WO2012074230A2 - Procédé de préparation d'un bois artificiel à l'aide d'un matériau fibroïde végétal naturel - Google Patents

Procédé de préparation d'un bois artificiel à l'aide d'un matériau fibroïde végétal naturel Download PDF

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Publication number
WO2012074230A2
WO2012074230A2 PCT/KR2011/008823 KR2011008823W WO2012074230A2 WO 2012074230 A2 WO2012074230 A2 WO 2012074230A2 KR 2011008823 W KR2011008823 W KR 2011008823W WO 2012074230 A2 WO2012074230 A2 WO 2012074230A2
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WIPO (PCT)
Prior art keywords
natural vegetable
artificial wood
vegetable fiber
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synthetic resin
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PCT/KR2011/008823
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English (en)
Korean (ko)
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WO2012074230A3 (fr
Inventor
김완식
김용태
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Kim Wan Sik
Kim Yong Tae
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Publication of WO2012074230A2 publication Critical patent/WO2012074230A2/fr
Publication of WO2012074230A3 publication Critical patent/WO2012074230A3/fr

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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
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/007—Manufacture of substantially flat articles, e.g. boards, from particles or fibres and at least partly composed of recycled material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate

Definitions

  • the present invention relates to a method for manufacturing artificial wood using natural vegetable fiber, and more particularly, by reducing the amount of synthetic resin, the gas generation rate is reduced in the event of a fire, and natural vegetable fiber contains a large amount of natural wood, but light weight natural wood It relates to a method for manufacturing artificial wood using natural vegetable fiber having the same texture.
  • natural wood is economical, has a relatively small specific gravity, and is easy to process, and is used for various purposes throughout the industry.
  • natural wood has the disadvantages of poor moisture resistance, pollution resistance and corrosion resistance.
  • artificial wood mixed with sawdust or wood chips and synthetic resin In order to solve this problem, it was intended to manufacture artificial wood mixed with sawdust or wood chips and synthetic resin.
  • artificial wood containing the sawdust or wood chips should include more than 60% by weight of synthetic resin to maintain the same properties as natural wood.
  • synthetic wood containing more than 60% by weight of synthetic resin is heavy weight, high resin content, and also disadvantageous price competitiveness, there is a risk that can release a large amount of harmful gas in the event of fire.
  • the present invention for solving the above problems is to provide a method for manufacturing artificial wood using natural vegetable fiber that can maintain the strength (physical properties) similar to natural wood even significantly reducing the content of synthetic resin.
  • the present invention provides a preferred embodiment, selected from polypropylene (MAPP), titanate and zirconate based on maleate treated synthetic resin mixed with polypropylene or high density polyethylene, ethylene vinyl acetate or linear low density polyethylene.
  • the drying step is the first drying step of drying so that the moisture content of the natural vegetable fiber powder at 80 ⁇ 100 °C less than 5% by weight; It provides a method for producing artificial wood using natural vegetable fiber comprising; and a second drying step of drying so that the water content of the natural vegetable fiber powder is less than 1% by weight at 100 ⁇ 130 °C.
  • the synthetic resin in the binder coating step comprises 13 to 29 parts by weight of polypropylene or high density polyethylene and 3 to 11 parts by weight of ethylene vinyl acetate or linear low density polyethylene based on a total of 100 parts by weight of artificial wood It provides a method for producing artificial wood using natural vegetable fiber.
  • the polypropylene in the binder coating step provides a method of manufacturing artificial wood using natural vegetable fibers of homopoly or impact polypropylene having a melt index of 7 to 15.
  • the high-density polyethylene in the binder coating step provides an artificial wood manufacturing method using natural vegetable fibers having a melt index of 2 ⁇ 10.
  • the linear low-density polyethylene in the binder coating step provides an artificial wood manufacturing method using natural vegetable fibers having a melt index of 1-4.
  • the binder coating step is to mix 16 to 40 parts by weight of synthetic resin, 0.8 to 3 parts by weight of binder and 0.2 to 0.5 parts by weight of silicone oil based on 100 parts by weight of artificial wood
  • a method for preparing artificial wood using vegetable fiber is to mix 16 to 40 parts by weight of synthetic resin, 0.8 to 3 parts by weight of binder and 0.2 to 0.5 parts by weight of silicone oil based on 100 parts by weight of artificial wood.
  • the method of manufacturing artificial wood in the first kneading step, 16 to 40 parts by weight of the synthetic resin coated with a binder and 50 to 75 parts by weight of the natural vegetable fiber powder dried in the drying step are added to 100 parts by weight of the artificial wood. It provides a method for producing artificial wood using natural vegetable fiber.
  • the first kneading step provides a method for manufacturing artificial wood using natural vegetable fiber that is kneaded at 80 ⁇ 110 °C for 7 to 15 minutes.
  • the content of the additive added in the second kneading step provides an artificial wood manufacturing method using natural vegetable fiber which is 2 to 6 parts by weight based on 100 parts by weight of the total artificial wood.
  • the additive added in the second kneading step is 0.2 to 1 parts by weight of lubricant, 0.1 to 0.3 parts by weight of antioxidant, 0.2 to 0.6 parts by weight of UV based on 100 parts by weight of artificial wood It may include a stabilizer, 0.3 to 0.7 parts by weight of nucleating agent, 1 to 3 parts by weight of filler, 0.2 to 0.4 parts by weight of inorganic pigment.
  • the second kneading step provides a method of manufacturing artificial wood using natural vegetable fiber, which is kneaded at 110 to 140 ° C. for 10 to 20 minutes.
  • the molding step provides an artificial wood manufacturing method using natural vegetable fibers that are molded by an extrusion molding machine heated to 180 ⁇ 230 °C.
  • the artificial wood manufacturing method between the second kneading step and the molding step using a pellet molding machine with a vacuum device heated to 170 ⁇ 200 °C gelled raw material through the second kneading step It provides a method for producing artificial wood using natural vegetable fiber, characterized in that it further comprises a; pelletizing step of producing a pellet of 2 ⁇ 3mm size.
  • FIG. 1 is a flow chart showing a method for manufacturing artificial wood using natural vegetable fiber according to an embodiment of the present invention.
  • a mixture of polypropylene (MAPP), titanate-based and zirconate-based silicone oil and silicone oil is mixed with a synthetic resin mixed with polypropylene or high-density polyethylene, ethylene vinyl acetate or linear low density polyethylene.
  • a binder coating step of coating the synthetic resin is
  • a second kneading step of kneading by adding one or more additives selected from the group consisting of a lubricant, an antioxidant, a UV stabilizer, a nucleating agent, a filler, and a pigment to the natural vegetable fiber powder which has undergone the first kneading step;
  • the step of adding an expanding agent and molding into an artificial wood product using an extrusion machine characterized in that it comprises a.
  • silicone oil is mixed with a binder selected from polypropylene (MAPP), titanate-based and zirconate-based maleates, in a synthetic resin containing polypropylene or high-density polyethylene, ethylene vinyl acetate or linear low density polyethylene.
  • a binder coating step of coating the synthetic resin the silicone oil not only makes the binder evenly coated on the synthetic resin, but also facilitates the kneading by improving the flow of the resin in the pelletization step or the molding step, thereby improving moldability and physical properties.
  • the content of the synthetic resin is less than the amount of natural vegetable fibrous powder in the above, when using the ethylene vinyl acetate or linear low-density polyethylene when processing in the pelletizing step or molding step to improve the flow of the mixture and facilitate uniform dispersion It is desirable to reduce the defective rate as well as to increase the physical properties (impact strength).
  • the synthetic resin is preferably 13 to 29 parts by weight of polypropylene or high density polyethylene and 3 to 11 parts by weight of ethylene vinyl acetate or linear low density polyethylene based on 100 parts by weight of artificial wood. More specifically, the synthetic resin is preferably a mixture of 20 to 70 parts by weight of ethylene vinyl acetate or linear low density polyethylene with respect to 100 parts by weight of polypropylene or high density polyethylene. In this case, it is preferable to use homo or impact polypropylene having a melt index of 7 to 15, and high density polyethylene preferably has a melt index of 2 to 10.
  • the ethylene vinyl acetate preferably has an acetic acid content of 3 to 21% (w / w), and the linear low density polyethylene preferably has a melt index of 1 to 4.
  • the synthetic resin is coated by mixing with a silicone oil and a binder selected from maleated polypropylene, titanate-based or zirconate-based. At this time, it is preferable to mix 16 to 40 parts by weight of synthetic resin, 0.8 to 3 parts by weight of binder and 0.2 to 0.5 parts by weight of silicone oil based on 100 parts by weight of artificial wood.
  • the binder is used to increase the binding force between the synthetic resin and the natural vegetable fiber powder.
  • the natural vegetable fibrous powder has a hydrophilic polarity and the synthetic resin has a hydrophobic nonpolarity, so the binding strength of the two materials is weak.
  • the interaction of these natural vegetable fiber powders with the synthetic resin is greatly improved by the addition of a binder, resulting in a new chemical bond at the interface between the two materials.
  • the binder of the present invention can be evenly dispersed in a large amount of natural vegetable fiber powder and a medium amount of synthetic resin even in a very small amount, and first mixed with a synthetic resin and then mixed with a large amount of natural vegetable fiber powder to increase dispersibility to the maximum. Can be.
  • the binder may also increase the bending strength, modulus of elasticity, and the like as well as improve the bonding strength between the natural vegetable fiber powder and the synthetic resin, and may improve dimensional stability, impact strength, and the like.
  • the size of the natural plant fiber powder is preferably 80 ⁇ 150mesh.
  • the use of sawdust has the advantage that can be used to obtain an artificial wood with excellent physical properties because it can utilize a uniform amount of fiber with the same ingredients, unlike the fiber content is not constant depending on the species.
  • natural vegetable fiber powder has an advantage that can be more light weight because the specific gravity is about 0.85 but the wood powder is 1.37. At this time, the ratio of the diameter to the particle length of the natural vegetable fiber powder is preferably 3: 1 to 5: 1.
  • the prepared natural vegetable fiber powder is dried.
  • the fiber powder is preferably dried so that the moisture content is less than 1% by weight. If the moisture content of the natural vegetable fiber powder is high, there is a possibility that the problem of not evenly kneading with the synthetic resin to be described later. More specifically, since a large amount of natural vegetable fiber powder is mixed compared to synthetic resins, the volume of the natural vegetable fiber powder is large. However, when the water content of the powder is high, the volume of the powder becomes larger, which may prevent uniform mixing.
  • the moisture content when the moisture content is high, it may be difficult to continuously proceed the process due to the static electricity generated in the natural vegetable fiber powder in the first kneading step, the second kneading step or the pelletizing step. In this case, not only the physical properties of the manufactured synthetic wood are lowered, but also a problem that the defective rate is increased in the pelletizing step or the molding step occurs. More specifically, when the water content of the natural vegetable fiber powder is high, carbonization may occur in the pelletizing or forming step, resulting in deterioration of physical properties or inability to flow in the mold, resulting in unmolding. Depression or smoothness may occur.
  • Specific examples of the method for drying the content of the prepared natural vegetable fiber powder to be less than 1% by weight include the first drying step of drying the natural vegetable fiber powder to a water content of less than 5% by weight at a temperature of 80 ⁇ 100 °C and There is a method of going through a secondary drying step of drying so that the water content is less than 1% by weight at a temperature of 100 ⁇ 130 °C.
  • the first drying step is preferably performed on the tunnel-type closed conveyor belt of 80 ⁇ 100 °C
  • the second drying step is preferably carried out for 7 to 15 minutes in a blender of 100 ⁇ 130 °C. Do.
  • the reason for this two-step drying step is that the initial moisture content of the natural vegetable fiber powder is 12 to 15%.
  • Desirable drying equipment to be used in the secondary drying step is preferably a structure that can automatically control the heat from the outside as a blender having a heating function therein. This drying facility can be completely mixed with the impeller can uniformly dry the natural vegetable fiber powder on the outside and inside.
  • the binder is coated with the synthetic resin and the natural vegetable fiber powder dried in the drying step.
  • the binder-coated synthetic resin is 13 to 29 parts by weight of polypropylene or high density polyethylene, 3 to 11 parts by weight of ethylene vinyl acetate or linear low density ethylene, 0.8 to 2.5 parts by weight of maleated polypropylene based on 100 parts by weight of artificial wood It is preferable that a binder selected from titanate-based and zirconate-based and 0.2-0.5 parts by weight of silicone oil are mixed.
  • Synthetic resin coated with the binder is evenly mixed with the dried natural vegetable fiber powder while being flexible in a blender at 80-110 ° C., resulting in a gel with evenly distributed natural vegetable fiber powder.
  • the additive is preferably added in an amount of 2 to 6 parts by weight based on 100 parts by weight of artificial wood.
  • the blender at 110 ⁇ 140 °C It is preferable to make a gel-like synthetic raw material by kneading by pressing and heating for 10 to 20 minutes in the mixture.
  • the additive is an important factor for the performance and processability (mixing, extrusion) of the natural vegetable fiber powder.
  • Natural vegetable fibrous powder often causes problems such as warping, cracking, discoloration and coloring, and is used as a structural material, so the role of additives to increase mechanical strength is very important. It is also essential for smoothing the surface of the composite and increasing yield while reducing product defects in the extrusion process.
  • the additive increases stability, serves as a preservative, enables weight reduction, and improves mechanical properties.
  • the natural vegetable fiber powder subjected to the first kneading step includes 0.2 to 1 parts by weight of lubricant, 0.1 to 0.3 parts by weight of antioxidant, 0.2 to 0.6 parts by weight of UV stabilizer, based on 100 parts by weight of artificial wood, It is preferable to add an additive including 0.3 to 0.7 parts by weight of a nucleating agent, 1 to 3 parts by weight of a filler, and 0.2 to 0.4 parts by weight of an inorganic pigment.
  • the lubricant may be added to improve the surface properties of the product by increasing the dispersibility of the natural vegetable fiber powder during kneading and molding because the high viscosity of the synthetic resin at high temperatures.
  • the lubricant one selected from the group consisting of fatty acids, acid amides, fluoropolymers, and hydrocarbons may be used.
  • the antioxidant may be added to prevent the natural vegetable fiber powder from receiving oxygen from the air, phenolic antioxidants are mainly used.
  • UV stabilizers may be added to block ultraviolet rays, one selected from the group consisting of benzotrizole-based, benzophenone-based, triamine-based may be used.
  • the nucleating agent may be added to shorten the molding cycle by improving the crystallization temperature at the same time to improve the physical properties such as the stiffness, heat deformation temperature of the synthetic resin (PP or PE) to refine the crystals
  • One is selected from the group consisting of acid metal salts, sorbitol-based and phosphate ester metal salts.
  • the filler may be added to improve the long-term deformation due to impact strength, bending strength, heat deformation temperature and load, it may be selected from the group consisting of calcium carbonate, talc, mica.
  • inorganic pigments are added to impart color to the present invention, and are mainly colored and colored on synthetic resins.
  • the binder mixed with the synthetic resin in the binder mixing step is an additive for increasing the binding force between the synthetic resin and the natural vegetable fiber powder, without separating the kneading step.
  • the binder is combined with the synthetic resin or the natural vegetable fiber powder before the other various additives (additives in the second kneading step) are first combined with the synthetic resin or the natural vegetable fiber powder, the bonding strength is lowered and the physical properties are reduced and uniform. This is because the dispersion is not dispersed so that the extrusion amount change in the pelletizing step or the forming step is severe and may cause mass defects.
  • the reason for the pelletization step as described above is that the amount of natural vegetable fiber powder is higher than that of the compounded synthetic resin. This is because it is difficult to uniformly disperse the powders and additives, which may cause not only physical properties but also deterioration of product quality (surface state, depression, color, etc.).
  • the moisture content of the natural vegetable fiber powder is lowered to less than 1% during the drying step, so that when the kneaded raw material is brought back into the stock, a problem of having to go through the previous step again due to moisture impregnation may occur. have.
  • the synthetic resin is coated on the natural vegetable fiber powder after the pelletization step, even if brought to inventory can be minimized moisture impregnation.
  • the expansion agent in the gelled raw material or pelletized raw material After mixing the expansion agent in the gelled raw material or pelletized raw material through the second kneading step, and heat-melting at 180 ⁇ 230 °C and molding into an artificial wood product containing a natural vegetable fiber powder using an extruder. More specifically, in the forming step, the expansion agent 0.86phr (Parts perhundred parts of Rubber) ⁇ 2.04phr based on the gelled raw material or pelletized raw material is mixed, and the mixed raw material is extruded with a heated vacuum apparatus There is a method of putting into a molding machine.
  • Parts perhundred parts of Rubber Parts perhundred parts of Rubber
  • the heating conditions of the extruder is set to 180 ⁇ 230 °C and heated and melted, passed through a die to convert into a continuum having a cross-section of the desired shape (plate, mold release, etc.), cooled, solidified, wound or cut can be have.
  • the swelling agent is to reduce the weight of the artificial wood product is to use a thermally expandable microspheres based on the acrylonitrile copolymer and containing a low boiling hydrocarbon.
  • This is a mechanical expansion method, not a chemical foaming agent or a gas foaming method that expands only to synthetic resins, and is an expansion method that has little relationship with the content of synthetic resins and is less affected by external conditions such as temperature and humidity.
  • Synthetic wood of the present invention according to the manufacturing method can be extruded according to the site in the form of a plate or a release shape, despite the synthetic resin contained 16 to 40% by weight, such as the strength (physical properties) and touch like natural wood Have

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de préparation d'un bois artificiel à l'aide d'un matériau fibroïde végétal naturel. Elle concerne plus particulièrement un procédé de préparation d'un bois artificiel comprenant: l'étape d'enduction d'un liant consistant à mélanger une résine synthétique comprenant du polypropylène ou du polyéthylène haute densité et de l'éthylène-acétate de vinyle ou du polyéthylène linéaire basse densité avec un liant sélectionné parmi un polypropylène maléaté (MAPP), un liant à base de titanate et un liant à base de zircone et une huile de silicone; l'étape de séchage consistant à sécher une ou plusieurs poudres fibroïdes végétales naturelles choisies dans le groupe constitué par des déchets de papier, de la paille de riz, des tiges de maïs, des tiges de millet d'Afrique, du chanvre, de la parche de café, des feuilles de noix de coco, des résidus de canne à sucre et des résidus de thé vert; la première étape de mélange consistant à mélanger la résine synthétique enduite de liant et les poudres fibroïdes végétales naturelles séchées à l'étape de séchage; la seconde étape de mélange consistant à ajouter un ou plusieurs additifs choisis dans le groupe constitué d'un lubrifiant, d'un agent antioxydant, d'un agent anti-UV, d'un agent de nucléation, d'une charge et d'un pigment inorganique aux poudres fibroïdes végétales naturelles séchées obtenues à la première étape de mélange; et l'étape de moulage consistant à ajouter un agent gonflant puis à mouler le mélange à l'aide d'une machine de moulage par extrusion pour obtenir un bois artificiel. Ce procédé de préparation d'un bois artificiel à l'aide d'un matériau fibroïde végétal naturel de l'invention permet d'obtenir un bois artificiel léger pouvant conserver une solidité (propriété physique) similaire à celle d'un bois naturel grâce à une réduction remarquable de la teneur d'une résine synthétique lourde présentant un taux élevé de production de gaz toxiques en cas d'incendie.
PCT/KR2011/008823 2010-12-02 2011-11-18 Procédé de préparation d'un bois artificiel à l'aide d'un matériau fibroïde végétal naturel WO2012074230A2 (fr)

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KR10-2010-0121873 2010-12-02
KR1020100121873A KR101042696B1 (ko) 2010-12-02 2010-12-02 천연 식물성 섬유질을 이용한 인조목재 제조방법

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US9334083B2 (en) 2012-09-06 2016-05-10 Lg Hausys, Ltd. Cargo support using wood polymer/plastic composite material
KR102413193B1 (ko) * 2021-12-30 2022-06-27 (주)지케이우드 폐배지를 재활용한 합성목재 및 그 제조방법
KR102413191B1 (ko) * 2021-12-30 2022-06-27 (주)지케이우드 커피박을 재자원화한 합성목재 및 그 제조방법

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KR101371070B1 (ko) * 2011-12-12 2014-03-07 한양소재 주식회사 천연섬유를 이용한 합성목재 및 그의 제조방법
KR101439036B1 (ko) * 2013-06-20 2014-09-05 주식회사 행복한에코 녹차를 함유한 시트 필름 및 그 제조방법
CN104217797B (zh) * 2014-09-03 2017-01-25 江苏兴华胶带股份有限公司 膨胀型无卤阻燃pp/eva复合电线电缆及其制备方法
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KR101639371B1 (ko) * 2016-01-08 2016-07-13 주식회사 진성아스타 친환경 합성목재보드 및 그 제조방법
KR102413654B1 (ko) * 2020-11-17 2022-06-28 조현순 커피박이 포함된 친환경 합성 목재 및 그 제조 방법

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