KR100432627B1 - Compositions of Synthetic Wood and their Manufacturing Process - Google Patents
Compositions of Synthetic Wood and their Manufacturing Process Download PDFInfo
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- KR100432627B1 KR100432627B1 KR1020030057589A KR20030057589A KR100432627B1 KR 100432627 B1 KR100432627 B1 KR 100432627B1 KR 1020030057589 A KR1020030057589 A KR 1020030057589A KR 20030057589 A KR20030057589 A KR 20030057589A KR 100432627 B1 KR100432627 B1 KR 100432627B1
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- 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
- B27N3/002—Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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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
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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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
- 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
Abstract
Description
본 발명은 외관 및 기계적물성이 우수한 합성목재조성물 및 이의 제조방법에 관한 것이다. 더욱 구체적으로 본 발명은 마루판, 문틀, 창호재, 걸레받이, 문선몰딩 등 각종 프로파일과 같은 건축자재로서 목재의 질감에 의한 외관 및 휨강도, 치수안정성 등 기계적 물성이 우수한 폴리염화비닐과 리그노셀루로오즈계 분말이 주재로 된 합성목재조성물 및 이의 제조방법에 관한 것이다.The present invention relates to a synthetic wood composition excellent in appearance and mechanical properties and a method for producing the same. More specifically, the present invention is a polyvinyl chloride and lignocellulosic material having excellent mechanical properties such as appearance, bending strength, and dimensional stability as a building material such as various profiles such as floorboards, door frames, window materials, floorboards, and door moldings. The present invention relates to a synthetic wood composition based on ozone powder and a method of manufacturing the same.
최근 천연목재에 대한 소비자의 선호도가 크게 증가하고 있으며 또한 목재의 벌목에 따른 이산화탄소 증가에 대한 환경파괴 우려가 증폭되면서 목재의 대체 소재 개발 목소리가 높아지고 있다. 특히 목재의 수요가 많은 건축자재 경우 더욱 그러하다. 이러한 배경하에 최근 천연목재와 유사한 질감 및 외관을 가진 합성목재에 관한 연구가 많이 이루어지고 있는데, 대표적인 사례가 폴리염화비닐, 폴리프로필렌 등 열가소성 수지에 목분, 왕겨분, 펄프 분말, 볏짚 분말 등 소위 리그노셀루로오즈계 분말을 혼합한 조성물을 압출가공에 의해 적당한 형상 및 크기의 합성목재를 만들고 있다. 특히 폴리염화비닐과 리그노셀루로오즈계 분말에 의한 합성목재는 가공성이 우수하고 건자재로서 필수적인 난연성도 가지며 가격이 저렴한 장점이 있어 그 수요가 크게 확대되고 있다.Recently, consumers' preference for natural wood has increased greatly, and voices of developing alternative materials for wood have increased as concerns over environmental destruction about carbon dioxide increase due to wood felling have increased. This is especially true for building materials, where demand for wood is high. Under these circumstances, many studies on synthetic wood having a texture and appearance similar to those of natural wood have been made. Typical examples are so-called rigs such as wood flour, rice husk powder, pulp powder, rice straw powder, and the like on thermoplastic resins such as polyvinyl chloride and polypropylene. The composition which mixed the nocellulosic type powder is manufactured by the extrusion process, and the synthetic timber of suitable shape and size is produced. Particularly, the synthetic wood made of polyvinyl chloride and lignocellulosic powder has excellent processability, essential flame retardancy as a building material, and low cost, and thus its demand is greatly expanded.
리그노셀루로오즈계 분말은 통상 목재의 가공공정상 발생한 폐목분 소위 톱밥이 주종이며 그 값이 매우 싼데, 이러한 리그노셀루로오즈계 분말을 폴리염화비닐중에 잘 분산시켜 많이 함유시키는 것이 목재의 질감을 높일 뿐 아니라 원가측면에서도 유리하다. 그러나 리그노셀루로오즈계 분말은 그 함유량이 높아질수록 분산이 매우 어려운 문제가 있어 이를 해결하고자 많은 시도가 있어왔다.The lignocellulose-based powder is usually made of wood chips, so-called sawdust, which is generated during the processing of wood, and is very inexpensive. The lignocellulose-based powder is well dispersed in polyvinyl chloride and contains a lot of wood. In addition to increasing the texture, it is also advantageous in terms of cost. However, as the content of the lignocellulose-based powder is higher, dispersion is very difficult, and many attempts have been made to solve this problem.
가령 대한민국 등록특허공보 314456호에서는 메틸메타크릴레이트계 공중합체를 리그노셀루로오즈계 분말과 폴리염화비닐과의 혼합물에 첨가함으로써 리그노셀루로오즈계 분말의 균일분산성에 의한 외관의 개선을 도모하고자 하였으나 그 분산효과가 충분치 못해 우수한 기계적 강도 및 목질감 발현을 달성하지 못하였다. 또한 대한민국 등록특허공보 301394호에서는 리그노셀루로오즈계 분말을 실란계, 티타네이트계 지르코네이트 커프링제와 같은 물성증강제로 리그노셀루로오즈계 분말을 표면처리시킨후 폴리염화비닐과의 혼합 조성물에 의해 합성목재를 얻고자하였으나, 사용한 물성증강제가 너무나 고가인 관계로 경제성이 떨어짐은 물론 리그노셀루로오즈계 분말의 표면처리 반응에 기여하지 못한 물성증강제 잉여분이 저분자인 관계로 표면에 쉽게 브루밍되어 외관을 오히려 나쁘게 하는 등 여러 문제가 있어왔다.For example, Korean Patent Publication No. 314456 improves the appearance by uniform dispersibility of lignocellulosic powder by adding a methylmethacrylate copolymer to a mixture of lignocellulosic powder and polyvinyl chloride. However, the dispersion effect was not sufficient, and thus excellent mechanical strength and wood texture were not achieved. In addition, Korean Patent Publication No. 301394 discloses lignocellulosic powder mixed with polyvinyl chloride after surface treatment of lignocellulosic powder with a physical property enhancer such as silane and titanate zirconate cuffing agent. Although it was intended to obtain the synthetic wood by the composition, the economical property of the used material enhancer is too expensive, and the economical efficiency is low, and the surplus of the material enhancer, which does not contribute to the surface treatment reaction of the lignocellulosic powder, is low molecular weight. There have been a number of problems, such as blooming and making the appearance worse.
이에 폴리염화비닐에 리그노셀루로오즈계 분말을 고도로 함유시키며 뛰어난분산력에 의해 목질감에 의한 우수한 외관 및 기계적 물성을 가지는 합성목재의 출현이 절실히 요청되고 있다.Accordingly, polyvinyl chloride has a high content of lignocellulosic powder, and the appearance of synthetic wood having excellent appearance and mechanical properties due to wood texture is urgently required by excellent dispersibility.
상기와 같은 문제점을 해결하기 위하여 본 발명자들은 예의 연구를 거듭한 결과 본 발명에 이르게 되었다. 본 발명의 주요 목적은 목재의 질감에 의한 외관 및 휨강도, 치수안정성 등 기계적 물성이 우수하고 가격이 저렴하여 마루판, 문틀, 창호재, 걸레받이, 문선몰딩 등 각종 프로파일과 같은 건축자재로서 사용하기에 적합한 폴리염화비닐과 리그노셀루로오즈계 분말이 주재로 된 합성목재를 제공하는 것이다.MEANS TO SOLVE THE PROBLEM In order to solve the said problem, the present inventors earnestly studied and came to this invention. The main object of the present invention is to use as a building material such as various profiles such as floorboards, door frames, window coverings, floorboards, door line moldings, etc. due to the excellent mechanical properties such as appearance, bending strength and dimensional stability due to the texture of wood and low price. It is to provide a synthetic wood based on a suitable polyvinyl chloride and lignocellulosic powder.
본 발명은 외관 및 기계적 물성이 우수하고 고도로 리그노셀루로오즈계 분말이 함유된 합성목재조성물 및 이의 제조방법에 관한 것이다. 즉, 본 발명은 폴리염화비닐 100중량부; 리그노셀루로오즈계 분말 20∼200중량부; 충진제, 안정제, 활제, 충격보강제, 발포제 및 가소제를 포함하는 폴리염화비닐에 통상 사용되는 첨가제 5∼50중량부; 상기 리그노셀루로오즈계 분말 100중량분에 대해 수산기, 카르복실산기, 카르복실산의 염, 술폰산기, 술폰산의 염, 인산기, 인산의 염 및 아미노기로 이루어진 그룹으로부터 어느 하나 이상의 관능기를 함유하는 염화비닐계 공중합체 0.5∼50중량부로 이루어진 조성물을 이용하는 것을 특징으로 하는 합성목재를제공하는 것이다.The present invention relates to a synthetic wood composition having excellent appearance and mechanical properties and highly contained lignocellulosic powder, and a method for producing the same. That is, the present invention 100 parts by weight of polyvinyl chloride; 20 to 200 parts by weight of lignocellulosic powder; 5 to 50 parts by weight of additives commonly used in polyvinyl chloride including fillers, stabilizers, lubricants, impact modifiers, foaming agents and plasticizers; It contains at least one functional group from the group consisting of hydroxyl group, carboxylic acid group, salt of carboxylic acid, sulfonic acid group, salt of sulfonic acid, phosphoric acid group, salt of phosphoric acid and amino group with respect to 100 parts by weight of the lignocellulosic powder. It is to provide a synthetic wood, characterized in that using a composition consisting of 0.5 to 50 parts by weight of vinyl chloride copolymer.
본 발명에 사용되는 폴리염화비닐은 현탁중합, 유화중합, 용액중합, 괴상중합 등 통상 알려진 어떤 제조법에 의해 제조되어도 무방하다. 폴리염화비닐의 평균중합도는 500∼1,300이 바람직하고, 700∼1,100 범위가 더욱 좋다. 평균중합도가 500 보다 작으면 기계적 물성이 취약해지는 문제가 있고, 반대로 1,300보다 크면 가공시 점도가 너무 높아 압출시간이 길어져 리그노셀루로오즈계 분말이 타는 문제가 발생할 우려가 있다.The polyvinyl chloride used in the present invention may be produced by any known production method such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization. The average degree of polymerization of polyvinyl chloride is preferably 500 to 1,300, and more preferably 700 to 1,100. If the average polymerization degree is less than 500, there is a problem that the mechanical properties are weak, on the contrary, if the average polymerization degree is greater than 1,300, the viscosity is too high during processing, the extrusion time is long, there is a fear that the lignocellulosic powder burns.
본 발명에 사용되는 리그노셀루로오즈계 분말은 그 예로 목분, 왕겨분, 펄프 분말, 볏짚 분말 등을 들 수 있고, 리그노셀루로오즈계 분말의 평균입경은 20∼500μm의 것이 좋은데, 입경이 커지면 합성목재의 외관이 나빠지는 경향이 있고, 입경이 작으면 외관은 우수해지나, 분산이 어려워지고 미분말로 만드는데 원가가 올라가 경제성이 떨어지는 취약점이 있다. 또한 리그노셀루로오즈계 분말의 수분은 비록 압출공정중 일부 잔여 수분이 벤트되어 제거되기도 하지만 물성 및 생산성을 고려할 때 10% 이하의 것이 좋고 5%이하의 것이 더욱 좋다. 리그노셀루로오즈계 분말의 첨가량은 폴리염화비닐 100중량부에 대해 20∼200중량부 범위로 첨가하는 것이 좋고, 50∼150중량부 범위가 더욱 좋다. 20중량부 미만일 경우 치수안정성의 개선효과가 떨어지고, 200중량부를 초과하면 외관이 거칠어지는 단점이 있다.Examples of the lignocellulosic powder used in the present invention include wood flour, chaff powder, pulp powder, rice straw powder, and the like. The average particle diameter of the lignocellulosic powder may be 20 to 500 μm. As the size increases, the appearance of the synthetic wood tends to deteriorate, and the smaller the particle size, the better the appearance, but it is difficult to disperse and the cost increases to make the fine powder. In addition, the moisture of the lignocellulosic powder is preferably less than 10% and less than 5% in consideration of physical properties and productivity, although some residual water is vented and removed during the extrusion process. The amount of lignocellulosic powder to be added is preferably added in the range of 20 to 200 parts by weight with respect to 100 parts by weight of polyvinyl chloride, and more preferably in the range of 50 to 150 parts by weight. If it is less than 20 parts by weight, the effect of improving the dimensional stability is inferior, and if it exceeds 200 parts by weight, the appearance is rough.
본 발명은 수산기 등 친수성 극성 관능기를 다수 함유하는 리그노셀루로오즈계 분말과 수산기, 카르복실산기, 카르복실산의 염, 술폰산기, 술폰산의 염, 인산기, 인산의 염 및 아미노기 등 관능기를 함유하는 염화비닐계 공중합체와의 쌍극자간 인력, 수소결합력, 쌍극자-이온간 인력 등 소위 2차 결합력을 이용한 분산효과를 노린 것이다. 특히 리그노셀루로오즈계 분말의 함량이 높아질수록 폴리염화비닐의 염소와 리그노셀루로오즈계 분말내 친수성 극성 관능기와의 인력효과만으로는 부족하여 분산이 어려워지는 관계로 얻어지는 합성목재의 외관이 나빠지고, 압출가공시 리그노셀루로오즈계 분말이 타는 문제가 발생하였으나, 본 발명에 의한 수산기, 카르복실산기, 카르복실산의 염, 술폰산기, 술폰산의 염, 인산기, 인산의 염 및 아미노기 등 관능기를 함유하는 염화비닐계 공중합체는 그 뼈대가 폴리염화비닐인 관계로 폴리염화비닐과의 좋은 상용성을 유지하면서 동시에 리그노셀루로오즈계 분말과의 뛰어난 분산성을 발휘하여 상기의 문제가 해결되게 된 것이다. 본 발명에 사용되는 카르복실산의 염, 술폰산의 염, 인산의 염 등 관능기를 함유하는 염화비닐계 공중합체에 있어서의 염은 Li, Na, K등 알카리금속염 뿐만 아니라 암모늄염 형태의 것도 있다. 수산기, 카르복실산기, 카르복실산의 염과 같은 관능기 함유 염화비닐계 공중합체의 구체적 예로서는 염화비닐-초산비닐-비닐알콜 공중합체(다우케미칼사 상품명 VAGH, 니신케미칼사 상품명 SOLBIN Grade A), 염화비닐-초산비닐-히드록시알킬아크릴레이트 공중합체(니신케미칼사 상품명 SOLBIN Grade TA2), 염화비닐-초산비닐-말레인산(니신케미칼사 상품명 SOLBIN Grade MF), 염화비닐-초산비닐-히드록시알킬레이트-말레인산 공중합체(니신케미칼사 상품명 SOLBIN Grade MK6)등을 들 수 있다. 황산기, 황산의 염, 인산기, 인산의 염과 같은 관능기를 함유하는 염화비닐계 공중합체는 미합중국 특허 제4,851,465호에 상세히 기재된 방법에 의해 얻어질 수 있으며, 구체적인 예로서 니혼제온사 상품명 MR-110을 들 수 있다.아미노기와 같은 관능기를 함유하는 염화비닐계 공중합체는 미합중국 특허 제5,418,285호에 상세히 기재된 방법에 의해 얻어질 수 있으며, 구체적인 예로서 니신케미칼사 상품명 SOLBIN Grade TAO를 들 수 있다. 본 발명에 있어서의 수산기, 카르복실산기, 카르복실산의 염, 술폰산기, 술폰산의 염, 인산기, 인산의 염 및 아미노기 등 관능기를 함유하는 염화비닐계 공중합체의 첨가량은 리그노셀루로오즈계 분말 100중량부에 대해 0.5∼50중량부가 좋고 2∼30중량부가 바람직하다. 0.5중량부 미만일 경우 리그노셀루로오즈계 분말에 대한 분산효과가 떨어져 외관 및 치수안정성이 악화되는 문제가 있고, 50중량부를 초과하게 되면 분산에 기여하지 못한 잉여분이 폴리염화비닐 대비 분자량이 작은 관계로 오히려 강도가 취약해지는 문제가 있다.The present invention contains lignocellulosic powder containing a large number of hydrophilic polar functional groups such as hydroxyl groups, and functional groups such as hydroxyl groups, carboxylic acid groups, salts of carboxylic acids, sulfonic acid groups, salts of sulfonic acids, phosphoric acid groups, salts of phosphoric acid and amino groups. It aims at the dispersion effect using so-called secondary bonding force such as dipole attraction, hydrogen bonding force, dipole-ion attraction and the like with a vinyl chloride copolymer. In particular, as the content of lignocellulosic powder increases, the appearance of synthetic wood obtained due to difficulty in dispersion due to insufficient attraction force between chlorine of polyvinyl chloride and hydrophilic polar functional groups in lignocellulosic powder. The lignocellulosic powder burns during the extrusion process, but the hydroxyl group, the carboxylic acid group, the salt of the carboxylic acid, the sulfonic acid group, the salt of the sulfonic acid, the phosphoric acid group, the salt of the phosphoric acid and the amino group, etc. The vinyl chloride-based copolymer containing a functional group is polyvinyl chloride in its skeleton and maintains good compatibility with polyvinyl chloride while exhibiting excellent dispersibility with lignocellulosic powders. It will be solved. Salts in vinyl chloride-based copolymers containing functional groups such as salts of carboxylic acids, salts of sulfonic acids, and salts of phosphoric acid used in the present invention are not only alkali metal salts such as Li, Na, K, but also ammonium salts. Specific examples of functional group-containing vinyl chloride copolymers such as hydroxyl groups, carboxylic acid groups, and salts of carboxylic acids include vinyl chloride-vinyl acetate-vinyl alcohol copolymers (DOW Chemical Co., Ltd., VAGH, Nisshin Chemical Co., Ltd., SOLBIN Grade A), chloride Vinyl-vinyl acetate-hydroxyalkyl acrylate copolymer (Nisshin Chemical company brand name SOLBIN Grade TA2), vinyl chloride-vinyl acetate-maleic acid (Nisshin Chemical company brand name SOLBIN Grade MF), vinyl chloride-vinyl acetate-hydroxyalkylate- Maleic acid copolymer (Nisshin Chemical Co., Ltd. product name SOLBIN Grade MK6) etc. are mentioned. Vinyl chloride-based copolymers containing functional groups such as sulfuric acid groups, salts of sulfuric acid, phosphoric acid groups, and salts of phosphoric acid can be obtained by the method described in detail in U.S. Patent No. 4,851,465. The vinyl chloride-based copolymer containing a functional group such as an amino group can be obtained by the method described in detail in U.S. Patent No. 5,418,285, and specific examples thereof include Nisshin Chemical Company's trade name SOLBIN Grade TAO. The addition amount of the vinyl chloride type copolymer containing functional groups, such as a hydroxyl group, a carboxylic acid group, a salt of a carboxylic acid, a sulfonic acid group, a salt of a sulfonic acid, a phosphoric acid group, a salt of a phosphoric acid, and an amino group, in this invention is a lignocellulosic type. 0.5-50 weight part is good with respect to 100 weight part of powders, and 2-30 weight part is preferable. If the amount is less than 0.5 parts by weight, the dispersing effect on lignocellulosic powder is poor, and the appearance and dimensional stability are deteriorated. If the amount is more than 50 parts by weight, the excess molecular weight is less than that of polyvinyl chloride. Rather, there is a problem that the strength is weak.
본 발명에 사용되는 충진제는 폴리염화비닐에 통상 사용되는 것으로, 탄산칼슘, 실리카, 탈크, 카올린, 알루미나, 산화티탄 등을 들 수 있고, 이중에서 값이 싼 탄산칼슘이 바람직하다. 충진제는 평균입경이 리그노셀루로오즈계 분말 보다 작고 비중이 큰 것이 바람직하다. 리그노셀루로오즈계 분말 보다 작고 비중이 큰 충진제는 리그노셀루로오즈계 분말 사이의 틈새에 파고드는 형태를 가져 리그노셀루로오즈계 분말만 사용했을 때보다 압출기에서 공급이 잘 되게 함으로써 리그노셀루로오즈계 분말이 타는 현상을 줄여줄 수 있다. 통상 충진제는 폴리염화비닐 100중량부에 대해 1∼20중량부를 사용하는 것이 효과적이다.Fillers used in the present invention are commonly used for polyvinyl chloride, and include calcium carbonate, silica, talc, kaolin, alumina, titanium oxide, and the like, of which cheap calcium carbonate is preferable. The filler preferably has an average particle diameter smaller than that of the lignocellulosic powder and has a higher specific gravity. Fillers smaller and more specific than lignocellulosic powder penetrate into the gaps between lignocellulosic powder so that they can be fed from the extruder better than lignocellulosic powder only. It is possible to reduce the burning phenomenon of the nocellulosic powder. Usually, it is effective to use 1-20 weight part of fillers with respect to 100 weight part of polyvinyl chlorides.
본 발명에 사용되는 안정제는 폴리염화비닐에 통상 사용되는 것으로, 삼염기성 황산연, 이염기성 아린산연, 이염기성 스테아린산연 등 무기산연류; 스테아린산바륨, 스테아린산 칼슘 등 금속비누류; 부틸주석머캅타이드, 옥틸주석머캅타이드 등 유기주석화합물 등을 들 수 있으며, 이들이 단독 또는 적정 비율로 혼합되어 사용되며 폴리염화비닐 100중량부에 대해 3∼10중량부를 사용하는 것이 효과적이다.Stabilizers used in the present invention are commonly used in polyvinyl chloride, and include inorganic acids such as tribasic lead sulfate, dibasic lead phosphate, and dibasic lead phosphate; Metal soaps such as barium stearate and calcium stearate; Organic tin compounds, such as butyl tin mercaptide and octyl tin mercaptide, etc. are mentioned, These are used individually or in mixture by a suitable ratio, It is effective to use 3-10 weight part with respect to 100 weight part of polyvinyl chlorides.
본 발명에 사용되는 활제는 폴리염화비닐에 통상 사용되는 것으로, 스테아린산 등 지방산류; 스테아린산 아미드, 올레인산 아미드 등 지방산 아미드류; 파라핀 왁스, 폴리에틸렌 왁스 등 왁스류 등을 들 수 있으며, 이들이 단독 또는 적정 비율로 혼합되어 사용되며 폴리염화비닐 100중량부에 대해 0.5∼5중량부를 사용하는 것이 효과적이다. 특히 리그노셀루로오즈계 분말 함량이 높아짐에 따라 압출기 벽면의 점착에 의해 리그노셀루로오즈계 분말이 타는 경향이 심해지기 때문에 활제의 선택 및 첨가량이 매우 중요하다.The lubricant used in the present invention is commonly used for polyvinyl chloride, and includes fatty acids such as stearic acid; Fatty acid amides such as stearic acid amide and oleic acid amide; Waxes, such as a paraffin wax and polyethylene wax, etc. are mentioned, These are used individually or in a suitable ratio, and it is effective to use 0.5-5 weight part with respect to 100 weight part of polyvinyl chlorides. In particular, since the lignocellulose-based powder tends to burn due to the adhesion of the extruder wall as the lignocellulosic powder content increases, the selection and addition amount of the lubricant is very important.
본 발명에 사용되는 충격보강제는 폴리염화비닐에 통상 사용되는 것으로 염소화폴리에틸렌, 메틸메타크릴레이트-부타디엔-스틸렌(MBS)수지, 아크릴로니트릴-부타디엔-스틸렌(ABS)수지 등을 들 수 있으며 폴리염화비닐 100중량부에 대해 3∼15중량부를 사용하는 것이 효과적이다.Impact modifiers used in the present invention are commonly used for polyvinyl chloride, and may include chlorinated polyethylene, methyl methacrylate-butadiene-styrene (MBS) resin, acrylonitrile-butadiene-styrene (ABS) resin, and the like. It is effective to use 3-15 weight part with respect to 100 weight part of vinyl.
본 발명에 사용되는 발포제는 폴리염화비닐에 통상 사용되는 것으로, 아조디카르본아미드, 벤조술포닐히드라지드 등 열분해형 유기발포제, 중탄산나트륨, 탄산암모늄 등 열분해형 무기발포제를 들수 있으며 폴리염화비닐 100중량부에 대해 0.01∼3중량부를 사용하는 것이 효과적이다.The foaming agent used in the present invention is commonly used for polyvinyl chloride, and thermally decomposable organic foaming agents such as azodicarbonamide and benzosulfonyl hydrazide, and thermally decomposable inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, etc. It is effective to use 0.01-3 weight part with respect to parts.
본 발명에 사용되는 가소제는 폴리염화비닐에 통상 사용되는 것으로, 디부리프타레이트, 디옥틸프탈레이트, 인산트리크레실 등을 들 수 있으며 폴리염화비닐100중량부에 대해 0.1∼10중량부를 사용하는 것이 효과적이다.Plasticizers used in the present invention are commonly used for polyvinyl chloride, and may include dibuphthalate, dioctylphthalate, tricresyl phosphate, and the like. It is preferable to use 0.1 to 10 parts by weight based on 100 parts by weight of polyvinyl chloride. effective.
본 발명에 있어서 폴리염화비닐, 리그노셀루로오즈계 분말 및 관능기 함유 염화비닐계 공중합체외에 첨가되는 상기 폴리염화비닐에 통상 사용되는 충진제, 안정제, 활제, 충격보강제, 발포제, 가소제 등 첨가제는 5∼50중량부로 조절하는 것이 좋고 10∼30중량부로 첨가하는 것이 더욱 좋다. 이러한 첨가제 함량이 5중량부 미만이 되면 열안정성, 가공성, 발포성 등 기본 물성이 나타나지 않고, 50중량부를 초과하게 되면 기계적물성이 나빠지는 경향이 있다.In the present invention, additives such as fillers, stabilizers, lubricants, impact modifiers, foaming agents, plasticizers, and the like, which are commonly used in the polyvinyl chloride, lignocellulosic powder and the functional group-containing vinyl chloride copolymer, are added. It is good to adjust to -50 weight part, and it is more preferable to add it at 10-30 weight part. If the additive content is less than 5 parts by weight, the basic properties such as thermal stability, processability, foamability does not appear, and if it exceeds 50 parts by weight, the mechanical properties tend to be worse.
보다 구체적으로 설명하면 본 발명에 의한 합성목재는 폴리염화비닐 100중량부; 리그노셀루로오즈계 분말 20∼200중량부; 충진제, 안정제, 활제, 충격보강제, 발포제 및 가소제를 포함하는 폴리염화비닐에 통상 사용되는 첨가제 5∼50중량부; 상기 리그노셀루로오즈계 분말 100중량분에 대해 수산기, 카르복실산기, 카르복실산의 염, 술폰산기, 술폰산의 염, 인산기, 인산의 염 및 아미노기로 이루어진 그룹으로부터 어느 하나 이상의 관능기를 함유하는 염화비닐계 공중합체 0.5∼50중량부를 계량하는 단계; 원료들을 호퍼를 통해 투입후 가열하면서 약20∼30분동안 회전분산시켜 혼합하는 단계; 혼합물을 냉각브렌더에서 냉각하는 단계; 냉각된 혼합물을 용융압출하면서 성형하는 단계; 냉각하고 인출하여 소정의 크기로 절단하는 단계에 의해 제조된다.In more detail, the synthetic wood according to the present invention is 100 parts by weight of polyvinyl chloride; 20 to 200 parts by weight of lignocellulosic powder; 5 to 50 parts by weight of additives commonly used in polyvinyl chloride including fillers, stabilizers, lubricants, impact modifiers, foaming agents and plasticizers; It contains at least one functional group from the group consisting of hydroxyl group, carboxylic acid group, salt of carboxylic acid, sulfonic acid group, salt of sulfonic acid, phosphoric acid group, salt of phosphoric acid and amino group with respect to 100 parts by weight of the lignocellulosic powder. Weighing 0.5 to 50 parts by weight of the vinyl chloride copolymer; Mixing the raw materials by rotating dispersion for about 20 to 30 minutes while heating the raw materials through a hopper; Cooling the mixture in a cold blender; Shaping the cooled mixture while melt extrusion; It is produced by the step of cooling, drawing out and cutting to a predetermined size.
원료를 혼합하는 단계는 계량된 원료를 호퍼를 통하여 배합기에 투입후 약120℃의 온도에서 20∼30분 동안 회전 분산시키는 방법으로 행한다. 회전분산시의 온도 및 시간은 상기의 조건에 반드시 한정되는 것은 아니고 폴리염화비닐, 리그노셀루로오즈계 분말 및 기타 첨가제의 특성을 고려하여 선정할 수 있지만, 사용되는 폴리염화비닐이 변성되지 않고 리그노셀루로오즈계 분말의 탄화가 발생하지 않으며 기타 첨가제들의 특성이 변화되지 않는 온도 및 시간 범위내에서 적절히 조절이 가능하며 약120℃의 온도에서 20∼30분 동안 회전 분산시키는 방법이 효과적이다.The mixing of the raw materials is carried out by rotating the dispersion of the weighed raw materials into the blender through a hopper for 20-30 minutes at a temperature of about 120 ℃. The temperature and time at the time of rotation dispersion are not necessarily limited to the above conditions and can be selected in consideration of the properties of polyvinyl chloride, lignocellulosic powder and other additives, but the polyvinyl chloride used is not modified. Carbonization of lignocellulosic powder does not occur and can be appropriately controlled within a temperature and time range in which the properties of other additives do not change, and a method of rotating dispersion for about 20 to 30 minutes at a temperature of about 120 ° C is effective. .
혼합물을 냉각하는 단계는 혼합물을 냉각수의 순환에 의하여 냉각이 이루어지는 냉각블렌더로 이송하고 약 15∼20분 동안 유지시켜 약60℃의 온도로 냉각하는 방법을 사용한다.The step of cooling the mixture uses a method in which the mixture is transferred to a cooling blender where cooling is performed by circulation of cooling water, held for about 15 to 20 minutes, and cooled to a temperature of about 60 ° C.
또한 혼합물을 용융압출하면서 합성목재를 성형하는 단계는 상기 혼합단계에서 주재료중 하나인 리그노셀루로오즈계 분말내 수분이 100% 제거되지 않아 약간의 수증기와 유해가스가 발생하므로 이를 진공모터를 이용하여 벤트 제거할 수 있는 벤트관이 부착된 실린더 구조의 압출기에서 행하며, 실린더에 투시창이 장착되어 있으면 실린더를 통하여 이송되는 재료의 흐름을 육안으로 관찰할 수 있어 매우 편리하다. 이 때 실린더는 5등분으로 분할하여 가열되는 온도가 상이하도록 하되 혼합물이 이송되는 순서에 따라 제 1구역(C-1)은 180∼220℃, 제 2구역(C-2)은 180∼210℃, 제 3구역(C-3)은 180∼200℃, 발생된 수증기와 유해가스를 배기시킨 지점 이후인 제 4구역(C-4)은 160∼190℃, 제 5구역(C-5)은 130∼180℃로 조절한다. 제 1구역 내지 제3구역은 사용되는 재료들의 완전 용융을 위하여 180℃ 이상을 유지하되 재료들의 이송 용이성을 위하여 최고온도를 제 1구역에서는 220℃, 제 2구역에서는 210℃, 제 3구역에서는 200℃로 조절하며 제 4구역 및 제 5구역은 혼합물들이 용융되면서 가열기와 인접하는 표면 부분이 탄화되는 것을 방지하기 위해서 각각 160∼190℃, 130∼180℃로 조절하는 것이 바람직하다.In addition, the step of forming a synthetic wood while melt-extrusion the mixture is not 100% moisture in the lignocellulosic powder, one of the main materials in the mixing step, so that some steam and harmful gases are generated, so that the vacuum motor is used. In the extruder of the cylinder structure is attached to the vent pipe that can be removed by venting, if the cylinder is equipped with a viewing window, it is very convenient to visually observe the flow of material conveyed through the cylinder. At this time, the cylinder is divided into five equal parts so that the heating temperature is different, but according to the order in which the mixture is transferred, the first zone (C-1) is 180 to 220 ° C and the second zone (C-2) is 180 to 210 ° C. In the third zone (C-3), 180 ~ 200 ℃, the fourth zone (C-4) after the point where the generated water vapor and harmful gas are exhausted is 160 ~ 190 ℃, and the fifth zone (C-5) Adjust it to 130-180 degreeC. Zones 1 to 3 are maintained at 180 ° C or higher for complete melting of the materials used, but the maximum temperature is 220 ° C in the 1st zone, 210 ° C in the 2nd zone and 200 in the 3rd zone for ease of transport of the materials. The fourth and fifth zones are preferably adjusted to 160 to 190 ° C and 130 to 180 ° C, respectively, to prevent carbonization of the surface portion adjacent to the heater as the mixture melts.
상기와 같이 실린더 및 다이스금형을 통한 압출기에서 압출하게 되면 미세 수분 또는 발포제에 의해 일부 발포가 일어나면서 성형품이 나오게 된다. 얻고자 하는 형상의 합성목재를 고려하여 다이스금형을 설계 장착하고, 얻어지는 압출성형품을 소정의 크기로 절단함으로써 본 발명에 따른 합성목재를 얻게 된다.When extruded from the extruder through the cylinder and the die mold as described above, the molded article comes out while some foaming occurs by the fine moisture or foaming agent. In consideration of the synthetic wood of the shape to be obtained, the die wood is designed and mounted, and the obtained extrusion molded product is cut into a predetermined size, thereby obtaining a synthetic wood according to the present invention.
이하 실시예를 통하여 본 발명을 보다 자세히 설명하고자 한다. 하기의 실시예는 하나의 예시일 뿐 실시예에 한정하지 않는다. 하기 실시예 및 비교예에 따라 제조된 합성목재의 휨강도, 치수변형율, 외관을 다음과 같이 측정하였다.Through the following examples will be described in more detail the present invention. The following examples are merely examples and are not limited to the examples. The flexural strength, dimensional strain, and appearance of the synthetic wood prepared according to the following Examples and Comparative Examples were measured as follows.
(휨강도)Flexural strength
KS F3126-96에 의거하여 휨강도(N/cm2)를 측정하였다.Flexural strength (N / cm2) was measured based on KS F3126-96.
(치수변형율)Dimensional Strain
KS F3126-96에 의거하여 치수변형율(%)를 측정하였다.Dimensional strain (%) was measured based on KS F3126-96.
(외관)(Exterior)
육안으로 표면상태, 형상의 매끈한 정도 등을 평가하였다(◎: 우수, ○: 양호, △: 보통, ×: 불량)The surface state and the smoothness of the shape were visually evaluated (◎: excellent, ○: good, △: normal, ×: poor)
[실시예 1∼6]EXAMPLES 1-6
중합도가 800인 폴리염화비닐(한화석유화학 P-800) 100중량부, 충진제인 탄산칼슘(경탄) 10중량부, 안정제인 스테아린산 바륨, 스테아린산 칼슘, 이염기성 스테아린산연 및 삼염기성 황산연으로 구성되는 복합안정제(단석산업 KD-300) 7중량부, 활제인 스테아린산 0.5중량부, 폴리에틸렌왁스 0.5중량부, 충격보강제인 메틸메타크릴레이트-부타디엔-스틸렌 수지(미쓰비시레이욘사 P530-A) 5중량부, 발포제인 아조디카르본아미드 0.2중량부로 구성된 혼합물에 리그노셀루로오즈계 분말로서의 평균입경 60㎛인 목분 및 관능기 함유 염화비닐계 공중합체를 표 1에 나타낸 바와 같이 여러 함량으로 조절 첨가하였다. 사용된 관능기 함유 염화비닐계 공중합체로서는 염화비닐(92중량%)-초산비닐(3중량%)-비닐알콜(5중량%) 공중합체(니신케미칼사 상품명 SOLBIN Grade A), 염화비닐(83중량%)-초산비닐(4중량%)-히드록시알킬아크릴레이트(13중량%) 공중합체(니신케미칼사 상품명 SOLBIN Grade TA2), 염화비닐(90중량%)-초산비닐(7중량%)-말레인산(3중량%)(니신케미칼사 상품명 SOLBIN Grade MF)가 사용되었다. 배합기에 투입후 120℃의 온도에서 20분간 회전 분산시키는 방법으로 원료들을 혼합한 다음 압출기 실린더의 제 1구역(C-1)은 210℃, 제 2구역(C-2)은 200℃, 제 3구역(C-3)은 190℃, 제 4구역(C-4)은 170℃, 제 5구역(C-5)은 160℃로 조절하였다. 압출이 완료된 제품은 냉각시킨 후에 인출기로 인출하여 소정의 크기로 절단하여 본 발명에 따른 합성목재를 얻었다. 얻어진 합성목재 시편의 물성을 표 1에 나타내었다.Consists of 100 parts by weight of polyvinyl chloride (Hanhwa Petrochemical P-800) having a degree of polymerization of 800, 10 parts by weight of calcium carbonate (hard coal) as a filler, barium stearate, calcium stearate, lead dibasic stearate and tribasic lead sulfate 7 parts by weight of a compound stabilizer (Tanseok Industrial KD-300), 0.5 part by weight of lubricant stearic acid, 0.5 part by weight of polyethylene wax, 5 parts by weight of methyl methacrylate-butadiene-styrene resin (Mitsubishi Rayon P530-A), an impact modifier, To the mixture consisting of 0.2 parts by weight of azodicarbonamide, which is a blowing agent, wood flour and functional group-containing vinyl chloride copolymers having an average particle diameter of 60 µm as lignocellulosic powder were adjusted and added in various contents as shown in Table 1. Examples of the functional group-containing vinyl chloride copolymer used include vinyl chloride (92% by weight)-vinyl acetate (3% by weight)-vinyl alcohol (5% by weight) copolymer (Nishin Chemical Co., Ltd. product name SOLBIN Grade A), vinyl chloride (83 weight %)-Vinyl acetate (4% by weight) -hydroxyalkyl acrylate (13% by weight) copolymer (Nisshin Chemical company name SOLBIN Grade TA2), vinyl chloride (90% by weight) -vinyl acetate (7% by weight) -maleic acid (3% by weight) (Nisshin Chemical company name SOLBIN Grade MF) was used. The raw materials were mixed by rotating dispersion for 20 minutes at a temperature of 120 ° C. after mixing into the blender, and the first zone (C-1) of the extruder cylinder was 210 ° C., the second zone (C-2) was 200 ° C., and third Zone (C-3) was adjusted to 190 ° C, Zone 4 (C-4) to 170 ° C, and Zone 5 (C-5) to 160 ° C. After the extrusion is completed, the product is cooled and then taken out by a drawer and cut into a predetermined size to obtain a synthetic wood according to the present invention. The physical properties of the obtained synthetic wood specimens are shown in Table 1.
[비교예 1∼2][Comparative Examples 1 and 2]
실시예 1∼6에 있어서의 관능기 함유 염화비닐계 공중합체를 첨가하지 않거나, 목분 및 관능기 함유 염화비닐계 공중합체를 동시에 첨가하지 않는 것을 제외하고는 실시예 1∼6과 동일하게 실시하였다. 얻어진 합성목재의 물성을 표 1에 나타내었다. 기계적 물성 및 외관이 열악함을 알 수 있다.The same procedure was followed as in Examples 1 to 6 except that the functional group-containing vinyl chloride copolymer in Examples 1 to 6 was not added or the wood powder and the functional group-containing vinyl chloride copolymer were not added at the same time. Table 1 shows the physical properties of the obtained synthetic wood. It can be seen that the mechanical properties and appearance is poor.
상기 실시예를 전체적으로 볼 때 본 발명에 의한 합성목재는 목재의 질감에 의한 외관 및 휨강도, 치수안정성 등 기계적 물성이 우수하고 가격이 저렴하여 마루판, 문틀, 창호재, 걸레받이, 문선몰딩 등 각종 프로파일과 같은 건축용 재료로서 사용하기에 적합함을 알 수 있는데, 이는 앞서 언급한대로 관능기 함유 염화비닐계 공중합체가 폴리염화비닐과의 좋은 상용성을 유지하면서 함유된 관능기와 목분내 수산기와 같은 관능기간의 2차 결합력에 의해 분산이 탁월하게 이루어져 획기적으로 물성이 개선된 것으로 생각한다. 실시예 3과 실시예 5를 비교해 볼 때 동일 함유량인데, SOLBIN A(염화비닐(92중량%)-초산비닐(3중량%)-비닐알콜(5중량%) 공중합체) 보다는 SOLBIN TA2(염화비닐(83중량%)-초산비닐(4중량%)-히드록시알킬아크릴레이트(13중량%) 공중합체)를 사용하였을 때가 더욱 좋은 물성을 보인 것은 공중합체내 함유된 수산기의 함유량이 높은 SOLBIN TA2의 목분에 대한 분산력인 훨씬 우수한 것에 기인한다고 본다. 또한 실시예 5와 실시예 6을 비교해보면 실시예 6의 경우가 관능기 함유 염화비닐계 공중합체 함량이 훨씬 적음에도 불구하고 비슷하게 좋은 물성을 보인 것은 SOLBIN MF(염화비닐(90중량%)-초산비닐(7중량%)-말레인산(3중량%))내 함유된 관능기인 말레인산의 산과 목분의 수산기와의 수소결합력이 SOLBIN TA2내 함유된 수산기와 목분의 수산기와의 수소결합력 보다 훨씬 탁월한 것에 기인한다고 본다. 한편 비교예 1을 보면 목분의 분산이 원활하지 않아 외관이 극히 불량하고 다른 물성도 열악함을 알 수 있으며, 단순 폴리염화비닐 및 기타 첨가제에 의한 제품은 휨강도는 우수하고, 외관도 양호하나 건축자재로서 매우 중요한 물성인 치수변형율이 목분이 첨가된 제품 대비 열악함을 알 수 있다.As a whole, the synthetic wood according to the present invention has excellent mechanical properties such as appearance and bending strength and dimensional stability due to the texture of wood, and is inexpensive, so that various profiles such as floorboards, door frames, window materials, floorboards, door line moldings, etc. It can be seen that it is suitable for use as a building material, such as mentioned above, which means that the functional group-containing vinyl chloride-based copolymer maintains good compatibility with polyvinyl chloride, Dispersion is excellent due to the secondary binding force, and it is thought that the physical properties are remarkably improved. Compared to Example 3 and Example 5, the same content, SOLBIN TA2 (vinyl chloride) than SOLBIN A (vinyl chloride (92% by weight)-vinyl acetate (3% by weight)-vinyl alcohol (5% by weight) copolymer) (83% by weight) -vinyl acetate (4% by weight) -hydroxyalkyl acrylate (13% by weight) copolymer) showed better physical properties of the wood powder of SOLBIN TA2 having high content of hydroxyl groups in the copolymer. I think it is due to much better dispersion of In addition, when comparing Example 5 and Example 6, in the case of Example 6, even though the functional group-containing vinyl chloride-based copolymer content is much smaller, similarly good physical properties were SOLBIN MF (vinyl chloride (90% by weight)-vinyl acetate) It is believed that the hydrogen bonding force of the maleic acid and the hydroxyl group of the maleic acid, which is a functional group contained in (7 wt%)-maleic acid (3 wt%), is due to the superior hydrogen bonding force of the hydroxyl group and the wood flour contained in SOLBIN TA2. . On the other hand, in Comparative Example 1, it is found that the appearance of wood powder is not very good and other physical properties are poor due to poor dispersion of wood powder. The products by simple polyvinyl chloride and other additives have excellent bending strength and good appearance, but construction materials As a very important physical property, the dimensional strain is inferior to that of wood powder.
따라서, 본 발명에 의한 합성목재는 건축자재에 적합한 것으로서 가격도 저렴한 목재의 훌륭한 대체재이며 목재의 벌목도 줄여줄 수 있는 환경친화적인 실로 획기적인 신소재인 것이다.Therefore, the synthetic wood according to the present invention is an excellent alternative to low-cost wood as suitable for building materials and is an innovative new material as an environmentally friendly yarn that can reduce the logging of wood.
본 발명의 합성목재는 폴리염화비닐 100중량부; 리그노셀루로오즈계 분말 20∼200중량부; 충진제, 안정제, 활제, 충격보강제, 발포제 및 가소제를 포함하는폴리염화비닐에 통상 사용되는 첨가제 5∼50중량부; 상기 리그노셀루로오즈계 분말 100중량분에 대해 수산기, 카르복실산기, 카르복실산의 염, 술폰산기, 술폰산의 염, 인산기, 인산의 염 및 아미노기로 이루어진 그룹으로부터 어느 하나 이상의 관능기를 함유하는 염화비닐계 공중합체 0.5∼50중량부로 이루어진 조성물에 의해 압출성형된 제품으로 외관 및 기계적 물성이 우수할 뿐 아니라 매우 저렴한 획기적인 것으로, 마루판, 문틀, 창호재, 걸레받이, 문선몰딩 등 각종 프로파일과 같은 건축자재로서 사용될 것으로 전망된다.Synthetic wood of the present invention is 100 parts by weight of polyvinyl chloride; 20 to 200 parts by weight of lignocellulosic powder; 5 to 50 parts by weight of additives commonly used in polyvinyl chloride including fillers, stabilizers, lubricants, impact modifiers, foaming agents and plasticizers; It contains at least one functional group from the group consisting of hydroxyl group, carboxylic acid group, salt of carboxylic acid, sulfonic acid group, salt of sulfonic acid, phosphoric acid group, salt of phosphoric acid and amino group with respect to 100 parts by weight of the lignocellulosic powder. Extruded products made of a composition consisting of 0.5 to 50 parts by weight of a vinyl chloride copolymer, which is excellent in appearance and mechanical properties as well as a very inexpensive breakthrough, such as various profiles such as floorboards, door frames, window materials, baseboards, and door line moldings. It is expected to be used as a building material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100682608B1 (en) | 2004-12-28 | 2007-02-15 | (주)동성기연 | Resin composite for a doorframe and doorframe using this thing |
| KR101239627B1 (en) | 2010-05-28 | 2013-03-07 | 충북대학교 산학협력단 | Heavy metal free-PVC/wood flour/nanosilica nanocomposites with good dimensional stability |
| KR101282820B1 (en) | 2011-01-26 | 2013-07-05 | 경상대학교산학협력단 | Lightweight wood-plastic composite and method for manufacturing the same |
| KR101283502B1 (en) * | 2013-01-14 | 2013-08-19 | (주)애니우드 | Composition for synthetic woods and its manufacturing methods |
| CN103980636A (en) * | 2014-05-30 | 2014-08-13 | 甘肃昱晖新材料有限公司 | Wood-plastic foamed composite material and preparation method thereof |
| KR101669951B1 (en) * | 2016-02-17 | 2016-10-28 | 주식회사 이노스 | Synthetic Wood Composition Containing Phytoncide And Method for Manufacturing Synthetic Wood Using the Same |
-
2003
- 2003-08-20 KR KR1020030057589A patent/KR100432627B1/en not_active IP Right Cessation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100682608B1 (en) | 2004-12-28 | 2007-02-15 | (주)동성기연 | Resin composite for a doorframe and doorframe using this thing |
| KR101239627B1 (en) | 2010-05-28 | 2013-03-07 | 충북대학교 산학협력단 | Heavy metal free-PVC/wood flour/nanosilica nanocomposites with good dimensional stability |
| KR101282820B1 (en) | 2011-01-26 | 2013-07-05 | 경상대학교산학협력단 | Lightweight wood-plastic composite and method for manufacturing the same |
| KR101283502B1 (en) * | 2013-01-14 | 2013-08-19 | (주)애니우드 | Composition for synthetic woods and its manufacturing methods |
| CN103980636A (en) * | 2014-05-30 | 2014-08-13 | 甘肃昱晖新材料有限公司 | Wood-plastic foamed composite material and preparation method thereof |
| KR101669951B1 (en) * | 2016-02-17 | 2016-10-28 | 주식회사 이노스 | Synthetic Wood Composition Containing Phytoncide And Method for Manufacturing Synthetic Wood Using the Same |
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