WO2009064052A1 - The composition for laminate coating of paper, and the food packaging paper using it - Google Patents

The composition for laminate coating of paper, and the food packaging paper using it Download PDF

Info

Publication number
WO2009064052A1
WO2009064052A1 PCT/KR2008/002981 KR2008002981W WO2009064052A1 WO 2009064052 A1 WO2009064052 A1 WO 2009064052A1 KR 2008002981 W KR2008002981 W KR 2008002981W WO 2009064052 A1 WO2009064052 A1 WO 2009064052A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
resin composition
composition
biodegradable resin
biodegradable
Prior art date
Application number
PCT/KR2008/002981
Other languages
French (fr)
Inventor
Pan-Kyu Kim
Jae-Gun Shim
Jae-Ho Shim
Gun-Gyu Lee
Original Assignee
Hanchang Paper Co., Ltd.
Npi Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hanchang Paper Co., Ltd., Npi Co., Ltd. filed Critical Hanchang Paper Co., Ltd.
Publication of WO2009064052A1 publication Critical patent/WO2009064052A1/en

Links

Classifications

    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • 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
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • PLA highly degradable biodegradable polylactic acid
  • a common resin may damage to the nature system since it is not degraded for decades due to its persistent properties when it is embedded.
  • a persistent resin film may cause trouble in a process for recycling.
  • a PVC resin generates dioxin, and thus it is difficult to incinerate it.
  • PLA has low expansibility, is very hard and has low thermal stability thereby causing fear that it pyrolyzed.
  • the aliphatic polyester has also low thermal stability, is difficult to form a thin membrane thereby thickening its thickness, and is too soft to process.
  • the present inventors disclosed a method of forming a film by mixing a PLA resin and an aliphatic polyester
  • PLA polylactic acid
  • PLA polylactic acid
  • PLA polylactic acid
  • PLA polylactic acid
  • PLA has advantages that not only it has high degradability, but also it is not harmful to the human body, and its caloric value is low thereby generating dioxin or carbon dioxide in little amounts when burnt.
  • a separate adhesive or double coating is needed on coating on a paper since PLA has weak adhesive force with a paper. Accordingly, costs rise, processes become complex and an environmental hormone due to use of an adhesive must be endured.
  • the present invention overcame the above shortcomings by mixing other material together.
  • a biodegradable resin composition for laminate coating of papers according to the present invention comprises 10 to 85% by weight of polylactic acid, 10 to 75% by weight of a biodegradable polyester resin (aliphatic polyester resin) and 0.05 to 5% by weight of a plasticizer.
  • the composition may further comprise 0.01 to 50% by weight of an additive in which at least one or more of a stabilizer, a slipping agent, a dispersant, a coupling agent, an anti-oxidizing agent, a UV stabilizer and a filler are mixed, relative to 100% by weight of the composition.
  • the polylactic acid is any one selected from the group consisting of a homopolymer of D-lactic acid, a homopolymer of L-lactic acid, or a copolymer of L-lactic acid and D- lactic acid;
  • the plasticizer is at least one selected from the group consisting of sorbitan monolaurate, sorbitan monopalmitate, sorbitan trioleate, sorbitan monostearate, polyethylene glycol, polyalkylene oxide, glycerol, glycerol acetate, propylene glycol and sorbitol.
  • the biodegradable polyester resin may be any aliphatic polyester resin, and includes polybutylene adipate/terephthalate (trade name Ecoflex) or polybutylene succinate • co • adipate (trade name Enpol) .
  • the filler may optionally employ at least one selected from the group consisting of talc, calcium carbonate, Limestone, TiO 2 and carbon black;
  • the stabilizer may optionally employs at least one selected from the group consisting of trimethyl phosphate, phosphoric acid and triphenyl phosphate;
  • the anti-oxidizing agent may optionally employ at least one selected from the group consisting of Irganox series, Ultranox series and TEP series;
  • the slipping agent may optionally employ at least one selected from the group consisting of calcium stearate, zinc stearate, PE wax and general wax.
  • the coupling agent may be anhydrous maleic acid and silane coupling agent (trimethoxysilane, triethoxysilane, tetraethoxysilane) etc.
  • the above resin composition is coated on a surface of papers having a thickness of 0.01 to 2 mm, thereby preventing moistures from entering and enhancing the exiting of moistures .
  • the present invention also incorporates a proper coupling agent to overcome the problem that PLA and other biodegradable resin are immiscible and thus coating may not be properly achieved when the resin is used as such.
  • a biodegradable resin composition according to the present invention is used in a disposable food container (a paper cup, a cup noodle container, a disposable tray, etc.) as a biodegradable coating paper manufactured by coating the composition on a surface or both surfaces of papers under a predetermined condition, it can be widely applied as an eco-friendly coating paper that is not harmful to the human body since there is no an environmental hormone as well as does not cause an environmental pollution.
  • FIG. 1 illustrates the food packaging paper according to the present invention.
  • the present invention provides a biodegradable resin composition for laminating on various food packaging papers comprising 10 to 85% by weight of polylactic acid, 10 to 75% by weight of a biodegradable polyester resin (aliphatic polyester resin) and 0.05 to 5% by weight of a plasticizer.
  • a polylactic acid, a polyester resin, a plasticizer and a filler are further incorporated.
  • the polylactic acid (PLA) is a biodegradable resin different from a general- purpose synthetic resin product, and is not harmful to the human body and does not change the physical strength of a paper. Further, the polylactic acid has a characteristic that can overcome a problem that previous PE or PP is not degraded thereby remaining wastes in the earth due to its biodegradability at natural state.
  • the present invention uses any one selected from the group consisting of a homopolymer of D-lactic acid, a homopolymer of L-lactic acid or a copolymer of L-lactic acid and D-lactic acid as the polylactic acid.
  • a biodegradable polyester resin is further incorporated.
  • the resin is obtained by performing polycondensation reaction after undergoing any one or more than two reaction selected from (1) polycondensation, (2) ester exchange reaction, or (3) esterificati ⁇ n reaction.
  • the resin is incorporated into the composition, it prevents moisture from entering and helps exiting vapors.
  • the composition according to the present invention is laminated on the surfaces of various food packaging papers or containers. For a noodle container on which the composition is laminated, the composition plays a role so that papers do not absorb moistures even when hot water is poured although materials are papers. Accordingly, even though the container is manufactured with a paper, it can contain water.
  • a plasticizer is further incorporated.
  • the plasticizer generally refers to an organic material that facilitates forming process at high temperatures by enhancing thermoplastic property when added to a thermoplastic material. It is the characteristic of the plasticizer to enhance heat resistance, cold resistance, flame resistance and electrical property, etc. in addition to compatibility and plasticity.
  • the plasticizer used most is DOP (dioctyl phthalate) , DOA (dioctyl adipate) and TCP (tricresyl phosphate) .
  • the present invention optionally mixes and uses at least one or more selected from the group consisting of sorbitan monolaurate, sorbitan monopalmitate, sorbitan trioleate, sorbitan monostearate, polyethylene glycol, polyalkylene oxide, glycerol, glycerol acetate, propylene glycol and sorbitol as a plasticizer. These materials are also used as food additives, and are not harmful to the human body.
  • a separate filler can be incorporated to the mixture.
  • the filler may optionally employ at least one selected from the group consisting of talc, calcium carbonate, Limestone, Ti ⁇ 2 and carbon black, and is added in order to increase blocking phenomenon when processed and cooling speed.
  • the average particle diameter of the filler is controlled in the range of 0.01 to 10 ⁇ m, and the filler can be used in an amount of 0.01 to 50% by weight when the above resin composition is referred to 100% by weight.
  • the resin composition prepared as above is applied on a food packaging paper or the surface of a packaging container, and hardened thereby forming a coated layer.
  • the composition according to the present invention can further comprise the following additives. That is, the composition may further comprise 1 to 20% by weight of an additive in which at least one or more of a stabilizer, a slipping agent, a dispersant, a coupling agent, an anti-oxidizing agent and a UV stabilizer are optionally mixed, relative to 100% by weight of the composition.
  • the stabilizer may optionally employ at least one selected from the group consisting of trimethyl phosphate, phosphoric acid and triphenyl phosphate in an amount of 0.01 to 10% by weight, relative to 100% by weight of the resin composition.
  • Irganox series, Ultranox series and TEP series can be used as the anti-oxidizing agent in an amount of 0.01 to 10% by weight, relative to 100% by weight of the resin composition
  • HALS (hindered amine light stabilizer) series can be used as the UV stabilizer in an amount of 0.01 to 10% by weight, relative to 100% by weight of the resin composition
  • calcium stearate, zinc stearate, PE wax and general wax can be used as the slipping agent in an amount of 0.01 to 10% by weight, relative to 100% by weight of the resin composition.
  • carboxylated polyethylene, phthalic acid and stearic acid, etc. can be used as the dispersant that is an additive to be added for compatibility between the used resins.
  • the dispersant can be used in an amount of 0.01 to 10% by weight, relative to 100% by weight of the resin composition.
  • the additives used in the present invention can be optionally added depending on the need of a product such as dispersibility or thermal stability.
  • an extruder (T-die) used in coating a biodegradable resin may be preferably downward type including T-shaped Die.
  • T-die an extruder used in coating a biodegradable resin
  • the present invention enlarged the diameter of the previous orifice tube to 5 to 10 mm to lessen the load of resin pressure, and improved the discharged amount to improve the same extruded amount of resin and productivity as the previous synthetic resin.
  • the temperature distribution of the screw and T-Die was set at 150 to 350°C considering the pyrolysis temperature of a biodegradable PLA and aliphatic polyester, and the problem of the previous paper coating of a biodegradable resin was overcome to improve the adhesive force with a paper substrate, coating speed and uniform coating thickness.
  • Various food-packaging papers are manufactured employing the resin composition prepared as described above. This is achieved by coating the resin composition in liquid state on the surfaces of various papers and simultaneously hardening.
  • the food packaging paper according to the present invention includes a coating layer 10 constituting upper layer by a composition for laminating, and papers 20 having a thickness of 0.01 to 2 mm. Accordingly, the coating layer is applied on the surface of the papers thereby preventing moistures from entering and enhancing the exiting of moistures.
  • This is a simple constitution that a resin composition is coated on various kinds of papers.
  • the thickness is preferably limited to 0.01 to 2 mm since the durability of the coating layer becomes weak in proportion to the thickness of papers if it is too thin or too thick.
  • the amount of all components including additives is based on 100% by weight of the resin composition in the preparation example below.
  • polybutylene succinate • co • adipate [trade name Enpol, Melt Index below 4, 2160g/10min] and 10% by weight of polybutylene adipate/terephthalate (BASF Corporation, Ecoflex, grade : F BX 7011) as biodegradable polyester resins, 0.1% by weight of polyethylene glycol as a plasticizer, 1.5% by weight of calcium stearate as a slipping agent and 1.5% by weight of n-octadecyl- ⁇ - (4 ' - hydroxy-3 ' , 5' -di-tert-butylphenyl) propionate (trade name Irganox 1076) as an anti-oxidizing agent were added to 46.9% by weight of polylactic acid [PLA, NatureWorks LLC, USA, Grade : 2002D, Melt Index 5 ⁇ 7], and the mixture was subjected to a twin screw extruder to prepare a composition in pellet.
  • polylactic acid PLA, NatureWorks LLC, USA, Grade : 2002
  • the pellets prepared according to the above preparation example were heated, melted and mixed, and then melt-extruded using T-shaped Die and simultaneously laminated on papers.
  • the resulting papers were evaluated for formability based on the following standard, and the results are shown in Table 1 below (Table 1 indicates main components only) .
  • the used plasticizer played a role in lowering thickness on extrusion by enhancing compatibility of polylactic acid and polyester resin, and was used properly in an amount of 0.05 to 5.0% by weight.
  • a biodegradable resin composition for laminate coating according to the present invention, and a food packaging paper employing the same can be widely applied in the industry since they do not exit an environmental hormone harmful to the human body and is biodegradable in a natural environment .

Abstract

Disclosed is a biodegradable resin composition for laminate coating of papers such as food packaging paper or a container. More particularly, disclosed are a biodegradable resin composition for laminate coating in which a previous problem that an environmental hormone detrimental to the human body was exited at a site for laminating a food packaging paper can be overcome and the food packaging paper can be biodegraded at a natural environment after its use by incorporating a highly degradable biodegradable polylactic acid (PLA) and a biodegradable polyester resin so that coating may achieved without an adhesive; and a food packaging paper employing the same.

Description

[DESCRI PTION]
[invention Title]
THE COMPOSITION FOR LAMINATE COATING OF PAPER, AND THE FOOD PACKAGING PAPER USING IT [Technical Field]
The present invention relates to a biodegradable resin composition for laminate coating of papers such as a food packaging paper or a container. More particularly, the present invention relates to a biodegradable resin composition for laminate coating which a previous problem that an environmental hormone detrimental to the human body was exited at a site for laminating a food packaging paper can be overcome and the food packaging paper can be biodegraded at a natural environment after its use by incorporating a highly degradable biodegradable polylactic acid (PLA) and a biodegradable polyester resin (= aliphatic polyester resin) so that coating may be achieved without an adhesive; and a food packaging paper employing the same.
[Background Art] For conventional laminate coating paper, various synthetic resins such as PE (LDPE, HDPE) , which is a general-purpose resin, and PP, PVC and URETHANE resin have been used. Harmful material such as a plasticizer or an adhesive is used in those synthetic resins to impart plasticity or thermal adhesiveness thereto. It is known that such adhesive or some plasticizers elute a harmful environmental hormone greatly in hot water.
Most of laminate coating papers are now used in articles, which contact with food directly, such as a general cup, a noodle cup and a food tray that are disposable food products. In such circumstances, the elution of an environmental hormone reaches a serious level since particularly a cup noodle container or a paper cup is under the condition in which it contacts with hot water.
Further, a common resin may damage to the nature system since it is not degraded for decades due to its persistent properties when it is embedded. A persistent resin film may cause trouble in a process for recycling. Further, a PVC resin generates dioxin, and thus it is difficult to incinerate it.
Continuous research and application for PHA, PCL, PLA (polylactic acid) , PHBV and PBS as a biodegradable resin for laminating on a paper have been achieved. As a coating method employing a biodegradable resin up to date, there are disclosed a method of coating after dissolving a polyhydroxyalkanoate (PHA) resin in a solvent to form a solution (Korean Patent Application No. 1994- 0011966) , a method of coating by dispersing an aliphatic polyester in water to form a solution (Korean Patent
Application No. 2003-0041254), a method of coating by dissolving an aliphatic/aromatic copolyester resin in water to form a solution (Korean Patent Application No. 2005- 0110211) . The disclosed methods described above coat by forming a solution of a biodegradable resin. However, that resin has excellent biodegradability, but has shortcomings in that equipment for drying and recovering the solvent is needed, and its property of matter is weak. Further, a melt coating method employing a PLA resin (Korean Patent Application No. 1999-7010885) and a melt coating method employing a biodegradable aliphatic polyester (Korean Patent Application No. 2000-0080964), etc. are disclosed. However, PLA has low expansibility, is very hard and has low thermal stability thereby causing fear that it pyrolyzed. The aliphatic polyester has also low thermal stability, is difficult to form a thin membrane thereby thickening its thickness, and is too soft to process.
The present inventors disclosed a method of forming a film by mixing a PLA resin and an aliphatic polyester
(Korean Patent Application No. 2001-0073862) . In the invention, it is possible to form a film alone, but it is difficult to process the film due to its low thermal stability when coated on a paper, and the film sticks to a cooling roll due to low cooling speed, or is difficult to obtain a uniform coating surface.
In fact, PLA (polylactic acid) is in itself used as material for a general-purpose product through injection, extrusion or forming, etc., but it is known that it is difficult to use as material for laminating on a paper substrate due to its slow solidification speed and weak properties of matter despite the excellent properties. In particular, PLA has advantages that not only it has high degradability, but also it is not harmful to the human body, and its caloric value is low thereby generating dioxin or carbon dioxide in little amounts when burnt. However, a separate adhesive or double coating is needed on coating on a paper since PLA has weak adhesive force with a paper. Accordingly, costs rise, processes become complex and an environmental hormone due to use of an adhesive must be endured. As described below, the present invention overcame the above shortcomings by mixing other material together.
For coating a resin on a paper, there are a way of dissolving a resin with T-Die to form a film and simultaneously hot melt coating on a paper (corresponding to the laminate coating according to the present invention) , a way of preparing a film for coating on a paper, and then adhering the film with an adhesive, and a way of dissolving a resin to be coated in a solvent and applying it to a paper to coat, etc. PLA made it difficult to apply a hot melt manner in terms of its property, but the present invention achieved this. [Disclosure]
[Technical Problem]
The object of the present invention is to provide a biodegradable resin composition for laminate coating of papers, which overcomes the previous problem that an environmental hormone harmful to the human body has been exited at a site for laminating a food packaging paper, as well as renders biodegradable in a natural environment by incorporating highly degradable polylactic acid and a biodegradable polyester resin (= aliphatic polyester resin) , etc. so that coating may be achieved without an adhesive.
[Technical Solution]
A biodegradable resin composition for laminate coating of papers according to the present invention comprises 10 to 85% by weight of polylactic acid, 10 to 75% by weight of a biodegradable polyester resin (aliphatic polyester resin) and 0.05 to 5% by weight of a plasticizer. The composition may further comprise 0.01 to 50% by weight of an additive in which at least one or more of a stabilizer, a slipping agent, a dispersant, a coupling agent, an anti-oxidizing agent, a UV stabilizer and a filler are mixed, relative to 100% by weight of the composition.
The polylactic acid is any one selected from the group consisting of a homopolymer of D-lactic acid, a homopolymer of L-lactic acid, or a copolymer of L-lactic acid and D- lactic acid; the plasticizer is at least one selected from the group consisting of sorbitan monolaurate, sorbitan monopalmitate, sorbitan trioleate, sorbitan monostearate, polyethylene glycol, polyalkylene oxide, glycerol, glycerol acetate, propylene glycol and sorbitol.
The biodegradable polyester resin may be any aliphatic polyester resin, and includes polybutylene adipate/terephthalate (trade name Ecoflex) or polybutylene succinate • co • adipate (trade name Enpol) . The filler may optionally employ at least one selected from the group consisting of talc, calcium carbonate, Limestone, TiO2 and carbon black; the stabilizer may optionally employs at least one selected from the group consisting of trimethyl phosphate, phosphoric acid and triphenyl phosphate; the anti-oxidizing agent may optionally employ at least one selected from the group consisting of Irganox series, Ultranox series and TEP series; the slipping agent may optionally employ at least one selected from the group consisting of calcium stearate, zinc stearate, PE wax and general wax.
The coupling agent may be anhydrous maleic acid and silane coupling agent (trimethoxysilane, triethoxysilane, tetraethoxysilane) etc.
The above resin composition is coated on a surface of papers having a thickness of 0.01 to 2 mm, thereby preventing moistures from entering and enhancing the exiting of moistures . As described previously, PLA had a shortcoming in that its adhesive force with a paper is weak despite its advantages; however, the present invention overcomes the problem by mixing a biodegradable polyester resin (= aliphatic polyester resin) together. That is, the present invention removes the need of an adhesive harmful to the human body by incorporating a biodegradable polyester resin in order to enhance the adhesive force of PLA to a paper. Further, the present invention further incorporates a proper stabilizer considering that the biodegradable resin is broken when heated. The present invention also incorporates a proper coupling agent to overcome the problem that PLA and other biodegradable resin are immiscible and thus coating may not be properly achieved when the resin is used as such. [Advantageous Effects] When the biodegradable resin composition according to the present invention is used in a disposable food container (a paper cup, a cup noodle container, a disposable tray, etc.) as a biodegradable coating paper manufactured by coating the composition on a surface or both surfaces of papers under a predetermined condition, it can be widely applied as an eco-friendly coating paper that is not harmful to the human body since there is no an environmental hormone as well as does not cause an environmental pollution. [Description of Drawings]
FIG. 1 illustrates the food packaging paper according to the present invention.
[Mode for Invention]
The present invention provides a biodegradable resin composition for laminating on various food packaging papers comprising 10 to 85% by weight of polylactic acid, 10 to 75% by weight of a biodegradable polyester resin (aliphatic polyester resin) and 0.05 to 5% by weight of a plasticizer. Herein, a polylactic acid, a polyester resin, a plasticizer and a filler are further incorporated. The polylactic acid (PLA) is a biodegradable resin different from a general- purpose synthetic resin product, and is not harmful to the human body and does not change the physical strength of a paper. Further, the polylactic acid has a characteristic that can overcome a problem that previous PE or PP is not degraded thereby remaining wastes in the earth due to its biodegradability at natural state. The present invention uses any one selected from the group consisting of a homopolymer of D-lactic acid, a homopolymer of L-lactic acid or a copolymer of L-lactic acid and D-lactic acid as the polylactic acid.
In the present invention, a biodegradable polyester resin is further incorporated. The resin is obtained by performing polycondensation reaction after undergoing any one or more than two reaction selected from (1) polycondensation, (2) ester exchange reaction, or (3) esterificatiόn reaction. When the resin is incorporated into the composition, it prevents moisture from entering and helps exiting vapors. The composition according to the present invention is laminated on the surfaces of various food packaging papers or containers. For a noodle container on which the composition is laminated, the composition plays a role so that papers do not absorb moistures even when hot water is poured although materials are papers. Accordingly, even though the container is manufactured with a paper, it can contain water.
In the present invention, a plasticizer is further incorporated. The plasticizer generally refers to an organic material that facilitates forming process at high temperatures by enhancing thermoplastic property when added to a thermoplastic material. It is the characteristic of the plasticizer to enhance heat resistance, cold resistance, flame resistance and electrical property, etc. in addition to compatibility and plasticity. The plasticizer used most is DOP (dioctyl phthalate) , DOA (dioctyl adipate) and TCP (tricresyl phosphate) . However, the present invention optionally mixes and uses at least one or more selected from the group consisting of sorbitan monolaurate, sorbitan monopalmitate, sorbitan trioleate, sorbitan monostearate, polyethylene glycol, polyalkylene oxide, glycerol, glycerol acetate, propylene glycol and sorbitol as a plasticizer. These materials are also used as food additives, and are not harmful to the human body.
Finally, in the present invention, a separate filler can be incorporated to the mixture. The filler may optionally employ at least one selected from the group consisting of talc, calcium carbonate, Limestone, Tiθ2 and carbon black, and is added in order to increase blocking phenomenon when processed and cooling speed. The average particle diameter of the filler is controlled in the range of 0.01 to 10 βm, and the filler can be used in an amount of 0.01 to 50% by weight when the above resin composition is referred to 100% by weight.
The resin composition prepared as above is applied on a food packaging paper or the surface of a packaging container, and hardened thereby forming a coated layer.
Meanwhile, the composition according to the present invention can further comprise the following additives. That is, the composition may further comprise 1 to 20% by weight of an additive in which at least one or more of a stabilizer, a slipping agent, a dispersant, a coupling agent, an anti-oxidizing agent and a UV stabilizer are optionally mixed, relative to 100% by weight of the composition. The stabilizer may optionally employ at least one selected from the group consisting of trimethyl phosphate, phosphoric acid and triphenyl phosphate in an amount of 0.01 to 10% by weight, relative to 100% by weight of the resin composition.
Further, Irganox series, Ultranox series and TEP series can be used as the anti-oxidizing agent in an amount of 0.01 to 10% by weight, relative to 100% by weight of the resin composition, and HALS (hindered amine light stabilizer) series can be used as the UV stabilizer in an amount of 0.01 to 10% by weight, relative to 100% by weight of the resin composition; calcium stearate, zinc stearate, PE wax and general wax can be used as the slipping agent in an amount of 0.01 to 10% by weight, relative to 100% by weight of the resin composition.
In addition, carboxylated polyethylene, phthalic acid and stearic acid, etc. can be used as the dispersant that is an additive to be added for compatibility between the used resins. The dispersant can be used in an amount of 0.01 to 10% by weight, relative to 100% by weight of the resin composition. As described above, the additives used in the present invention can be optionally added depending on the need of a product such as dispersibility or thermal stability.
In the present invention, an extruder (T-die) used in coating a biodegradable resin may be preferably downward type including T-shaped Die. There was a problem that much load of resin pressure are generated, and the extruded amount becomes less thereby decreasing product efficiency in the T-Die used in coating a previous synthetic resin. In order to improve such problem, the present invention enlarged the diameter of the previous orifice tube to 5 to 10 mm to lessen the load of resin pressure, and improved the discharged amount to improve the same extruded amount of resin and productivity as the previous synthetic resin. Further, the temperature distribution of the screw and T-Die was set at 150 to 350°C considering the pyrolysis temperature of a biodegradable PLA and aliphatic polyester, and the problem of the previous paper coating of a biodegradable resin was overcome to improve the adhesive force with a paper substrate, coating speed and uniform coating thickness.
Various food-packaging papers are manufactured employing the resin composition prepared as described above. This is achieved by coating the resin composition in liquid state on the surfaces of various papers and simultaneously hardening.
The food packaging paper according to the present invention includes a coating layer 10 constituting upper layer by a composition for laminating, and papers 20 having a thickness of 0.01 to 2 mm. Accordingly, the coating layer is applied on the surface of the papers thereby preventing moistures from entering and enhancing the exiting of moistures. This is a simple constitution that a resin composition is coated on various kinds of papers. Herein, the thickness is preferably limited to 0.01 to 2 mm since the durability of the coating layer becomes weak in proportion to the thickness of papers if it is too thin or too thick. Preparation example
The amount of all components including additives (a slipping agent, an anti-oxidizing agent and a filler) is based on 100% by weight of the resin composition in the preparation example below.
1) 1.5% by weight of calcium stearate as a slipping agent and 1.5% by weight of n-octadecyl-Jβ - (4 ' -hydroxys' , 5 ' -di-tert-butylphenyl) propionate (trade name Irganox 1076) as an anti-oxidizing agent were added to 97% by weight of polylactic acid [PLA, NatureWorks LLC, USA, Grade : 2002D, Melt Index 5~7], and the mixture was subjected to a twin screw extruder to prepare a composition in pellet.
2) 20% by weight of polybutylene adipate/terephthalate (BASF Corporation, trade name Ecoflex, grade : F BX 7011) as a biodegradable polyester resin, 0.5% by weight of polyethylene glycol as a plasticizer, 1.5% by weight of calcium stearate as a slipping agent, 1.5% by weight of n- octadecyl- β - ( 4 ' -hydroxy-3 ' , 5 ' -di-tert-butylphenyl ) propionate (trade name Irganox 1076) as an anti-oxidizing agent were added to 76.5% by weight of polylactic acid [PLA, NatureWorks LLC, USA, Grade : 2002D, Melt Index 5-7], and the mixture was subjected to a twin screw extruder to prepare a composition in pellet. 3) 10% by weight of polybutylene succinate • co • adipate [trade name Enpol, Melt Index below 4, 2160g/10min] and 10% by weight of polybutylene adipate/terephthalate (BASF Corporation, Ecoflex, grade : F BX 7011) as biodegradable polyester resins, 0.3% by weight of polyethylene glycol as a plasticizer, 1.5% by weight of calcium stearate as a slipping agent and 1.5% by weight of n-octadecyl-β - (4 ' - hydroxy-3 ' , 51 -di-tert-butylphenyl) propionate (trade name Irganox 1076) as an anti-oxidizing agent were added to 76.7% by weight of polylactic acid [PLA, NatureWorks LLC, USA, Grade : 2002D, Melt Index 5-7], and the mixture was subjected to a twin screw extruder to prepare a composition in pellet.
4) 30% by weight of polybutylene succinate • co • adipate [trade name Enpol, Melt Index below 4, 2160g/10min] as a biodegradable polyester resin, 10% by weight of calcium carbonate (particle size 2.5 (M) as a filler, 0.2% by weight of polyethylene glycol as a plasticizer, 1.5% by weight of calcium stearate as a slipping agent and 0.5% by weight of n-octadecyl-β - ( 4 ' -hydroxy-3 ' , 5 ' -di-tert-butylphenyl ) propionate (trade name Irganox 1076) as an anti-oxidizing agent were added to 57.8% by weight of polylactic acid [PLA, NatureWorks LLC, USA, Grade : 2002D, Melt Index 5-7], and the mixture was subjected to a twin screw extruder to prepare a composition in pellet.
5) 40% by weight of polybutylene succinate • co • adipate [trade name Enpol, Melt Index below 4, 2160g/10min] and 10% by weight of polybutylene adipate/terephthalate (BASF Corporation, Ecoflex, grade : F BX 7011) as biodegradable polyester resins, 0.1% by weight of polyethylene glycol as a plasticizer, 1.5% by weight of calcium stearate as a slipping agent and 1.5% by weight of n-octadecyl-β - (4 ' - hydroxy-3 ' , 5' -di-tert-butylphenyl) propionate (trade name Irganox 1076) as an anti-oxidizing agent were added to 46.9% by weight of polylactic acid [PLA, NatureWorks LLC, USA, Grade : 2002D, Melt Index 5~7], and the mixture was subjected to a twin screw extruder to prepare a composition in pellet.
6) 1.5% by weight of n-octadecyl-β - (4 ' -hydroxy-3 ', 5 '- di-tert-butylphenyl) propionate (trade name Irganox 1076) as an anti-oxidizing agent were added to 67% by weight of polybutylene succinate • co • adipate [trade name Enpol, Melt Index below 4, 2160g/10min] and 20% by weight of polybutylene adipate/terephthalate (BASF Corporation, Ecoflex, grade : F BX 7011) as biodegradable polyester resins, 10% by weight of calcium carbonate (particle size 2.5 IM) as a filler and 1.5% by weight of calcium stearate as a slipping agent, and the mixture was subjected to a twin screw extruder to prepare a composition in pellet.
7) 1.5% by weight of n-octadecyl-β - (4 ' -hydroxy-3 ' , 5 ' - di-tert-butylphenyl) propionate (trade name Irganox 1076) as an anti-oxidizing agent were added to 97% by weight of polybutylene succinate • co • adipate [trade name Enpol, Melt Index below 4, 2160g/10min] as a biodegradable polyester resin, and 1.5% by weight of calcium stearate as a slipping agent, and the mixture was subjected to a twin screw extruder to prepare a composition in pellet. Example
The pellets prepared according to the above preparation example were heated, melted and mixed, and then melt-extruded using T-shaped Die and simultaneously laminated on papers. The resulting papers were evaluated for formability based on the following standard, and the results are shown in Table 1 below (Table 1 indicates main components only) .
(Evaluation for formability) O : papers and coating are good, and the coated face is in excellent state since there was no thick or thin coated face
Δ : papers and coating are good, and the coated face is in good state X : papers and coating are bad, and the coated face is in bad state Table 1
Figure imgf000020_0001
* Evaluation for coating characteristic and formability characteristic according to the mixing ratio of polylactic acid and a biodegradable polyester resin.
* When polylactic acid is used alone (Example 1), adhesion to a paper was difficult due to high cooling speed after extrusion, however, the property of matter satisfactory for post-processing was obtained by lowering cooling speed and the hardness of a film after extrusion through adding a biodegradable polyester resin.
* If the amount of polylactic acid is too low (Examples 6 and 7), the formability was lowered due to excessively low cooling speed, while if the amount of polylactic acid is too high (Examples 2 and 3) , the adhesive force was weakened.
* The used plasticizer played a role in lowering thickness on extrusion by enhancing compatibility of polylactic acid and polyester resin, and was used properly in an amount of 0.05 to 5.0% by weight.
[industrial Applicability]
A biodegradable resin composition for laminate coating according to the present invention, and a food packaging paper employing the same can be widely applied in the industry since they do not exit an environmental hormone harmful to the human body and is biodegradable in a natural environment .
Although the present invention has been described with reference to several embodiments of the invention, the description is illustrative of the invention and is not to be construed as limiting the invention. Various modifications and variations may occur to those skilled in the art, without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

[CLAIMS] [Claim l]
A biodegradable resin composition for laminate coating of papers, the composition comprising 10 to 85% by weight of polylactic acid, 10 to 75% by weight of a biodegradable polyester resin (aliphatic polyester resin) and 0.05 to 5% by weight of a plasticizer.
[Claim 2]
The biodegradable resin composition of claim 1, wherein the composition further comprises 0.01 to 50% by weight of an additive in which at least one or more of a stabilizer, a slipping agent, a dispersant, a coupling agent, an anti-oxidizing agent, a UV stabilizer and a filler are mixed, relative to 100% by weight of the composition of claim 1.
[Claim 3]
The biodegradable resin composition of claim 1, wherein the polylactic acid is any one selected from the group consisting of a homopolymer of D-lactic acid, a homopolymer of L-lactic acid, or a copolymer of L-lactic acid and D-lactic acid. [Claim 4]
The biodegradable resin composition of claim 1, wherein the plasticizer is at least one selected from the group consisting of sorbitan monolaurate, sorbitan monopalmitate, sorbitan trioleate, sorbitan monostearate, polyethylene glycol, polyalkylene oxide, glycerol, glycerol acetate, propylene glycol and sorbitol. [Claim 5]
The biodegradable resin composition of claim 2, wherein the filler is at least one selected from the group consisting of talc, calcium carbonate, Limestone, TiC>2 and carbon black. [Claim 6]
The biodegradable resin composition of claim 2, wherein the stabilizer is at least one selected from the group consisting of trimethyl phosphate, phosphoric acid and triphenyl phosphate. [Claim 7]
The biodegradable resin composition of claim 2, wherein the anti-oxidizing agent is at least one selected from the group consisting of Irganox series, Ultranox series and TEP series. [Claim 8]
The biodegradable resin composition of claim 2, wherein the slipping agent is at least one selected from the group consisting of calcium stearate, zinc stearate, PE wax and general wax. [Claim 9]
A food packaging paper on which a biodegradable resin composition for laminate coating of papers is applied, wherein a coating layer 10 comprised of the composition according to any one of claims 1 to 8 is formed on the surfaces of papers 20 having a thickness of 0.01 to 2 mm thereby preventing moistures from entering and enhancing the exiting of moistures.
PCT/KR2008/002981 2007-11-14 2008-05-28 The composition for laminate coating of paper, and the food packaging paper using it WO2009064052A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020070115879A KR100875104B1 (en) 2007-11-14 2007-11-14 The composition of pla resin and the packing paper using it
KR10-2007-0115879 2007-11-14

Publications (1)

Publication Number Publication Date
WO2009064052A1 true WO2009064052A1 (en) 2009-05-22

Family

ID=40372924

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2008/002981 WO2009064052A1 (en) 2007-11-14 2008-05-28 The composition for laminate coating of paper, and the food packaging paper using it

Country Status (2)

Country Link
KR (1) KR100875104B1 (en)
WO (1) WO2009064052A1 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011110750A1 (en) * 2010-03-12 2011-09-15 Stora Enso Oyj Heat-sealable biodegradable packaging material, a method for its manufacture, and a product package made from the material
WO2013007872A1 (en) 2011-07-12 2013-01-17 Stora Enso Oyj A heat-sealable biodegradable packaging material, a package or a container made thereof, and use of a resin in extrusion coating
US8389107B2 (en) 2008-03-24 2013-03-05 Biovation, Llc Cellulosic biolaminate composite assembly and related methods
US8652617B2 (en) 2008-03-24 2014-02-18 Biovation, Llc Biolaminate composite assembly including polylactic acid and natural wax laminate layer, and related methods
CN103965596A (en) * 2014-04-23 2014-08-06 清华大学深圳研究生院 Biodegradable polylactic acid based composite and application thereof
US20150274367A1 (en) * 2012-10-26 2015-10-01 Stora Enso Oyj Method for manufacturing biodegradable packaging material, biodegradable packaging material and a package or a container made thereof
CN105419266A (en) * 2015-12-17 2016-03-23 宁夏共享能源有限公司 3D (three dimensional) printing material and preparation method thereof
WO2017091392A1 (en) * 2015-11-25 2017-06-01 Westrock Mwv, Llc Biopolymer coating for compostable paperboard packaging
US10214316B2 (en) 2012-10-26 2019-02-26 Stora Enso Oyj Method for manufacturing biodegradable packaging material, biodegradable packaging material and packages and containers made thereof
CN109844221A (en) * 2016-08-09 2019-06-04 维实洛克Mwv有限责任公司 The cardboard of oil resistant, grease resistance and moisture-proof
CN110240791A (en) * 2019-06-11 2019-09-17 安徽三绿实业有限公司 A kind of advertisement character 3D printing material and preparation method thereof
WO2021021319A1 (en) * 2019-07-30 2021-02-04 Westrock Mwv, Llc Compostable paperboard structure and method for manufacturing the same
WO2022114262A1 (en) * 2020-11-25 2022-06-02 고의석 Paper-based, bio-based plastic laminating packaging material

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101086537B1 (en) 2009-09-03 2011-11-23 주식회사 성은바이오 Method for laminating PLA film on PLA non-woven fabric and PLA non-woven fabric manufactured by using method thereof
KR20190097934A (en) 2018-02-13 2019-08-21 주식회사 그린동화 Absorbent sheet for food and apparatus for manufacturing the same
KR102115881B1 (en) 2018-10-25 2020-05-27 (주)세림비앤지 Biodegradable paper cup coated with multilayered biodegradable laminating for coffee and beverage
KR102041870B1 (en) 2019-06-11 2019-11-06 남경보 An biodegradable resin composition wit excellent paper moldability and addhesive properties
KR102347527B1 (en) * 2020-03-31 2022-01-06 주식회사 신세계푸드 Eco-friendly sheet, ice pack using the same and manufacturing method for the ice pack

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5753724A (en) * 1993-10-15 1998-05-19 H. B. Fuller Licensing & Financing, Inc. Biodegradable/compostable hot melt adhesives comprising polyester of lactic acid
KR20010066970A (en) * 2000-07-29 2001-07-12 정효식 Resin compositions having biodegradation and hydrolysis properties
KR20030042945A (en) * 2001-11-26 2003-06-02 심재호 Biodegradable resin composition, method for preparing the same and biodegradable resin film produced therefrom
KR20060003580A (en) * 2004-07-07 2006-01-11 도레이새한 주식회사 Biodegradable polyester resin composition containing nano particles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5753724A (en) * 1993-10-15 1998-05-19 H. B. Fuller Licensing & Financing, Inc. Biodegradable/compostable hot melt adhesives comprising polyester of lactic acid
KR20010066970A (en) * 2000-07-29 2001-07-12 정효식 Resin compositions having biodegradation and hydrolysis properties
KR20030042945A (en) * 2001-11-26 2003-06-02 심재호 Biodegradable resin composition, method for preparing the same and biodegradable resin film produced therefrom
KR20060003580A (en) * 2004-07-07 2006-01-11 도레이새한 주식회사 Biodegradable polyester resin composition containing nano particles

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8389107B2 (en) 2008-03-24 2013-03-05 Biovation, Llc Cellulosic biolaminate composite assembly and related methods
US8652617B2 (en) 2008-03-24 2014-02-18 Biovation, Llc Biolaminate composite assembly including polylactic acid and natural wax laminate layer, and related methods
CN102858649B (en) * 2010-03-12 2015-02-11 斯塔诺阿埃索澳吉有限公司 Heat-sealable biodegradable packaging material, a method for its manufacture, and a product package made from the material
CN102858649A (en) * 2010-03-12 2013-01-02 斯塔诺阿埃索澳吉有限公司 Heat-sealable biodegradable packaging material, a method for its manufacture, and a product package made from the material
AU2011225959B2 (en) * 2010-03-12 2015-12-03 Stora Enso Oyj Heat-sealable biodegradable packaging material, a method for its manufacture, and a product package made from the material
US9181010B2 (en) 2010-03-12 2015-11-10 Stora Enso Oyj Heat-sealable biodegradable packaging material, a method for its manufacture, and a product package made from the material
WO2011110750A1 (en) * 2010-03-12 2011-09-15 Stora Enso Oyj Heat-sealable biodegradable packaging material, a method for its manufacture, and a product package made from the material
US20140147604A1 (en) * 2011-07-12 2014-05-29 Stora Enso Oyj Heat-sealable biodegradable packaging material, a package or a container made thereof, and use of a resin in extrusion coating
EP3708514A1 (en) * 2011-07-12 2020-09-16 Stora Enso Oyj A heat-sealable biodegradable packaging material, a package or a container made thereof, and use of a resin in extrusion coating
EP2731887A4 (en) * 2011-07-12 2015-05-27 Stora Enso Oyj A heat-sealable biodegradable packaging material, a package or a container made thereof, and use of a resin in extrusion coating
US10081168B2 (en) 2011-07-12 2018-09-25 Stora Enso Oyj Heat-sealable biodegradable packaging material, a package or a container made thereof, and use of a resin in extrusion coating
CN103702908A (en) * 2011-07-12 2014-04-02 斯塔诺阿埃索澳吉有限公司 A heat-sealable biodegradable packaging material, a package or a container made thereof, and use of a resin in extrusion coating
WO2013007872A1 (en) 2011-07-12 2013-01-17 Stora Enso Oyj A heat-sealable biodegradable packaging material, a package or a container made thereof, and use of a resin in extrusion coating
AU2012282429B2 (en) * 2011-07-12 2016-12-15 Stora Enso Oyj A heat-sealable biodegradable packaging material, a package or a container made thereof, and use of a resin in extrusion coating
AU2013336508B2 (en) * 2012-10-26 2016-11-03 Stora Enso Oyj A method for manufacturing biodegradable packaging material, biodegradable packaging material and a package or a container made thereof
US20150274367A1 (en) * 2012-10-26 2015-10-01 Stora Enso Oyj Method for manufacturing biodegradable packaging material, biodegradable packaging material and a package or a container made thereof
US10167594B2 (en) 2012-10-26 2019-01-01 Stora Enso Oyj Method for manufacturing biodegradable packaging material, biodegradable packaging material and a package or a container made thereof
US10214316B2 (en) 2012-10-26 2019-02-26 Stora Enso Oyj Method for manufacturing biodegradable packaging material, biodegradable packaging material and packages and containers made thereof
EP2911878A4 (en) * 2012-10-26 2016-06-29 Stora Enso Oyj A method for manufacturing biodegradable packaging material, biodegradable packaging material and a package or a container made thereof
US11434605B2 (en) 2012-10-26 2022-09-06 Stora Enso Oyj Method for manufacturing biodegradable packaging material, biodegradable packaging material and a package or a container made thereof
CN103965596B (en) * 2014-04-23 2016-03-30 清华大学深圳研究生院 A kind of biodegradable polylactic acid based composites and application
CN103965596A (en) * 2014-04-23 2014-08-06 清华大学深圳研究生院 Biodegradable polylactic acid based composite and application thereof
CN108350666B (en) * 2015-11-25 2021-10-08 维实洛克Mwv有限责任公司 Biopolymer coating for compostable paperboard packaging
WO2017091392A1 (en) * 2015-11-25 2017-06-01 Westrock Mwv, Llc Biopolymer coating for compostable paperboard packaging
CN108350666A (en) * 2015-11-25 2018-07-31 维实洛克Mwv有限责任公司 Biopolymer coatings for compost carton package
US10655277B2 (en) 2015-11-25 2020-05-19 Westrock Mwv, Llc Biopolymer coating for compostable paperboard packaging
CN105419266A (en) * 2015-12-17 2016-03-23 宁夏共享能源有限公司 3D (three dimensional) printing material and preparation method thereof
CN109844221A (en) * 2016-08-09 2019-06-04 维实洛克Mwv有限责任公司 The cardboard of oil resistant, grease resistance and moisture-proof
CN110240791B (en) * 2019-06-11 2021-04-23 安徽三绿实业有限公司 Advertisement word 3D printing material and preparation method thereof
CN110240791A (en) * 2019-06-11 2019-09-17 安徽三绿实业有限公司 A kind of advertisement character 3D printing material and preparation method thereof
WO2021021319A1 (en) * 2019-07-30 2021-02-04 Westrock Mwv, Llc Compostable paperboard structure and method for manufacturing the same
US20220275585A1 (en) * 2019-07-30 2022-09-01 Westrock Mwv, Llc Compostable paperboard structure and method for manufacturing the same
WO2022114262A1 (en) * 2020-11-25 2022-06-02 고의석 Paper-based, bio-based plastic laminating packaging material

Also Published As

Publication number Publication date
KR100875104B1 (en) 2008-12-19

Similar Documents

Publication Publication Date Title
WO2009064052A1 (en) The composition for laminate coating of paper, and the food packaging paper using it
US5405887A (en) Porous film
US8604123B1 (en) Biodegradable polymer composition with calcium carbonate and methods and products using same
JP4824579B2 (en) High transparency film with improved thermal properties
EP3079907B1 (en) Polymer composition for barrier film
CN113631657B (en) Polyhydroxyalkanoate-based resin composition, molded article thereof, and film or sheet
CA2230944A1 (en) Compostable multilayer structures and articles prepared therefrom
KR20150082355A (en) A method for manufacturing biodegradable packaging material, biodegradable packaging material, and packages and containers made thereof
KR20090054434A (en) Mastermatch and polymer composition
KR102194850B1 (en) A biodegradable resin composition Polylactic acid, Polybutyleneadipate-co-terephthalate and Polyethylene oxide
TW200427775A (en) Poly(glycolic acid)-based resin composition and formed article therefrom
KR20180032896A (en) Biodegradable resin composition and biodegradable articles prepared therefrom
KR101288445B1 (en) Biodegradable resin composition havign excellent thermostability and vessels comprising the same
EP1348541A1 (en) Multi-layered polyester film
KR101423371B1 (en) Resin composition for flooring material with excellent dimension stability
JP6102315B2 (en) Polyester resin composition and film formed by molding the polyester resin composition
JP3797868B2 (en) Biodegradable thermoforming sheet and container
JP2008031472A (en) Tubular molded product made of biodegradable resin
De Carvalho et al. Preparation and characterization of extruded PBAT/organoclay films
JP2009096096A (en) Laminated film
KR20190004748A (en) 3D printed PLA article
CN102282018A (en) Multilayer film
JP5620190B2 (en) Biodegradable resin laminate
US20190085214A1 (en) Flexible, thermally stable and simultaneously transparent bio-based film based on poly(lactic acid), formulation for producing the film and use of said film
KR102587591B1 (en) Biodegradable composition and application products using the composition

Legal Events

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

Ref document number: 08765951

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08765951

Country of ref document: EP

Kind code of ref document: A1