TW483919B - Polyoxymethylene compositions and its reparation method and uses - Google Patents
Polyoxymethylene compositions and its reparation method and uses Download PDFInfo
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- TW483919B TW483919B TW088100066A TW88100066A TW483919B TW 483919 B TW483919 B TW 483919B TW 088100066 A TW088100066 A TW 088100066A TW 88100066 A TW88100066 A TW 88100066A TW 483919 B TW483919 B TW 483919B
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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
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/02—Polyacetals containing polyoxymethylene sequences only
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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
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/04—Copolyoxymethylenes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
- C08L2666/06—Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
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Abstract
Description
五、發明說明(l) ' ' --- ---- ijj背景 本發明係有關一種具改良模造丨棰及具改良模造物件之物 h生質之聚曱醛(本文亦稱為聚縮醛)樹脂組合物。 取,縮駿樹脂係由大部分曱酿單體或曱駿三聚物(三噚烧) 也3而得。縮醛均聚物為曱醛均聚物(例如,由Ε·丨· du 尸〇rU de Nemours 公司制、生七ι · η一价,丄 、 %私总丄加a戸—衣造之 n#細鉍樹脂)。縮醛共 勿係由例如衣氧烷與例如三噚烷共聚合而得。 疲勞抗 汽車用 聚:娜旨由於其高機械強度、優異摩擦抗性 、杈造性寺,而廣泛用於例如電器及電子用 途及精密機械用途。 聚曱酸樹脂為工鞋令人从士 | θ 中板% ^合物中最具結晶性者且因此於模具 #、k凍…。但该等樹脂亦具高度皺縮性。近來,已導人 核化之聚曱醛樹脂以改良時 、木已蜍入 進-步之改良,尤立2;;:減少敏縮。但仍需要 質上消除模造物件中之空隙。 而罟4 C或声、 概要 J發,括—種聚甲趁樹脂與 數烷酯聚合核化物質、晳丰枋个靶^羧鮫低石反 之摻合物。此二1 化物質及成核劑之組合物 伸長;亦具f良設定時間及減少敏縮及改良之 除♦所上、、肖^ ,% °M立之熱變形。使用本組合物可消 除或只貝上4除模造物件中之空 :: 添加劑,亦即伸燒基(甲基)丙烯 ::::,,明在 乙暴甲基丙烯g夂酯(EMA)、蠟質去 、V甲 成核劑如滑石之間之气、f去4、夕切核化物質如聚乙烯蠟及 <間之刖述未知之協同性。V. Description of the invention (l) '' --- ---- ijj BACKGROUND The present invention relates to a polyacetal (also referred to herein as polyacetal) with improved molding ) Resin composition. Taken, the shrinkage resin is obtained from most of the brewing monomers or the trimer terpolymers (Miyazaki). The acetal homopolymer is a homopolymer of acetal (for example, manufactured by Ε · 丨 · du 〇〇orU de Nemours company, and has a single price, 丄,% private total plus a 衣 —clothing n #Finebismuth resin). The acetal copolymer is obtained by copolymerizing, for example, oxyoxane and, for example, trioxane. Fatigue resistance for automotive applications Poly: Nagumi is widely used in, for example, electrical and electronic applications and precision machinery applications due to its high mechanical strength, excellent friction resistance, and nature-saving characteristics. Polyacrylic acid resin is the most crystalline of the work shoes | θ middle plate% ^ compound and therefore frozen in the mold #, k ... However, these resins are also highly shrinkable. Recently, the nucleated polyfluorinated resin has been improved to improve upon the improvement, especially for the improvement, especially Li 2 ;;: reduce the shrinkage. However, there is still a need to substantially eliminate voids in the molded article. And 4C or sound, summary J hair, including a kind of polymethyl methacrylate resin and polyalkyl ester polymerized nucleation material, a clear target ^ carboxyl low stone blend. The combination of these two chemical substances and nucleating agents elongs; it also has a good set time and reduces sensitivity and improvement. In addition to the above, Xiao ^,% ° M thermal deformation. The use of this composition can eliminate or remove only 4 voids in molded articles :: Additives, that is, elongation-based (meth) propylene ::: ,,, Ethyl methacrylate g-methyl ester (EMA) , Wax removal, V-form nucleating agents such as gas between talc, f to 4, cutting nucleating materials such as polyethylene wax and < unknown synergy between the description.
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五、發明說明(2) 圖式之簡單說明 圖1 a及1 b顯示結晶作用1 / 2時間對各種聚甲搭樹雜铒含 物之作圖。 ^ 圖2 a、2 b及2 c藏示由含各種添加劑之聚曱駿樹腐搞遠 桿狀物切面之影印複製。 ' 圖3a及3b顯示由含各種添加劑之聚甲醛樹脂模造么捧狀 物切面之影印複製。 圖4 a及4 b顯示由含各種添加劑之聚甲駿樹脂模造之桿狀 物切面之影印複製。 發明之詳細說明 本發明細有關一種組合物’其含有聚甲醛樹脂及包括下 列成分之組合: a) 聚伸烷/不飽和羧酸低碳數烧酯聚合核化物質; b) 蠟質去核化物質;及 c) 成核劑。 詳言之,本組合物含有聚甲醛樹脂及包括下列成分之組 合: a ) 0 · 5至3 w t %之聚伸炫/不飽和羧酸低碳數烷酯聚合核 化物質; Μ0· 1至1 wt%之蠟質丧核化物質;及 〇0· 01至3 wt%之成核劑。 較佳之組合物含有聚甲搭樹脂及包括下列成分之組合: a) 1至3 wt%之酯核化物質; b) 〇· 1至1 wt%之蠟質去核化物質;及V. Description of the invention (2) Brief description of the diagrams Figures 1a and 1b show the crystallization time 1/2 time map to various polycarboxylate inclusions. ^ Figures 2a, 2b, and 2c show photocopy reproductions of cut-away sections of rod-shaped rots from the jujube tree with various additives. 'Figures 3a and 3b show photocopy reproductions of cut surfaces of molded articles molded from polyacetal resins containing various additives. Figures 4a and 4b show photocopy reproductions of cut surfaces of rod-shaped objects molded from poly-Jun resins containing various additives. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition 'comprising a polyoxymethylene resin and a combination comprising the following components: a) polyalkylene / unsaturated carboxylic acid low-carbon burnt ester polymerization nucleation substance; b) waxy enucleation Chemical substances; and c) nucleating agents. In detail, the composition contains a polyoxymethylene resin and a combination including the following components: a) 0. 5 to 3 wt% of a polysexen / unsaturated carboxylic acid low-carbon alkyl ester polymerization nucleation material; M0 · 1 to 1 wt% waxy funnel nucleating substance; and 0.01 to 3 wt% nucleating agent. A preferred composition contains a polymethyl resin and a combination comprising the following components: a) 1 to 3 wt% of an ester nucleating substance; b) 0.1 to 1 wt% of a waxy denucleating substance; and
苐5頁 483919 五、發明說明(3) c) 〇 · 〇 1至3 w t %之成核劑。 需了解重s百分比係以全部組合物為主。剩餘之組合物 係由聚曱駿樹脂與其他添加劑所構成。 T用於本舍明之承曱駿树脂包含本技藝已知之廣泛種類 之均承物及共聚物。該等聚合物為其中聚合物鏈(鏈之端 部除外)係一系列之伸甲基與氧鍵結之一般甲盤聚合物。 此聚合物鏈亦可包含下列通式: R1 -(C)m-尺2 /、中m為1至5之整數及|^與|^為不會於聚合物中引起不良 反應之惰性取代基。聚合物鏈之此種額外成分係以少量比 例之重複單元存在。 洋a之’本文所用之π聚甲醛樹脂”成分包含甲醛之均聚 物或1駿之環狀寡聚物,其端基係經酯化或醚化封端;以 及甲駿或甲醛環狀寡聚物與其他可產生主鏈中具有至少兩 個相鄰碟原子之氧伸烷基之單體之共聚物,該共聚物之端 基可為經基端或可經酯化或醚化封端者。 本發明所用之聚曱醛可為直鏈或僅含少量分支之實質上 圍鍵者且通常重量平均分子量在40, 000至175, 000之範 含有較好為5 0,0 0 0至1 5 0,0 0 〇之間。較好該聚甲醛樹脂不 ^ 1可測得量之分支。分子量可便利地以凝膠滲透層析儀 仏 C之閒曱酚或在室溫之六氟異丙醇中測量。雖然視 子旦=及加工性質而定,可使用較高或較低重量平均分 樹111甲輕樹脂,但以具前述重量平均分子量之聚甲酸 曰車Λ <土 ’以提供欲熔融摻合至具有所需組合物理性質之苐 Page 5 483919 V. Description of the invention (3) c) 〇 · 〇 1 to 3 wt% of nucleating agent. It is understood that the percentage of weight s is based on the total composition. The rest of the composition is made up of Poly-Jun resin and other additives. The resin used in Ben Sheming contains a wide variety of homogeneous resins and copolymers known in the art. These polymers are general formazan polymers in which the polymer chain (except the end of the chain) is a series of methyl and oxygen bonds. This polymer chain may also include the following general formula: R1-(C) m-foot 2 /, where m is an integer from 1 to 5 and | ^ and | ^ are inert substituents that do not cause adverse reactions in the polymer . Such additional components of the polymer chain are present in small proportions of repeating units. The component of 'π polyformaldehyde resin used herein' includes a homopolymer of formaldehyde or a cyclic oligomer of Jun, whose end groups are terminated by esterification or etherification; and a Jun or formaldehyde cyclic oligomer A copolymer of a polymer and other monomers which can generate an oxyalkylene group having at least two adjacent disk atoms in the main chain, and the end group of the copolymer may be a base end or may be terminated by esterification or etherification The polyacetaldehyde used in the present invention may be a linear chain or a substantially fenced bond with only a small number of branches and usually has a weight average molecular weight in the range of 40,000 to 175,000, and preferably contains 50,000 to 5,000. 1 50, 0 0 〇. It is preferred that the polyoxymethylene resin does not have a measurable amount of branching. The molecular weight can be conveniently measured by gel permeation chromatography (C) or hexafluorophenol at room temperature. Measured in isopropanol. Although depending on the properties and processing properties, a higher or lower weight average molecular weight 111A light resin can be used, but polyacetic acid with the aforementioned weight average molecular weight is referred to as Λ < To provide melt blending to the desired combination of physical properties
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修正 案號 88100066 五、發明說明(4) 組合物中之各種成分於由此種組合物製得之成分中之良好 混合之最佳平衡。 如上所述,聚曱醛樹脂可為具不同重量平均分子量之均 聚物、具不同重量平均分子量之共聚物或其混合物。共聚 物可含一或多種共單體,如一般用於製造聚曱酸組合物 者。更常用之共單體包含2至12個碳原子之環氧烷及其與 曱醛之環狀加成產物。共單體之量不超過20重量%,較好 不超過15重量%,且最好約2重量%。常用之共單體包含環 氧乙烷、二氧雜環戊烷及環氧丁烷。通常,聚曱醛均聚物 比共聚物佳,因其具較高之張力強度及堅硬度。較佳之聚 曱醛均聚物包含其羥端基已藉化學反應封端形成酯或醚基 者,較好分別為乙酸酯或甲氧基。 聚伸烷/不飽和羧酸低碳數烷酯聚合核化物質通常為低 碳數(C2- C4)伸烷及不飽和酸之低碳數烷酯之共聚物或三聚 物。可用於本發明之聚合核化物質實例為式E/X/Y,較好 為E/X之以乙烯為主之聚合物。式E/X中,E為乙烯及X為不 飽和羧酸酯。 不飽和羧酸酯包含含3至8個碳原子之不飽和羧酸烷酯 (C^-Cs,較好C4)。例舉之不飽和酸包含丙烯酸及曱基丙 烯酸。酯之特別實例為丙烯酸曱酯、丙烯酸乙酯、丙烯酸 丙酯、丙烯酸異丙酯、丙烯酸正丁酯、甲基丙烯酸曱酯、 曱基丙烯酸乙酯、曱基丙烯酸丙酯、曱基丙烯酸異丙酯、 曱基丙烯酸正丁酯及曱基丙烯酸異丁酯,其中以丙烯酸乙 酯及曱基丙烯酸甲酯較佳。Amendment No. 88100066 V. Description of the Invention (4) The best balance of the good mixing of the various ingredients in the composition with the ingredients made from such a composition. As described above, the polyacetal resin may be a homopolymer having a different weight average molecular weight, a copolymer having a different weight average molecular weight, or a mixture thereof. The copolymer may contain one or more comonomers, such as those commonly used in the manufacture of polyacid compositions. More commonly used comonomers include alkylene oxides of 2 to 12 carbon atoms and their cyclic addition products with formaldehyde. The amount of comonomer is not more than 20% by weight, preferably not more than 15% by weight, and most preferably about 2% by weight. Common comonomers include ethylene oxide, dioxolane, and butylene oxide. In general, polyacetal homopolymers are better than copolymers because of their higher tensile strength and stiffness. Preferred polyacetal homopolymers include those whose hydroxyl end groups have been blocked by a chemical reaction to form an ester or ether group, preferably acetate or methoxy, respectively. Polynuclear alkylene / unsaturated carboxylic acid lower alkyl ester polymerized nucleating materials are usually copolymers or trimers of lower carbon number (C2-C4) alkylene and unsaturated acid lower alkyl esters. An example of a polymeric nucleating substance which can be used in the present invention is an ethylene-based polymer of the formula E / X / Y, preferably E / X. In the formula E / X, E is ethylene and X is an unsaturated carboxylic acid ester. The unsaturated carboxylic acid ester contains an unsaturated carboxylic acid alkyl ester (C ^ -Cs, preferably C4) having 3 to 8 carbon atoms. Exemplary unsaturated acids include acrylic acid and methacrylic acid. Specific examples of esters are ethyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, ethyl methacrylate, ethyl ethyl acrylate, ethyl propyl acrylate, ethyl isopropyl acrylate Esters, n-butyl fluorenyl acrylate and isobutyl fluorenyl acrylate, of which ethyl acrylate and methyl methacrylate are preferred.
O:\56V56383.ptc 第7頁 2001.08. 03.007 483919 五、發明說明(5) ------- ^佳之^稀两烯酸甲酯共聚物(π EMA")成分通常為市售 物負且可藉已知方式製得。EMA中丙烯酸甲酯之量通常為 EMt之3至4〇重量% ,較好為15至25重量% 。 、 聚伸烧/不飽和缓酸低碳數烷酯核化添加劑亦可為式 E/X/Y之以乙烯為主之無規聚合物,其中e為乙烯,χ係選 自甲基丙稀酸甲§旨、丙烯酸乙酯及丙烯酸丁酯,及Υ係選 自甲基丙稀酸縮水甘油酯及丙烯酸縮水甘油酯,且γ較佳 為曱基丙烯酸縮水甘油酯。Ε/χ/γ主要由5-99%之Ε,〇〜35% 之X及0.5-10 %之γ所構成。 以乙烯為主之無規聚合物實例主要由9〇 — 99重量%之乙稀: 及1 1 0重里 < 之曱基丙烯酸縮水甘油酯所構成。較好,此 乙稀/甲基丙稀酸縮水甘油酯("EGMA”)無規聚合物主要由 9 0-9 7重量%之乙烯及3 —丨〇重量%之甲基丙烯酸縮水甘油 ("GMA”)所構成。 另一較佳之以乙烯為主之無規聚合物主要由6〇_985重 量%之乙烯、〇· 5 —35重量%之丙烯酸丁酯(,,BA”)及丨―1〇重量 %之=基丙烯酸縮水甘油酯("GMA")所構成。較好,此乙烯 /丙稀酸丁醋/甲基丙烯酸縮水甘油酯(,,EBAGMAn )無規聚合 物主要由5 5- 84重量%之乙烯、15 —35重量%之^及卜1〇重; \之GMA所構成。更好,此EBAGMA主要由57· 5-74重量%之^ 稀、2 5 -3 5重量% iBA及丨—7· 5重量% iGMA所構成。 ^以乙烯為主之!規聚合物成分可藉本技藝已知之技術 得:EgAGMA無規聚合物實例提供於usp. 4,75 3 。 蠟負去核化成分為可分散於聚縮醛樹脂且在正常室溫下O: \ 56V56383.ptc Page 7 2001.08. 03.007 483919 V. Description of the invention (5) ------- ^ Good ^ Dilute dienoic acid methyl ester copolymer (π EMA ") components are usually negative for commercial products It can be prepared by known methods. The amount of methyl acrylate in the EMA is usually 3 to 40% by weight of EMt, preferably 15 to 25% by weight. 1. Poly-elongated / unsaturated slow-acid low-carbon alkyl ester nucleating additives can also be ethylene-based random polymers of formula E / X / Y, where e is ethylene and χ is selected from methyl propylene Acid methyl ester, ethyl acrylate and butyl acrylate, and fluorene are selected from glycidyl methacrylate and glycidyl acrylate, and γ is preferably glycidyl acrylate. E / χ / γ is mainly composed of 5-99% of E, 0 ~ 35% of X, and 0.5-10% of γ. Examples of ethylene-based random polymers are mainly composed of 90 to 99% by weight of ethylene: and 110 gram of glycidyl methacrylate. Preferably, the ethylene / methacrylic acid glycidyl ester (" EGMA ") random polymer is mainly composed of 90-97% by weight of ethylene and 3-0% by weight of methacrylic acid glycidyl ( " GMA "). Another preferred random polymer mainly composed of ethylene is mainly composed of 60-985% by weight of ethylene, 0.5-35% by weight of butyl acrylate (,, BA ") and 10-10% by weight = Glycidyl acrylate (" GMA "). Preferably, this ethylene / butyl acrylate / glycidyl methacrylate (,, EBAGMAn) random polymer is mainly composed of 5 to 84% by weight. Ethylene, 15-35% by weight ^ and bu 10 weight; \ of GMA. Better, this EBAGMA is mainly composed of 57.5-74% by weight ^ dilute, 2 5-3 5% by weight iBA and 丨- 7.5% by weight of iGMA. ^ It is mainly ethylene! The polymer component can be obtained by techniques known in the art: Examples of EgAGMA random polymer are provided at usp. 4,75 3. Wax negative denuclearization component Dispersible in polyacetal resin and at normal room temperature
483919 五、發明說明(6) 為液體之物質。或者,若此物質在正常室溫為固體,則其 需在低於聚縮醛加工或模造溫度之溫度下變成流體化。可 用之蠟質去合化成分實例為天然或合成蠟,例如烴及聚合 蠟。烴蠟包含地蠟、石油蠟、石蠟或微晶蠟及合成蠟,例 如乙烯系聚合物或氯化蔡。聚合蠟包含聚乙烯、聚丙烯及 乙烯/丙烯共聚物。較佳之物質包含石壤及聚乙稀堪。若 諸成分在雙軸擠出機(其為較佳之混合裝置)中混合在一 起,則可得到良好摻合。 本發明可用之成核劑為任何細粒固體,例如氮化硼、滑 石、氧化矽、聚醯亞胺、分支或交聯縮醛共聚物或三聚 物、密胺-甲醛樹脂、碳酸鈣、矽藻土、白雲石或其他用 於聚曱搭之已知成核劑。以氮化硼、三聚物或滑石較佳, 以分支三聚物最佳。成核劑可視需要以標準製程進行表面 處理。 本發明中使用作為成核劑之分支或交聯聚(氧伸甲基)可 以下列製得。 a. 使三噚烷與至少一種可與三噚烷多官能性反應且共聚 合之化合物及視情況與至少一種可與三噚烷單官能性反應 且共聚合之化合物共聚合,或 b. 隨後與具側鏈或鏈鍵結之官能基之直鏈聚(氧伸曱基) 進行分支或交聯反應,或 c. 使三噚烷與至少一種可與三噚烷單官能性反應且共聚 合之化合物與分支或交聯聚醚共聚合,或使直鏈聚(氧伸 甲基)與分支或交聯聚醚反應。483919 V. Description of the Invention (6) Liquid substances. Alternatively, if the substance is solid at normal room temperature, it needs to be fluidized at a temperature below the polyacetal processing or molding temperature. Examples of useful waxy desalination components are natural or synthetic waxes, such as hydrocarbons and polymeric waxes. Hydrocarbon waxes include ceresin, petroleum wax, paraffin or microcrystalline wax, and synthetic waxes, such as ethylene-based polymers or chlorinated zeolites. Polymeric waxes include polyethylene, polypropylene, and ethylene / propylene copolymers. Preferred materials include rocky soil and polyethylene. Good blending can be achieved if the ingredients are mixed together in a biaxial extruder, which is the preferred mixing device. The nucleating agent useful in the present invention is any fine-grained solid, such as boron nitride, talc, silica, polyimide, branched or cross-linked acetal copolymer or terpolymer, melamine-formaldehyde resin, calcium carbonate, Diatomaceous earth, dolomite, or other known nucleating agents used for polymerization. Boron nitride, trimer or talc is preferred, and branched trimer is most preferred. Nucleating agents can be surface-treated in standard processes as required. The branched or crosslinked poly (oxymethyl) group used as a nucleating agent in the present invention can be prepared as follows. a. Trioxane is copolymerized with at least one compound that is reactive with trioxane polyfunctionality and copolymerized and optionally with at least one compound that is reactive with trioxane monofunctionality and copolymerized, or b. subsequently Branching or cross-linking with a linear poly (oxyalkylene) functional group with a side chain or chain bond, or c. Allowing trioxane to react with and copolymerize with at least one trifunctional monofunctional The compound is copolymerized with a branched or crosslinked polyether, or a linear poly (oxymethylene group) is reacted with the branched or crosslinked polyether.
第9頁 五、發明說明(7) 成核劑較好具有小的平 於2。微米較好小於!。微】拉:最:,;的平均粒徑需小 成核劑可為包封之成核齊卜本==幾米。 由包封劑聚合物及成核劑所構成。 匕封成核劑主要 、包封劑聚合物可為任何適度熔人 成核劑之聚甲醛樹脂加工溫度融化之::2 1即在包封 包封劑聚合物包含直鏈低密度聚己烯 ^合物。例示之 聚乙烯("HDPE”)及聚丙烯,其各具 E”)、高密度 之固體密度(以ASTM D1 5 0 5測得)。_ ,不;勺或等於1克/cm3 LLDPE或HDPE之一。包封劑聚合物在公二丨2劑聚合物為 長鍵聚合物分支或主要為直鏈。缺之'/赫八%構中可缺乏 包封劑聚合物之方法之故。 、〜刀支是因為製造 包封劑聚合物係選自本技藝悉知之聚人 物可以商業購得或可藉纟技藝已;巷包巧聚合 封劑聚合物係由乙稀或乙稀與“_烯烴丘衣備。通_,包 氣相反應器中,用配位„,尤其是齊、體於溶液相或 飛利細UUP)型觸媒製得。較好lldpe^ 有熔融私數(以ASTM D1 2 38方法條件E測得)在5至55克/1〇 分鐘fc圍内。較好HDPE包封劑聚合物具有熔融指數(以 A STM D 1 2 38方法條件e測得)在約〇· 5至7克/1〇分鐘範圍 内。含有炼融指數在上述範圍以外iLLDpE *HDpE之組合 物可產生具良好孔隙度值之材料形狀,但卻提高具有其他 不希望特性之化合樹脂及擠出之材料形狀,例如降低聚曱 酸與LLDPE或HDPE之安定性或產生分離(亦即脫層)。Page 9 V. Description of the invention (7) The nucleating agent preferably has a smaller ratio than 2. Micron is preferably smaller than!. Micro] pull: most:,; The average particle size needs to be small. The nucleating agent can be the encapsulating nucleation zibbon == a few meters. Consists of an encapsulant polymer and a nucleating agent. The main nucleating agent, the encapsulant polymer can be melted at any moderate melting nucleating agent polyacetal resin at the processing temperature: 2: 1 means that the encapsulating polymer contains linear low-density polyhexene ^组合。 The compound. Exemplified polyethylene (" HDPE ") and polypropylene, each with E"), high density solid density (measured by ASTM D1 5 0 5). _, No; spoon or equal to 1 g / cm3 of one of LLDPE or HDPE. The polymer of the encapsulant is a long-chain polymer branch or mainly a straight-chain polymer. The lack of '/ Height% structure may lack the method of encapsulant polymer. , ~ Knife is because the manufacture of the encapsulant polymer is selected from the polymer known in the art can be purchased commercially or can be borrowed from the arts; the lane package smart polymer sealant polymer is made of ethylene or ethylene and "_ Preparation of olefins. It is prepared in a gas-phase reactor using coordination catalysts, especially homogeneous, solution-phase or fine UUP catalysts. It is preferred that the molten private number (measured under ASTM D1 2 38 Method Condition E) be within the range of 5 to 55 g / 10 minutes fc. Preferred HDPE encapsulant polymers have a melt index (measured under A STM D 1 2 38 method condition e) in the range of about 0.5 to 7 g / 10 minutes. Compositions with a melting index outside of the above range iLLDpE * HDpE can produce material shapes with good porosity values, but improve the shape of compound resins and extruded materials with other undesired properties, such as reducing polyacid and LLDPE Or the stability of HDPE or separation (ie delamination).
第10頁 483919 五、發明說明(8) 需避免對聚曱醛之氧化或熱安定性有不良影響之添加 劑或成分。 本發明之組合物除了前述成分以外,可視情況包含一 般用於聚縮醛組合物之其他成分、改質劑及添加劑,包含 熱安定劑及共安定劑、抗氧化劑、著色劑(包含顏料)、韋刃 化劑(如熱塑性聚胺基曱酸酯)、補強劑、紫外光安定劑 (笨并***或二笨甲酮)、包含受阻胺光安定劑(尤其是其 中受阻之氮為三級胺官能度者或其中受阻胺光安定劑含有 六氫吡啶或六氫吡畊酮及三畊環者)、玻璃及填料。適宜 熱安定劑包含聚醯胺(包含耐綸6 6、耐綸6 / 1 0及耐綸6之耐 綸三聚物以及U. S. P. 3, 9 6 0, 984之聚醯胺安定劑);可熔 融之含羥基聚合物及共聚物,包含乙烯乙烯醇共聚物及述 於 U.S.P. 4,8 1 4,3 9 7 及 U.S.P. 4,7 6 6,168 之安定劑;述於 U. S. P. 5,0 1 1,8 9 0之非可熔融之含羥基或含氮之聚合物且 尤其是聚丙烯醯胺;及微晶纖維素;聚/5苯胺(如述於德 國公開申請案3715 117者);聚丙烯醯胺;或揭示於U. S. P. 4,814, 397; 4, 766, 168; 4, 64 0, 949 及4, 098, 984 之安定 劑;及上述之任何混合物。典型之抗氧化劑包含受阻酚如 三乙二醇雙(3-(3’ -第三丁基-4’-羥基-5’-甲基苯基)丙酸 酯,N,Ν’ -六伸甲基雙(3, 5- 第三丁基-4-羥基氫桂皮醯 胺)及其混合物以及揭示於U . S. Ρ · 4,9 7 2,0 1 4之抗氧化 劑。 本文所述之組合物可藉本技藝已知之方法,在高於縮盤 聚合物熔點之溫度下混合所有成分及縮醛聚合物而製得。Page 10 483919 V. Description of the invention (8) It is necessary to avoid additives or ingredients that have an adverse effect on the oxidation or thermal stability of polyacetal. In addition to the aforementioned ingredients, the composition of the present invention may include other ingredients, modifiers, and additives generally used in polyacetal compositions, including heat stabilizers and co-stabilizers, antioxidants, colorants (including pigments), Welding agents (such as thermoplastic polyurethanes), reinforcing agents, ultraviolet light stabilizers (benzotriazole or dibenzone), containing hindered amine light stabilizers (especially where the blocked nitrogen is tertiary Those with amine functionality or those in which the hindered amine light stabilizers contain hexahydropyridine or hexahydropyridone and the three-field ring), glass and filler. Suitable thermal stabilizers include polyamides (including nylon 6 6, nylon 6/10, and nylon terpolymers of nylon 6 and polyamide stabilizers of USP 3, 96, 984); meltable The hydroxyl-containing polymers and copolymers include ethylene vinyl alcohol copolymers and stabilizers described in USP 4,8 1 4,3 9 7 and USP 4,7 6 6,168; described in USP 5,0 1 1, 8 9 0 non-meltable hydroxyl- or nitrogen-containing polymers and especially polypropylene fluoramide; and microcrystalline cellulose; poly / 5 aniline (as described in German published application 3715 117); polypropylene 醯Amines; or stabilizers disclosed in USP 4,814, 397; 4, 766, 168; 4, 64 0, 949 and 4, 098, 984; and any mixtures of the foregoing. Typical antioxidants include hindered phenols such as triethylene glycol bis (3- (3'-third butyl-4'-hydroxy-5'-methylphenyl) propionate, N, N'-hexamethylene Bis (3,5-tert-butyl-4-hydroxyhydrocinnamide) and mixtures thereof and the antioxidants disclosed in U.S.P. 4,9 7 2,0 1 4. Combinations described herein Materials can be prepared by methods known in the art by mixing all ingredients and the acetal polymer at a temperature above the melting point of the shrink polymer.
第11頁 483919 五、發明說明(9) 已知可使用強力混合裝置如橡膠研磨機、内部混合機如” 班伯里(Banbury )"及"伯班德(Brabender)n混合機’具外 部加熱或摩擦加熱孔穴之單或多葉片内部混合機\共捏 合機”,多葉片混合機如π法拉(Farrel)連續混合機π,射 出模造機及單軸以及雙軸擠出機,共旋轉及反向方疋轉機以 製備熱塑性聚縮醛組合物。該等裝置可單獨使用或與靜電 混合機、混合渦流機及/或各種裝置組合使用’以增加如 設計供此目的之閥、閘或軸之内部壓力及/或混合強度。 以擠出機較佳,以雙軸擠出機最佳。當然,’此混合需在低 於聚縮醛會明顯降解之溫度進行。通常聚縮醛組合物在 1 7 0至2 9 0 °c,較好1 8 5至2 4 0 °C且最好1 9 5至2 2 5 °C之間熔融 加工。 本發明可使用本技藝已知方法製成成型物件,包含壓縮 模造、射出模造、擠出、吹塑模造、旋轉模造、熔融紡絲 及熱成型法。以射出模造較佳。 成型物件實例包含片材、輪廓、桿狀材、薄膜、單絲、 纖維、皮繩、帶子、管子及導管。此種成型物件可藉定 向、拉伸、包覆、淬火、塗覆、層壓及電鍍進行後處理。 此種成型物件及其碎片可研磨並再模造。 本技藝者將了解在不違離本發明精神及範圍下,可對上 述本發明作各種修飾及取代。據此,需了解本發明將舉例 說明但不用以限制本發明。 實驗 下列貫驗使用得自達拉威霍克辛ECHIP工業之稱為Page 11 483919 V. Description of the invention (9) It is known that powerful mixing devices such as rubber mills, internal mixers such as "Banbury " and " Brabender n mixers " Single or multi-blade internal mixer \ co-kneader for external heating or friction heating of holes ", multi-blade mixers such as π Farrel continuous mixer π, injection molding machine and single-shaft and double-shaft extruder, co-rotation And reversed square turn to prepare a thermoplastic polyacetal composition. These devices can be used alone or in combination with electrostatic mixers, hybrid eddy current machines and / or various devices' to increase internal pressure and / or mixing strength of valves, gates or shafts as designed for this purpose. An extruder is preferred, and a biaxial extruder is most preferred. Of course, 'this mixing needs to be performed at a temperature lower than that at which the polyacetal will degrade significantly. The polyacetal composition is usually melt-processed at 170 to 290 ° C, preferably 185 to 240 ° C, and most preferably 195 to 25 ° C. The present invention can be formed into shaped articles using methods known in the art, including compression molding, injection molding, extrusion, blow molding, rotary molding, melt spinning, and thermoforming. It is better to use injection molding. Examples of molded objects include sheets, contours, rods, films, monofilaments, fibers, leather cords, tapes, tubes, and conduits. Such shaped articles can be post-processed by orientation, stretching, cladding, quenching, coating, laminating, and electroplating. Such shaped articles and their fragments can be ground and re-molded. Those skilled in the art will understand that various modifications and substitutions can be made to the above-mentioned invention without departing from the spirit and scope of the invention. Accordingly, it should be understood that the present invention will be exemplified but not intended to limit the present invention. Experiments The following tests were performed using the ECHIP Industry
第12頁 五、發明說明(ίο) -- 1P’’之實驗設計軟體設置。此設計實驗包含可以統計 +平估誤差之重複貫驗。由於此為設計實驗,因此無法僅 以「個可變變數比較成對實驗。反而,需倚賴結果***法 之統計學分析。使用重量平均分子量72,0 0 0之乙酸酯封端 之水曱駿(Ρ Ο Μ)製備樣品。使用威納(w e r n e r )及非德洛 (Pfleiderer) 40笔米雙軸擠出機製得表中所列之樣品。 以每小時2 0 0碎製得50磅樣品。機器在2 25-400 rpm且筒溫 設定在20 0-2 25 °C下進行。含P561蠟但不含EMA之樣品難以 進行,因為蠟會干擾POM融化,因此需使用較高之溫度及 機器轉速。EMA為得自Chevron化學公司之EMAC® SP2 2 0 5, 其為80 %乙烯及20 %丙烯酸甲酯之共聚物且熔融指數為2克 / 1 0分鐘。P5 6 1為Moore及Munger銷售之非極性烴壤。 Celcon® U-10 為Hoeschst-Celanese(現在的Ticona)製造 之分支縮醛三聚物。Ultratalc® 6 0 9為Barretts礦業工 業供應之滑石。Z e m i d® 6 4 1為杜邦公司供應之於聚乙烯中 之 40% 滑石。U-Talc 6 0 9 /EMA 為 Ultratalc 於 EMA 中之 40% 分 散液。11-丁31〇 6 0 9 斤5 61為1111^3七31(:於1)5 61中之40%分散 液0Page 12 V. Description of the Invention (ίο)-1P ’’ experimental design software setup. This design experiment includes repeated runs that can count + estimate errors. Because this is a design experiment, it is not possible to compare pairs of experiments with only “variable variables. Instead, you need to rely on statistical analysis of the result insertion method. Use acetate-terminated water with a weight average molecular weight of 72,000 Samples were prepared. The samples listed in the table were obtained using a 40-meter biaxial extrusion mechanism of Werner and Pfleiderer. A 50-pound sample was produced at 200 per hour. The machine is performed at 2 25-400 rpm and the barrel temperature is set at 20 0-2 25 ° C. Samples containing P561 wax but not EMA are difficult to perform because wax will interfere with the melting of POM, so higher temperatures and temperatures are required. Machine speed. EMA is EMAC® SP2 2 0 5 from Chevron Chemical Company, which is a copolymer of 80% ethylene and 20% methyl acrylate with a melt index of 2 g / 10 minutes. P5 61 is Moore and Munger Non-polar hydrocarbon soil sold. Celcon® U-10 is a branched acetal trimer made by Hoeschst-Celanese (now Ticona). Ultratalc® 6 0 9 is talc supplied by Barretts mining industry. Zemid® 6 4 1 is 40% talc in polyethylene supplied by DuPont. U-Talc 609 / EM A is the 40% dispersion of Ultratalc in EMA. 11-Ding 3 0 6 0 9 kg 5 61 is 1111 ^ 3 7 31 (: 1) 5 61 40% dispersion 0
第13頁 483919 五、發明說明(π) 表1 組合物 編號 ΕΜΑ% Ρ561 % U-Talc % U-Talc來源 DSC結晶 Tl/2 158C (分鐘) 模具中之結 晶時間(衫、) 1 0 0 0 ZEMID 641 2.9 6.7 2 3 L5 0 ZEMID 641 3.28 73 3 0 L5 0.08 ZEMID 641 2.18 6.5 4 3 1.5 0 U-TALC 609 j.j 1 6.9 5 3 0 0.08 U-TALC 609/P561 2.39 5.6 6 0 1.5 0.08 U-TALC 609/P561 2.12 6.8 7 0 0 0.08 U-TALC 609 1.96 5.9 8 3 0 0 U-TALC 609/EMA 7.2 7 9 0 1.5 0.08 U-TALC 609/EMA 2.03 6.3 10 3 1.5 0 U-TALC 609/P561 13.43 7.2 11 3 0 0.08 U-TALC 609 2.14 5.8 12 3 0 0.08 ZEMID 641 2.74 5.6 13 0 1.5 0 U-TALC 609 8.42 6.4 14 0 0 0 U-TALC 609/P561 3.26 7 15 3 1.5 0.08 U-TALC 609/EMA 2.26 6.1 16 0 0 0 U-TALC 609/EMA 10.47 6.8 17 1.5 0.75 0.04 ZEMID 641 2.87 6.6 18 1.5 0.75 0.04 U-TALC 609 1.75 5.5 19 1.5 0.75 0.04 U-TALC 609/P561 6.24 5.7 20 1.5 0.75 0.04 U-TALC 609/EMA 5.74 5.8 21 0 0 0 ZEMID 641 3.69 6.3 22 3 1.5 0 U-TALC 609 3.25 6.9 23 3 0 0.08 U-TALC 609/P561 2.43 5.5 24 3 0 0 U-TALC 609/EMA 7.94 6.6 ΙΙϋϋΙ 第14頁 483919 五、發明說明(12) 使用示差掃描卡計(DSC)測定結晶一半之時間。1〇克樹 脂在Perkin - Elmer DSC 7中以50°C/分鐘加熱至21(rc保持 3分鐘,再以2 00 t/分鐘快速冷卻至158艺之結晶溫度,並 、准持在該度直至結晶完全。自結晶放熱峰位置取得結晶 一半之時間。 自樣品射出磨造成i x 8 X 0.0 7 0吋棒狀物期間熔融壓力 曲線圖形獲得模具中之結晶時間。接著使用,,Echi〆軟體 統計分析該等物質所測得之DSC及模具中結晶數 EMA與P 561蠟之效果圖示說明。注意在以 /、 ' /月a馬主之坊4卜 劑存在中,通常具有減缓結晶作用效果(D 一 人 加)之"Zemid”蠟現在具有反效果,其增加紝曰t時間增 品在158 t結晶一半之時間減少)。 日日V率(DSC樣 亦注意檢閱下表2之數據顯示EMA及蠟個別或*人, 中結晶作用影響很小,僅與0. 04%滑石成Ί合對模具 劑本身效果大0. 0 8 %。 Θ、、。比成核Page 13 483919 V. Description of the invention (π) Table 1 Composition number ΕΜΑ% P561% U-Talc% U-Talc source DSC crystal Tl / 2 158C (minutes) Crystallization time in the mold (shirt,) 1 0 0 0 ZEMID 641 2.9 6.7 2 3 L5 0 ZEMID 641 3.28 73 3 0 L5 0.08 ZEMID 641 2.18 6.5 4 3 1.5 0 U-TALC 609 jj 1 6.9 5 3 0 0.08 U-TALC 609 / P561 2.39 5.6 6 0 1.5 0.08 U-TALC 609 / P561 2.12 6.8 7 0 0 0.08 U-TALC 609 1.96 5.9 8 3 0 0 U-TALC 609 / EMA 7.2 7 9 0 1.5 0.08 U-TALC 609 / EMA 2.03 6.3 10 3 1.5 0 U-TALC 609 / P561 13.43 7.2 11 3 0 0.08 U-TALC 609 2.14 5.8 12 3 0 0.08 ZEMID 641 2.74 5.6 13 0 1.5 0 U-TALC 609 8.42 6.4 14 0 0 0 U-TALC 609 / P561 3.26 7 15 3 1.5 0.08 U-TALC 609 / EMA 2.26 6.1 16 0 0 0 U-TALC 609 / EMA 10.47 6.8 17 1.5 0.75 0.04 ZEMID 641 2.87 6.6 18 1.5 0.75 0.04 U-TALC 609 1.75 5.5 19 1.5 0.75 0.04 U-TALC 609 / P561 6.24 5.7 20 1.5 0.75 0.04 U -TALC 609 / EMA 5.74 5.8 21 0 0 0 ZEMID 641 3.69 6.3 22 3 1.5 0 U-TALC 609 3.25 6.9 23 3 0 0.08 U-TALC 609 / P561 2.43 5.5 24 3 0 0 U-TALC 609 / EMA 7.94 6.6 Ι II. Page 14 483919 V. Description of the invention (12) Use a differential scanning card meter (DSC) to measure half the time of crystallization. 10 grams of resin was heated in Perkin-Elmer DSC 7 at 50 ° C / min to 21 ° C for 3 minutes, and then quickly cooled to 200 ° C crystallization temperature at 200 t / min, and held at that temperature until Crystallization is complete. It takes half the time to crystallize from the position of the exothermic peak of the crystal. The melting time curve graph during the ix 8 X 0.0 7 inch bar formed from the injection mill of the sample is used to obtain the crystallization time in the mold. Then, use Echi〆 software for statistical analysis The effect of DSC and the number of crystals EMA and P 561 wax in the mold measured by these substances is illustrated. Note that in the presence of /, '/ month a horse owner's square 4 agent, usually has a slowing effect of crystallization ( D one person plus) of the "Zemid" wax now has an adverse effect, which increases the time at which t increases the time at which the crystallization time is reduced by half at 158 t). Day-to-day V rate (DSC samples also pay attention to review the data in Table 2 below to show EMA 0 8%。 Θ 、、。 Compared to nucleation, the effect of crystallization is small, and it has only a small effect on the crystallization.
第15頁 483919Page 15 483919
五、發明說明(13) 表2_平均數據 實例 EMA% P561% 滑石% 平均結晶時間(秒) — 1 0 0 0 ------— 6.7 2 3 0 0 ________ ^ 6.8 3 0 1.5 0 6.4 4 3 1.5 0 _______—-—— 7.1 5 0 0 0.08 5.9 6 3 0 0.08 5.8 7 0 1.5 0.08 6.8 8 1.5 0.75 0.04 5.7 9 1.5 0.75 l%CelconU10 5.6 於聚曱酸中含有可變量Ε Μ A及P 5 6 1之組合物中結晶一半 之時間繪圖示於圖1 a。圖1 b顯示含0 · 〇 8 0%成核劑(z em丨d) 及可變量之EMA及P 561之聚曱醛組合物之結晶一半時間圖 形。 藉射出模造含聚甲醛樹脂及下表3所示之添加劑之樣品 而形成棒狀物’對未核化之樹脂其週期太短而無法產生無 孔隙之零件。此棒狀物縱向切割以分析其内部結構。切割V. Explanation of the invention (13) Table 2_ Examples of average data EMA% P561% Talc% Average crystallization time (seconds) — 1 0 0 0 ------— 6.7 2 3 0 0 ________ ^ 6.8 3 0 1.5 0 6.4 4 3 1.5 0 _______ ------- 7.1 5 0 0 0.08 5.9 6 3 0 0.08 5.8 7 0 1.5 0.08 6.8 8 1.5 0.75 0.04 5.7 9 1.5 0.75 l% Celcon U10 5.6 Polyvariable acid contains variable ΕΜ A and P A plot of half the time of crystallization in the 5 6 1 composition is shown in Figure 1a. Figure 1b shows a half-time graph of the crystallization of a polyacetal composition containing 0. 080% nucleating agent (z em 丨 d) and a variable amount of EMA and P 561. By injection molding a sample containing the polyoxymethylene resin and the additives shown in Table 3 below to form a rod-like object, the period of the non-nucleated resin is too short to produce non-porous parts. This rod was cut longitudinally to analyze its internal structure. Cut
第16頁 483919 五、發明說明(14) 之棒狀物之影印複製示於圖2a、2b及2c。可看出舆圖2b及 2 c之不含本發明所用之三種添加劑之棒狀物比較,本發明 實例之樣品1 (圖2a)實質上不含孔隙。 表3 成核劑/% EMA {PE蠟 1. Celcon U-10*/2% 1.5% .75% 2. 0.17Zemid® 含有 0.08% 滑石 0 0 3. 0 0 0 *分支三聚物之mw=109,000 下表4所示之添加劑在4 0 m m W & P雙軸播出機中混合在一 起且接著模造成1 / 4吋厚之張力棒狀物,未改質之對照樹 脂#3之模造週期太短。棒狀物接著以機器製程1 /8吋厚以 分析内部孔隙度。注意對照樣品# 3具有許多孔隙而本發明 之樣品1 4則非常少。後者對模造應用而言更是所需。Page 16 483919 V. Photocopy of the rod of the invention description (14) is shown in Figures 2a, 2b and 2c. It can be seen that in comparison of rods 2b and 2c which do not contain the three additives used in the present invention, sample 1 (FIG. 2a) of the example of the present invention is substantially free of pores. Table 3 Nucleating agent /% EMA {PE wax 1. Celcon U-10 * / 2% 1.5% .75% 2. 0.17Zemid® contains 0.08% talc 0 0 3. 0 0 0 * mw of branched trimer = 109,000 The additives shown in Table 4 below were mixed together in a 40 mm W & P twin-shaft broadcaster and then molded into a 1/4 inch thick tension rod, unmodified control resin # 3. The molding cycle is too short. The rods were then machine-processed 1/8 inch thick to analyze internal porosity. Note that control sample # 3 has many pores and sample 14 of the present invention is very small. The latter is even more desirable for molding applications.
第17頁 483919 五、發明說明(15) 表4 測試數 縮醛MW 添加劑 合支三聚物 MW=109,000 3 85000 益 無 6 85000 ΕΜΑ/2,Ρ561/·4 無 12 85000 1 14 85000 ΕΜΑ/2,Ρ561/·4 1 機器加工以顯現内部孔隙度之棒狀物之影印再製示於圖 3a,3b及圖4a及4b。圖3a相當於表4之樣品3 ;圖3b相當於 表4之樣品6 ;圖4a相當於表4之樣品12 ;及圖4b相當於表4 之樣品1 4。Page 17 483919 V. Description of the invention (15) Table 4 Tests Acetal MW Additive Branched trimer MW = 109,000 3 85000 Yiwu 6 85000 ΕΜΑ / 2, P561 / · 4 No 12 85000 1 14 85000 ΕΜΑ / 2 Photographs of P561 / · 4 1 machined to reveal the internal porosity of rods are reproduced in Figures 3a, 3b and 4a and 4b. Figure 3a corresponds to Sample 3 of Table 4; Figure 3b corresponds to Sample 6 of Table 4; Figure 4a corresponds to Sample 12 of Table 4; and Figure 4b corresponds to Sample 14 of Table 4.
第18頁Page 18
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DE69019474T2 (en) * | 1989-11-28 | 1996-03-07 | Asahi Chemical Ind | Wear-resistant polyoxymethylene resin composition and process for its manufacture. |
CA2109630C (en) * | 1991-05-23 | 2003-04-01 | Tatsuhiro Takahashi | Polyacetal resin composition |
TW245733B (en) * | 1991-11-21 | 1995-04-21 | Du Pont | |
ATE165388T1 (en) * | 1993-03-22 | 1998-05-15 | Du Pont | WEAR-RESISTANT POLYACETAL COMPOSITIONS |
-
1999
- 1999-01-05 KR KR1020007007420A patent/KR20010081920A/en not_active Application Discontinuation
- 1999-01-05 EP EP99901289A patent/EP1045884A1/en not_active Withdrawn
- 1999-01-05 CA CA002314081A patent/CA2314081A1/en not_active Abandoned
- 1999-01-05 JP JP2000527585A patent/JP2002500256A/en active Pending
- 1999-01-05 WO PCT/US1999/000071 patent/WO1999035191A1/en not_active Application Discontinuation
- 1999-01-12 TW TW088100066A patent/TW483919B/en active
Also Published As
Publication number | Publication date |
---|---|
WO1999035191A1 (en) | 1999-07-15 |
JP2002500256A (en) | 2002-01-08 |
KR20010081920A (en) | 2001-08-29 |
EP1045884A1 (en) | 2000-10-25 |
CA2314081A1 (en) | 1999-07-15 |
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