KR910000813B1 - Polyolefins of ultrahigh molecular weight process for their manufacture and their use - Google Patents
Polyolefins of ultrahigh molecular weight process for their manufacture and their use Download PDFInfo
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- KR910000813B1 KR910000813B1 KR1019880012919A KR880012919A KR910000813B1 KR 910000813 B1 KR910000813 B1 KR 910000813B1 KR 1019880012919 A KR1019880012919 A KR 1019880012919A KR 880012919 A KR880012919 A KR 880012919A KR 910000813 B1 KR910000813 B1 KR 910000813B1
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- Prior art keywords
- molecular weight
- polyolefins
- fibers
- plasma
- filaments
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 17
- 229920000098 polyolefin Polymers 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000000835 fiber Substances 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 15
- 238000009832 plasma treatment Methods 0.000 claims description 11
- 239000004744 fabric Substances 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000012779 reinforcing material Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B19/00—Treatment of textile materials by liquids, gases or vapours, not provided for in groups D06B1/00 - D06B17/00
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
- D06M10/025—Corona discharge or low temperature plasma
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/50—Modified hand or grip properties; Softening compositions
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Reinforced Plastic Materials (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
내용 없음.No content.
Description
본 발명은 분자량이 600,000g/몰(중량 평균 분자량)로 초고분자인 고도로 배향된 폴리올레핀, 특히 습윤성 및 종래의 매트릭스 물질에 대한 접착성이 양호한 필라멘트, 화이버, 얀, 직물 및 필름과 이들의 제조방법 및 조성물의 제조시 이들을 이용하는 용도에 관한 것이다. EP-A-0,006,275호에는 방향족 폴리아미드 화이버의 접착성을 개선시키는 방법이 기술되어 있는데 이 방법은 화이버를 플라즈마 처리하는 것이다.The present invention relates to filaments, fibers, yarns, fabrics and films and highly prepared polyolefins having high molecular weight of 600,000 g / mol (weight average molecular weight), in particular wettability and good adhesion to conventional matrix materials and methods for their preparation. And the use of these in the preparation of the compositions. EP-A-0,006,275 describes a method for improving the adhesion of aromatic polyamide fibers, which is a plasma treatment of the fibers.
이 방법의 단점은 화이버의 인장 강도가 플라즈마 처리에 의해 저하된다는 것이다. EP-A-0,062,491호에는 조성물의 제조방법이 기술되어 있는데, 그 방법은 분자량이 300,000이하인 폴리올레핀의 필라멘트 및 화이버로 이루어진 보강물질을 플라즈마 처리하여 매트릭스 물질에 대한 접착성을 증가시켜서 종래의 폴리머 매트릭스에 매립하는 것이다. 이 경우에도 역시 플라즈마 처리된 보강 물질의 인장강도 저하가 허용될 수 있는 정도여야 한다.The disadvantage of this method is that the tensile strength of the fibers is lowered by the plasma treatment. EP-A-0,062,491 describes a process for the preparation of a composition, in which a reinforcing material consisting of filaments and fibers of polyolefin having a molecular weight of 300,000 or less is subjected to plasma treatment to increase adhesion to the matrix material, thereby increasing the adhesion to matrix polymers. Landfill. In this case too, the drop in tensile strength of the plasma treated reinforcing material should be such that it is acceptable.
본 발명의 목적은 특히 필라멘트, 화이버, 얀, 직물 및 필름과 같은 폴리올레핀 물건의 인장 강도를 저하시키는 일이 없이 습윤성 및 종래의 매트릭스 물질에 대한 접착성을 개선시키는 것이다.It is an object of the present invention, in particular, to improve wettability and adhesion to conventional matrix materials without reducing the tensile strength of polyolefin articles such as filaments, fibers, yarns, fabrics and films.
본 발명은 분자량이 600,000g/몰(중량 평균분자량) 이상으로 초고분자인, 특히 필라멘트, 화이버, 얀, 직물 및 필름과 같은 고도로 배향된 폴리올레핀의 표면을 플라즈마 처리함으로써 상기 목적을 이루었다. 놀랍게도 플라즈마 처리된 물건의 인장 강도는 높은 배향도 및 초고분자량으로 인해 매우 높아서 본 발명에 따른 물건은 종래의 매트릭스 물질을 사용하여 조성물을 제조하는데 있어서 보강물질로서 매우 적절하다. 본 발명에 따른 물건은 폴리에틸렌, 특히 분자량이 600,000-6,000,000g/몰 또는 그 이상으로 극도로 큰 선형 폴리에틸렌으로 구성되어 있는 것이 바람직하다.The present invention has achieved the above object by plasma treating the surface of highly oriented polyolefins, particularly ultra-high molecular weight, in particular filaments, fibers, yarns, fabrics and films, having a molecular weight of 600,000 g / mol (weight average molecular weight) or more. Surprisingly, the tensile strength of plasma treated articles is very high due to their high degree of orientation and ultra high molecular weight, so that the articles according to the invention are very suitable as reinforcing materials in preparing compositions using conventional matrix materials. The article according to the invention is preferably composed of polyethylene, in particular linear polyethylene with an extremely large molecular weight of 600,000-6,000,000 g / mol or more.
본 발명에 따른 물건은 특히 필라멘트, 화이버, 얀, 직물 및 필름으로 무엇보다도 먼저 조성물 물질의 제조에 보강물질로서 이용되는데, 적절하다면 유리섬유, 흑연섬유 등과 같은 그밖의 종래의 보강 물질과 함께, 예를 들어 페놀수지, 에폭시수지, 비닐에스테르수지, 폴리에스테르수지, 아크릴레이트수지 등과 같은 열경화성 수지 또는 폴리메틸(메타)아크릴레이트와 같은 극성의 열가소성 매트릭스 물질 등 폴리머성 매트릭스 물질에 매립되는 식으로 이용된다.The article according to the invention is used, first of all, as a reinforcing material in the preparation of the composition material, especially in filaments, fibers, yarns, fabrics and films, together with other conventional reinforcing materials such as glass fibers, graphite fibers and the like, for example For example, thermosetting resins such as phenol resins, epoxy resins, vinyl ester resins, polyester resins, acrylate resins, or the like are embedded in polymeric matrix materials such as polar thermoplastic matrix materials such as polymethyl (meth) acrylates. .
본 발명에 따른 플라즈마 처리결과 인장 강도는 전혀 저하되지 않고 본 발명에 따라 제조된 필라멘트, 화이버등은 매트릭스 물질에 대한 접착성이 양호하여 이들의 높은 인장 강도가 완전하게 발휘된다. 필라멘트 또는 화이버, 얀 및 이들로부터 제조되는 직물에 있어서 본 발명에 따른 고도의 배향은 필라멘트가 광범위한 연신, 특히 20이상, 더욱 특히 30이상의 연신율로 연신되는 식으로 하여 이루어지며 필름은 단일축 또는 이축방향으로 비슷한 연신율로 연신될 수 있다.As a result of the plasma treatment according to the present invention, the tensile strength is not lowered at all, and the filaments, fibers, etc. prepared according to the present invention have good adhesiveness to the matrix material, so that their high tensile strength is fully exhibited. In the filaments or fibers, yarns and fabrics made therefrom, the high orientation according to the invention is such that the filaments are drawn in a wide range of elongation, in particular at least 20, more in particular at least 30, and the film is uniaxial or biaxial. Can be drawn at a similar elongation.
고도로 배향된 폴리올레핀으로 구성되어 있고 본 발명에 따라 플라즈마 처리된 물건은 소위 겔 방법에 의해 제조되는 것이 바람직한데 이 방법은, 특정 폴리올레핀, 특히 초고분자량의 폴리에틸렌을 용매에 용해하고, 폴리올레핀의 용해온도보다 높은 온도에서 용매를 필라멘트 또는 테이프로 만들고, 겔화 또는 용매 제거를 위해 필라멘트 또는 테이프를 용해온도 아래로 냉각하고 이어서 연신시키는 것으로써 이루어진다.Articles composed of highly oriented polyolefins and plasma treated according to the invention are preferably produced by the so-called gel process, which dissolves certain polyolefins, in particular ultra high molecular weight polyethylene in a solvent, By making the solvent into a filament or tape at high temperature and cooling the filament or tape below the dissolution temperature and then stretching for gelation or solvent removal.
필라멘트를 제조하기 위한 이러한 방법은 예를 들어 GB-A-2,042,414 및 2,051,667호에 기술되어 있으며 초고분자량의 폴리올레핀으로부터 고도로 배향된 이축 방향으로 연신된 필름을 제조하는 방법은 예를 들어 독일연방공화국 특허 제3,724,434호에 기술되어 있다.Such methods for producing filaments are described, for example, in GB-A-2,042,414 and 2,051,667, and methods for producing films oriented in the highly oriented biaxial direction from ultra high molecular weight polyolefins are described, for example, in the Federal Republic of Germany Patent No. 3,724,434.
본 발명에 따른 물건은 폴리에틸렌, 특히 프로필렌, 부틸렌, 펜텐, 헥센, 4-메틸펜텐, 옥텐등과 같은 공중합될 수 있는 알켄을 한 종류 또는 그 이상으로 소량, 바람직하기로는 5몰%이하 함유하고 있는 폴리에틸렌으로 구성되는 것이 바람직하다.The article according to the invention contains one or more small amounts, preferably up to 5 mol%, of polyethylene, in particular copolymerizable alkenes such as propylene, butylene, pentene, hexene, 4-methylpentene, octene and the like. It is preferably composed of polyethylene.
또한 폴리에틸렌은 탄소원자 1000개당 메틸 또는 에틸 그룹을 1-10개 특히 2-6개 가지고 있는 것이 바람직하다.It is also preferable that polyethylene has 1-10, in particular 2-6, methyl or ethyl groups per 1000 carbon atoms.
그러나 이미 언급한 바와 같이 폴리프로필렌 호모폴리머 및 코폴리머와 같은 그 밖의 폴리올레핀이 사용될수 있고 폴리올레핀은 특히 1-알켄 폴리머와 같은 다른 폴리머를 한 종류 또는 그 이상으로 소량 함유할 수도 있다.However, as already mentioned, other polyolefins such as polypropylene homopolymers and copolymers may be used and the polyolefins may contain one or more small amounts of other polymers, in particular other polymers such as 1-alkene polymers.
본 발명에 따르면 필라멘트 및 이들로부터 제조되는 생성물과 필름은 다공성일 수 있으며, 이 경우에 밀도는 0.1-0.9g/㎤인 것이 바람직하다.According to the invention the filaments and the products and films made therefrom may be porous, in which case the density is preferably 0.1-0.9 g / cm 3.
이들은 겔 필라멘트 또는 테이프로부터 용매를 제거할때 기공이 생기도록 용매의 증발을 조절함으로써 제조될 수 있다.They can be prepared by controlling the evaporation of the solvent to create pores when removing the solvent from the gel filament or tape.
초고분자량의 고도로 배향된 폴리올레핀으로 구성되어 있는 플라즈마 처리된 물건을 제조하기 위한 본 발명에 따른 방법은 필요하다면 전-세척후에 물건의 표면을 플라즈마 처리하는 것으로써 이루어진다.The method according to the invention for producing a plasma treated article composed of ultra high molecular weight, highly oriented polyolefin consists of subjecting the surface of the article after pre-washing if necessary.
전-세척은 예를 들어, 표면에 부착되어 있는 풀을 제거하기 위한 용매 처리로 이루어질 수 있으며 이에 따라 플라즈마 처리될 물건의 표면이 세정된다.Pre-cleaning may, for example, consist of solvent treatment to remove glue attached to the surface, thereby cleaning the surface of the object to be plasma treated.
플라즈마 처리는 불활성 및/또는 반응성 기체 또는 기체 화합물을 사용함으로써 이루어지는데 그중에서도 반응성 기체를 사용하는 것이 바람직하다.Plasma treatment is accomplished by using an inert and / or reactive gas or gaseous compound, of which reactive gas is preferred.
질소와 헬륨이 불확성 기체로서, 공기, 산소, 이산화탄소 및 암모니아가 반응성 기체로서 각각 언급될 수 있다. 플라즈마 처리는 0.2-5mmHg의 압력, 특히 1mmHg의 압력, 5-100KW/㎥, 특히 15-50KW/㎥의 에너지밀도, 특히 실온에서 5-200초의 체류시간인 조건하에서 이루어지는 것이 바람직하다.Nitrogen and helium may be mentioned as the uncertainty gas, and air, oxygen, carbon dioxide and ammonia, respectively, as reactive gases. The plasma treatment is preferably carried out under conditions of a pressure of 0.2-5 mmHg, in particular a pressure of 1 mmHg, an energy density of 5-100 KW / m 3, in particular 15-50 KW / m 3, in particular a residence time of 5-200 seconds at room temperature.
또한 플라즈마 처리직후에 플라즈마 처리된 물건의 습윤성 및 흉착성을 증진시키기 위해 화학처리를 실시하는 것이 바람직한데, 화학처리결과 예를 들어 카르복실기, 수산기 또는 카르보닐기와 같은 활성기와 물건의 표면에 부차적으로 제공된다.In addition, it is preferable to perform a chemical treatment to improve the wettability and squeezability of the plasma-treated article immediately after the plasma treatment, and the chemical treatment is additionally provided on the surface of the article and an active agent such as a carboxyl group, a hydroxyl group or a carbonyl group. .
이러한 처리는 예를 들어 아크릴산, 아크릴아미드, 말레인산, 글리시딜 메타크릴레이트, 히드록시에틸메타크릴레이트, 이타코닌산, 비닐 아세테이트등과 같은 불포화 화합물을 이용함으로써 이루어질 수 있다. 이 경우에 불포화 화합물의 공중합을 피하기 위해 철(III) 화합물과 같은 공중합 저해제를 사용하는 것이 바람직하다.Such treatment may be achieved by using unsaturated compounds such as, for example, acrylic acid, acrylamide, maleic acid, glycidyl methacrylate, hydroxyethyl methacrylate, itaconic acid, vinyl acetate and the like. In this case, it is preferable to use a copolymerization inhibitor such as an iron (III) compound in order to avoid copolymerization of an unsaturated compound.
예를 들어, 이러한 화학처리는 플라즈마 처리된 물건을 아크릴산 용액과 같은 상기의 불포화 화합물중의 한 종류의 용액에 주입시킴으로써 이루어질 수 있으나 화학 후처리는 기체상에서 이루어질 수도 있다.For example, such chemical treatment may be accomplished by injecting a plasma treated article into a solution of one of the above unsaturated compounds, such as acrylic acid solution, but chemical aftertreatment may also be performed in the gas phase.
플리올레핀의 흡착성을 증진시키기 위한 이러한 유형의 화학적 방법은 공지되어 있는 것이다.Chemical methods of this type for enhancing the adsorptivity of polyolefins are known.
바람직한 방법에 있어서, 화이버, 얀 및 직물의 제조에 사용되는 폴리올레핀 필라멘트가 본 발명에 따른 방법을 시행하는데 이용된다.In a preferred method, polyolefin filaments used in the manufacture of fibers, yarns and fabrics are used to implement the process according to the invention.
필라멘트의 플라즈마 처리를 위한 창치는 EP-A-0,006,275호에 기술되어 있다.The device for plasma treatment of filaments is described in EP-A-0,006,275.
이 장치에는 모세관으로 된 인렛과 아웃렛 또는 이러한 인렛 및 아웃렛이 여러개 있으며, 이를 통해 필라멘트가 연속적으로 연신되어 플라즈마 처리를 가진다.The apparatus includes a capillary inlet and an outlet or several such inlets and outlets, through which the filaments are continuously drawn to have a plasma treatment.
그러나 필라멘트가 플라즈마 챔버의 내부에서 순환되는 장치도 이용될 수 있는데, 이 경우에는 원하는 체류시간에 따라 필라멘트가 원하는 회전수대로, 편향 로울러에 감길 수 있다.However, a device in which the filament is circulated inside the plasma chamber may also be used, in which case the filament may be wound around the deflection roller at a desired rotational speed, depending on the desired residence time.
그러나 면적이 큰 직물 또는 필름은 이에 맞는 크기를 지닌 플라즈마 처리 장치로 처리할 수도 있다.However, a large area fabric or film may be treated with a plasma processing apparatus having a size that is suitable for it.
보강재로서 본 발명에 따라 만들어진 필라멘트, 화이버, 얀 및 직물을 이용함으로써 제조된 조성물로부터 특히 테니스라켓, 골프 클럽등과 같은 스포츠용품이 제조되며, 헬맷, 보트, 대탄도탄, 고압호스등도 이들 조성물로부터 제조될 수 있다.From the composition prepared by using the filaments, fibers, yarns and fabrics made in accordance with the present invention as reinforcement, in particular sporting goods such as tennis rackets, golf clubs and the like, helmets, boats, antiballistic bullets, high pressure hoses and the like are also produced from these compositions. Can be prepared.
[실시예]EXAMPLE
분자량이 약 1.9×106인 폴리에틸렌 모노필라멘트 약 400개로 이루어진 강도가 2.4GPa이고 탄성모듈러스가 90GPa인 800dtex 얀을 사염화탄소로 세척하여 풀기를 제거했다. 1mmHg, 25℃, 30KW/㎥의 에너지 밀도에서 50초 동안 공기 플라즈마의 작용으로 상기 얀을 플라즈마 처리했다. 이 얀을 이용하여 50v.%의 얀과, 50v.%의 수지(100부의 Eurepox 730, 쉐링제조, 20부의 경화제(XE278))로 이루어진 조성물 시편을 폭 3mm, 높이 4mm, 길이 150mm의 크기로 제조했다.800 dtex yarns with a strength of 2.4 GPa and an elastic modulus of 90 GPa consisting of about 400 polyethylene monofilaments having a molecular weight of about 1.9 × 10 6 were washed with carbon tetrachloride to remove the loosening. The yarns were plasma treated by the action of air plasma for 50 seconds at an energy density of 1 mmHg, 25 ° C. and 30 KW / m 3. Using this yarn, a composition specimen consisting of 50v.% Yarn and 50v.% Resin (100 parts of Eurepox 730, manufactured by Schering, 20 parts of curing agent (XE278)) was prepared in the size of 3 mm wide, 4 mm high and 150 mm long. did.
이 시편을 23℃에서 1½시간 동안, 80℃에서 1시간 동안 완전히 경화시켜 길이 18mm의 시편으로 잘라내어 2mm/분의 벤딩속도로 ASTM Method D 23 44(가속 벤딩시험)에 따라 라미나르간 전단 강도를 측정했다.This specimen was fully cured for 1½ hours at 23 ° C for 1 hour at 80 ° C, cut into 18 mm length specimens, and the shear strength between laminars was measured according to ASTM Method D 23 44 (accelerated bending test) at a bending rate of 2 mm / min. Measured.
대조용으로 플라즈마 처리를 하지 않은 얀을 이용하여 제조한 동일한 조성물시편을 준비했다.The same composition specimens prepared using yarns that were not plasma treated were prepared for control.
라미나르간 전단 강도는 플라즈마 처리된 얀의 경우에는 30.6±0.7MPa이고 플라즈마 처리되지 않은 얀의 경우에는 12.9±0.8MPa였다. 또한 이에 상응하는 인장강도는 각각 2.5±0.15Gpa 및 2.4±0.05Gpa였다.Laminagan shear strength was 30.6 ± 0.7 MPa for the plasma treated yarn and 12.9 ± 0.8 MPa for the yarn that was not plasma treated. Corresponding tensile strengths were 2.5 ± 0.15 Gpa and 2.4 ± 0.05 Gpa, respectively.
이러한 결과는 본 발명에 따른 얀이 동일한 인장강도에서 플라즈마 처리되지 않은 얀에 비해 흡착강도가 2배라는 것을 나타낸다.These results indicate that the yarn according to the present invention has twice the adsorptive strength compared to yarns that are not plasma treated at the same tensile strength.
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| DE3733426 | 1987-10-02 | ||
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| KR101460446B1 (en) * | 2013-07-24 | 2014-11-10 | 다이텍연구원 | High-durability dyeing method of super high strength fiber fabric |
| KR20150038287A (en) * | 2012-07-27 | 2015-04-08 | 허니웰 인터내셔널 인코포레이티드 | Novel uhmwpe fiber and method to produce |
| KR101980371B1 (en) * | 2018-04-24 | 2019-05-20 | 가온스포츠 주식회사 | Environmentally friendly artificial turf yarn modified by plasma treatment and artificial turf structure using the same |
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| JPH02194033A (en) * | 1989-01-23 | 1990-07-31 | Mitsui Petrochem Ind Ltd | Production of polyolefin molding of improved adhesiveness |
| US5006390A (en) * | 1989-06-19 | 1991-04-09 | Allied-Signal | Rigid polyethylene reinforced composites having improved short beam shear strength |
| EP0436918B1 (en) * | 1990-01-03 | 1995-06-28 | Wolff Walsrode Aktiengesellschaft | Process for treating a polyolefin film |
| FR2677368B1 (en) * | 1991-06-10 | 1994-09-30 | Inst Textile De France | GRAFTING PROCESS COMPRISING AN ELECTRIC TREATMENT UNDER NITROGEN ATMOSPHERE. |
| US5805264A (en) * | 1992-06-09 | 1998-09-08 | Ciba Vision Corporation | Process for graft polymerization on surfaces of preformed substates to modify surface properties |
| JP2007520371A (en) * | 2004-01-01 | 2007-07-26 | ディーエスエム アイピー アセッツ ビー．ブイ． | Bulletproof articles |
| EA016944B1 (en) * | 2005-08-17 | 2012-08-30 | ИННЕГРИТИ, ЭлЭлСи | Composite laminatates |
| CN101532244B (en) * | 2008-12-19 | 2012-07-25 | 东华大学 | Method for modifying ultrahigh molecular weight polyethylene fiber by plasma treatment |
| US9023451B2 (en) * | 2011-09-06 | 2015-05-05 | Honeywell International Inc. | Rigid structure UHMWPE UD and composite and the process of making |
| US9023450B2 (en) * | 2011-09-06 | 2015-05-05 | Honeywell International Inc. | High lap shear strength, low back face signature UD composite and the process of making |
| US9023452B2 (en) | 2011-09-06 | 2015-05-05 | Honeywell International Inc. | Rigid structural and low back face signature ballistic UD/articles and method of making |
| US10132006B2 (en) | 2012-07-27 | 2018-11-20 | Honeywell International Inc. | UHMWPE fiber and method to produce |
| ITBO20120612A1 (en) * | 2012-11-07 | 2014-05-08 | Veneto Nanotech S C P A | PROCEDURE FOR THE TREATMENT OF A SUBSTRATE IN FIBER AND MACHINE TO IMPLEMENT THIS PROCEDURE. |
| CN103213652A (en) * | 2013-04-26 | 2013-07-24 | 东华大学 | Landing boat and manufacturing method thereof |
| CN103213651B (en) * | 2013-04-26 | 2016-04-20 | 东华大学 | A kind of collapsible canoe and manufacture method thereof |
| CN103213653B (en) * | 2013-04-26 | 2016-04-06 | 东华大学 | A kind of assault boat and manufacture method thereof |
| JP2015227519A (en) * | 2014-06-02 | 2015-12-17 | 株式会社フジックス | Sewing thread coloring method using plasma treatment and sewing thread colored by the method |
| US9909240B2 (en) | 2014-11-04 | 2018-03-06 | Honeywell International Inc. | UHMWPE fiber and method to produce |
| DE102015106749A1 (en) | 2015-04-30 | 2016-11-03 | Technische Universität Darmstadt | Multifunctional ultrasonic cutting device for attachment to a device for a minimally invasive procedure |
| KR102230480B1 (en) * | 2019-11-19 | 2021-03-24 | 주식회사 비즈링크 | Manufacturing method of towel with hygroscopic heat-releasing fiber |
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| US3477902A (en) * | 1965-10-14 | 1969-11-11 | Radiation Res Corp | Process for making tires by exposure to an ionized gas and treatment with resorcinol-formaldehyde/latex composition and the product |
| EP0062491B2 (en) * | 1981-04-04 | 1991-12-11 | National Research Development Corporation | Polymers in matrix reinforcement |
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- 1988-09-30 JP JP63248931A patent/JPH026657A/en active Pending
- 1988-09-30 EP EP88202157A patent/EP0311197A3/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20150038287A (en) * | 2012-07-27 | 2015-04-08 | 허니웰 인터내셔널 인코포레이티드 | Novel uhmwpe fiber and method to produce |
| KR101460446B1 (en) * | 2013-07-24 | 2014-11-10 | 다이텍연구원 | High-durability dyeing method of super high strength fiber fabric |
| KR101980371B1 (en) * | 2018-04-24 | 2019-05-20 | 가온스포츠 주식회사 | Environmentally friendly artificial turf yarn modified by plasma treatment and artificial turf structure using the same |
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| Publication number | Publication date |
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| AU2336988A (en) | 1989-04-06 |
| EP0311197A2 (en) | 1989-04-12 |
| EP0311197A3 (en) | 1990-03-28 |
| CN1035308A (en) | 1989-09-06 |
| KR890006898A (en) | 1989-06-16 |
| ZA887381B (en) | 1989-06-28 |
| AU607544B2 (en) | 1991-03-07 |
| JPH026657A (en) | 1990-01-10 |
| BR8805048A (en) | 1989-05-09 |
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