is presented as a solution to the above problems is to use a biodegradable resin. As the biodegradable resin, polylactic acid (PLA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate-co-terephthalate (PBAT), etc. are commercially available. . These resins can be biodegraded due to the action of the enzymes produced by environmentally existing microorganisms to break down into low molecular weight materials and finally to water and carbon dioxide.
이 중 PLA는 생분해성 이외에도 강성이 우수하고 투명성이 좋다는 장점을 가지고 있지만, 취성(brittle)이 강하여 깨지기 쉽고, 열변형 온도가 60℃ 정도로 낮아 열안정성이 떨어지며, 유연성 및 인열특성이 매우 부족하여 필름으로 제조할 경우 쉽게 찢어지는 단점이 있다. Among these, PLA has the advantage of excellent rigidity and good transparency in addition to biodegradability, but brittle is strong, brittle, brittle, heat deformation temperature is low as low as 60 ℃ low thermal stability, very low flexibility and tear characteristics film If manufactured with a disadvantage that is easily torn.
이러한 문제점을 극복하기 위하여, PLA와 다른 생분해성 폴리에스테르 수지를 블렌딩하여 물성의 향상을 꾀하는 연구가 활발하게 진행 중이다.In order to overcome this problem, research is being actively conducted to improve physical properties by blending PLA and other biodegradable polyester resins.
예컨대, 특허문헌 1(대한민국 공개특허공보 제10-2001-0032052호)은 폴리락트산계(polylactic acid-family) 중합체와 다른 지방족 폴리에스테르를 80:20 ~ 20:80의 중량 비율로 함유하여 만들어지는 필름에 대해 개시하고 있고, 상기 방법에 따르면 취성이 개량되고, 실링 특성이 우수한 생분해성 필름이 얻어진다고 기재하고 있다. 그러나, 상기 폴리락트산계 중합체와 다른 지방족 폴리에스테르 간의 상용성이 부족하여 제조된 필름의 인장강도가 떨어진다는 문제가 있었다.For example, Patent Document 1 (Korean Unexamined Patent Publication No. 10-2001-0032052) is made by containing a polylactic acid-family polymer and other aliphatic polyester in a weight ratio of 80:20 to 20:80. It discloses about a film and it is described that according to the said method, a brittleness improves and the biodegradable film excellent in sealing property is obtained. However, there is a problem that the tensile strength of the film produced is poor due to lack of compatibility between the polylactic acid polymer and other aliphatic polyester.
이에, 특허문헌 2(대한민국 공개특허공보 제10-2012-0131961호)는 PLA와 PBSA 블렌드 제조시 몬트모릴로나이트(montmorillonite) 계열의 나노클레이를 함께 사용하여 수지 간의 상용성을 향상시킴으로써 상기 블렌드를 이용하여 제조된 생분해성 필름의 인장강도 및 신장률을 증가시키는 방안을 제시하였다. 그러나, 상기 특허문헌 2에 따르면, 제조된 필름의 인장강도 및 신장율은 다소 개선되었지만, 인열강도에 대한 개선효과는 나타내지 못하였다.Accordingly, Patent Document 2 (Korean Patent Publication No. 10-2012-0131961) uses the montmorillonite-based nanoclay together with PLA to manufacture a PBSA blend to improve the compatibility between the resins. A method of increasing the tensile strength and the elongation rate of the biodegradable film prepared using the present invention was suggested. However, according to Patent Document 2, although the tensile strength and elongation of the produced film was slightly improved, it did not show an improvement effect on the tear strength.
또한, 선행문헌들에 따라 제조된 생분해성 필름은 백색도, 은폐력, 광택도 등이 불충분하여 마트용 쇼핑백이나 쓰레기 봉투 등과 같은 제품의 응용에 크게 제한을 받을 수 있다.In addition, the biodegradable film prepared according to the prior documents may be insufficiently limited to the application of products such as shopping bags or garbage bags for mart due to insufficient whiteness, hiding power, glossiness, and the like.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) KR1020010032052 A (Patent Document 1) KR1020010032052 A
(특허문헌 2) KR1020120131961 A (Patent Document 2) KR1020120131961 A
본 발명이 해결하고자 하는 과제는, 인장강도, 인장신율 및 인열강도가 우수하면서도 백색도 및 은폐력이 향상되고 광택도가 낮아진 생분해성 물품을 제조할 수 있는 PLA 및 무기물을 포함하는 생분해성 수지 조성물을 제공하는 것이다.The problem to be solved by the present invention is a biodegradable resin composition comprising PLA and an inorganic material capable of producing a biodegradable article having excellent tensile strength, tensile elongation and tear strength and improved whiteness and hiding power and low gloss To provide.
본 발명이 해결하고자 하는 다른 과제는, 상기 생분해성 수지 조성물로부터 제조된 생분해성 물품을 제공하는 것이다.Another object of the present invention is to provide a biodegradable article prepared from the biodegradable resin composition.
상기와 같은 과제를 해결하기 위하여, 본 발명은 (a) 폴리락트산(poly lactic acid; PLA) 20 ~ 30중량%, (b) 상기 PLA 이외의 지방족 폴리에스테르 수지와 지방족/방향족 폴리에스테르 수지로 이루어진 군에서 선택된 일종 이상의 생분해성 폴리에스테르 수지 60 ~ 70중량%, (c) 탄산칼슘(CaCO3) 3 ~ 10중량% 및 (d) 이산화티탄(TiO2) 3 ~ 10중량%로 이루어지고, (e) 상기 탄산칼슘 및 이산화티탄의 합계 함량이 10 ~ 20중량%인 기초 수지 조성물; 가소제; 및 상용화제를 포함하는 생분해성 수지 조성물을 제공한다.In order to solve the above problems, the present invention (a) 20 to 30% by weight of poly lactic acid (PLA), (b) made of an aliphatic polyester resin and aliphatic / aromatic polyester resin other than the PLA 60 to 70% by weight of at least one biodegradable polyester resin selected from the group, (c) 3 to 10% by weight of calcium carbonate (CaCO 3 ) and (d) 3 to 10% by weight of titanium dioxide (TiO 2 ), ( e) a basic resin composition having a total content of calcium carbonate and titanium dioxide in an amount of 10 to 20% by weight; Plasticizers; And it provides a biodegradable resin composition comprising a compatibilizer.
상기 기초 수지 조성물에서, 상기 이산화티탄:탄산칼슘의 함량 비율은 1:1 ~ 1:2(중량기준)인 것이 바람직하다.In the base resin composition, the content ratio of titanium dioxide: calcium carbonate is preferably 1: 1 to 1: 2 (by weight).
상기 (b) 생분해성 폴리에스테르 수지는 폴리부틸렌 아디페이트-코-테레프탈레이트(poly butylene adipate-co-terephthalate; PBAT), 폴리부틸렌 숙시네이트(poly butylenes succinate; PBS), 폴리부틸렌 숙시네이트-코-아디페이트(poly butylene succinate-co-adipate; PBSA) 및 폴리하이드록시 알카노에이트(poly hydroxyl alkanoate; PHA)로 이루어진 군에서 선택된 일종 이상을 포함할 수 있다.The (b) biodegradable polyester resin is poly butylene adipate-co-terephthalate (PBAT), poly butylenes succinate (PBS), polybutylene succinate It may include at least one selected from the group consisting of poly butylene succinate-co-adipate (PBSA) and poly hydroxyl alkanoate (PHA).
상기 가소제의 함량은 상기 기초 수지 조성물 100중량부를 기준으로 0.1 ~ 1.0중량부일 수 있으며, 상기 가소제는 디옥틸아디페이트(dioctyl adipate; DOA), 시트르산 에스테르(citric acid ester) 및 지방산 에스테르로 이루어진 군에서 선택된 일종 이상의 에스테르계 가소제, 시트르산 (citric acid), 폴리에틸렌 글리콜(polyethylene glycol; PEG) 및 폴리프로필렌 글리콜(polypropylene glycol; PPG)로 이루어진 군에서 선택된 일종 이상을 포함할 수 있다. The amount of the plasticizer may be 0.1 to 1.0 parts by weight based on 100 parts by weight of the base resin composition, the plasticizer in the group consisting of dioctyl adipate (DOA), citric acid ester and fatty acid ester It may include at least one selected from the group consisting of at least one ester plasticizer, citric acid (citric acid), polyethylene glycol (PEG) and polypropylene glycol (PPG).
상기 상용화제의 함량은 상기 기초 수지 조성물 100중량부를 기준으로 0.1 ~ 0.5중량부일 수 있으며, 상기 상용화제는 폴리이소시아네이트(polyisocyanate), 에폭시 관능기를 가진 스티렌-아크릴레이트 공중합체 및 카보디이미드(carbodiimide)로 이루어진 군에서 선택된 일종 이상을 포함할 수 있다.The content of the compatibilizer may be 0.1 to 0.5 parts by weight based on 100 parts by weight of the base resin composition, the compatibilizer is a polyisocyanate, a styrene-acrylate copolymer having an epoxy functional group and a carbodiimide It may include one or more selected from the group consisting of.
또한, 본 발명은 상기 생분해성 수지 조성물로부터 제조된 생분해성 물품을 제공한다. The present invention also provides a biodegradable article prepared from the biodegradable resin composition.
이때, 상기 생분해성 물품은 생분해성 필름일 수 있으며, 또는 상기 생분해성 필름으로부터 제조된 생분해성 봉투일 수 있다.In this case, the biodegradable article may be a biodegradable film, or may be a biodegradable envelope prepared from the biodegradable film.
본 발명에 따른 폴리락트산을 포함하는 생분해성 수지 조성물은 탄산칼슘(CaCO3) 및 이산화티탄(TiO2)을 적절한 함량 및 비율로 포함함으로써 백색도 및 은폐력이 우수하면서도 광택도가 감소된 생분해성 물품을 제조할 수 있다.The biodegradable resin composition comprising polylactic acid according to the present invention comprises calcium carbonate (CaCO 3 ) and titanium dioxide (TiO 2 ) in an appropriate content and ratio to provide a biodegradable article having excellent whiteness and hiding power and reduced gloss. It can manufacture.
또한, 상기 생분해성 수지 조성물은 적정한 가소제 및 상용화제를 포함함으로써 인장강도, 인장신율 및 인열강도와 같은 기계적 물성이 우수한 생분해성 물품을 제조할 수 있다.In addition, the biodegradable resin composition may include a suitable plasticizer and a compatibilizer to prepare a biodegradable article having excellent mechanical properties such as tensile strength, tensile elongation and tear strength.
본 발명은 (a) 폴리락트산(poly lactic acid; PLA) 20 ~ 30중량%, (b) 상기 PLA 이외의 지방족 폴리에스테르 수지와 지방족/방향족 폴리에스테르 수지로 이루어진 군에서 선택된 일종 이상의 생분해성 폴리에스테르 수지 60 ~ 70중량%, (c) 탄산칼슘(CaCO3) 3 ~ 10중량% 및 (d) 이산화티탄(TiO2) 3 ~ 10중량%로 이루어지고, (e) 상기 탄산칼슘 및 이산화티탄의 합계 함량이 10 ~ 20중량%인 기초 수지 조성물; 가소제; 및 상용화제를 포함하는 생분해성 수지 조성물 및 이로부터 제조된 생분해성 물품에 관한 것이다.The present invention (a) 20 to 30% by weight of poly lactic acid (PLA), (b) at least one biodegradable polyester selected from the group consisting of aliphatic polyester resins and aliphatic / aromatic polyester resins other than the PLA Resin 60 to 70% by weight, (c) 3 to 10% by weight of calcium carbonate (CaCO 3 ) and (d) 3 to 10% by weight of titanium dioxide (TiO 2 ), (e) of the calcium carbonate and titanium dioxide A basic resin composition having a total content of 10 to 20% by weight; Plasticizers; And a biodegradable resin composition comprising a compatibilizer and a biodegradable article prepared therefrom.
먼저, 본 발명에 따른 생분해성 수지 조성물에 대해 상세히 살펴보면 하기와 같다.First, look at in detail for the biodegradable resin composition according to the present invention.
상기 (a) PLA는 락트산을 중합하거나 또는 락타이드를 개환 중합하여 얻어진 것으로서, 상대적으로 가격이 저렴하여 생분해성 수지의 원료로서 장점을 갖는다. 이러한 PLA는 폴리 L-락트산, 폴리 D-락트산 및 폴리 L, D-락트산으로 이루어지는 군으로부터 선택된 일종 이상일 수 있다. The above (a) PLA is obtained by polymerizing lactic acid or ring-opening polymerization of lactide, which is relatively inexpensive and has advantages as a raw material for biodegradable resins. Such PLA may be at least one selected from the group consisting of poly L-lactic acid, poly D-lactic acid and poly L, D-lactic acid.
상기 PLA의 함량은 상기 기초 수지 조성물 중량대비 20 ~ 30중량%이다. 상기 PLA의 함량이 20중량% 미만일 경우 최종적으로 제조되는 생분해성 물품의 인장강도 등과 같은 기계적 물성이 떨어지고 상대적으로 고가인 생분해성 폴리에스테르 수지의 함량이 높아지므로 경제성이 떨어지게 된다. 반면, 상기 PLA의 함량이 30중량%를 초과할 경우에는 생분해성 물품의 취성(brittleness)이 증가하여 인장신율, 인열강도 및 충격강도가 저하되는 문제가 발생된다.The content of PLA is 20 to 30% by weight based on the weight of the base resin composition. When the content of PLA is less than 20% by weight, the mechanical properties such as tensile strength of the finally produced biodegradable article are lowered, and the content of relatively expensive biodegradable polyester resin is increased, thereby reducing economic efficiency. On the other hand, when the content of PLA exceeds 30% by weight, brittleness of the biodegradable article is increased, resulting in a problem in that tensile elongation, tear strength and impact strength are lowered.
상기 (b) PLA 이외의 지방족 폴리에스테르 수지 및 지방족/방향족 폴리에스테르 수지로 이루어진 군에서 선택된 일종 이상의 생분해성 폴리에스테르 수지는, 상기 PLA의 취성문제를 개선하여 인장신율, 인열강도 및 충격강도가 우수한 생분해성 물품을 제조하기 위하여 상기 PLA와 함께 본 발명에 따른 생분해성 수지 조성물의 기초수지로 사용된다. (B) at least one biodegradable polyester resin selected from the group consisting of aliphatic polyester resins and aliphatic / aromatic polyester resins other than PLA, improves the brittleness of the PLA to improve tensile elongation, tear strength and impact strength It is used as a base resin of the biodegradable resin composition according to the present invention together with the PLA to produce a good biodegradable article.
이러한 생분해성 폴리에스테르 수지의 함량은 상기 기초 수지 조성물 중량대비 60 ~ 70중량%이다. 상기 생분해성 폴리에스테르 수지 조성물의 함량이 60중량% 미만일 경우 PLA의 취성 개선 효과가 미미하여 생분해성 물품의 인장신율 및 인열강도가 떨어지는 문제가 발생되고, 반면 70중량%를 초과할 경우에는 생분해성 물품의 인장강도 등과 같은 기계적 물성이 떨어지고 경제성이 낮은 단점이 있다.The content of such biodegradable polyester resin is 60 to 70% by weight based on the weight of the base resin composition. When the content of the biodegradable polyester resin composition is less than 60% by weight, the effect of improving the brittleness of the PLA is insignificant, resulting in a problem that the tensile elongation and tear strength of the biodegradable article are lowered. The mechanical properties such as tensile strength of the article is poor and has the disadvantage of low economic efficiency.
상기 생분해성 폴리에스테르 수지는 폴리부틸렌 아디페이트-코-테레프탈레이트(poly butylene adipate-co-terephthalate; PBAT), 폴리부틸렌 숙시네이트(poly butylenes succinate; PBS), 폴리부틸렌 숙시네이트-코-아디페이트(poly butylene succinate-co-adipate; PBSA) 및 폴리하이드록시 알카노에이트(poly hydroxyl alkanoate; PHA)로 이루어진 군에서 선택된 일종 이상을 포함할 수 있으며, 바람직하게 PBAT일 수 있다.The biodegradable polyester resin is poly butylene adipate-co-terephthalate (PBAT), poly butylenes succinate (PBS), polybutylene succinate-co- It may include at least one selected from the group consisting of adipate (poly butylene succinate-co-adipate (PBSA) and poly hydroxyl alkanoate (PHA), preferably PBAT.
본 발명에 따른 생분해성 수지 조성물은 생분해성 물품의 은폐력 및 백색도 향상과 광택도 감소 효과를 동시에 얻기 위한 목적으로 탄산칼슘(CaCO3) 및 이산화티탄(TiO2)으로 이루어진 2종의 무기첨가제를 적정 함량으로 포함한다.The biodegradable resin composition according to the present invention is titrated with two inorganic additives consisting of calcium carbonate (CaCO 3 ) and titanium dioxide (TiO 2 ) for the purpose of simultaneously obtaining the hiding power, the whiteness improvement and the gloss reduction effect of the biodegradable article. Include in content.
상기 (c) 탄산칼슘(CaCO3)의 함량은 상기 기초 수지 조성물 중량대비 3 ~ 10중량% 이다. 상기 탄산칼슘(CaCO3)의 함량이 3중량% 미만일 경우에는 생분해성 물품의 은폐력이 떨어지는 문제가 발생하고, 반면 10중량%를 초과할 경우 색도 값중 b값이 떨어져 백색도가 낮아지는 문제가 발생한다. The content of (c) calcium carbonate (CaCO 3 ) is 3 to 10% by weight based on the weight of the base resin composition. When the content of the calcium carbonate (CaCO 3 ) is less than 3% by weight, there is a problem that the hiding power of the biodegradable article is lowered, whereas when the content of more than 10% by weight, the b value of the chromaticity value is lowered and the whiteness is lowered. .
상기 (d) 이산화티탄(TiO2)의 함량은 상기 기초 수지 조성물 중량대비 3 ~ 10중량% 이다. 상기 이산화티탄(TiO2)의 함량이 3중량% 미만일 경우에는 생분해성 물품의 백색도가 떨어지는 문제가 발생한다. 반면, 상기 이산화티탄(TiO2)의 함량이 10중량%를 초과할 경우에는 연신이 잘되지 않아, 예컨대 필름 형태의 생분해성 물품을 제조하는 데에 어려움이 있다.The content of the (d) titanium dioxide (TiO 2 ) is 3 to 10% by weight based on the weight of the base resin composition. When the content of the titanium dioxide (TiO 2 ) is less than 3% by weight, a problem arises in that the whiteness of the biodegradable article is lowered. On the other hand, when the content of the titanium dioxide (TiO 2 ) is more than 10% by weight is not well stretched, there is a difficulty in producing a biodegradable article in the form of a film, for example.
본 발명의 조성물 중 상기 기초 수지 조성물에서, 바람직하게는, 상기 탄산칼슘 및 이산화티탄의 합계 함량이 10 ~ 20중량%이고, 특히, 상기 이산화티탄:탄산칼슘의 함량 비율은 1:1 ~ 1:2(중량기준)인 것이 더욱 바람직하다.In the base resin composition of the composition of the present invention, preferably, the total content of the calcium carbonate and titanium dioxide is 10 to 20% by weight, and in particular, the content ratio of the titanium dioxide: calcium carbonate is 1: 1 to 1: It is more preferable that it is 2 (weight basis).
상기 탄산칼슘 및 이산화티탄의 합계 함량이 10중량% 미만인 경우, 은폐력이 불충분하고 광택도가 너무 높은 문제점이 남으며, 본 발명에 따른 생분해성 수지 조성물을 이용하여 필름 등과 같은 물품을 제조할 경우 뻣뻣함(stiffness)이 부족하여 상기 필름을 쇼핑백 등 최종 제품으로 가공할 때 생산성이 저하되는 문제점을 야기한다. 한편, 상기 탄산칼슘 및 이산화티탄의 합계 함량이 20중량%를 넘게 되면, 필름 등과 같은 물품으로 제조될 경우 인장신율이 저하되고, 쇼핑백 등 최종 제품 가공시 실링 강도가 저하되는 문제점을 초래한다.When the total content of the calcium carbonate and titanium dioxide is less than 10% by weight, there is a problem of insufficient hiding power and high glossiness, and stiffness when manufacturing an article such as a film using the biodegradable resin composition according to the present invention. Lack of stiffness causes a problem that productivity is lowered when the film is processed into a final product such as a shopping bag. On the other hand, when the total content of the calcium carbonate and titanium dioxide exceeds 20% by weight, the tensile elongation is lowered when the article is made of an article such as a film, resulting in a problem that the sealing strength when processing the final product, such as shopping bags.
그리고, 상기 이산화티탄:탄산칼슘의 함량 비율이 1:1 미만인 경우에는 광택도가 높아질 우려가 있으며, 상기 비율이 1:2를 초과하게 되면 생분해성 물품의 색상이 노랗게 되는 문제점이 발생할 수 있다.When the content ratio of titanium dioxide: calcium carbonate is less than 1: 1, glossiness may increase, and when the ratio exceeds 1: 2, a problem may occur in that the color of the biodegradable article becomes yellow.
한편, 상기 가소제는 고분자에 첨가되어 가공성, 유연성 등의 물성 및 기능을 개질하는 첨가제로, 상기 가소제의 함량은 상기 기초 수지 조성물 100중량부를 기준으로 0.1 ~ 1.0중량부인 것이 바람직하다. 상기 가소제의 함량이 0.1중량부 미만일 경우 물성 개선의 효과가 미미할 우려가 있고, 반면 1.0중량부를 초과할 경우에는 가소제가 과량 포함되어 생분해성 물품 제조 후 표면으로 마이그레이션(migration)될 수 있으며, 이에 따라 쇼핑백의 실링 강도가 점차 약해지는 등 생분해성 최종 제품의 품질이 저하되는 문제점을 발생시킬 수 있다. On the other hand, the plasticizer is an additive that is added to the polymer to modify the properties and functions, such as processability, flexibility, the content of the plasticizer is preferably 0.1 to 1.0 parts by weight based on 100 parts by weight of the base resin composition. If the content of the plasticizer is less than 0.1 parts by weight, there is a concern that the improvement of physical properties may be insignificant. On the other hand, if the content of the plasticizer exceeds 1.0 parts by weight, the plasticizer may be included in an excessive amount to migrate to the surface after the biodegradable article is manufactured. The sealing strength of the shopping bag may be gradually weakened, which may cause a problem of degrading the quality of the biodegradable final product.
상기 가소제는 디옥틸아디페이트(dioctyl adipate; DOA), 시트르산 에스테르(citric acid ester) 및 지방산 에스테르로 이루어진 군에서 선택된 일종 이상의 에스테르계 가소제, 시트르산 (citric acid), 폴리에틸렌 글리콜(polyethylene glycol; PEG) 및 폴리프로필렌 글리콜(polypropylene glycol; PPG)로 이루어진 군에서 선택된 일종 이상을 포함할 수 있다. 이때, 상기 에스테르계 가소제는 PLA와 유사한 에스테르 구조를 가지고 있으므로 PLA의 취성 및 생분해성 물품의 인장신율을 개선시킬 수 있어 바람직하게 사용될 수 있다. 특히, 상기 에스테르계 가소제 중에서 DOA는 PLA와의 상용성이 우수해 생분해성 물품표면 마이그레이션 현상이 최소화될 수 있고, 이로 인해 실링강도가 우수한 생분해성 물품을 제조할 수 있어 더욱 바람직하게 사용될 수 있다.The plasticizer may be at least one ester plasticizer selected from the group consisting of dioctyl adipate (DOA), citric acid ester and fatty acid ester, citric acid, polyethylene glycol (PEG) and It may include one or more selected from the group consisting of polypropylene glycol (PPG). At this time, since the ester plasticizer has an ester structure similar to PLA, it can improve the tensile elongation of the brittle and biodegradable articles of PLA can be preferably used. In particular, DOA in the ester-based plasticizer is excellent in compatibility with PLA can minimize the surface migration of biodegradable articles, thereby making it possible to prepare a biodegradable article with excellent sealing strength can be used more preferably.
상기 상용화제는 PLA와 PLA 이외의 생분해성 폴리에스테르 수지의 상용성 확보를 위해 첨가되는 것으로, 생분해성 물품의 인장강도 및 인열강도 등의 기계적 물성을 개선시키는 역할을 한다. 상기 상용화제의 함량은 상기 기초 수지 조성물 100중량부를 기준으로 0.1 ~ 0.5중량부인 것이 바람직하다. 상기 상용화제의 함량이 0.1중량부 미만일 경우 수지들 간의 상용성이 떨어져 기계적 물성이 저하될 우려가 있고, 반면 0.5중량부를 초과할 경우 용융지수(melt index; MI)가 과도하게 낮아져 생분해성 물품의 가공성이 불량해질 우려가 있다.The compatibilizer is added to ensure compatibility of PLA and biodegradable polyester resins other than PLA, and serves to improve mechanical properties such as tensile strength and tear strength of biodegradable articles. The content of the compatibilizer is preferably 0.1 to 0.5 parts by weight based on 100 parts by weight of the base resin composition. When the content of the compatibilizer is less than 0.1 parts by weight, the compatibility between the resins may be lowered, whereas mechanical properties may be lowered. On the other hand, when the content of the compatibilizer exceeds 0.5 parts by weight, the melt index (MI) may be excessively low, resulting in a biodegradable article. There is a fear that the workability is poor.
상기 상용화제는 폴리이소시아네이트(polyisocyanate), 에폭시 관능기를 가진 스티렌-아크릴레이트 공중합체 및 카보디이미드(carbodiimide)로 이루어진 군에서 선택된 일종 이상을 포함할 수 있다. 상기 에폭시 관능기를 가진 스티렌-아크릴레이트 공중합체로서는 예컨대, 바스프(BASF)사의 "JONCRYL"(등록 상표) 시리즈가 사용될 수 있다.The compatibilizer may include at least one selected from the group consisting of polyisocyanate, styrene-acrylate copolymer having an epoxy functional group, and carbodiimide. As the styrene-acrylate copolymer having the epoxy functional group, for example, the "JONCRYL" (registered trademark) series of BASF can be used.
바람직하게, 상기 상용화제로서 폴리이소시아네이트가 사용될 수 있으며, 더욱 바람직하게 삼관능성 폴리이소시아네이트, 예컨대 하기의 화학식 1로 표시되는 삼관능성 폴리이소시아네이트가 사용될 수 있다.Preferably, polyisocyanate may be used as the compatibilizer, and more preferably trifunctional polyisocyanate, such as trifunctional polyisocyanate represented by Formula 1 below, may be used.
화학식 1Formula 1
Figure PCTKR2017003780-appb-I000001
Figure PCTKR2017003780-appb-I000001
이 밖에도, 본 발명에 따른 생분해성 수지 조성물은 산화방지제를 더 포함할 수 있다.In addition, the biodegradable resin composition according to the present invention may further include an antioxidant.
상기 산화방지제는 가공과정의 진행 중에 발생할 수 있는 고분자의 가교를 막아주고, 완제품의 장기적 물성을 유지할 뿐만 아니라, 변색을 막아주는 역할을 한다. 상기 산화방지제의 함량은 상기 기초 수지 조성물 100중량부를 기준으로 0.1 ~ 5중량부인 것이 바람직하다. 상기 산화방지제의 함량이 0.1중량부 미만일 경우 산화방지 효과가 미미해져 생분해성 물품의 내구성이 저하될 수 있다. 반면, 상기 산화방지제의 함량이 5중량부를 초과하면 함량 대비 효과가 미흡할 수 있고, 오히려 과도한 함량으로 산화방지제가 표면으로 이행될 수 있어 외관상 좋지 않을 수 있다. The antioxidant prevents crosslinking of the polymer that may occur during the process of processing, and serves to prevent discoloration as well as to maintain long-term physical properties of the finished product. The content of the antioxidant is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the base resin composition. When the content of the antioxidant is less than 0.1 parts by weight, the antioxidant effect is insignificant, which may lower the durability of the biodegradable article. On the other hand, if the content of the antioxidant is more than 5 parts by weight, the effect of the content may be insufficient, rather, the excessive amount of the antioxidant may be transferred to the surface may not look good.
상기 산화방지제는 1차 산화방지제 및 2 산화방지제를 포함할 수 있다. 구체적으로, 상기 1차 산화방지제는 산화 작용으로 생성되는 불안정한 자유 라디칼(free radical)의 발생을 억제하거나 자유 라디칼을 안정한 형태로 만들어주는 역할을 하는 것으로, 페놀계 또는 방향족 아민계 산화방지제가 대표적이다. 상기 2차 산화방지제는 불안정한 자유 라디칼이 산소와 결합되어 생성되는 히드로퍼옥사이드(hydroperoxide)의 산화로 발생할 수 있는 또 다른 불안정한 자유 라디칼의 생성을 억제하는 역할을 하는 것으로, 인계 또는 티오계 산화방지제가 사용될 수 있다.The antioxidant may include a primary antioxidant and a secondary antioxidant. Specifically, the primary antioxidant is to inhibit the generation of unstable free radicals generated by the oxidation action or to make the free radicals in a stable form, phenolic or aromatic amine-based antioxidants are typical . The secondary antioxidant serves to inhibit the production of another unstable free radical that may be caused by the oxidation of hydroperoxides formed by the combination of unstable free radicals with oxygen, and phosphorus or thio-based antioxidants Can be used.
또한, 본 발명은 상기 생분해성 수지 조성물로부터 제조된 생분해성 물품을 제공한다.The present invention also provides a biodegradable article prepared from the biodegradable resin composition.
상기 생분해성 물품은 상기 생분해성 수지 조성물로부터 제조된 생분해성 필름일 수 있다. 상기 생분해성 필름은 통상의 방법에 따라 필름 제작기를 이용하여 제조할 수 있다. 이때, 탄산칼슘(CaCO3) 및 이산화티탄(TiO2)는 분산성 개선을 위하여 마스터배치(master batch, M/B) 칩 형태로 필름제조에 사용될 수 있다. The biodegradable article may be a biodegradable film prepared from the biodegradable resin composition. The biodegradable film can be produced using a film maker according to a conventional method. In this case, calcium carbonate (CaCO 3 ) and titanium dioxide (TiO 2 ) may be used for film production in the form of a master batch (M / B) chip to improve dispersibility.
이렇게 제조된 생분해성 필름은 인장강도, 인장신율 및 인열강도가 우수하여 기존의 합성수지를 대체하여 사용될 수 있다.Thus prepared biodegradable film is excellent in tensile strength, tensile elongation and tear strength can be used to replace the existing synthetic resin.
상기 생분해성 물품은 상기 생분해성 필름으로부터 제조된 생분해성 봉투일 수 있으며, 예컨대 쓰레기 봉투, 롤백, 쇼핑백 등과 같은 용도로 사용될 수 있다. 이 밖에도 상기 생분해성 물품은 식품포장재 등의 분야에서 폭넓게 상용화될 수 있다. 특히, 본 발명에 따라 제조된 생분해성 필름은 백색도 및 은폐력이 뛰어나고 광택도가 낮으므로 마트용 쇼핑백 용도로 사용될 경우, 소비자의 니즈를 만족시킬 수 있어 더욱 바람직하다. The biodegradable article may be a biodegradable bag made from the biodegradable film, and may be used, for example, in a garbage bag, a roll bag, a shopping bag, or the like. In addition, the biodegradable article may be widely commercialized in fields such as food packaging materials. In particular, the biodegradable film prepared according to the present invention is excellent in whiteness, hiding power and low glossiness, when used as a shopping bag for mart, it is more preferable to satisfy the needs of consumers.
이하, 실시예들을 들어 본 발명에 관하여 더욱 상세히 설명하지만, 본 발명이 이러한 실시예들에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
실시예Example 1 One
폴리부틸렌아디페이트-코-테레프탈레이트(poly butylene adipate-co-terephthalate; PBAT)(ENPOL PBG7070, S-Enpol사) 67중량%, 폴리락트산(poly lactic acid; PLA)(PLA 4032D, NatureWorks) 23중량%, TiO2 (코스모화학) 7중량% 및 CaCO3(GTL chemical) 3중량%를 혼합기에 투입하여 기초 수지 조성물 혼합물을 제조하였다.Poly butylene adipate-co-terephthalate (PBAT) (ENPOL PBG7070, S-Enpol) 67% by weight, poly lactic acid (PLA) (PLA 4032D, NatureWorks) 23 A wt%, 7 wt% TiO 2 (Cosmo Chemical) and 3 wt% CaCO 3 (GTL chemical) were added to the mixer to prepare a base resin composition mixture.
이어서, 이축 압출기(창성 P&R사 제품, L/D: 36/1, 직경: 24.2mm)에 상기 기초 수지 조성물 혼합물과 상기 기초 수지 조성물 100중량부를 기준으로 가소제(DOA(dioctyl adipate), 애경유화) 0.3중량부 및 상용화제(삼관능성 폴리이소시아네이트, 애경화학) 0.25중량부를 투입하고 170℃에서 용융혼련하여 생분해성 수지 조성물 펠렛을 제조하였다. Subsequently, a plasticizer (dioctyl adipate, Aekyung emulsification) based on 100 parts by weight of the base resin composition mixture and the base resin composition in a twin-screw extruder (manufactured by Changsung P & R, L / D: 36/1, diameter: 24.2 mm) 0.3 parts by weight and 0.25 parts by weight of a compatibilizer (trifunctional polyisocyanate, Aekyung Chemical) were added and melt kneaded at 170 ° C. to prepare a biodegradable resin composition pellet.
이후, 상기 펠렛을 유진엔지니어링사 YJF-2(직경: 60mm) 필름 성형기를 사용하여 가공온도 170℃에서 용융혼련하여 폭 400mm x 두께 50㎛의 생분해성 필름을 300m 제조하였다.Thereafter, the pellets were melt kneaded at a processing temperature of 170 ° C. using a Eugene Engineering Co., Ltd. YJF-2 (diameter: 60 mm) film molding machine to prepare a biodegradable film having a width of 400 mm and a thickness of 50 μm, 300 m.
실시예 2 내지 4 및 비교예 1 내지 3Examples 2-4 and Comparative Examples 1-3
상기 PBAT, PLA, TiO2, CaCO3, 가소제 및 상용화제의 함량을 하기의 표 1에 기재된 바와 같은 조절한 것을 제외하고는 실시예 1과 동일한 방법으로 생분해성 필름을 제조하였다.Biodegradable film was prepared in the same manner as in Example 1 except that the content of PBAT, PLA, TiO 2 , CaCO 3 , plasticizer and compatibilizer were adjusted as described in Table 1 below.
위 각 실시예 및 비교예들에서 제조한 필름의 물성을 다음과 같은 방법으로 평가하였다. The physical properties of the films prepared in the above Examples and Comparative Examples were evaluated by the following method.
< 평가방법 ><Evaluation Method>
1. 용융지수(melt index, MI)1. Melt index (MI)
상기 실시예 1 내지 4 및 비교예 1 내지 3에 따라 제조된 생분해성 수지 조성물(펠렛 상태)의 용융지수를 ASTM D1238에 의거하여 측정하였다. 구체적으로, 190℃의 온도 및 2.16kg 하중 하에서 10분간 오리피스(반지름: 2mm, 길이: 8mm)를 통과하여 흘러나오는 양(g)을 용융지수(MI)로 측정하였다. The melt index of the biodegradable resin composition (pellet state) prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 was measured according to ASTM D1238. Specifically, the amount (g) flowing through an orifice (radius: 2 mm, length: 8 mm) for 10 minutes under a temperature of 190 ° C. and a 2.16 kg load was measured as a melt index (MI).
2. 색도2. Chromaticity
상기 실시예 1 내지 4 및 비교예 1 내지 3에 따라 제조된 생분해성 필름의 색도 L*, a* 및 b*를 Konica Minolta 색차계를 사용하여 CIE-L*a*b*(CIE 1976) 표색계에서 측정하였다. 상기 "L*"값, "a*"값 및 "b*"값은 CIE-L*a*b* (CIE1976) 표색계에서 표시되는 색조의 지표이다. "L*"값은 밝기를 나타내고, 이 수치가 클수록 밝다. "a*"값은 적색 정도를 나타내고, 이 수치가 클수록 적색도가 높다. "b*"값은 황색 정도를 나타내고, 이 수치가 클수록 황색도가 높아 백색도가 떨어진다.The chromaticities L *, a * and b * of the biodegradable films prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 were obtained using a CIE-L * a * b * (CIE 1976) colorimeter using a Konica Minolta colorimeter. Measured at The " L * ", " a * " values and " b * " values are indices of color tone displayed in the CIE-L * a * b * (CIE1976) colorimeter. The value "L *" represents brightness, and the larger this value, the brighter it is. The value "a *" indicates the degree of redness, and the larger this value, the higher the degree of redness. The value "b *" indicates the degree of yellowness, and the larger this value, the higher the yellowness and the lower the whiteness.
3. 인열강도3. Tear strength
상기 실시예 1 내지 4 및 비교예 1 내지 3에 따라 제조된 생분해성 필름의 종방향(MD) 및 횡방향(TD)에서의 인열강도를 엘멘도르프(Elmendorf)식 인열강도 분석기를 이용하여 측정하였다.The tear strength in the longitudinal direction (MD) and the transverse direction (TD) of the biodegradable films prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 using an Elmendorf tear strength analyzer Measured.
4. 인장강도 및 인장신율4. Tensile Strength and Tensile Elongation
상기 실시예 1 내지 4 및 비교예 1 내지 3에 따라 제조된 생분해성 필름의 종방향(MD) 및 횡방향(TD)에서의 인장강도 및 인장신율을 JIS K6251-1에 의거하여 측정하였다.The tensile strength and tensile elongation in the longitudinal direction (MD) and the transverse direction (TD) of the biodegradable films prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 were measured based on JIS K6251-1.
5. 은폐력 및 광택도5. hiding power and glossiness
상기 실시예 1 내지 4 및 비교예 1 내지 3에 따라 제조된 생분해성 필름의 은폐력을 은폐율 측정기(NOVO-SHOADE DUO, Rhopoint Instrument사)를 이용하여 측정하였다. 또한, 생분해성 필름의 광택도는 광택계(Micro-TRI-Gloss, BKY사)를 이용하여 측정하였다.The hiding power of the biodegradable films prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 was measured using a hiding rate measuring instrument (NOVO-SHOADE DUO, Rhopoint Instrument). In addition, the glossiness of the biodegradable film was measured using a gloss meter (Micro-TRI-Gloss, BKY).
실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예3Comparative Example 3
PBAT(중량%)PBAT (% by weight) 6767 6767 6262 6262 7474 7474 7070
PLA(중량%)PLA (% by weight) 2323 2323 2525 2525 1919 1919 2323
TiO2(중량%)TiO 2 (% by weight) 77 55 99 4.54.5 55 55 55
CaCO3(중량%)CaCO 3 (% by weight) 33 55 44 8.58.5 22 22 22
합계(중량%)Total (% by weight) 100100 100100 100100 100100 100100 100100 100100
가소제(중량부)Plasticizer (parts by weight) 0.300.30 0.300.30 0.300.30 0.300.30 -- 0.300.30 0.300.30
상용화제(중량부)Compatibilizer (parts by weight) 0.250.25 0.250.25 0.250.25 0.250.25 -- 0.250.25 0.250.25
MI(g/10min)MI (g / 10min) 3.53.5 3.63.6 3.43.4 3.83.8 4.74.7 4.04.0 3.93.9
필름 색도Film chromaticity LL 9696 9696 9797 9696 9696 9696 9696
aa -0.5-0.5 -0.5-0.5 -0.3-0.3 -0.4-0.4 -0.7-0.7 -0.4-0.4 -0.5-0.5
bb 1.11.1 1.01.0 0.80.8 1.01.0 1.31.3 1.21.2 1.31.3
인열강도(gf)Tear strength (gf) MDMD 4949 4949 4848 4848 5050 6060 5757
TDTD 155155 156156 156156 164164 152152 165165 163163
인장강도(kgf/cm2)Tensile strength (kgf / cm 2 ) MDMD 390390 385385 380380 398398 332332 364364 360360
TDTD 251251 253253 251251 260260 250250 286286 284284
인열신율(%)Tear elongation (%) MDMD 212212 215215 196196 200200 196196 230230 220220
TDTD 331331 337337 310310 324324 350350 410410 390390
은폐력(%)Hiding power (%) 6868 7474 7272 7676 6060 6161 6262
광택도 (60o)Glossiness (60 o ) 2727 2424 2626 2222 3636 3535 3434
* 상기 표 1에서 가소제, 상용화제의 함량 단위는 상기 PBAT, PLA, TiO2 및 CaCO3의 합계량 100중량부를 기준으로 한 중량부이다.* The content units of the plasticizer and the compatibilizer in Table 1 are parts by weight based on 100 parts by weight of the total amount of PBAT, PLA, TiO 2 and CaCO 3 .
상기 표 1을 참조하면, 실시예 1내지 4에 따라 제조된 생분해성 필름이 비교예 1 내지 3에 따라 제조된 생분해성 필름에 비하여 백색도 및 은폐력이 우수하고 광택도가 낮은 것을 확인할 수 있다. 특히, 이산화티탄:탄산칼슘의 투입비율이 중량기준으로 1:1 ~ 1:2 범위에 속하는 실시예 2 및 4에 따라 제조된 생분해성 필름의 경우, 은폐력이 현저히 높게 나타나고 광택도 또한 낮게 나타나는바, 마트용 쇼핑백 등과 같은 생분해성 봉투의 용도로 더욱 바람직하게 사용될 수 있다.Referring to Table 1, it can be seen that the biodegradable film prepared according to Examples 1 to 4 is excellent in whiteness and hiding power and low glossiness as compared to the biodegradable film prepared according to Comparative Examples 1 to 3. In particular, in the case of the biodegradable film prepared according to Examples 2 and 4 in which the input ratio of titanium dioxide: calcium carbonate is in the range of 1: 1 to 1: 2 by weight, the hiding power is markedly high and the gloss is also low. It may be more preferably used for the use of biodegradable bags such as shopping bags for marts and the like.
또한, 실시예 1 내지 4에 따라 제조된 생분해성 수지 조성물로부터 제조된 펠렛의 경우, 비교예 1 내지 3에 따라 제조된 수지 펠렛에 비하여 용융지수가 낮게 나타나는 바, 가공성이 우수한 생분해성 수지 조성물이 제조되었음을 확인할 수 있다.In addition, in the case of pellets prepared from the biodegradable resin compositions prepared according to Examples 1 to 4, the melt index is lower than that of the resin pellets prepared according to Comparative Examples 1 to 3, and thus the biodegradable resin compositions having excellent processability are It can be confirmed that the manufacturing.
이 밖에, 가소제 및 상용화제를 첨가하여 제조된 비교예 2 및 3에 따른 생분해성 필름의 경우 비교예 1의 생분해성 필름에 비하여 높은 인장강도, 인장신율 및 인열강도를 나타내는 것을 확인 할 수 있다. 이에 따라, 비교에 2 및 3과 동일한 가소제 및 상용화제 함량을 적용하여 실시예 1 내지 실시예 4의 생분해성 필름을 제조하였으며, 우수한 물성을 나타내는 생분해성 필름을 제조할 수 있었다.In addition, the biodegradable films according to Comparative Examples 2 and 3 prepared by adding a plasticizer and a compatibilizer may be confirmed to exhibit higher tensile strength, tensile elongation and tear strength than the biodegradable films of Comparative Example 1. . Accordingly, the biodegradable films of Examples 1 to 4 were prepared by applying the same plasticizer and compatibilizer content as in Comparative Examples 2 and 3, and a biodegradable film showing excellent physical properties could be prepared.
이상, 본 발명에 개시된 실시예들은 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것으로서, 본 발명의 권리범위는 아래의 특허청구범위에 의하여 해석되어야 하며 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.As described above, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention but to explain the present invention, and the scope of the present invention should be interpreted by the following claims, and all technical ideas within the scope equivalent thereto. Should be construed as being included in the scope of the present invention.

Claims (10)

  1. (a) 폴리락트산(poly lactic acid; PLA) 20 ~ 30중량%, (b) 상기 PLA 이외의 지방족 폴리에스테르 수지와 지방족/방향족 폴리에스테르 수지로 이루어진 군에서 선택된 일종 이상의 생분해성 폴리에스테르 수지 60 ~ 70중량%, (c) 탄산칼슘(CaCO3) 3 ~ 10중량% 및 (d) 이산화티탄(TiO2) 3 ~ 10중량%로 이루어지고, (e) 상기 탄산칼슘 및 이산화티탄의 합계 함량은 10 ~ 20중량%인 기초 수지 조성물;(a) 20 to 30% by weight of poly lactic acid (PLA), (b) at least one biodegradable polyester resin selected from the group consisting of aliphatic polyester resins and aliphatic / aromatic polyester resins other than the above PLA 60 ~ 70% by weight, (c) 3-10% by weight of calcium carbonate (CaCO 3 ) and (d) 3-10% by weight of titanium dioxide (TiO 2 ), and (e) the total content of calcium carbonate and titanium dioxide is Basic resin composition of 10 to 20% by weight;
    가소제; 및Plasticizers; And
    상용화제를 포함하는 생분해성 수지 조성물.Biodegradable resin composition comprising a compatibilizer.
  2. 제1항에 있어서,The method of claim 1,
    상기 이산화티탄:탄산칼슘의 함량 비율은 1:1 ~ 1:2(중량기준)인 것을 특징으로 하는 생분해성 수지 조성물.Biodegradable resin composition, characterized in that the content ratio of titanium dioxide: calcium carbonate is 1: 1 to 1: 2 (by weight).
  3. 제1항에 있어서,The method of claim 1,
    상기 (b) 생분해성 폴리에스테르 수지는 폴리부틸렌 아디페이트-코-테레프탈레이트(poly butylene adipate-co-terephthalate; PBAT), 폴리부틸렌 숙시네이트(poly butylenes succinate; PBS), 폴리부틸렌 숙시네이트-코-아디페이트(poly butylene succinate-co-adipate; PBSA) 및 폴리하이드록시 알카노에이트(poly hydroxyl alkanoate; PHA)로 이루어진 군에서 선택된 일종 이상을 포함하는 것을 특징으로 하는 생분해성 수지 조성물.The (b) biodegradable polyester resin is poly butylene adipate-co-terephthalate (PBAT), poly butylenes succinate (PBS), polybutylene succinate A biodegradable resin composition comprising at least one selected from the group consisting of poly butylene succinate-co-adipate (PBSA) and poly hydroxyl alkanoate (PHA).
  4. 제1항에 있어서,The method of claim 1,
    상기 가소제의 함량은 상기 기초 수지 조성물 100중량부를 기준으로 0.1 ~ 1.0중량부인 것을 특징으로 하는 생분해성 수지 조성물.The amount of the plasticizer is biodegradable resin composition, characterized in that 0.1 to 1.0 parts by weight based on 100 parts by weight of the base resin composition.
  5. 제4항에 있어서,The method of claim 4, wherein
    상기 가소제는 디옥틸아디페이트(dioctyl adipate; DOA), 시트르산 에스테르(citric acid ester) 및 지방산 에스테르로 이루어진 군에서 선택된 일종 이상의 에스테르계 가소제, 시트르산 (citric acid), 폴리에틸렌 글리콜(polyethylene glycol; PEG) 및 폴리프로필렌 글리콜(polypropylene glycol; PPG)로 이루어진 군에서 선택된 일종 이상을 포함하는 것을 특징으로 하는 생분해성 수지 조성물.The plasticizer may be at least one ester plasticizer selected from the group consisting of dioctyl adipate (DOA), citric acid ester and fatty acid ester, citric acid, polyethylene glycol (PEG) and Biodegradable resin composition comprising at least one selected from the group consisting of polypropylene glycol (PPG).
  6. 제1항에 있어서,The method of claim 1,
    상기 상용화제의 함량은 상기 기초 수지 조성물 100중량부를 기준으로 0.1 ~ 0.5중량부인 것을 특징으로 하는 생분해성 수지 조성물.The content of the compatibilizer is biodegradable resin composition, characterized in that 0.1 to 0.5 parts by weight based on 100 parts by weight of the base resin composition.
  7. 제6항에 있어서,The method of claim 6,
    상기 상용화제는 폴리이소시아네이트(polyisocyanate), 에폭시 관능기를 가진 스티렌-아크릴레이트 공중합체 및 카보디이미드(carbodiimide)로 이루어진 군에서 선택된 일종 이상을 포함하는 것을 특징으로 하는 생분해성 수지 조성물.The compatibilizer is a biodegradable resin composition comprising at least one selected from the group consisting of polyisocyanate, styrene-acrylate copolymer having an epoxy functional group, and carbodiimide.
  8. 제1항 내지 제7항 중 어느 한 항에 따른 생분해성 수지 조성물로부터 제조된 생분해성 물품. A biodegradable article made from the biodegradable resin composition according to any one of claims 1 to 7.
  9. 제8항에 있어서,The method of claim 8,
    상기 생분해성 물품이 상기 생분해성 수지 조성물로부터 제조된 생분해성 필름인 것을 특징으로 하는 생분해성 물품.And wherein the biodegradable article is a biodegradable film made from the biodegradable resin composition.
  10. 제9항에 있어서,The method of claim 9,
    상기 생분해성 물품이 상기 생분해성 필름으로부터 제조된 생분해성 봉투인 것을 특징으로 하는 생분해성 물품.And wherein said biodegradable article is a biodegradable envelope made from said biodegradable film.
PCT/KR2017/003780 2016-09-23 2017-04-06 Biodegradable resin composition and biodegradable article manufactured therefrom WO2018056539A1 (en)

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