1281494 九、發明說明： ^ 【發明所屬之技術領域】 本發明運用化學合成方法來製造包含金屬離子之高分 子抗靜電壓克力聚氨酯樹脂和其塗料，及製造包含金屬離 、 子之鬲分子抗靜電聚氨酯樹脂和其塗料·其合成方法包括 乳化聚合，溶液聚合，和本體聚合. 【先前技術】 •靜電的產生往往造成工業上或是民生上之損害與困 擾’因此防止靜電之產生是今日世界上急欲解決之課題。 目前市面上既有之抗靜電製劑種類繁多，包括碳黑或碳纖， 界面活性劑，低分子抗靜電劑，導電塑膠，含矽樹脂，或一些 樹脂和其相關之塗料·然而這些產品或有的會產生遷移而 -析出污染和不穩定及效果短暫；如低分子抗靜電劑或有的 會產生污染和不易控制，如碳黑或碳纖或有的在低溼度的 衰境下將無法產生抗靜電之效果如界面活性劑及低分子抗 鲁靜電劑.或有的因含矽而不被接受·或是因為添加量過高且 影響物性，如碳黑和某些抗靜電劑或因成本太高和施工不 易，如導電塑膠一類· 【發明内容】 本發明之主要技術特徵，係利用適當金屬化合物或金 屬鹽類、聚多元醇、鍊延長劑、壓克力聚多元醇、異氰酸 酯、溶劑與水，在適當之反應條件下，合成俱有長效功能 5 1281494 及穩疋性之金屬鹽類之高分子樹酯和塗料·它們可以使用 很間易的方式在需要抗靜電的材料或物件上作塗佈，噴塗 和’又/包.也可以直接添加在製品之生產過程。同時此高分子 的穩定性提供本抗靜電樹脂和其塗料倶備效果長久之功 效· 本發明採用以下數類原料為主要反應物·它們在適當 的反應條件下運用乳化聚合，溶液聚合，和本體聚合製造出 包含金屬離子之高分子抗靜電壓克力聚氨酯樹脂和其塗料， 馨及製造出包含金屬離子之高分子抗靜電聚氨酯樹脂和其塗 料·而採用的原料和添加比如下： (A )聚多元醇採用分子量在六百到八千之間· (B)壓克力聚多元醇採用分子量在五百到兩千五百之 間· - (c)鍊延長劑和聚多元醇之當量莫耳比在零點五到十 ^ 之間. (D) 壓克力聚多元醇和聚多元醇之當量莫耳比在百分 Φ 之一到百分之四十之間· (E) 金屬鹽類或金屬化合物和聚多元醇之莫耳比在零 點一到二十之間. (F)異氰酸i旨和壓克力聚多元醇，聚多元醇及鍊延長 劑等之總合當量莫耳比；在百分之一百到百分之一百四十 之間· 【實施方式】 6 1281494 下列實施例之用意在於示範說明本發明。這些實施例 不以任何形式限制本發明所及之範圍。 . 1·含鹼金屬離子之高分子抗靜電壓克力聚氨酯之溶 '劑型塗料的製造··（運用溶液聚合法） 於反應槽中加入分子量約兩千，含兩個官能基之聚醚 多元醇約一百公斤；加入分子量約一千，含兩個官能基之壓 克力聚多元醇約七點五公斤；加入乙二醇九點三公斤；加入 刀子里約百之驗金屬鹽一十六公斤；加入4，4，-雙異氰酸 _ 酯環己基甲烷五十七公斤及丁酮四百六十公斤，並攪拌和 升溫，再加入少量有機金屬觸媒·整個反應過程之溫度保持 在四十度和八十二度之間·反應時間約為十二到二十四小 時，攪拌器轉速在每分鐘六十轉到七百二十轉之間·反應完 成後降至室溫並停止攪拌· 2·含鹼金屬離子之高分子抗靜電聚氨酯之溶劑型塗 料的製造：（運用溶液聚合法） 於反應槽中加入分子量約兩千含兩個官能基之聚醋 多元醇約一百公斤；加入乙二醇十公斤，·加入分子量約一百 之鹼金屬鹽十五公斤;加入雙異氰酸酯環己基甲烷六 十三公斤及丁酮三百六十公斤並攪拌和升溫再加入少量 有機金屬觸媒.整個反應過程之溫度保持在四十度和八十 二度之間.反應時間約為十二到二十小時，然後加入一百公 斤丙酮再攪拌約兩小時，攪拌器轉速在每分鐘六十轉到七 百十轉之間.反應完成後降至室溫停止攪拌· 7 1281494 二鹼金屬離子之高分子抗靜電壓克力聚氨酯 溶液型塗料的製造…田：……見力聚1 (運用本體聚合及乳化聚合法） 於反應槽中加入分子 多元醇約兩百公斤.加入八 千，s兩個官能基之聚翻 克力聚多元醇約二點五八^子$約—千’含兩個官能基之1 分子量約-百之驗金屬斤二:九點三公斤 保持在四十度和九十八;然後升溫並授拌，且 度之間；反應時間約五至三十五分 :·、,然後加入4,4’ —雙異氰酸酯環己基甲烷五十七公斤並 =約五至四十五分.待反應接近完成且產物未固化時慢 反加入風乳化納稀溶液約三百公斤，並攪拌約五至十小時 整個反應過程之溫度保持在六十至九十八度和度之間铁 後以脫切酸慢慢中和並㈣約三小時·再慢慢加入約三 百：十公斤的水並攪拌約十八小時應，攪#器轉速在每分 鐘六十轉到七百二十轉之間·反應完成後降至室溫並停止 攪拌. 4·含鹼金屬離子之高分子抗靜電聚氨酯之水溶液型 塗料的製造：（運用本體聚合及乳化聚合法） 於反應槽中加入分子量約四千，含兩個官能基之聚酯 多元醇約兩百公斤；加入乙二醇九點五公斤；加入分子量約 一百之鹼金屬鹽五點五公斤；然後升溫並攪拌且保持在四 十度和九十八度之間；反應時間約十至五十五分鐘·然 1281494 入4,4，-雙異氰酸酯環己基甲院五十九公斤，並授拌約十至 ，五十五分·待反應接近完成且產物未固化時慢慢加入氫氧 化鈉稀溶液約兩百八十百公斤，並攪拌約七至十小時整個 反應過私之溫度保持在六十至九十八度和度之間·然後以 - 脫水醋酸慢慢中和並攪拌約三小時·再慢慢加入約三百六 十公斤的水並攪拌約二十小時·攪拌器轉速在每分鐘六十 轉到七百二十轉之間·反應完成後降至室溫並停止攪拌 5.含鹼金屬離子之高分子抗靜電壓克力聚氨酯樹脂 春 的製造：（運用本體聚合法） 於反應槽中加入分子量約兩千，含兩個官能基之聚醚 多元醇約四百公斤；加入分子量約一千，含兩個官能基之壓 克力聚多元醇約三十公斤；加入乙二醇三十七點二公斤；加 入分子量約一百之驗金屬鹽七十公斤；然後升溫並攪拌且 -保持在四十度和一百二度之間；反應時間約二小時至五小 ' 時，並確認鹼金屬鹽已完全溶化·然後加入4, 4、雙異氮酸 ▲ 酯環己基曱烷約兩百三十公斤，並快速攪拌約五至十分鐘· Φ 然後在產物未固化時，將產物排出或擠出，再經過保溫固 化，熟成和粉碎或造粒製成產品· 6·含鹼金屬離子之高分子抗靜電聚氨酯樹脂的製造： (運用本體聚合法） 於反應槽中加入分子量約兩千，含兩個官能基之聚酯 多元醇約四百公斤；加入丁二醇約九十公斤；加入分子量約 一百之鹼金屬鹽八十公斤；然後升溫並攪拌且保持在四十 度和一百二度之間；反應時間約二小時至五小時並確認鹼 9 ^281494 金屬鹽已完全溶化.然後加入二苯基甲烷4, 4，-二異氰酸酯 約三百三十公斤，並快攪拌約二至五分鐘·然後在產物未固 化時，將產物排出；並經由單轴或雙軸混合擠壓機擠出，再 經過造粒成產品. 7 ·附註：運用本發明之基礎亦可製造抗靜電聚氨酯發 泡體及其他各類型的聚氨酯·其方法是將適量的金屬鹽類 或金屬化合物與聚多元醇，鍊延長劑充分溶解並反應；然後 以適當比例添加於二液型聚氨酯製程的聚多元醇之中或預 聚合物之中.再與異氰酸酯及水做聚合發泡反應或聚合反 應·以這種技術所製造的抗靜電發泡體可獲得十的六次方 至七次方Ω -cm,其他製品可獲得十的七次方Ω / Sq.而且 這些製品是長效型的抗靜電高分子· 試驗結果和討論.· 依據上述方法，在精確的配方，純熟的技術，和嚴格的 反應控制之下，所製備獲得之塗料產品可低達十的六次方 至七次方Ω / Sq，而樹脂產品可低達十的五次方至六次方 Ω / sq 〇 綜上所述，由於本發明係利用適當的反應條件，以金 屬化口物或金屬鹽類與聚胺酯樹酯及壓克力聚胺酯樹酯做 成配位鍵結的抗靜電樹酯或塗料，故其倶有良好之抗靜電 特丨生·且由於本發明為咼分子樹酯，因此不會有遷移污染之 現象毛生，並倶備持久的抗靜電效果·由於它們也不含有矽 10 1281494 成份，故能提供各種電子產業之使用. 本發明之抗靜電樹脂係可添加在塑膠或樹酯等製品之 生產過程中，用做製造射出成型、壓出成型或是吹模成型 等製品·或是將本發明之抗靜電塗料用於製品之表面塗 佈、喷塗、浸泡、淋膜。此外，本發明之抗靜電塗料於使 用時，具有谷易乾無且乾爽而不回黏之特性，以及經過塗 佈後形成一平滑結實之表層等優點·同時亦具有良好之延 展性，故使用於塑膠片材或膜材時倶備優1281494 IX. INSTRUCTIONS: ^ Technical Field of the Invention The present invention utilizes a chemical synthesis method to manufacture a polymer anti-static voltage urethane resin containing metal ions and a coating thereof, and to manufacture a molecular antimony comprising a metal ion Electrostatic polyurethane resin and its coatings. Its synthesis methods include emulsion polymerization, solution polymerization, and bulk polymerization. [Prior Art] • The generation of static electricity often causes damage and trouble in industry or people's lives. Therefore, the prevention of static electricity is the world today. An urgent problem to solve. There are a wide variety of antistatic preparations available on the market, including carbon black or carbon fiber, surfactants, low molecular antistatic agents, conductive plastics, antimony resins, or some resins and related coatings. However, these products may have Will cause migration - precipitation pollution and instability and short-lived effects; such as low molecular antistatic agents or some will cause pollution and difficult to control, such as carbon black or carbon fiber or some will not produce antistatic under low humidity The effects are surfactants and low molecular anti-static agents, or some are not accepted due to bismuth, or because the amount added is too high and affects physical properties, such as carbon black and some antistatic agents or because the cost is too high. And the construction is not easy, such as conductive plastics. 1. SUMMARY OF THE INVENTION The main technical features of the present invention utilize appropriate metal compounds or metal salts, polyhydric alcohols, chain extenders, acrylic polyhydric alcohols, isocyanates, solvents and water. , under the appropriate reaction conditions, the synthesis of long-acting functions 5 1281494 and stable metal salts of polymer resins and coatings, they can be used in a very easy way Coatings, sprays, and/or packages may be applied directly to the antistatic material or article. At the same time, the stability of the polymer provides the long-lasting effect of the antistatic resin and the coating preparation effect thereof. The present invention uses the following types of raw materials as main reactants. They employ emulsion polymerization, solution polymerization, and bulk under appropriate reaction conditions. Polymerization produces a polymer-resistant static-voltage gram-resin polyurethane resin containing metal ions and a coating thereof, and a raw material and an additive used for producing a polymer antistatic polyurethane resin containing metal ions and a coating thereof, and the like is as follows: (A) The polyhydric alcohol uses a molecular weight of between 600 and 8,000. (B) Acrylic polyhydric alcohols have a molecular weight of between 500 and 2,500. - (c) Equivalents of chain extenders and polyhydric alcohols The ear ratio is between 5:00 and 10,000. (D) The equivalent molar ratio of acrylic poly-polyol to poly-polyol is between one-tenth and four-tenth percent. (E) Metal salts Or the molar ratio of the metal compound to the polyhydric alcohol is between 0.1 and 20 degrees. (F) Isocyanate is the total equivalent of acrylic polyhydric alcohol, polyhydric alcohol and chain extender. Ear ratio; at one hundred to one hundred and forty Inter-61281494 [Embodiment The following exemplary embodiments is intended that the embodiments of the present invention is described. These examples are not intended to limit the scope of the invention in any way. 1. Preparation of a polymer-resistant anti-static voltage urethane polyurethane solution containing an alkali metal ion · (using a solution polymerization method) Adding a polyether polyol having a molecular weight of about two thousand and containing two functional groups in a reaction tank Alcohol is about one hundred kilograms; about 1,000 kilograms of acrylic polymer with two functional groups is added, about 7.5 kilograms of acrylic polyol containing two functional groups; 9.3 kilograms of ethylene glycol is added; and about one hundred metal salts are added to the knife. Six kilograms; add 4,4,-bisisocyanate-ester cyclohexylmethane 57 kilograms and butanone 460 kilograms, stir and heat up, then add a small amount of organometallic catalyst · temperature throughout the reaction process Between 40 degrees and 82 degrees, the reaction time is about 12 to 24 hours, the stirrer speed is between 60 and 720 rpm, and the reaction temperature is reduced to room temperature. Stop stirring · 2 · Preparation of solvent-based coatings of polymer antistatic polyurethane containing alkali metal ions: (using solution polymerization method) Add about 2,000 polyhydric alcohols with two functional groups of about two thousand in the reaction tank. Kilogram; add ten kilograms of ethylene glycol , adding 15 kg of alkali metal salt with a molecular weight of about 100; adding 63 kg of diisocyanate cyclohexylmethane and 366 kg of butanone and stirring and heating to add a small amount of organometallic catalyst. The temperature of the whole reaction process Keep between forty degrees and eighty-two degrees. The reaction time is about twelve to twenty hours, then add one hundred kilograms of acetone and stir for about two hours. The stirrer speed is sixty to seven hundred and ten turns per minute. Between the completion of the reaction, the temperature is lowered to room temperature to stop the stirring. 7 1281494 The production of the polymer anti-static voltage urethane polyurethane solution of di-alkali metal ions... Field: ... see force poly 1 (using bulk polymerization and emulsion polymerization) Adding about 200 kilograms of molecular polyol to the reaction tank. Adding eight thousand, s two functional polycondensation poly-polyols about 2.58 ^ about $ - thousand ' containing two functional groups The molecular weight is about -100. The metal is 2: 9:3 kg is kept at 40 degrees and 98; then the temperature is raised and the mixture is mixed, and the reaction time is about 5 to 35 points: ·, then join 4,4' —bisisocyanate cyclohexylmethane 17 kilograms and = about 5 to 45 minutes. When the reaction is nearing completion and the product is not solidified, add about 300 kilograms of the air-emulsified nano-dilute solution slowly, and stir for about five to ten hours. The temperature of the whole reaction process is maintained at six. After ten to ninety-eight degrees and between degrees of iron, slowly neutralize with de-cutting acid and (iv) about three hours. Then slowly add about three hundred: ten kilograms of water and stir for about eighteen hours. At 60 to 720 rpm, the reaction temperature is reduced to room temperature and the stirring is stopped. 4. Manufacture of aqueous solution type antistatic polyurethane containing alkali metal ions: (using bulk polymerization and Emulsification polymerization method) Adding about 4,000 molecular weights to the reaction tank, about two hundred kilograms of polyester polyol containing two functional groups; adding 9.5 kilograms of ethylene glycol; adding alkali metal salt with a molecular weight of about one hundred and five Kg; then warmed up and stirred and maintained between forty and ninety-eight degrees; reaction time is about ten to fifty-five minutes; then 1281494 into 4,4,-bisisocyanate cyclohexyl forty-nine kilograms, and Give about ten to five, fifty-five minutes to be reacted Nearly completed and the product is uncured, slowly add about 280 kilograms of dilute sodium hydroxide solution, and stir for about seven to ten hours. The entire reaction is kept at a temperature between 60 and 98 degrees and between degrees. Then slowly neutralize with - dehydrated acetic acid and stir for about three hours. Then slowly add about three hundred and sixty kilograms of water and stir for about twenty hours. The stirrer rotates at 60 to 720 rpm. After the completion of the reaction, the temperature is lowered to room temperature and the stirring is stopped. 5. The production of the polymer anti-static voltage urethane resin containing alkali metal ions: (using bulk polymerization method) The molecular weight is about 2,000 in the reaction tank, including two a functional polyether polyol of about 400 kg; a molecular weight of about 1,000, an acrylic polyhydric alcohol containing two functional groups of about 30 kg; adding ethylene glycol 37.2 kg; One hundred test metal salt seventy kilograms; then warmed up and stirred and - maintained between forty degrees and one hundred two degrees; reaction time of about two hours to five small ', and confirmed that the alkali metal salt has completely dissolved · then Add 4, 4, bisisoxamic acid ▲ ester Cyclohexyl decane is about two hundred and thirty kilograms and is rapidly stirred for about five to ten minutes. Φ Then, when the product is not cured, the product is discharged or extruded, then cured by heat, matured, pulverized or granulated to make a product. 6. Preparation of polymer antistatic polyurethane resin containing alkali metal ions: (using bulk polymerization method) Adding about 200 kilograms of polyester polyol having two functional groups to the reaction tank is about 400 kilograms; Alcohol is about 90 kg; 80 kg of alkali metal salt with a molecular weight of about 100 is added; then it is heated and stirred and kept between forty and one hundred degrees; the reaction time is about two to five hours and the alkali 9 ^ is confirmed. 281494 The metal salt has been completely dissolved. Then add about 300 kg of diphenylmethane 4,4,-diisocyanate and stir for about two to five minutes. Then, when the product is not cured, the product is discharged; Extrusion by a shaft or twin-shaft mixing extruder, and then granulation into a product. 7 · Note: The antistatic polyurethane foam and other types of polyurethane can also be manufactured by using the basis of the invention. The method is to apply an appropriate amount of gold. The salt or metal compound is sufficiently dissolved and reacted with the polyhydric alcohol and the chain extender; and then added to the polyhydric alcohol of the two-component polyurethane process or the prepolymer in an appropriate ratio. The polymerization is carried out with the isocyanate and water. Bubble reaction or polymerization. The antistatic foam produced by this technique can obtain ten to six powers Ω-cm, and other products can obtain ten seventh power Ω / Sq. And these products are Long-acting antistatic polymer · Test results and discussion. · According to the above method, under the precise formula, skillful technology, and strict reaction control, the prepared coating products can be as low as ten to six powers. To the seventh power Ω / Sq, and resin products can be as low as ten to five to six degrees Ω / sq 〇, because the present invention utilizes appropriate reaction conditions to metallize the mouth or metal salt It is a coordination-bonded antistatic resin or coating with a polyurethane resin and an acrylic polyurethane resin, so it has good antistatic properties and is not a molecular macromolecular ester. There will be migration pollution It has a long-lasting antistatic effect. Because it does not contain 矽10 1281494, it can be used in various electronic industries. The antistatic resin of the present invention can be added to the production process of products such as plastics or resins. It is used for manufacturing products such as injection molding, extrusion molding or blow molding. Or the antistatic coating of the present invention is applied to the surface coating, spraying, immersion, and coating of the product. In addition, the antistatic coating of the present invention has the advantages of being easy to dry and dry without sticking back when used, and having the advantages of forming a smooth and strong surface layer after coating, and also having good ductility, so it is used in plastics. Excellent sheet or film
是拉伸延展的功能·是以，v發明正符合目前工業之 根據本發明可作出不同配方和製造方法的修正及變化 對於熟悉該項技術者而言 ，^ .、、、疋不會偏離本發明的範圍 與精神。雖然本發明已敛 疋符疋的具體實施例，然而本發 明不應被限制於該等特定之實施例上。本發明是提出一種 糸統性的的製造方案 k出種 為1造本發明所涵蓋的各種產品· 【圖式簡單說明】 【主要元件符號說明】It is a function of stretching and stretching. Therefore, the invention is in conformity with the current industry. According to the present invention, corrections and changes can be made to different formulations and manufacturing methods. For those skilled in the art, ^., , 疋 will not deviate from this. The scope and spirit of the invention. Although the present invention has been embodied in a specific embodiment, the present invention should not be limited to the specific embodiments. The present invention proposes a versatile manufacturing scheme. k is a variety of products covered by the present invention. [Simplified description of the drawing] [Explanation of main component symbols]