TW557286B - Impregnated glass fiber strands and products including the same - Google Patents
Impregnated glass fiber strands and products including the same Download PDFInfo
- Publication number
- TW557286B TW557286B TW89115359A TW89115359A TW557286B TW 557286 B TW557286 B TW 557286B TW 89115359 A TW89115359 A TW 89115359A TW 89115359 A TW89115359 A TW 89115359A TW 557286 B TW557286 B TW 557286B
- Authority
- TW
- Taiwan
- Prior art keywords
- particles
- patent application
- coating
- item
- materials
- Prior art date
Links
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
557286 A7 經濟部智慧財產局員工消費合作社印製 五、發明說明(1 ) 本發明大致關於用以強化複合物之經塗覆纖維股,而且 更特別地關於與股所加入之基質材料相容之經塗覆纖維 股。 ’、、 在熱固性模塑操作中,良好之”濕透”(聚合 透襯物或纖物)及"濕、潤"(聚合基質料穿透觀物或織物; 之個別纖維束或股)性質爲希望的。相對地,良好之分散 性質(即,纖維在熱塑性材料内之良好分布性質)在典=熱 塑性模塑操作中爲主要之顧慮。 W 在將由纖維股形成之複合物或層合物紡織成織物之情 形,除了提供股良好之濕透及良好之濕潤性質,希望纖維 股表面上之塗層在處理時保護纖維免於磨損,提供良好之 織動力,特別是在空氣噴射織布機,及與纖維股加入之聚 合基質材料相容。然而,許多上槳成分不與聚合基質材料 相容且負面地影響玻璃纖維及聚合基質材料間之黏附。例 如,澱粉,其爲用於紡織纖維之常用上漿成分,通常不與 聚合基質材料相容。結果,在以聚合基質材料浸潰之前必 須自織物去除這些不相容材料。 此種非樹脂相容性上漿材料之去除,即,將織物脱脂或 脱油,可經許多種技術而完成。這些非樹脂相容性上漿材 料之去除最常藉由將纺織織物長時間暴露於高溫以熱分解 上漿料而完成(經常稱爲熱清除)。習知熱清除過程涉及在 380 C將織物加熱60-80小時。然而,此熱清除步驟對於 玻璃纖維之強度爲有害的,而且始終無法成功地去除不相 谷材料及以上漿分解產物進一步污染織物。已嘴試其他去 — — — — — — — II — ^.1 ---------訂---------線赢 f請先閱讀背面之注意事項再填寫本頁) -^1 1 1 ^1 -4. ^紙張尺度適用中國國家標準(CNS)A4規格(21〇 x 297公釐) 557286 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(2 ) 除上漿材料之方法,如水洗及/或化學去除。然而,此種 方法通常需要將上漿組合物大爲重配以與此種水洗及/或 化學去除相容,而且通常在去除所有不相容材料不如熱清 除有效。 此外,由於織動過程對纖維玻璃紗爲相當磨損性,作爲 經紗之紗一般在織動前接受第二塗覆步驟,其通常稱爲" 漿紗",而以耐磨塗層塗覆經紗(通常稱爲”漿紗上聚")以 助於使玻璃纖維之磨耗最小。漿紗上漿通常塗佈於在纖維 形成操作時先前塗佈於玻璃纖維之第一上漿料上。然而, 由於典型之漿紗上漿通常亦不與聚合基質材料相容,其亦 必須自加入樹脂之前自纺織織物去除。 此外,爲了改良脱脂或脱油織物與聚合樹脂間之磨損, 在另一個處理步驟將最終之上漿料(一般爲矽烷偶合劑及 水)塗佈於織物以重塗玻璃纖維(通常稱爲"修整”)。 所有這些無附加價値處理步驟:漿紗、脱脂或脱油、及 修整,增加織物製造循環時間及成本。此外,其通常需要 對資本設備及勞力大量投資。此外,伴隨這些處理步骤之 織物附加處理造成織物損壞及降低之品質。 已努力改良一些這些處理步驟之效率或效果。但對塗層 仍持續完成以下之一或更多之需求:抑制玻璃纖維之磨損 及破裂;與廣泛種類之基質材料相容;及提供良好之被基 質材料濕潤與濕透。此外,如果塗層與現代空氣噴射織動 裝置相容而增加生產力則爲特別有利的。此外,排除織物 形成操作中之無附加價値處理步驟,同時維持電子撑體應 — — ilk'J — f»— — — — — - I I I l· I I I ^ « — — — — — I — I (請先閱讀背面之注意事項再填寫本頁) -11 -5 - 557286 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(4 本發明 <纖維股具有獨特之塗層’其不僅較佳地在處理 時抑制纖維(磨損與破裂,亦在形成複合物時提供至少一 種以下之1±質·良好之濕透、濕潤與分散性質。如以下所 詳、、’疋義版包含多個個別織維,即,至少兩個織維。 在此使用之複合物"表示本發明之經塗覆纖維股與額外材 料之組合,例如,但不限於,將一或更多層加入經塗覆纖 維股〈織物組合聚合基質材料以形成層纟物。良好之層合 強度良好之熱安定力、良好之水解安定力(即,對水沿 纖維/聚口基質材料界面移動之抗力)、在高濕度、反應性 酸與驗存在下之低腐蚀與反應性、及與各種聚合基質材料 之相谷性(其可在層合前排除去除塗層之需求,特別是熱 或加壓水π除中),爲可由本發明之經塗覆纖維股呈現之 其他所需特徵。 較佳爲,本發明之經塗覆纖維股提供良好之織動與針織 處理力。低細毛與孔環、低破裂纖絲、低股張力、高飄動 力與低插入時間爲本發明之經塗覆玻璃纖維股提供之較佳 個別或組合特徵,其較佳地利於織動及針織,而且一致地 提供具有極少表面缺陷之用於印刷電路板應用之織物。此 外,本發明之經塗覆纖維股適合用於空氣噴射織動法。在 此使用之"空氣噴射織動"表示其中以來自一或更多個空氣 喷射噴嘴 < 強壓縮空氣將填紗(緯紗)插入經紗棚中之織物 織動型式。 本發明之經塗覆纖維股較佳爲具有可利於沿纖維之經塗 覆表面導熱之獨特塗層。在作爲用於電子電路板之連續強 (請先閱讀背面之注意事項再填寫本頁) — — — — — — — — — — — — — — - I I I l· I I I — — — — — — — — — -—7557286 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (1) The present invention relates generally to coated fiber strands used to reinforce composites, and more particularly to compatibility with matrix materials added to the strands. Coated fiber strands. ', In thermosetting molding operations, good "wet penetration" (polymeric lining or fiber) and "wet, moist" (polymer matrix material penetrates the view or fabric; individual fiber bundles or strands; ) The nature is hopeful. In contrast, good dispersion properties (i.e., the good distribution of fibers within the thermoplastic material) are a major concern in typical thermoplastic molding operations. W In the case of weaving a composite or laminate formed from fiber strands into a fabric, in addition to providing good wet penetration and good wetting properties, it is hoped that the coating on the surface of the fiber strands protects the fibers from abrasion during processing, providing Good weaving power, especially in air jet loom, and compatible with polymer matrix materials added to the fiber strands. However, many upper paddle components are not compatible with the polymeric matrix material and negatively affect the adhesion between the glass fibers and the polymeric matrix material. For example, starch, which is a commonly used sizing ingredient for textile fibers, is generally not compatible with polymeric matrix materials. As a result, these incompatible materials must be removed from the fabric before being impregnated with a polymeric matrix material. The removal of such non-resin-compatible sizing materials, that is, degreasing or degreasing the fabric, can be accomplished by a variety of techniques. Removal of these non-resin-compatible sizing materials is most often accomplished by prolonged exposure of the textile fabric to high temperatures to thermally decompose the sizing (often referred to as thermal removal). The conventional heat removal process involves heating the fabric at 380 C for 60-80 hours. However, this heat removal step is detrimental to the strength of the glass fibers, and it has not always been possible to successfully remove non-grain materials and pulp decomposition products to further contaminate the fabric. Already tried other — — — — — — — — II — ^ .1 --------- Order --------- line win f Please read the notes on the back before filling this page )-^ 1 1 1 ^ 1 -4. ^ The paper size is applicable to the Chinese National Standard (CNS) A4 (21 × 297 mm) 557286 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Invention Description (2) Methods for removing sizing material, such as water washing and / or chemical removal. However, this method usually requires that the sizing composition be heavily reconstituted to be compatible with such washing and / or chemical removal, and is generally not as effective as thermal removal in removing all incompatible materials. In addition, because the weaving process is quite abrasive to fiberglass yarns, the yarns used as warp yarns generally undergo a second coating step before weaving, which is commonly called " sizing ", and is coated with a wear-resistant coating Warp yarns (commonly referred to as "sizing on sizing yarns") to help minimize the abrasion of glass fibers. Sizing of sizing yarns is typically applied to the first sizing previously applied to the glass fibers during the fiber forming operation. However, since the typical sizing of the sizing yarn is also generally not compatible with the polymeric matrix material, it must also be removed from the textile fabric before adding the resin. In addition, in order to improve the wear between the degreased or deoiled fabric and the polymeric resin, The processing step coats the final size (usually a silane coupling agent and water) on the fabric to recoat the glass fiber (commonly referred to as " finishing "). All of these have no additional processing steps: sizing, degreasing or degreasing, and finishing, increasing fabric manufacturing cycle time and cost. In addition, they often require significant investments in capital equipment and labor. In addition, the additional fabric treatments accompanying these treatment steps cause fabric damage and reduced quality. Efforts have been made to improve the efficiency or effectiveness of some of these processing steps. However, the coating continues to fulfill one or more of the following requirements: to suppress wear and tear of glass fibers; to be compatible with a wide variety of matrix materials; and to provide good wetting and wetting of the matrix material. Furthermore, it is particularly advantageous if the coating is compatible with modern air-jet weaving devices to increase productivity. In addition, the elimination of no additional processing steps in the fabric forming operation, while maintaining the electronic support should — — ilk'J — f »— — — — — III l · III ^« — — — — — I (Please Read the notes on the back before filling out this page) -11 -5-557286 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Invention Description (4 The invention < The fiber stock has a unique coating 'It is not only better In the process of inhibiting fibers (abrasion and cracking), it also provides at least one of the following 1 ± quality, good wet through, wet and disperse properties when forming a composite. As detailed below, the “疋 义 版” contains multiple individual Weaving dimension, that is, at least two weaving dimensions. The compound used herein refers to a combination of the coated fiber strands of the present invention and additional materials, such as, but not limited to, adding one or more layers to the coated Fiber strands <fabric combined polymer matrix materials to form laminates. Good lamination strength Good thermal stability, good hydrolytic stability (ie, resistance to water moving along the fiber / polyester matrix material interface), high Degree, low acidity and reactivity in the presence of reactive acids, and compatibility with various polymeric matrix materials (which can eliminate the need to remove the coating before lamination, especially hot or pressurized water) ) Are other desirable characteristics that can be exhibited by the coated fiber strands of the present invention. Preferably, the coated fiber strands of the present invention provide good weaving and knitting processing power. Silk, low strand tension, high floating power, and low insertion time are the preferred individual or combined features provided by the coated glass fiber strands of the present invention, which are better for weaving and knitting, and provide consistently with fewer surface defects It is used for printed circuit board applications. In addition, the coated fiber strands of the present invention are suitable for air jet weaving. As used herein " air jet weaving " Air jet nozzle < Strong weaving air inserts the filling yarn (weft yarn) into the warp shed. The coated fiber strand of the present invention preferably has a unique feature that facilitates heat conduction along the coated surface of the fiber. Coating. As a continuous strength for electronic circuit boards (please read the precautions on the back before filling out this page) — — — — — — — — — — — — — III l · III — — — — — — — — — -—7
——__ - ~—----B7___ 五、發明說明(5 ) " ---- 化物時’本恭日日、 ^ ^ ^ 又此種經塗覆玻璃纖維可提供沿強化物促 谈’:、、源(如晶片、或電路)熱散逸,以將熱導離電子組件之 因而抑帝J電子、组件、纟璃纖維及聚合基質材料之熱 :奪解及^或退化。本發明之經塗覆纖維股較佳爲提供比基 處材料问之導熱相’即,熱散逸與分布之偏好路徑,因 而’減4 f子電路板之熱膨脹與捲曲差且改良焊接可靠 度。 本發月之、、二塗覆玻璃纖維股較佳爲減少或排除在基質樹 月日中加入導熱材料之需求,其改良層合物製造操作及減少 昴貴之基質材料供應槽沖洗與維護。 本發明之經塗覆纖維股較佳爲呈現高股開放性。在此使 用之”高股開放性"表示股具有大橫切面面積及股之纖絲不 緊密地彼此結合。高股開放性可利於基質材料對股束之穿 透或濕潤。 由本發明之纖維股製造之本發明複合物,特別是層合 物’較佳爲呈現至少一種以下之性質:低熱膨脹係數;良 好之撓性強度;良好之層間結合強度;及良好之水解安定 力’即,對水沿纖維/基質界面移動之抗力。此外,由依 照本發明之纖維股製造之本發明電子撑體與印刷電路板較 佳爲具有至少一種以下之性質:良好之鑽洞力;及金屬移 動(亦/稱爲陰極-陽極纖絲形成或CAF)抗力。參見 Tummala (編者)等人之 Microelectronics Packaging Handbook, (1989)第 896-897 頁,及 IPC-TR-476B,"Electrochemical Migration: Electrochemically Induced Failures in Printed Wiring 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注音?事項再填寫本頁) — — — — — — b, J Ik I I I I I I I I l· I I I a — — — — — — — — ▲ 經濟部智慧財產局員工消費合作社印製 -i· 557286 A7——__-~ —---- B7___ V. Description of the invention (5) " ---- Chemical time, 'Birthday, ^ ^ ^ Also this kind of coated glass fiber can be provided along the reinforcement to promote the talk ': ,, source (such as wafer, or circuit) heat dissipation to conduct heat away from electronic components and thus suppress the heat of J-electronics, components, glass fiber and polymeric matrix materials: deconstruction and degradation. The coated fiber strand of the present invention preferably provides a preferred path of thermal conduction phase, that is, heat dissipation and distribution, than the material at the base, thereby reducing the thermal expansion and curl of the 4 f daughter circuit board and improving soldering reliability. The first and second coated glass fiber strands in this issue are preferably to reduce or eliminate the need to add a thermally conductive material to the substrate tree, which improves the laminate manufacturing operation and reduces the expensive substrate material supply tank flushing and maintenance. The coated fiber strands of the present invention preferably exhibit high openness. As used herein, "high strand openness" means that the strands have a large cross-sectional area and the filaments of the strands are not closely combined with each other. The high strand openness can facilitate the penetration or wetting of the strands by the matrix material. The fiber of the present invention The composite of the present invention made of strands, especially the laminate, preferably exhibits at least one of the following properties: low thermal expansion coefficient; good flexible strength; good interlayer bonding strength; and good hydrolytic stability. Resistance to the movement of water along the fiber / matrix interface. In addition, the electronic support and printed circuit board of the present invention made from fiber strands according to the present invention preferably have at least one of the following properties: good drilling force; and metal movement ( Also known as cathode-anode filament formation or CAF) resistance. See Tummala (ed.) Microelectronics Packaging Handbook, (1989) pages 896-897, and IPC-TR-476B, " Electrochemical Migration: Electrochemically Induced Failures in Printed Wiring This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) (Please read the phonetic on the back? Then fill out this page) - - - - - - b, J Ik I I I I I I I I l · I I a - - - - - - - - ▲ Ministry of Economic Affairs Intellectual Property Office employees consumer cooperatives printed -i · 557286 A7
經濟部智慧財產局員工消費合作社印製 五、發明說明 Boards and Assemblies”,(1"7),其特別地在此併入作爲參 考。依照本發明具有良好鑽洞力之纖維股具有鑽洞時低工 具磨耗及良好之鑽孔位置正確性至少之一。 如上所述,典型之織物形成操作涉及使纖維破璃紗與由 其製造之織物接受許多無附加價値處理步驟,如漿紗、熱 清除及修整。本發明較佳地提供形成織物、層合物、電子 撑體與印刷電路板之方法,其自織物形成過程排除無附加 價値處理步驟,同時提供具有適合用於電子封裝應用之。 質之織物。本發明較佳具體實施例之其他優點包括降低2 生產循環時間、資本設備之排除、降低之織物處理與勞力 成本、良好之織物品質及良好之最終產品性質。 本發明亦提供藉由選擇具有本發明獨特塗層之纖維股而 抑制纖維股因接觸其他固體物件(如捲動、織動或針織裝 置之一部份)或因纖絲間磨損而磨耗之方法。 爲了本説明書之目的,應了解,除了在操作實例中,或 在指定之處,用於本説明書及申請專利範圍之所有表示成 分、反應條件等之數量在所有之情形以名詞”約"修飾。因 此,除非相反地表示,以下説明書及所附申請專利範圍中 敘述之數量參數爲約略値,其可視本發明尋求得到之所需 性質而改變。至少,而且並非限制對申請專利範園等致物 學理之應用之嚐試,各數量參數應至少就所報告之主要位 數之數量及應用一般捨去技術而視之。 儘管敘述本發明廣義之數量範圍與參數爲約略値,儘可 能地精確地報告特定實例中敘述之數値。然而,任何數値 (請先閱讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. "Instructions on Boards and Assemblies", (1 " 7), which are specifically incorporated herein by reference. When a fiber strand with good drilling power according to the present invention has holes Low tool wear and good drilling position accuracy at least one. As mentioned above, a typical fabric forming operation involves subjecting fiberglass yarns and fabrics made from them to many non-additive processing steps such as sizing, heat removal and Trimming. The present invention preferably provides a method for forming a fabric, a laminate, an electronic support, and a printed circuit board, which eliminates no additional processing steps from the fabric formation process, and at the same time provides a method suitable for electronic packaging applications. Fabrics. Other advantages of preferred embodiments of the present invention include reduced production cycle time, exclusion of capital equipment, reduced fabric handling and labor costs, good fabric quality, and good end product properties. The present invention also provides a choice by The fiber strand with the unique coating of the present invention inhibits the fiber strand from contacting other solid objects such as rolling A part of the weaving or knitting device) or abrasion due to abrasion between filaments. For the purpose of this specification, it should be understood that it is used in this specification and applications except in operating examples or at designated places. All the quantities in the patent scope indicating ingredients, reaction conditions, etc. are modified in all cases by the term "about". Therefore, unless stated to the contrary, the quantitative parameters set forth in the following description and the scope of the appended patent applications are approximate, and may vary depending on the desired properties sought to be obtained by the present invention. At a minimum, and not to limit attempts to apply physiology such as patent application parks, each quantitative parameter should be considered at least in terms of the number of reported major digits and the application of general round-off techniques. Although the quantitative ranges and parameters of the broad description of the present invention are approximate, the numbers described in the specific examples are reported as accurately as possible. However, any data (please read the notes on the back before filling this page)
r---^---------II -J0 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286r --- ^ --------- II -J0 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 557286
五、發明說明(7 ) 固有地含由在其各試驗測量中發現之標準差必然地生成之 特定誤差。 現在參考圖1 ,其中同樣之號碼表示同樣之元件,在圖 1中顯示包含多個纖維12之依照本發明之經塗覆纖維股 1〇 。在此使用之"股”表示多個個別纖維,即,至少兩個 纖維,而且股可包含由不同可纖維化材料製造之纖維。 (纖維束亦可稱爲"紗")。名詞”纖維"表示個別之纖絲。雖 然不限制本發明,纖維12較佳爲具有範園爲3至35微米 之平均公稱纖維直徑。較佳爲,本發明之平均公稱纖維直 徑爲5微米及更大。對於”細紗”應用,平均公稱纖維直徑 較佳爲範圍爲5至7微米。 纖維12可由熟悉此技藝者已知之任何型式之可纖維化 材料形成,其包括可纖維化無機材料、可纖維化有機材 料、及以上任何之混合物。無機及有機材料可爲人造或天 然發生材料。熟悉此技藝者應了解,可纖維化無機及有機 材料亦可爲聚合材料。在此使用之名詞,,聚合材料"表示由 鍵結在一起且在溶液或固相中混雜之長鏈原子組成之巨分 子形成之材料1。在此使用之名詞"可纖維化”表示可形成 大致連續之纖絲、纖維、股或紗之材料。 較佳爲,纖維12由無機、可纖維化玻璃材料形成。用 於本發明之可纖維化玻璃材料包括但不限於由如” 玻璃” James Mark 等人之 Inorganic Poly mers. Prentice Hall Polymer Science and Engineering Series,(1992),第 1 頁,其在此併入 作爲參考。 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -----r---訂---------線 | 經濟部智慧財產局員工消費合作社印製 -1. 557286 A7 ----___ B7 五、發明說明(8 ) 、"A_玻璃"、” C-玻璃"、"D-玻璃”、” R_玻璃”、”S_玻璃” 、與E-玻璃衍生物之可纖維化玻璃組合物製備者。在此 使用之"E_玻璃衍生物"表示包括少量氟及/或硼,而且最 佳爲無氟及/或無硼之玻璃組合物。此外,在此使用之"少 量氟”表示少於0.5重量%之氟,較佳爲少於oj重量。/〇之 氟,及”少量硼”表示少於5重量%之硼,較佳爲少於2重 量%之硼。玄武岩及礦物羊毛爲用於本發明之其他可纖維 化玻璃材料之實例。較佳之玻璃纖維由E_玻璃或E-玻璃 衍生物形成。此組合物對熟悉此技藝者爲已知的,而且就 本發明而言,其進一步討論據信不爲必要的。 本發明之玻璃纖維可由此技藝中已知用於形成玻璃纖維 之任何適當方法形成。例如,玻璃纖維可在直接熔化纖維 形成操作或間接或彈珠溶化纖維形成操作形成。在直接溶 化纖維形成操作中,原料在玻璃化爐中組合、熔化及均 化。熔融之玻璃由爐移動至前爐且進入形成裝置中,熔融 玻璃在此變細成爲連續玻璃纖維。在彈珠熔化纖維形成操 作中,預先形成具有最終所需玻璃組合物之玻璃片或彈 珠,並且進料至襯套中,其在此熔化及變細成爲連續玻璃 纖維。如果使用預熔器,則首先將彈珠進料至預熔器中, 熔化,然後將熔化之玻璃進料至纖維形成裝置中,玻璃在 此變細以形成連續纖維。在本發明中,玻璃纖維較佳爲藉 直接熔化纖維形成操作形成。有關玻璃組合物及形成玻璃 纖維之方法之額外資訊,參見K. Loewenstein之The Manufacturing Technology of Continuous Glass Fibres (第 3 -11 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) ----l·---訂---------線_ 經濟部智慧財產局員工消費合作社印製 -i. 557286 經濟部智慧財產局員Η消費合作社印製 A7 B7 五、發明說明(9 ) 版,1993 )第 30-44 、47-103 、及 115-165 頁;美國專利 4,542,106 與 6,789,329 ;及 IPC-EG-140 "Specification for5. Description of the invention (7) inherently contains certain errors necessarily generated by the standard deviation found in each of its experimental measurements. Reference is now made to FIG. 1, where the same numbers indicate the same elements. In FIG. 1, a coated fiber strand 10 according to the present invention comprising a plurality of fibers 12 is shown. As used herein, " strand " means a plurality of individual fibers, that is, at least two fibers, and the strand may contain fibers made of different fiberizable materials. (Fiber bundles may also be referred to as " yarn "). "Fiber" means individual filaments. Although not limiting the invention, the fiber 12 preferably has an average nominal fiber diameter of 3 to 35 microns. Preferably, the average nominal fiber diameter of the present invention is 5 m or more. For "spinning" applications, the average nominal fiber diameter is preferably in the range of 5 to 7 microns. The fibers 12 may be formed from any type of fiberizable material known to those skilled in the art, including fiberizable inorganic materials, fiberizable organic materials, and mixtures of any of the foregoing. Inorganic and organic materials can be man-made or naturally occurring materials. Those skilled in the art should understand that inorganic and organic materials that can be fiberized can also be polymeric materials. As used herein, the term "polymeric material" means a material formed of macromolecules 1 composed of long-chain atoms bonded together in a solution or solid phase. The term " fibrillable " as used herein means a material that can form substantially continuous filaments, fibers, strands, or yarns. Preferably, the fibers 12 are formed of an inorganic, fiberizable glass material. Fibrous glass materials include, but are not limited to, Inorganic Poly mers. Prentice Hall Polymer Science and Engineering Series, such as "glass" James Mark et al. (1992), page 1, which is incorporated herein by reference. This paper standard applies China National Standard (CNS) A4 Specification (210 X 297 mm) (Please read the precautions on the back before filling this page) ----- r --- Order --------- Line | Economy Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau-1. 557286 A7 ----___ B7 V. Description of Invention (8), " A_glass ", "C-glass ", " D-glass", "R_Glass", "S_Glass", and the producer of fiberizable glass compositions with E-glass derivatives. "E_Glass derivatives" as used herein means a small amount of fluorine and / or boron, Moreover, it is preferably a fluorine-free and / or boron-free glass composition. In addition, "less" used here "Amount of fluorine" means less than 0.5% by weight of fluorine, preferably less than oj by weight. /? Of fluorine, and "a small amount of boron" means less than 5% by weight of boron, preferably less than 2% by weight of boron. Basalt and mineral wool are examples of other fiberizable glass materials used in the present invention. Preferred glass fibers are formed from E-glass or E-glass derivatives. This composition is known to those skilled in the art, and further discussion of this composition is not considered necessary for the purposes of the present invention. The glass fibers of the present invention can be formed by any suitable method known in the art for forming glass fibers. For example, glass fibers can be formed in a direct melting fiber forming operation or an indirect or marble-dissolving fiber forming operation. In a direct dissolving fiber formation operation, the raw materials are combined, melted, and homogenized in a vitrification furnace. The molten glass moves from the furnace to the forehearth and enters the forming device, where the molten glass is thinned into continuous glass fibers. In the marble-melting fiber forming operation, a glass sheet or marble having a final desired glass composition is previously formed and fed into a liner, where it is melted and thinned into continuous glass fibers. If a pre-melter is used, the marbles are first fed into the pre-melter, melted, and then the molten glass is fed into the fiber forming device where the glass is thinned to form continuous fibers. In the present invention, the glass fibers are preferably formed by a direct melting fiber forming operation. For additional information on glass compositions and methods of forming glass fibers, see K. Loewenstein's The Manufacturing Technology of Continuous Glass Fibres (3-11)-This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) ) (Please read the precautions on the back before filling out this page) ---- l · --- Order --------- Line _ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-i. 557286 Economy Printed by the Intellectual Property Bureau of the Ministry of Consumers and Consumer Cooperatives A7 B7 V. Invention Description (9) Edition, 1993) Pages 30-44, 47-103, and 115-165; US Patents 4,542,106 and 6,789,329; and IPC-EG-140 " Specification for
Finished Fabric Woven from Έ* Glass for Printed Board’·第 1 頁,The Institute for Interconnecting and Packaging Electronic Circuits之刊物(1997年6月),其特別地在此併入作爲參 考。 適合之非玻璃纖維化無機材料之非限制實例包括陶瓷材 料,如碳化矽、碳、石墨、富鋁紅柱石、氧化鋁及壓電陶 瓷材料。適合之可纖維化有機材料之非限制實例包括棉 花、纖維素、天然橡膠、亞麻、苧麻、麻、瓊麻及羊毛。 適合之可纖維化有機聚合材料之非限制實例包括由聚醯胺 (如耐綸與芳族醯胺)、熱塑性聚酯(如聚對酞酸伸乙酯與 聚對酞酸伸丁酯)、丙烯基(如聚丙烯腈)、聚烯烴、聚胺 基甲酸酯及乙晞基聚合物(如聚乙晞醇)形成者。用於本發 明之非玻璃纖維化材料及製備與處理此種纖維之方法在 Encyclopedia of Polymer Science and Technology,第 6 卷(1967) 第505-712頁詳細討論,其特別地在此併入作爲參考。 應了解,如果需要,任何以上材料之掺合物或共聚物及 由任何以上材料形成之纖維之組合可用於本發明。此外, 名詞股包含至少兩種由不同之可纖維化材料製造之不同纖 維。在較佳具體實施例中,本發明之纖維股含至少一個玻 璃纖維,雖然其可含其他型式之纖維。 本發明現在大致關於玻璃纖維股之内容討論,雖然熟悉 此技藝者應了解,股10可包含由以上討論之此技藝已知 -12- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注音?事項再填寫本頁)Finished Fabric Woven from Έ * Glass for Printed Board ’, page 1, The Institute for Interconnecting and Packaging Electronic Circuits publication (June 1997), which is specifically incorporated herein by reference. Non-limiting examples of suitable non-glass fiberized inorganic materials include ceramic materials such as silicon carbide, carbon, graphite, mullite, alumina, and piezoelectric ceramic materials. Non-limiting examples of suitable fiberizable organic materials include cotton, cellulose, natural rubber, linen, ramie, hemp, ramie, and wool. Non-limiting examples of suitable fiberizable organic polymeric materials include polyamines (such as nylon and aromatic amines), thermoplastic polyesters (such as polyethylene terephthalate and polybutylene terephthalate), Formers of acryl (such as polyacrylonitrile), polyolefin, polyurethane and acetamyl polymers (such as polyethylene glycol). The non-glass fiberized materials used in the present invention and methods for making and processing such fibers are discussed in detail in Encyclopedia of Polymer Science and Technology, Vol. 6 (1967), pages 505-712, which is specifically incorporated herein by reference . It should be understood that if desired, a blend or copolymer of any of the above materials and a combination of fibers formed from any of the above materials can be used in the present invention. In addition, the noun strand contains at least two different fibers made from different fiberizable materials. In a preferred embodiment, the fiber strand of the present invention contains at least one glass fiber, although it may contain other types of fibers. The present invention is now generally discussed about the content of glass fiber strands, although those skilled in the art should understand that the strand 10 may contain the technique known from the above discussion. -12- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the phonetic on the back? Matters before filling out this page)
557286 A7 五、發明說明(10 ) 之可纖維化材料形成之纖維12 。 颂准以因此,以下關於玻璃纖 維之討論大致應用於以上討論之其他纖維。 繼續參考圖!,在較佳具體實施例中,本發明纖維股 10至少之-而且較佳爲所有之纖維12具有塗層组合物(其 較佳爲塗層組合物殘渣)在纖維12表面16之至少一部份 17上I層14 ,以在處理時保護纖維表面16免於磨損及抑 制纖維破裂。較佳爲,層14存在於全部外表面16或纖維 12之週邊上。 本發明之塗層组合物較佳爲水性塗層組合物,而且較佳 爲水性樹脂相容塗層組合物。雖然因安全原因而不佳,塗 層組合物可如所需含揮發性有機溶劑,如醇或丙酮,但是 較佳爲無此種溶劑。此外,本發明之塗層組合物可作爲第 一上漿組合物及/或第二上漿或塗層組合物。 在較佳具體實施例中,在此使用之名詞"上漿料”、 上漿料sized ”或”上漿料Sizillg ”指在纖維形成後塗佈於纖 維之任何塗層組合物。名詞”第二上漿料sec〇ndary以汉,·、 "第二上漿料secondary sizing ”或,,第二塗層,,表示在塗佈第 一上漿料後塗佈於纖維之塗層組合物。名詞”第三上漿料 tertiary size ”、”第三上漿料tertiary sizing ”或"第三塗層,,表 示在塗佈弟一上漿料後塗佈於纖維之塗層組合物。例如, 藉由塗覆織物,這些塗層可在纖維加入織物之前塗佈於纖 維’或者其可在纖維加入織物之後塗佈於纖維。在替代具 體實施例中,名詞,,上漿料size,,、”上漿料sized ”或”上漿 料sizing ’’另外指在已藉熱或化學處理去除至少一部份,而 (請先閱讀背面之注意事項再填寫本頁) ------^----訂---------線* 經濟部智慧財產局員工消費合作社印製 -X. -13- 557286 A7 ---~_— 五、發明說明(11 ) 且較佳爲所有之習知非樹脂相容上漿組合物之後,塗佈於 纖維之塗層組合物(亦已知爲,,修整上漿料”),即,修整上 桌料塗佈於加入織物形式中之裸玻璃纖維。 在此使用之名詞”樹脂相容"表示塗佈於玻璃纖維之塗層 組合物與玻璃纖維所加入之基質材料相容,使得塗層組合 物(或經選擇塗層成分)得到至少一種以下之性質:在加入 基質材料之前不需要去除(如藉脱脂或脱油)、在習知處理 時利於基質材料之良好濕潤與濕透、及生成具有所需物理 性質與水解安定力之最終複合產物。 本發明之塗層組合物包含一或更多個,而且較佳爲多個 顆粒18 ,其在塗佈於多個纖維12之至少一個纖維23時 黏附至少一個纖維23之外表面16 ,並且在股10之相鄰 玻璃纖維23 ,25之間提供一或更多個間隙空間21 ,如 圖1所示。這些間隙空間21大致相當於位於相鄰纖維間 之顆粒18之大小19。本發明之顆粒is較佳爲不連續顆 粒。在此使用之名詞π不連續”表示顆粒在習知處理條件下 不趨於聚結或組合而形成連續膜,而是實質上保留其個別 差異性,而且通常保留其個別形狀或形式。本發明之不連 續顆粒在習知纖維處理時可進行剪切,即,去除顆粒中之 一層或一片原子,縮頸,即,至少兩個顆粒間之第二級相 轉移,及部份聚結,而且仍可視爲”不連續"顆粒。 本發明之顆粒18較佳爲尺寸安定的。在此使用之名詞 Η尺寸安定顆粒π表示顆粒在習知纖維處理條件下,如在織 動、纺條及其他處理操作時相鄰纖維間產生之力,通常維 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) ------r---訂---------線* 經濟部智慧財產局員工消費合作社印製 -1. 五、發明說明(u) 2其平均粒度及形狀,而維持相鄰纖維23,25間之間隙 換》之,在典型玻璃纖維處理條件下,如暴露 於達25。(:,較佳爲$ 1〇〇 r,而且更佳爲達i4〇 ec之溫 $,尺寸安定顆粒較佳爲在塗層组合物中不崩潰溶解或 質上變形而形成具有小於其經選擇平均粒度之最大尺寸 之顆粒。此外,在玻璃纖維處理條件下,而且更佳爲在處 ^度超過15〇 X:之複合物處理條件下,顆粒Μ大小應 質上不變大或膨脹。在此有關顆粒使用之名詞"大小應 實質上不變大••表示在處理時顆粒應不膨服或增加大小至 :過其起始大小〈三倍。此外,在此使用之名詞"尺寸安 疋顆粒”涵蓋結晶與非晶顆粒。 較佳爲,本發明之塗層組合物實質上無熱可膨脹顆粒。 ^此使用之名詞"熱可膨脹顆粒"表示充填或含某種材料之 '粒’其在暴露於足以使材料揮發之溫度時 資上變大。這些熱可膨脹顆粒因此由於顆粒中材料^ 口劑)在正常處理條件下之相變化而造成膨服。結 =名詞不可熱膨脹顆粒"指由於顆粒中材料在正常處理 條件下之相變化而不膨脹之顆粒’而且在本發明 施例中,塗層组合物包含至少-個不可熱膨服顆粒: 、,常’熱可膨脹顆粒爲具中央穴之中空顆粒。在本發明 <非限制具體實施例中,穴可 、 料,如氣體、液體、及/或凝膠。V邵伤地充填非固體材 之名詞"實質上無熱可膨脹顆粒"表示基於總固 Μ V、於5G重量%之熱可膨脹顆粒,更佳爲少於%重量 557286 A7 B7 五、發明說明(13 ) (請先閱讀背面之注咅S事項再填寫本頁) %。更佳爲,本發明之塗層組合物本質上無熱可膨脹顆 粒。在此使用之名詞”本質上無熱可膨脹顆粒”表示上漿組 合物包含基於總固體爲少於20重量%之熱可膨脹顆粒, 更佳爲少於5重量% ’而且最佳爲少於0.001重量%。 顆粒18較佳爲非蠟狀。名詞"非蠟狀”表示形成顆粒之 材料爲非壤狀。在此使用之名詞”壌狀”表示材料主要由具 有範圍爲25至100個碳原子之平均碳鏈長之不混雜烴鏈 組成2’3。 在本發明之較佳具體實施例中,本發明之顆粒18爲不 連續、尺寸安定、非蠟狀顆粒。 顆粒18可具有任何所需之形狀或組態。雖然在本發明 中不限制,適合之顆粒形狀之實例包括球形(如顆粒、微 粒或中空球形)、立方體、板狀或針狀(長形或纖維狀)。 此外,顆粒18可具有中空、多孔性或無孔隙之内部結 構,或其組合’例如’中2中央及多孔性或實心壁。更多 適合顆粒特徵之資訊參見Η. Katz等人(編者)之Handbook of Fillers and Plastics (1987)第9·10頁,其特別地在此併入作 經濟部智慧財產局員工消費合作社印製 2 L. H. Sperling 之 Introduction of Physical Polymer Science, John Wiley and Sons公司(1986)第2-5頁,其特別地在此併入作 爲參考。 3 W. Pushaw 等人"Use of Micronised Waxes and Wax Dispersions in Waterborne Systems1 丨 Polymers. Paint. Colours JournaL,第 189 卷,第 4412 期,1999 年 1 月第 18-21 頁, 其特別地在此併入作爲參考。 -16- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7 B7_ 五、發明說明(l4 ) 爲參考。 (請先閱讀背面之注音?事項再填寫本頁) 顆粒18可由選自聚合與非聚合無機材料、聚合與非聚 合有機材料、複合材料、及以上任何之混合物之材料形 成。在此使用之名詞”聚合無機材料"表示具有以碳以外之 元素爲主之主幹重複單位之聚合材料。更多之資訊參見L K. Mark答人第5頁,其特別地在此併入作爲參考。在此 使用之名詞’,聚合有機材料”表示具有以碳爲主之主幹重複 單位之合成聚合材料、半合成聚合材料與天然聚合材料。 在此使用之”有機材料”表示含碳化合物,其中碳一般鍵 結至其本身及氫,而且亦經常至其他元素,並且排除如碳 氧化物、碳化物、二硫化碳等之二元化合物;如金屬氰化 物、金屬羰基、光氣、羰基硫等之三元化合物;及如金屬 碳酸鹽之含碳離子性化合物,如碳酸鈣與碳酸鈉。參見R· Lewis,Sr·之 Hawlev’s Condensed Chemical Dictionary·(第 12 版,1993 )第 761-762 頁,及 Μ· Silberberg 之 Chemistry IM Molecular Nature of Matter and Change Π996)第 58ό 頁,其特 別地在此併入作爲參考。 在此使用之名詞”無機材料”表示任何不爲有機材料之材 經濟部智慧財產局員工消費合作社印製 料。 在此使用之名詞”複合材料”表示二或更多種不同材料之 組合。由複合材料形成之顆粒在其表面通常具有異於其表 面下之顆粒内部硬度之硬度。更特別地,顆粒之表面可以 此技藝已知之任何方法修改,其包括但不限於使用此技藝 已知之技術化學地或物理地改變其表面特徵,使得顆粒之 __- 17- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7557286 A7 Fifth, the description of the invention (10) fiber 12 formed of a fiberizable material. Therefore, the following discussion of glass fibers applies broadly to the other fibers discussed above. Continue to refer to the figure! In a preferred embodiment, at least one of the fiber strands 10 of the present invention-and preferably all of the fibers 12 have a coating composition (which is preferably a residue of the coating composition) on at least a portion of the surface 16 of the fiber 12 Part 17 has an I layer 14 to protect the fiber surface 16 from abrasion and inhibit fiber breakage during processing. Preferably, the layer 14 is present on the entire outer surface 16 or the periphery of the fiber 12. The coating composition of the present invention is preferably an aqueous coating composition, and more preferably an aqueous resin-compatible coating composition. Although it is not preferable for safety reasons, the coating composition may contain a volatile organic solvent, such as alcohol or acetone, as desired, but it is preferably free of such a solvent. In addition, the coating composition of the present invention can be used as a first sizing composition and / or a second sizing or coating composition. In a preferred embodiment, the terms " sizing ", sizing ", or " sizing Sizillg " as used herein refer to any coating composition that is applied to the fibers after the fibers are formed. The term "second sizing secondary" refers to the "secondary sizing" or, "second coating", which refers to the coating of fibers after the first sizing is applied.层 组合 物。 Layer composition. The term "third sizing tertiary size", "third sizing tertiary sizing", or "third coating" means a coating composition that is applied to the fibers after the first coating is sized. For example, by coating the fabric, these coatings may be applied to the fiber ' before the fiber is added to the fabric or it may be applied to the fiber after the fiber is added to the fabric. In alternative embodiments, the noun, size size, or "size sizing" or "sizing sizing" additionally means that at least a portion has been removed by heat or chemical treatment, and (please first (Read the notes on the back and fill in this page) ------ ^ ---- Order --------- line * Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-X. -13- 557286 A7 --- ~ _-- V. Description of the invention (11) and preferably all conventional non-resin compatible sizing compositions are applied to the fiber coating composition (also known as, trimming) "Sizing"), that is, trimming the bare glass fibers that are applied to the fabric form. The term "resin compatible" as used herein means that the coating composition applied to the glass fiber is compatible with the matrix material to which the glass fiber is added, so that the coating composition (or selected coating component) has at least one of the following Properties: It does not need to be removed before adding the matrix material (such as degreasing or degreasing), it is good for the good wetting and penetration of the matrix material during the conventional processing, and it can produce the final composite product with the required physical properties and hydrolytic stability. The coating composition of the present invention comprises one or more, and preferably a plurality of particles 18, which adhere to the outer surface 16 of at least one fiber 23 when applied to at least one fiber 23 of a plurality of fibers 12, and One or more interstitial spaces 21 are provided between adjacent glass fibers 23, 25 of the strand 10, as shown in Fig. 1. These interstitial spaces 21 are roughly equivalent to the size 19 of particles 18 located between adjacent fibers. The present invention The particles is preferably discontinuous particles. The term "π discontinuity" as used herein means that the particles do not tend to agglomerate or combine to form a continuous film under conventional processing conditions, but essentially retain their Individual differences and often retain their individual shape or form. The discontinuous particles of the present invention can be sheared during the conventional fiber treatment, that is, removing a layer or a piece of atoms in the particles, necking, that is, second-order phase transfer between at least two particles, and partial coalescence. And can still be regarded as "discontinuous" particles. The particles 18 of the present invention are preferably dimensionally stable. The term "size-stable particles" as used herein means that the particles are under conventional fiber processing conditions, such as weaving, spinning The force generated between adjacent fibers during strip processing and other processing operations. Generally, the dimensions of the dimension paper are applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)- ---- r --- Order --------- line * Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-1. V. Description of the invention (u) 2 Its average particle size and shape, while maintaining relative phase The gap between adjacent fibers 23 and 25 is changed. In other words, under typical glass fiber processing conditions, such as exposure to up to 25. (:, preferably $ 100r, and more preferably up to i4oec temperature $, The size-stable particles are preferably formed in the coating composition without dissolving or qualitatively deforming. Particles smaller than the maximum size of the selected average particle size. In addition, under glass fiber processing conditions, and more preferably in composite processing conditions where the degree exceeds 150 × :, the size of the particles M should not be qualitatively larger. Or swell. The term "particles" used here should be substantially unchanged in size. • indicates that the particles should not be swelling or increased in size during processing: beyond their initial size <three times. In addition, the term used here The term " size-safe particle " encompasses both crystalline and amorphous particles. Preferably, the coating composition of the present invention is substantially free of thermally expandable particles. ^ The term used herein " thermally expandable particles " means filled or A 'grain' containing a certain material becomes larger when exposed to a temperature sufficient to volatilize the material. These heat-swellable particles therefore swell due to the phase change of the material in the particles (oral agent) under normal processing conditions. . Knot = noun non-thermally expandable particles " refers to particles that do not swell due to the phase change of the material in the particles under normal processing conditions'; and in the embodiment of the present invention, the coating composition contains at least one non-thermally expandable particle:, Often, thermally expandable particles are hollow particles with a central cavity. In a non-limiting specific embodiment of the present invention, cavities, materials, such as gas, liquid, and / or gel. The term “filling non-solid materials with wounds” is “substantially no thermally expandable particles” means thermally expandable particles at 5G% by weight based on the total solid M V, more preferably less than 5% by weight 557286 A7 B7 V. Description of the Invention (13) (Please read Note S on the back before filling out this page)%. More preferably, the coating composition of the present invention is essentially free of thermally expandable particles. The term "essentially thermally expandable particles" as used herein means that the sizing composition contains less than 20% by weight of thermally expandable particles based on total solids, more preferably less than 5% by weight, and most preferably less than 0.001% by weight. The particles 18 are preferably non-wax. The term " non-wax-like " means that the material forming the particles is non-soily. The term " 壌 -like " as used herein means that the material is mainly composed of an immiscible hydrocarbon chain having an average carbon chain length ranging from 25 to 100 carbon atoms 2'3. In a preferred embodiment of the present invention, the particles 18 of the present invention are discontinuous, dimensionally stable, non-wax particles. The particles 18 may have any desired shape or configuration. Although in the present invention Without limitation, examples of suitable particle shapes include spherical (such as particles, particles, or hollow spheres), cubes, plates, or needles (long or fibrous). In addition, the particles 18 may have a hollow, porous, or non-porous shape. Internal structure, or a combination of 'for example', 2 central and porous or solid walls. For more information on particle characteristics see Η. Katz et al. (Eds.) Handbook of Fillers and Plastics (1987) p. 9.10, It is specifically incorporated here as the Printing of 2 LH Sperling's Introduction of Physical Polymer Science, John Wiley and Sons Company (1986) pages 2-5. 3 W. Pushaw et al. &Quot; Use of Micronised Waxes and Wax Dispersions in Waterborne Systems1 丨 Polymers. Paint. Colours JournaL, Vol. 189, No. 4412, 18-21 January 1999 Page, which is specifically incorporated herein by reference. -16- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 557286 A7 B7_ V. Description of the invention (l4) for reference. (Please first Read the note on the back? Matters and then fill out this page) Particles 18 may be formed of materials selected from the group consisting of polymeric and non-polymeric inorganic materials, polymeric and non-polymeric organic materials, composite materials, and any mixtures thereof. The term "polymeric inorganic" used herein Material " means a polymeric material with a backbone repeating unit mainly composed of elements other than carbon. More information can be found on page 5 of the answer by L K. Mark, which is specifically incorporated herein by reference. The term 'polymeric organic material' as used herein refers to synthetic polymeric materials, semi-synthetic polymeric materials, and natural polymeric materials with carbon-based backbone repeating units. "Organic materials" as used herein refers to carbon-containing compounds, of which carbon Generally bonded to itself and hydrogen, and often to other elements, and excludes binary compounds such as carbon oxides, carbides, carbon disulfide, etc .; ternary such as metal cyanide, metal carbonyl, phosgene, carbonyl sulfur, etc. Compounds; and carbon-containing ionic compounds such as metal carbonates, such as calcium carbonate and sodium carbonate. See R. Lewis, Sr., Hawlev's Condensed Chemical Dictionary, (12th edition, 1993), pages 761-762, and M. Silberberg's Chemistry IM Molecular Nature of Matter and Change (p.996), page 58, which is specifically incorporated herein by reference. The term "inorganic materials" as used herein means any material that is not an organic material and is consumed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed materials. The term "composite material" as used herein means a combination of two or more different materials. Particles formed from composite materials usually have a hardness on their surface that is different from the internal hardness of the particles below the surface. More specifically, the surface of the particles can be modified by any method known in the art, including but not limited to using technical chemistry known in the art Change the surface characteristics physically or physically, so that the __- of the particles 17- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 557286 A7
557286 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(l6 ) 於彼此滑動,因此在纖維表面(較佳爲玻璃纖維表面)與相 鄰固體表面之間產生抗磨擦潤滑效果,其中至少之一移 動。參見 R. Lewis,Sr·之 Hawlev丨s Condensed Chemical Dictionary.(第12版,1993 )第712頁,其特別地在此併入 作爲參考。磨擦力爲固體彼此滑動之抗力。F· Clauss之 Solid Lubricants and Self-Lubricating Solids (1972)第 1 頁,其 特別地在此併入作爲參考。 在本發明之非限制具體實施例中,顆粒18具有薄平結 構。具有薄平結構之顆粒由六面體陣列之原子片或板組 成,其在片内具有強键結及在片間具有弱凡德瓦鍵結,而 提供片間之低剪切強度。薄平結構之非限制實例爲六面體 結晶結構。K. Ludema 之 Friction,Wear,Lubrication (1996)第 125 頁, Solid Lubricants and Self-Lubricating Solids 第 19-22、42-54、75-77、80-81、82、90-102、113-120 與 128 頁;及 W. Campbell 之 ’’Solid Lubricants’’,Boundary Lubrication: An Appraisal of World Literature, ASME Research Committee on Lubrication (1969)第 202-203 頁,其特別地在此 併入作爲參考。具有薄平fullerene (大球)結構之無機實心 顆粒亦可用於本發明。 具有可用於形成本發明顆粒18之薄平結構之適合材料 之非限制實例包括氮化硼、石墨、金屬二硫族化合物、雲 母、滑石、石骨、高嶺土、方解石、破化鎘、硫化銀、及 以上任何之混合物。較佳之材料包括氮化硼、石墨、金屬 二硫族化合物、及以上任何之混合物。適合之金屬二硫族 -19- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注咅?事項再填寫本頁) ------^----訂---------線 | IV— - 557286 A7 B7 五、發明說明(17 ) 化合物包括二硫化鉬、二硒化鉬、二硫化鉅、二硒化鋰、 二硫化鎢、二硒化鎢、及以上任何之混合物。 (請先閱讀背面之注意事項再填寫本頁) 在具體實施例中,顆粒18由具有薄平結構之無機固態 潤滑劑材料形成。用於本發明塗層組合物之具有薄平結構 之無機固態潤滑劑材料之非限制實例爲氮化硼,較佳爲具 有六面體結晶結構之氮化硼。由氮化硼,硫化鋅與微晶高 嶺石形成之顆粒亦在具有如耐綸6,6之聚合基質材料之複 合物中提供良好之白度。 經濟部智慧財產局員工消費合作社印製 由適合用於本發明之氮化硼形成之顆粒之非限制實例爲 POLARTHERM® 100 系列(PT 120、PT 140、PT 160 與 PT 180) ; 300 系列(PT 350)及 600 系列(PT 620、PT 630、PT 640與PT 670)氮化硼粉末顆粒,其商業得自俄亥俄州 Lakewood 之 Advanced Ceramics 公 司 0 ’’PolarTherm® Thermally Conductive Fillers for Polymeric Materials”,俄亥俄 州 Lakewood 之 Advanced Ceramics 公司之技術公告(1996), 其特別地在此併入作爲參考。這些顆粒具有在25 °C爲每 米。K 250-300瓦之傳熱度,3.9之介電常數及1015歐姆-公 分之體積電阻率。100系列粉末顆粒具有範園爲5至14 微米之平均粒度,300系列粉末顆粒具有範圍爲100至 150微米之平均粒度,及600系列粉末顆粒具有範園爲15 至大於200微米之平均粒度。特別地,如其供應者所報 告,POLARTHERM 160顆粒具有6至12微米之平均粒 度,次微米至70微米之粒度範圍,及如下之粒度分布: -20- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7 B7 五、發明說明(is % 10 50 90 大小(微米) 18.4 7.4 0.6 依照此分布’所測量之P〇LARTHERM(g) 16〇氮化硼顆粒之 1〇/〇具有大於18.4微米之平均粒度。在此使用之•,平均粒 度”指顆粒之平均顆粒大小。 依照本發明之顆粒之平均粒度可依照已知之雷射散射技 術測量。在本發明之非限制具體實施例中,使用Beckmai] Coulter LS 230雷射繞射粒度儀測量粒度,其使用具75〇奈 米波長之雷射束測量粒度,並且假設顆粒具有球形,即, "粒度”指完全封包顆粒之最小球粒。例如,發現使用 Beckman Coulter LS 23〇 粒度儀測量之 p〇LARTHER娜⑽氮 化测顆粒之顆粒具有U.9微米之平均粒度,顆粒範園爲次 微米至36微米,及具有以下之顆粒分布: 依照此分布,所測量之P〇LARTHERM⑧1ό〇氮化硼顆 10%具有大於20.6微米之平均粒度。 在本發明之另一個非限制具體實施例中,顆粒Μ 可水合無機材料形成。在此使用之”不可 ·· J 口 衣不無 粒不反應水分之以形成水合物,而且不含水合水或' 水。”水合物”藉由水分子與其中Η-〇Η鍵不斷裂之2 __ _21_ $適用中國國家標準(CNS)A4規格(210 X 297公髮)— (請先閱讀背面之注意事項再填寫本頁) ---------^--------- 經濟部智慧財產局員工消費合作社印製 557286 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(19 ) 反應製造0 參見 R· Lewis,Sr·之 Hawley’s Condensed Chemical Dictionary,(第 12 版,1993 )第 609-610 頁,及 T。Perros 之 Chemistry> (1967)第186-187頁,其特別地在此併入作爲參 考。在水合物之式中,水分子之加成習知上以中央點表 示,例如,3Mg0.4Si〇2.H2〇 (滑石)、Al2O3.2SiO2.2H2O (高嶺土)。結構上,可水合無機材料在一層晶格内包括 至少一個羥基(但是不包括在其表面平面上藉毛細作用吸 水之材料之單位結構表面平面之羥基),例如,如J. Mitchell 之 Fundamentals of Soil Behavior (1976)第 34 頁之第 3.6圖所示之高嶺土之結構所示,及各如H. van Olphen之 Clav Colloid Chemistry.(第 2 版,1977)第 62 頁之圖 18 與 19所示之1:1與2:1層礦物之結構所示,其特別地在此併 入作爲參考。一”層π晶格爲片(其爲原子平面之組合)之組 合 0 (參見 Minerals in Soil Environments. Soil Science Society of America (1977)第196-199頁,其特別地在此併入作爲參 考)。層與層間材料(如陽離子)之聚集稱爲單位結構。 水合物含配位水,其將陽離子配位於水合材料中且無法 不將結構及/或結構水(其佔據結構中間隙以增加靜電能量 而不破壞電荷平衡)破碎而去除。R. Evnas之An Introduction to Crystal Chemistry Π948^ 第 276 頁,其特別地 在此併入作爲參考。通常,塗層組合物含不超過50重量 %之可水合顆粒。在本發明之非限制具體實施例中,塗層 組合物較佳爲本質上無可水合顆粒。在此使用之名詞”本 質上無可水合顆粒"表示塗層組合物包含基於總固體爲少 -22- 表紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) · (請先閱讀背面之注意事項再填寫本頁) ------r---訂---------線 j 557286 A7 、發明說明(2〇 ) B7 經濟部智慧財產局員工消費合作社印製 於20重量%之可水合顆 估^、 、又’更佳爲少於5重量0/〇,而且最 佳馬少於0.001重量%。 , Α 。在本發明之具體實施例中,顆粒 :不可水合無機固態潤滑劑材料形成。 馬了代替或除了以上討論之不可水合無機材料,依照本 發明之塗層組合物可本. 。由了水合或經水合無機材料形成之 :粒。此種可水合無機材料之非限制實例爲黏土礦頁料 其包括雲母(如白雲母)、滑石微晶高嶺石高嶺土 及石霄。如以上所解釋,由此種可水合或經水合無機材料 形成之顆粒通常組成不超過塗層組合物中顆粒之50重量 〇/〇 0 在本發明之另-個具體實施例中,顆粒18可由非聚合 有機材料形成1於本發明之非聚合有機材料包括但不二 於硬脂酸鹽(如硬脂酸鋅與硬脂酸鋁)' 碳黑及硬脂醯胺。 在本發明之另—個具體實施例中,顆粒18可由無機聚 合材料形成。可用無機聚合材料之非限制實例包括㈣嗅、聚梦烷、聚碎氧燒、聚錯捷、聚硫、聚栖、聚碎氧、 及以上任何之混合物。由適合用於本發明之無機聚合材料 形成之顆粒之特定非限制實例爲T〇SPEARL4,其爲由交聯矽氧烷形成之顆粒,而且商業得自日本之東芝聚矽氧公 司 0 在本發明之另一個具體實施例中,顆粒18可由合成有 機聚合材料形成。適合之有機聚合材料包括但不限於熱固 性材料及熱塑性材料。適合之熱固性材料包括熱固性聚 酯、乙晞酯、環氧材料、盼系、胺基塑料、熱固性聚胺基 .23 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) n ϋ I .1 ϋ ϋ ϋ i-i J1 · -l· L-----------r---訂 --------線‘ 557286 A7 B7 五、發明說明(21 ) 甲酸酯、及以上任何之混合物。由環氧材料形成之較佳合 成聚合顆粒之特定非限制實例爲環氧微膠顆粒。 適合之熱塑性材料包括熱塑性聚酯、聚碳酸酯、聚烯 烴、丙烯聚合物、聚醯胺、熱塑性聚胺基甲酸酯、乙烯基 聚合物、及以上任何之混合物。較佳之熱塑性聚醋包括但 不限於聚對酞酸伸乙酯、聚對酞酸伸丁酯及聚莕酸伸乙 酯。較佳之聚烯烴包括但不限於聚乙烯、聚丙烯及聚異丁 烯。較佳之丙烯聚合物包括苯乙烯與丙烯酸單體之共聚物 及含甲基丙晞酸之聚合物。由丙晞共聚物形成之合成聚合 顆粒之非限制實例爲RHOPLEX® B-855,其爲不透明、非 交聯固態丙烯顆粒乳液,ROPAQUE® HP-10556,其爲具有 1.0微米粒度、26.5重量%固體含量及55%孔隙體積之不 透明、非膜形成苯乙烯丙烯聚合合成顏料,ROPAQUE® OP-967與ROPAQUE® HP-543P8,其爲具有0.55微米粒度及 30.5重量%固體含量之相同不透明、非膜形成苯乙烯丙晞 聚合合成顏料分散液,及ROPAQUE® OP-62 L09,其亦爲 具有0.40微米粒度及36.5重量%固體含量之不透明、非膜 形成苯乙烯丙烯聚合合成顏料分散液。各指定顆粒商業得 自賓州費城之Rohm and Haas公司0 4 參見 R· J. Perry 之,’Applications for Cross-Linked Siloxane Particles" Chemtech· 1999 年 2 月第 39-44 頁0 5參見得自賓州費城之Rohm and Haas公司之"Chemicals for the Textile Industry" 1987 年 9 月。 6參見得自賓州費城之Rohm and Haas公司之產品性質單, -24- 紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注咅?事項再填寫本頁)557286 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (l6) slides on each other, so the anti-friction lubrication effect is produced between the fiber surface (preferably glass fiber surface) and the adjacent solid surface, where At least one moves. See R. Lewis, Sr., Hawlev, Condensed Chemical Dictionary. (12th edition, 1993) at page 712, which is specifically incorporated herein by reference. Friction is the resistance of solids to sliding against each other. F. Clauss, Solid Lubricants and Self-Lubricating Solids (1972), page 1, which is specifically incorporated herein by reference. In a non-limiting specific embodiment of the invention, the particles 18 have a thin flat structure. The particles having a thin flat structure are composed of atomic sheets or plates of a hexahedral array, which have strong bonds in the sheets and weak Van der Waals bonds between the sheets, and provide low shear strength between the sheets. A non-limiting example of a thin flat structure is a hexahedral crystal structure. Friction by K. Ludema, Wear, Lubrication (1996) p. 125, Solid Lubricants and Self-Lubricating Solids 19-22, 42-54, 75-77, 80-81, 82, 90-102, 113-120 and 128 pages; and `` Solid Lubricants '' by W. Campbell, Boundary Lubrication: An Appraisal of World Literature, ASME Research Committee on Lubrication (1969), pages 202-203, which are specifically incorporated herein by reference. Inorganic solid particles having a thin flat fullerene (large sphere) structure can also be used in the present invention. Non-limiting examples of suitable materials having a thin flat structure that can be used to form the particles 18 of the present invention include boron nitride, graphite, metal dichalcogenides, mica, talc, stone bone, kaolin, calcite, cadmium cracking, silver sulfide, And any mixture of the above. Preferred materials include boron nitride, graphite, metal dichalcogenides, and mixtures of any of the above. Suitable metal disulfide-19- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) ------ ^ ---- Order --------- line | IV—-557286 A7 B7 V. Description of the invention (17) Compounds include molybdenum disulfide, molybdenum diselenide, giant disulfide, lithium diselenide, two Tungsten sulfide, tungsten diselenide, and mixtures of any of the above. (Please read the notes on the back before filling this page.) In a specific embodiment, the particles 18 are formed of an inorganic solid lubricant material with a thin flat structure. A non-limiting example of an inorganic solid lubricant material having a thin flat structure for use in the coating composition of the present invention is boron nitride, preferably boron nitride having a hexahedral crystal structure. Particles formed from boron nitride, zinc sulfide, and microcrystalline kaolinite also provide good whiteness in composites with a polymeric matrix material such as nylon 6,6. Non-limiting examples of particles formed from boron nitride suitable for use in the present invention are printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics, which are POLARHERM® 100 series (PT 120, PT 140, PT 160, and PT 180); 300 series (PT 350) and 600 series (PT 620, PT 630, PT 640, and PT 670) boron nitride powder particles, commercially available from Advanced Ceramics, Lakewood, Ohio. 0 `` PolarTherm® Thermally Conductive Fillers for Polymeric Materials, '' Ohio Technical Bulletin by Advanced Ceramics of Lakewood (1996), which is specifically incorporated herein by reference. These particles have a heat transfer at 25 ° C per meter. K 250-300 watts of heat transfer, a dielectric constant of 3.9 and 1015 Ohm-centimeter volume resistivity. 100 series powder particles have an average particle size ranging from 5 to 14 microns, 300 series powder particles have an average particle size ranging from 100 to 150 microns, and 600 series powder particles have a range from 15 to Average particle size greater than 200 microns. In particular, as reported by its supplier, POLARTHERM 160 particles have an average particle size of 6 to 12 microns, with submicrons to 7 0 micron particle size range, and the following particle size distribution: -20- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 557286 A7 B7 V. Description of the invention (is% 10 50 90 Size (micron ) 18.4 7.4 0.6 According to this distribution, 10% of POLARTHERM (g) 16 boron nitride particles have an average particle size greater than 18.4 microns. As used herein, “average particle size” refers to the average particle size of the particles Size. The average particle size of the particles according to the present invention can be measured according to known laser scattering techniques. In a non-limiting embodiment of the present invention, the particle size is measured using a Beckmai] Coulter LS 230 laser diffraction particle size analyzer, which uses 75 〇 Nanometer wavelength laser beam measurement particle size, and assuming that the particles have a spherical shape, that is, " particle size " refers to the smallest sphere that completely encapsulates the particles. For example, it was found that the pOLARTHER was measured using a Beckman Coulter LS 23〇 particle size analyzer. Nitrided particles have an average particle size of U.9 microns, the particle size range is from sub-microns to 36 microns, and have the following particle distribution: According to this distribution, the measured POLARTHER 10% of boron nitride particles have an average particle size greater than 20.6 microns. In another non-limiting embodiment of the invention, the particles M are formed from a hydrated inorganic material. As used herein, "Non-J .. J-shirts do not have particles and do not react with water to form hydrates, and do not contain hydrated water or 'water." "Hydrate" does not break through the water molecule and the Η-〇Η bond in it. 2 __ _21_ $ Applicable to China National Standard (CNS) A4 specification (210 X 297) — (Please read the precautions on the back before filling this page) --------- ^ ------ --- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (19) Reaction Manufacturing 0 See R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, ( 12th edition, 1993) pages 609-610, and T. Perros Chemistry > (1967) pages 186-187, which are specifically incorporated herein by reference. In the formula for hydrates, the addition of water molecules Conventionally, it is represented by a central point, for example, 3Mg0.4Si〇2.H2〇 (talc), Al2O3.2SiO2.2H2O (kaolin). Structurally, the hydratable inorganic material includes at least one hydroxyl group in a layer of a lattice (but not Unit structure surface including material that absorbs water by capillary action on its surface plane Planar hydroxyl), for example, as shown in the structure of kaolin as shown in Figure 3.6, J. Mitchell's Fundamentals of Soil Behavior (1976), page 34, and Clav Colloid Chemistry, each by H. van Olphen. Edition, 1977) The structure of the 1: 1 and 2: 1 layers of minerals shown in Figures 18 and 19 on page 62 is specifically incorporated herein by reference. A "layer of π lattice is a sheet (which is Combination of atomic planes) 0 (see Minerals in Soil Environments. Soil Science Society of America (1977) pp. 196-199, which is specifically incorporated herein by reference). The aggregation of layers and interlayer materials (such as cations) is called a unit structure. Hydrates contain coordination water that coordinates cations in the hydrated material and cannot be removed without breaking up the structure and / or structured water (which occupies gaps in the structure to increase electrostatic energy without disrupting charge balance). An Introduction to Crystal Chemistry by R. Evnas Π948 ^ p. 276, which is specifically incorporated herein by reference. Generally, the coating composition contains no more than 50% by weight of hydratable particles. In a non-limiting embodiment of the invention, the coating composition is preferably essentially free of hydratable particles. As used herein, the term "essentially free of hydratable particles" means that the coating composition contains less than -22-based on total solids. Table paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) · (Please (Please read the notes on the back before filling this page) ------ r --- Order --------- line j 557286 A7, invention description (2) B7 employee consumption of Intellectual Property Bureau, Ministry of Economic Affairs Cooperatives are printed on 20% by weight of hydratable granules, more preferably less than 5% by weight 0/0, and the best horse is less than 0.001% by weight. In the specific embodiment of the present invention, Granules: formed of a non-hydratable inorganic solid lubricant material. The coating composition according to the present invention may be replaced by or in addition to the non-hydratable inorganic materials discussed above. ... formed from a hydrated or hydrated inorganic material: granules. This A non-limiting example of a hydratable inorganic material is a clay mineral sheet that includes mica (such as muscovite), talc, microcrystalline kaolinite, kaolin, and stone. As explained above, formed from such hydratable or hydrated inorganic materials The particles usually have a composition not exceeding that of the coating composition 50 weight of the granules 0/000 In another specific embodiment of the present invention, the granules 18 may be formed of a non-polymeric organic material. The non-polymeric organic materials of the present invention include, but not less than, stearates (such as stearates). Zinc acid and aluminum stearate) 'carbon black and stearylamine. In another specific embodiment of the present invention, the particles 18 may be formed from an inorganic polymeric material. Non-limiting examples of useful inorganic polymeric materials include tritium Dreamane, polyoxygen, polythioxan, polysulfide, polyhabit, polyoxygen, and any mixture of the above. A specific, non-limiting example of particles formed from an inorganic polymeric material suitable for use in the present invention is TOSPEARL4 , Which is a particle formed from cross-linked siloxane, and is commercially available from Toshiba Polysilicon, Japan. In another embodiment of the present invention, the particle 18 may be formed from a synthetic organic polymer material. Suitable organic polymer material Including but not limited to thermosetting materials and thermoplastic materials. Suitable thermosetting materials include thermosetting polyester, ethyl acetate, epoxy material, hope system, amine-based plastic, thermosetting polyamine. 23 This paper applies National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) n ϋ I .1 ϋ ϋ ϋ J1 · -l · L ------- ---- r --- order -------- line '557286 A7 B7 V. Description of the invention (21) Formate, and any mixture of the above. Better synthetic polymeric particles formed from epoxy materials Specific non-limiting examples are epoxy micelle particles. Suitable thermoplastic materials include thermoplastic polyesters, polycarbonates, polyolefins, propylene polymers, polyamides, thermoplastic polyurethanes, vinyl polymers, and A mixture of any of the above. Preferred thermoplastic polyacetates include, but are not limited to, poly (ethylene terephthalate), poly (butylene terephthalate), and poly (ethylene terephthalate). Preferred polyolefins include, but are not limited to, polyethylene, polypropylene, and polyisobutylene. Preferred propylene polymers include copolymers of styrene and acrylic monomers and polymers containing methacrylic acid. A non-limiting example of a synthetic polymeric particle formed from a propylene copolymer is RHOPLEX® B-855, which is an opaque, non-crosslinked solid propylene particle emulsion, ROPAQUE® HP-10556, which has a particle size of 1.0 microns and 26.5% by weight solids Content and 55% pore volume of opaque, non-film-forming styrene-propylene polymerized synthetic pigments, ROPAQUE® OP-967 and ROPAQUE® HP-543P8, which are the same opaque, non-film-forming with a particle size of 0.55 micrometers and a solid content of 30.5% by weight Styrene acryl polymer synthetic pigment dispersion liquid, and ROPAQUE® OP-62 L09, which is also an opaque, non-film-forming styrene acryl polymer synthetic pigment dispersion liquid with a particle size of 0.40 microns and a solid content of 36.5% by weight. Each designated particle is commercially available from Rohm and Haas, Philadelphia, PA 0 4 See R.J. Perry, 'Applications for Cross-Linked Siloxane Particles " Chemtech, February 1999, pages 39-44 0 5 See also from the guest "Chemicals for the Textile Industry" by Rohm and Haas, Inc., Philadelphia, September 1987. 6Refer to the property sheet from Rohm and Haas Company of Philadelphia, PA, -24- The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back first? Matters to be filled out (This page)
-----r---訂---------線 I 經濟部智慧財產局員工消費合作社印製 557286 A7 B7 五、發明說明(22) 標題:"ROPAQUE® HP-1055,Hollow Sphere Pigment for Paper and Paperboard Coatings" 1994 年 10 月,第 1 頁,其在此併 (請先閱讀背面之注意事項再填寫本頁) 入作爲參考。 7參見得自賓州費城之Rohm and Haas公司之產品技術公 告,標題:"Architectural Coatings· ROPAQUE® OP-96. The All Purpose Pigment·· 1 "7年4月,第1頁,其在此併入作爲參 考。 8 ROPAQUE® HP-543P 及 ROPAQUE® OP-96 爲相同之材 料;此材料在塗料界視爲ROPAQUE®HP-543P及在塗層界 視爲 ROPAQUE® OP-96。 9參見得自賓州費城之Rohm and Haas公司之產品技術公 告,標題:"Architectural Coatings- ROPAQUE® OP-96· The All Purpose Pigment" 1"7年4月,第1頁,其在此併入作爲參 考0 經濟部智慧財產局員工消費合作社印製 依照本發明之顆粒18亦可由半合成有機聚合材料及天 然聚合材料形成。在此使用之”半合成材料"爲經化學修改 之天然發生材料。可由其形成顆粒18之適合半合成有機 聚合材料包括但不限於纖維素,如甲基纖維素與纖維素乙 酸酯;及經修改澱粉,如澱粉乙酸酯與澱粉羥乙醚。可由 其形成顆粒18之適合天然聚合材料包括但不限於聚醣, 如澱粉;多肽,如酪蛋白;及天然烴,如天然橡膠與古搭 帕恰膠。 在本發明之非限制具體實施例中,聚合顆粒18由疏水 性聚合材料形成,以藉塗覆股降低或限制吸水性。此種疏 -25- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7 B7 五、發明說明(23 ) 水性聚合材料之非限制實例包括但不限於聚乙晞、聚丙 烯、聚苯乙晞及聚甲基丙烯酸甲酯。聚苯乙烯共聚物之非 限制實例包括 ROPAQUE® HP-1055、ROPAQUE® OP-96、 ROPAQUE® HP-543P、及 ROPAQUE® OP-62 L0 顏料(各如 以上所討論)。 在本發明之另一個非限制具體實施例中,聚合顆粒18 由具有大於25 °C而且較佳爲大於50 °C之玻璃轉移溫度(Tg) 及/或熔點之聚合材料形成。 在本發明之另一個非限制具體實施例中,顆粒18可爲 由選自聚合與非聚合無機材料、聚合與非聚合有機材料、 複合材料、及以上任何之混合物之材料形成之中空顆粒。 由其形成中空顆粒之適合材料之非限制實例如上所述。用 於本發明之中空聚合顆粒之非限制實例爲ROPAQUE® HP-1055 、ROPAQUE® OP-96 、ROPAQUE® HP-543P 、及 ROPAQUE® OP-62LO顏料(各如以上所討論)。用於本發明 之中空顆粒之其他非限制實例參見H. Katz等人(編 者)(1987)第437-452頁,其特別地在此併入作爲參考。 經濟部智慧財產局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁)----- r --- Order --------- Line I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 B7 V. Invention Description (22) Title: " ROPAQUE® HP-1055 , Hollow Sphere Pigment for Paper and Paperboard Coatings " October 1994, page 1, which is here (please read the precautions on the back before filling this page) for reference. 7 See product technical bulletin from Rohm and Haas, Philadelphia, PA, title: " Architectural Coatings · ROPAQUE® OP-96. The All Purpose Pigment ·· 1 " April 7, page 1, which is available in This is incorporated as a reference. 8 ROPAQUE® HP-543P and ROPAQUE® OP-96 are the same material; this material is considered ROPAQUE® HP-543P in the paint world and ROPAQUE® OP-96 in the coating world. 9 See product technical bulletin from Rohm and Haas, Philadelphia, PA, title: " Architectural Coatings- ROPAQUE® OP-96 · The All Purpose Pigment " 1 April, page 1, which is hereby incorporated herein Included as reference 0 The particles 18 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs may be formed from semi-synthetic organic polymer materials and natural polymer materials. "Semi-synthetic materials" as used herein are chemically modified naturally occurring materials. Suitable semi-synthetic organic polymeric materials from which particles 18 can be formed include, but are not limited to, cellulose, such as methyl cellulose and cellulose acetate; And modified starches, such as starch acetate and starch hydroxyether. Suitable natural polymeric materials from which particles 18 can be formed include, but are not limited to, glycans such as starch; peptides such as casein; and natural hydrocarbons such as natural rubber and paleo In the non-limiting specific embodiment of the present invention, the polymer particles 18 are formed of a hydrophobic polymer material to reduce or limit the water absorption by the coating strand. This kind of paper is -25- This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) 557286 A7 B7 V. Description of the invention (23) Non-limiting examples of water-based polymeric materials include, but are not limited to, polyethylene, polypropylene, polystyrene, and polymethacrylate Non-limiting examples of polystyrene copolymers include ROPAQUE® HP-1055, ROPAQUE® OP-96, ROPAQUE® HP-543P, and ROPAQUE® OP-62 L0 pigments (as discussed above). In another non-limiting embodiment of the invention, the polymeric particles 18 are formed of a polymeric material having a glass transition temperature (Tg) and / or melting point of greater than 25 ° C and preferably greater than 50 ° C. In another aspect of the invention In a non-limiting specific embodiment, the particles 18 may be hollow particles formed of a material selected from the group consisting of polymeric and non-polymeric inorganic materials, polymeric and non-polymeric organic materials, composite materials, and any mixtures thereof. Non-limiting examples of materials are as described above. Non-limiting examples of hollow polymeric particles used in the present invention are ROPAQUE® HP-1055, ROPAQUE® OP-96, ROPAQUE® HP-543P, and ROPAQUE® OP-62LO pigments (each as (Discussed above). For other non-limiting examples of hollow particles used in the present invention, see H. Katz et al. (Ed.) (1987) at 437-452, which is specifically incorporated herein by reference. Bureau of Intellectual Property, Ministry of Economic Affairs Printed by employee consumer cooperatives (please read the precautions on the back before filling this page)
用於本發明塗層組合物之顆粒18可存在於水中之分散 液、懸浮液或乳液。如果需要,其他之溶劑,如礦物油或 醇(較佳爲少於5重量% ),可包括於分散液、懸浮液或乳 液中。由無機材料形成之顆粒之較佳分散液之非限制實例 爲 ORPAC BORON NITRIDE RELEASECOAT-CONC,其爲 25 重量°/❶之氮化硼顆粒於水中之分散液,而且商業得自田納 西州 Oak Ridge 之 ZYP Coatings 公司。’ORPAC BORON •26- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明(24 ) NITRIDE RELEASECOAT-CONC··,ZYP Coatings 公司之技術 公告,特別地在此併入作爲參考。依照此技術公告,此產 品中之氮化硼顆粒具有小於3微米之平均粒度,並且包括 1%之鎂-鋁矽酸鹽以將氮化硼顆粒黏合至分散液塗佈之基 材。ORPAC BORON NITRIDE RELEASECOAT-CONC 25 氮化 硼使用Beckman Coulter LS 230粒度分析儀之獨立試驗發現 6.2微米之平均粒度,顆粒範圍爲次微米至35微米,及具 有以下之顆粒分布: % 10 50 90 大小(微米) 10.2 5.5 2.4 依照此分布,所測量之 ORPAC BORON NITRIDE RELEASECOAT-CONC 25氮化硼顆粒之10%具有大於10.2 微米之平均粒度。 其他商業得自ZYP Coatings公司之可用產品包括BORON NITRIDE LUBRICOAT® 塗料,及 BRAZE STOP 與 WELD RELEASE產品。由丙烯聚合物與共聚物形成之合成聚合顆 粒之乳液與分散液之特定非限制實例包括:RHOPLEX® B-85丙烯乳液(如以上所討論)、RHOPLEX® GL-62310,其爲 具有45重量%固體含量及98 °C之玻璃轉移溫度之全丙晞 硬聚合物乳液;EMULSION E-232111,其爲具有45重量% 固體含量及105 °C之玻璃轉移溫度之硬甲基丙烯酸酯聚合 物乳液;ROPAQUE® ΟΡ·96 與 ROPAQUE® HP-543P (如以 -27· 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 卜 卜—! — — — — - I I I l· I I I 一: 0’ a — — — — — — — — (請先閱讀背面之注咅?事項再填寫本頁) 557286 A7 B7 五、發明說明(25 ) (請先閱讀背面之注意事項再填寫本頁) 上所討論),其如具有〇·55微米粒度及30.5重量%固體含 量之分散液而供應;ROPAQUE® OP-62 LO (如以上所討 論),其如具有0.40微米粒度及36.5重量%固體含量之分 散液而供應;及ROPAQUE® HP-1055 (如以上所討論),其 如具有26.5重量%固體含量之分散液而供應;其均商業得 自賓州費城之Rohm and Haas公司。 1Q參見得自賓州費城之Rohm and Haas公司之產品性質單, 標題:"Rhoplex® GL-623,Self-Crosslinking Acrylic Binder of Indrustrial NonwovensM,1997年3月,其在此併入作爲參 考0 11參見得自賓州費城之Rohm and Haas公司之產品性質單, 標題:"Building Products Industrial Coatings- Emulsion E-2321”, 1"0,其在此併入作爲參考。 經濟部智慧財產局員工消費合作社印製 在本發明之特佳具體實施例中,塗層組合物包含至少一 個無機顆粒(特別是氮化硼,而且更特別是以商標名 POLARTHERM® 及 / 或 ORPAC BORON NITRIDE RELEASECOAT-COISTC得到之氮化棚)及至少一種熱塑性材 料(特別是苯乙烯與丙烯單體之共聚物,而且更特別是以 商標名ROPAQUE®得到之共聚物)之混合物。 選擇顆粒18以得到足以在相鄰纖維間進行所需間隔之 平均粒度19。例如,較佳地選擇加入上漿組合物(其塗佈 於在空氣噴射織布機處理之纖維12)之顆粒18之平均粒度 19 ,以在至少兩個相鄰纖維間提供足以將纖維股1〇空氣 喷射運輸通過織布機之間隔。在此使用之”空氣噴射織布 •28- >紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(26 ) 機π表示其中以熟悉此技藝者已知之方法以來自一或更多 個空氣噴射噴嘴之強壓縮空氣將填紗(緯紗)插入經紗棚中 <織物織動型式。在另一個實例中,選擇加入上漿組合物 (其塗佈於以聚合基質材料浸潰之纖維12)之顆粒18之平 均粒度19 ,以在至少兩個相鄰纖維間提供足以將纖維股 10良好地濕潤及濕透之間隔。 雖然不限制本發明,顆粒18較佳爲具有使用雷射散射 技術測量爲不大於1000微米之平均粒度,更佳爲〇 〇〇1至 1〇〇微米,而且最佳爲〇」至25微米之平均粒度。 在本發明之特定非限制具體實施例中,顆粒18之平均 粒度19爲至少〇·1微米,較佳爲至少〇 5微米,及範圍爲 〇·1微米至5微米,而且較佳爲〇5微米至2微米。在本發 明之具體實施例中,顆粒18具有通常比塗層組合物塗佈 之纖維12之平均直徑小之平均粒度19。已觀察到,由具 有一層丨4第一上衆組合物(其包含具有以上討論之平均粒 度19之顆粒18)殘渣之纖維股1〇製造之交織紗在以聚合 基質材料浸潰時,可有利地在相鄰纖維23,25間提供足以 允許2氣嘴射織動力(即,空氣噴射運輸通過織布機),同 時維持纖維股1〇之整體性且提供可接受濕透及濕潤特徵 之間隔。 在本發明之另—個㈣非限制具體實施例中,顆粒μ =平均粒度19爲至少3微米’較佳爲至少5微米,及範 :馬3微米至100微米’較佳爲5微米至刪微米,而且 更佳爲…微米。在此具體實施例中,亦較佳爲顆粒 ___ -29- 本紙張尺度適^?^標準(CNS)A4 χ挪公釐· 11 l· J l· L.-----------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) 557286 A7 經濟部智慧財產局員工消費合作社印製The particles 18 used in the coating composition of the present invention may be present as a dispersion, suspension or emulsion in water. If desired, other solvents, such as mineral oil or alcohol (preferably less than 5% by weight) may be included in the dispersion, suspension, or emulsion. A non-limiting example of a preferred dispersion of particles formed from an inorganic material is ORPAC BORON NITRIDE RELEASECOAT-CONC, which is a 25 weight ° / ° dispersion of boron nitride particles in water, and is commercially available from Oak Ridge, Tennessee ZYP Coatings. 'ORPAC BORON • 26- This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 557286 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Α7 Β7 V. Invention Description (24) NITRIDE RELEASECOAT-CONC · · The technical bulletin of ZYP Coatings, specifically incorporated herein by reference. According to this technical bulletin, the boron nitride particles in this product have an average particle size of less than 3 microns and include 1% magnesium-aluminosilicate to bond the boron nitride particles to the dispersion-coated substrate. ORPAC BORON NITRIDE RELEASECOAT-CONC 25 Boron Nitride Independent tests using a Beckman Coulter LS 230 particle size analyzer found an average particle size of 6.2 microns, with particles ranging from sub-microns to 35 microns, and having the following particle distribution:% 10 50 90 size ( Micron) 10.2 5.5 2.4 According to this distribution, 10% of the measured ORPAC BORON NITRIDE RELEASECOAT-CONC 25 boron nitride particles have an average particle size greater than 10.2 microns. Other commercially available products from ZYP Coatings include BORON NITRIDE LUBRICOAT® coatings, and BRAZE STOP and WELD RELEASE products. Specific non-limiting examples of emulsions and dispersions of synthetic polymeric particles formed from propylene polymers and copolymers include: RHOPLEX® B-85 propylene emulsion (as discussed above), RHOPLEX® GL-62310, which has 45% by weight Full acrylic hard polymer emulsion with solid content and glass transition temperature of 98 ° C; EMULSION E-232111, which is a hard methacrylate polymer emulsion with 45% solids content and glass transition temperature of 105 ° C; ROPAQUE® ΟΡ · 96 and ROPAQUE® HP-543P (such as -27 · This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm).… — — — — —-III l · III 一: 0 'a — — — — — — — — (Please read the note on the back? Matters before filling out this page) 557286 A7 B7 V. Description of the invention (25) (Please read the notes on the back before filling out this page) (Discussed above), which is supplied as a dispersion having a particle size of 0.55 micron and a solid content of 30.5% by weight; ROPAQUE® OP-62 LO (as discussed above), which has a particle size of 0.40 micron and a solid content of 36.5% by weight Dispersion Supplied; and ROPAQUE® HP-1055 (as discussed above), which as a dispersion having a solids content of 26.5 wt% of the supplied; both of which are commercially available from Rohm and Haas of Philadelphia, Pennsylvania company. 1Q See product property sheet from Rohm and Haas, Philadelphia, PA, title: " Rhoplex® GL-623, Self-Crosslinking Acrylic Binder of Indrustrial NonwovensM, March 1997, incorporated herein by reference 0 11 See the property sheet from Rohm and Haas, Philadelphia, Pennsylvania, titled: "Building Products Industrial Coatings- Emulsion E-2321", 1 " 0, which is incorporated herein by reference. Employees ’Consumption, Intellectual Property Office Printed by a cooperative In a particularly preferred embodiment of the present invention, the coating composition comprises at least one inorganic particle (especially boron nitride, and more particularly obtained under the brand name POLARTHERM® and / or ORPAC BORON NITRIDE RELEASECOAT-COISTC Nitriding shed) and a mixture of at least one thermoplastic material (especially a copolymer of styrene and propylene monomers, and more particularly a copolymer obtained under the trade name ROPAQUE®). The particles 18 are selected to obtain sufficient space between adjacent fibers. The average particle size required for the desired interval is 19. For example, it is preferably selected to add a sizing composition (which is applied to Machine-treated fibers 12), with an average particle size 19 of particles 18, to provide a space between at least two adjacent fibers sufficient to transport the strands of air 10 through the loom. "Air-jet weaving fabrics" used herein 28- > Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 557286 Printed by A7 of the Consumer Property Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (26) Machine π indicates that it is familiar with the artist The known method inserts the filling yarns (weft yarns) into the warp shed with strong compressed air from one or more air jet nozzles < weaving pattern. In another example, the average particle size 19 of particles 18 added to a sizing composition (coated on fibers 12 impregnated with a polymeric matrix material) is selected to provide a sufficient amount of fiber strands 10 between at least two adjacent fibers Good moisturizing and soaking interval. Although not limiting the present invention, the particles 18 preferably have an average particle size of not more than 1000 micrometers as measured using laser scattering technology, more preferably 0.001 to 100 micrometers, and most preferably 0 to 25 micrometers. Average granularity. In a specific, non-limiting embodiment of the present invention, the average particle size 19 of the particles 18 is at least 0.1 micron, preferably at least 0.05 micron, and ranges from 0.1 micron to 5 micron, and preferably 0.5 Micrometer to 2 micrometers. In a specific embodiment of the invention, the particles 18 have an average particle size 19 which is generally smaller than the average diameter of the fibers 12 coated by the coating composition. It has been observed that interwoven yarns made from fiber strands 10 with the residue of a layer of the first superior composition (which contains particles 18 with an average particle size of 19 as discussed above) 10 can be beneficial when impregnated with a polymeric matrix material Provide sufficient space between adjacent fibers 23, 25 to allow 2 nozzles to shoot weaving power (ie, air jet transport through the loom), while maintaining the integrity of the fiber strands 10 and providing acceptable wet through and wetness characteristics . In another non-limiting specific embodiment of the present invention, the particle μ = the average particle size 19 is at least 3 microns, preferably at least 5 microns, and the range: horse 3 microns to 100 microns, preferably 5 microns to Micrometers, and more preferably ... micrometers. In this specific embodiment, it is also preferable that the particles are ___ -29- The paper size is suitable ^? ^ Standard (CNS) A4 χ Nomm · 11 l · J l · L .-------- --- r --- Order --------- line (Please read the precautions on the back before filling this page) 557286 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
557286 A7 五、發明說明(28 ) 璃纖維之磨耗。例如,交織框、織布機及針織裝置之許多 邵份由如鋼之金屬材料形成,其具有達8·5ΐ2之莫氏硬 度。玻璃纖維股因接觸這些固體物件之粗面之磨耗造成在 處理時之股破碎及如織布與複合物之產品之表面缺陷,其 增加浪費及製造成本。 12557286 A7 V. Description of the invention (28) Wear of glass fiber. For example, many parts of interlaced frames, looms, and knitting devices are formed of a metal material such as steel, which has a Mohs hardness up to 8.5ΐ2. The abrasion of the glass fiber strands due to the rough surface contacting these solid objects causes the strands to be broken during processing and surface defects of products such as woven fabrics and composites, which increase waste and manufacturing costs. 12
Handbook of Chemistry and Physics 第 F-22 頁。 爲了使磨耗最小,在本發明之非限制具體實施例中,顆 粒18具有不超過(即,小於或等於)玻璃纖維硬度値之硬 度値。顆粒及玻璃纖維之硬度値可由任何習知硬度測量方 法測定,如Vickers或Brinell硬度,但是較佳爲依照原始 莫氏硬度尺度測定’其表示材料表面由1至1 〇之相對抗 刮性。玻璃纖維之莫氏硬度値通常範園爲4.5至6.5 ,而 且通常爲 6。R· Weast (編者)之 Handbook of Chem^try and £11处1£旦,01^?代88(1975)第1^22頁,其特別地在此併入作 爲參考。在此具體實施例中,顆粒18莫氏硬度値較佳爲 範圍爲0.5至6 。許多由適合用於本發明之無機材料形成 之顆粒之非限制實例之莫氏硬度値示於以下表A。 (請先閱讀背面之注意事項再填寫本頁)Handbook of Chemistry and Physics on page F-22. To minimize abrasion, in a non-limiting specific embodiment of the present invention, the particles 18 have a hardness 値 that does not exceed (i.e., less than or equal to) the glass fiber hardness 玻璃. The hardness 値 of particles and glass fibers can be measured by any conventional hardness measurement method, such as Vickers or Brinell hardness, but it is preferably measured according to the original Mohs hardness scale, which indicates the relative scratch resistance of the surface of the material from 1 to 10. The Mohs hardness 値 of glass fiber is usually in the range of 4.5 to 6.5, and is usually 6. R. Weast (ed.) Handbook of Chem ^ try and £ 11, £ 1, 01 ^? 88 (1975), page 1 ^ 22, which is specifically incorporated herein by reference. In this specific embodiment, the particle 18 Mohs hardness 値 is preferably in the range of 0.5 to 6. The Mohs hardness of many non-limiting examples of particles formed from inorganic materials suitable for use in the present invention is shown in Table A below. (Please read the notes on the back before filling this page)
.-----r---訂---------線 I 經濟部智慧財產局員工消費合作社印製 31- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 AB7 五、發明說明(29 ) 經濟部智慧財產局員工消費合作社印製 表A 顆粒材料 莫氏硬度,(原始尺度) 氮化棚 213 石墨 0.5-114 二硫化鉬 I15 滑石 1-1.516 雲母 2.8-3.217 高嶺土 2.0-2.518 石膏 1.6-219 方解石(碳酸鈣) 320 氟化鈣 421 氧化鋅 4.522 姜呂 2.523 銅 2.5-324 鐵 4-525 金 2.5-326 鎳 527 !巴 4.828 鉑 4.329 銀 2.5-430 硫化鋅 3.5-431 13 Κ· Ludema,Friction, Wear, Lubrication, (1996)第 27 頁,其 -32- 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) 卜-£ — 1 — 1— I — I — — — — (請先閱讀背面之注意事項再填寫本頁) 557286 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(3〇 ) 在此併入作爲參考。 14 R· Weast (編者),Handbook of Chemistry and Physics. CRC Press (1975)第 F-22 頁。 15 R· Lewis,Sr·,Hawley’s Condensed Chemical Dictionary·(第 l2版1993 )第793頁,其在此併入作爲參考。 16 Hawley’s Condensed Chemical Dictionary·(第 12 版 1993 )第 1113頁,其在此併入作爲參考。 17 Hawley’s Condensed Chemical Dictionary·(第 12 版 1993 )第 784頁,其在此併入作爲參考。 18 Handbook of Chemistry and Physics 第 F_22 頁。 19 Handbook of Chemistry and Physics 第 F-22 頁。 20 Friction. Wear· Lubrication 第 27 頁。 21 Friction, Wear. Lubrication 第 27 頁。 22 Friction, Wear. Lubrication 第 27 頁。 23 Friction· Wear· Lubrication 第 27 頁。 24 Handbook of Chemistry and Physics 第 F-22 頁。 25 Handbook of Chemistry and Physics,第 F-22 頁。 26 Handbook of Chemistry and Physics ,第 F-22 頁。 27 Handbook of Chemistry and Physics,第 F-22 頁。 28 Handbook of Chemistry and Physics,第 F-22 頁。 29 Handbook of Chemistry and Physics,第 F_22 頁。 30 Handbook of Chemistry and Physics,第 F-22 頁。 31 R. Weast (編者),Handbook of Chemistry and Physics, CRC Press (第 71 版 1990),第 4-158 頁。 -33- 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) 卜 — — — — · I I I h I I I (請先閱讀背面之注意事項再填寫本頁) 557286 A7 可由第一材料 護面或封包, 顆粒可由第一 護面或封包, 五、發明說明(31 如上所述,莫氏硬度尺度有關材料之挽刮性。本發 此更意“在其表面具有異於其表面下之顆粒内部硬度之 硬度之顆粒。更特別地,而且如以上 丄W砹淪,可以此技蓺 已知I任何万法修改顆粒之表面,其 ^ m 丹巴括但不限於使用此 技藝已知之技術化學地改變顆粒之表面特徵,使得顆粒之 表面硬度小於或等於玻璃纖維之硬度,而表面下之顆粒 度大於玻璃纖維之硬度。至於另一個替代 形成顆粒’其被一或更多種第二材料塗覆 以形成具有較柔軟表面之複合材料。或者 材料形成,其被不同形式之第一材料塗覆 以形成具有較柔軟表面之複合材料。 在實例中,而且不限制本發明,由如碳切或氮化銘之 無機材料形成之無機顆粒可具有矽石、碳酸鹽或奈微黏土 以形成有用之複合顆粒。在另一個非限制實例中,具烷基 側鏈之矽烷偶合劑可反應由無機氧化物形成之無機顆2之 表面,以提供具有"較柔軟”表面之有用複合顆粒。其^之 實例包括由非聚合或聚合材料與不同之非聚合或聚合材料 形成之護面、封包或塗覆顆粒。此種複合顆粒之特定非限 制實例爲DUALITE ,其爲塗覆碳酸鈣之合成聚合顆粒, 其商業得自紐約州Buffalo之Pierce and Stevens公司。在本 發明之具體實施例中,顆粒IS爲導熱性,即,較佳爲具 有在300K之溫度測量爲每米κ至少〇 2瓦,更佳爲每米 K至少0.5瓦之傳熱度。在非限制具體實施例中,顆粒μ 具有在300K之溫度測量爲每米κ至少1瓦,更佳爲每米 ------ΦΜ----l·---訂---------線· (請先閱讀背面之注意事項再填寫本頁} 經濟部智慧財產局員工消費合作社印製.----- r --- Order --------- Line I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 31- This paper size applies to China National Standard (CNS) A4 (210 X 297) (Mm) 557286 AB7 V. Description of the invention (29) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics. Table A Mohs hardness of granular materials, (original scale) Nitrided shed 213 Graphite 0.5-114 Molybdenum disulfide I15 Talc 1.1.516 Mica 2.8-3.217 Kaolin 2.0-2.518 Gypsum 1.6-219 Calcite (Calcium Carbonate) 320 Calcium Fluoride 421 Zinc Oxide 4.522 Jiang Lu 2.523 Copper 2.5-324 Iron 4-525 Gold 2.5-326 Nickel 527! Bar 4.828 Platinum 4.329 Silver 2.5- 430 Zinc sulfide 3.5-431 13 K Ludema, Friction, Wear, Lubrication, (1996), page 27, its -32- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 x 297 mm) BU- £ — 1 — 1— I — I — — — — (Please read the notes on the back before filling out this page) 557286 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (3〇) Reference. 14 R. Weast (editor), Handbook of Chemistry and Physics. CRC Press (1975) at page F-22. 15 R. Lewis, Sr., Hawley's Condensed Chemical Dictionary, (12th edition 1993) p. 793, which is incorporated herein by reference. 16 Hawley's Condensed Chemical Dictionary, (12th edition 1993) p. 1113, which is incorporated herein by reference. 17 Hawley's Condensed Chemical Dictionary, (12th edition 1993) p. 784, which is incorporated herein by reference. 18 Handbook of Chemistry and Physics page F_22. 19 Handbook of Chemistry and Physics on page F-22. 20 Friction. Wear · Lubrication p. 27. 21 Friction, Wear. Lubrication p. 27. 22 Friction, Wear. Lubrication p. 27. 23 Friction · Wear · Lubrication p. 27. 24 Handbook of Chemistry and Physics on page F-22. 25 Handbook of Chemistry and Physics, page F-22. 26 Handbook of Chemistry and Physics, page F-22. 27 Handbook of Chemistry and Physics, page F-22. 28 Handbook of Chemistry and Physics, page F-22. 29 Handbook of Chemistry and Physics, page F_22. 30 Handbook of Chemistry and Physics, page F-22. 31 R. Weast (editor), Handbook of Chemistry and Physics, CRC Press (71st Edition 1990), p. 4-158. -33- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 χ 297 mm). — — — — III h III (Please read the precautions on the back before filling out this page) 557286 A7 Can be the first material The surface or package, the particles can be the first surface or package. V. Description of the invention (31 As mentioned above, the scratch resistance of the material related to the Mohs hardness scale. The internal hardness of the particles. More specifically, as described above, the surface of the particles can be modified by any method known in the art, which includes but is not limited to the use of known techniques. The technology chemically changes the surface characteristics of the particles so that the surface hardness of the particles is less than or equal to the hardness of the glass fibers, and the particle size below the surface is greater than the hardness of the glass fibers. As for another alternative to form the particles, it is replaced by one or more second The material is coated to form a composite material with a softer surface. Or the material is formed to be coated with a first material in a different form to form a composite material with a softer surface. In examples, and without limiting the invention, inorganic particles formed from inorganic materials such as carbon cuts or nitrides may have silica, carbonate or nanoclay to form useful composite particles. In another non-limiting example, Silane coupling agents with alkyl side chains can react the surface of inorganic particles 2 formed from inorganic oxides to provide useful composite particles with " softer " surfaces. Examples of these include non-polymeric or polymeric materials and different Non-polymeric or polymeric materials for the formation, encapsulation or coating of particles. A specific, non-limiting example of such composite particles is DUALITE, a synthetic polymer particle coated with calcium carbonate, commercially available from Pierce and Buffalo, NY Stevens Company. In a specific embodiment of the present invention, the particles IS are thermally conductive, that is, they preferably have a heat transfer measured at 300 K of at least 0 2 watts per meter k, and more preferably at least 0.5 watts per meter K. In a non-limiting specific embodiment, the particle μ has a temperature of 300K measured at least 1 watt per meter κ, and more preferably per meter ------ ΦM ---- l ------ ------- Line · (Please read the back first Please fill out this page before printing} Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
A7A7
557286 五、發明說明(32 ) K至少5瓦之傳熱度。在較佳具體實施例中,顆粒之導熱 度在300K之溫度測量爲每米κ至少25瓦,更佳爲每米κ 至少30瓦,而且甚至更佳爲每米κ至少1〇〇瓦。在另一 個較佳具體實施例中,顆粒之導熱度在3〇〇κ之溫度測量 範圍爲每米Κ 5至2000瓦,較佳爲每米κ 25至2000瓦, 更佳爲每米Κ 30至2000瓦’而且最佳爲每米κ 1〇〇至 2000瓦。在此使用之”導熱度”表示敘述其經本身轉移熱 之能力之顆粒性質。參見R· Lewis,Sr.之Hawlev^ rQndenRpH Chemical Dictionary,(第 12 版,1993 )第 305 頁,其特別地 在此併入作爲參考。 材料之導熱度可由熟悉此技藝者已知之任何方法測定。 例如,如果被試驗材料之導熱度範圍爲每米Κ 0·001瓦至 每米Κ 100瓦,則可在300Κ之溫度依照ASTM C-177-85 (其特別地在此併入作爲參考)使用較佳之隔離加熱板法測 定材料之導熱度。如果被試驗材料之導熱度範圍爲每米κ 20瓦至每米Κ 1200瓦,則可依照ASTM C_518_91 (其特別 地在此併入作爲參考)使用隔離熱通量感應法測定材料之 導熱度。換言之,如果導熱度範圍爲每米K 0.001瓦至每 米K 20瓦,則使用隔離加熱板法。如果導熱度範園爲每 米κ超過1〇〇瓦,則使用隔離熱通量感應法。對於每米κ 20至100瓦之範圍,可使用任一種方法。 在隔離加熱板法中,使用含一個隔離加熱單位、兩個輔 助加熱板、兩個冷卻單位、邊緣絕熱、溫度控制第二隔 離、及溫度感應器讀取系統之隔離加熱板裝置,試驗兩個 -35- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) "" ---— ι-r-卜 T卜 L·· — — — — 卜 — — — (請先閱讀背面之注咅?事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 557286 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(33 ) 本質上相同之樣品。將樣品置於隔離加熱單位之任一侧, 樣品之相反表面接觸輔助加熱單位。然後將此裝置加熱至 所需試驗溫度且保持得到熱穩定狀態所需之時間。一但達 到穩定狀態條件,記錄通過樣品之熱流(Q)及通過樣品之 溫度度(ΔΤ)。然後使用下式⑴計算樣品之平均導熱度 (KTC):557286 5. Description of the invention (32) K has a heat transfer of at least 5 watts. In a preferred embodiment, the thermal conductivity of the particles is measured at a temperature of 300K as at least 25 watts per meter, more preferably at least 30 watts per meter, and even more preferably at least 100 watts per meter. In another preferred embodiment, the thermal conductivity of the particles ranges from 5 to 2000 watts per meter at a temperature of 300 κ, preferably 25 to 2000 watts per meter, and more preferably 30 watts per meter. To 2000 watts' and optimally 100 to 2000 watts per meter. As used herein, "thermal conductivity" means the nature of a particle that describes its ability to transfer heat through itself. See R. Lewis, Sr., Hawlev ^ RQndenRpH Chemical Dictionary, (12th edition, 1993) at page 305, which is specifically incorporated herein by reference. The thermal conductivity of a material can be determined by any method known to those skilled in the art. For example, if the thermal conductivity of the material under test ranges from 0.001 watts per meter to 100 watts per meter, it can be used at a temperature of 300K in accordance with ASTM C-177-85 (which is specifically incorporated herein by reference) The preferred method of isolating the heating plate measures the thermal conductivity of the material. If the thermal conductivity of the material under test ranges from κ 20 watts per meter to 1200 watts per meter κ, the thermal conductivity of the material can be measured using an isolated heat flux induction method in accordance with ASTM C_518_91 (which is specifically incorporated herein by reference). In other words, if the thermal conductivity ranges from 0.001 watts per metre to 20 watts per metre, use an isolated heating plate method. If the thermal conductivity range is more than 100 watts per meter, use the isolated heat flux sensing method. For the range of κ 20 to 100 watts per meter, either method can be used. In the isolated heating plate method, an isolated heating plate device including one isolated heating unit, two auxiliary heating plates, two cooling units, edge insulation, a second temperature control isolation, and a temperature sensor reading system was used to test two -35- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) First read the note on the back? Matters and then fill out this page) Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 5. Inventive Note (33) Essentially the same sample Place the sample on either side of the isolated heating unit with the opposite surface of the sample in contact with the auxiliary heating unit. The device is then heated to the required test temperature and maintained for the time required to obtain a thermally stable state. Once the steady state conditions are reached, record the heat flow (Q) through the sample and the temperature (ΔΤ) through the sample. The average thermal conductivity (KTC) of the sample is then calculated using the following formula:
Ktc=QL/A.AT 其中L爲樣品之平均厚度且A爲樣品組合面積之平均。 據信具有較高導熱度之材料較快地散逸在鑽洞操作時由 孔區域產生之為,生成延長之鑽頭壽命。表八中之經選擇 材料之導熱度包括於表Β中。 雖然並非必要,在用於本發明之另一具體實施例中,顆 粒爲電絕緣或具有高電阻率,即,具有大於刪微歐姆· 公分之電阻率。對於習知電子電路板應用,使用具有高電 阻率之顆粒較佳,以抑制由於電子經強化物傳導造成之電 信號損失。對於特殊之應用,如用於微波爐 '無線頻率干 擾及電磁平擾應用之電路板,不需要具有高電阻率之顆 粒。表Α中之經選擇材料之電阻率包括於表Β中。 本紙張尺度翻巾國國家鮮(CNS)A4規格(21〇 -36- 297^7 1 卜 J-u-l-----------r-- —訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 557286 A7 __ —_B7 五、發明說明(34 )Ktc = QL / A.AT where L is the average thickness of the sample and A is the average of the combined area of the sample. It is believed that materials with higher thermal conductivity dissipate faster from the hole area during drilling operations, resulting in extended drill life. The thermal conductivity of the selected materials in Table 8 is included in Table B. Although not necessary, in another embodiment used in the present invention, the particles are electrically insulating or have a high resistivity, that is, a resistivity greater than a microohm · cm. For conventional electronic circuit board applications, it is better to use particles with high resistivity to suppress the loss of electrical signals due to electron conduction through the reinforcement. For special applications, such as circuit boards used in microwave oven's radio frequency interference and electromagnetic interference suppression applications, particles with high resistivity are not required. The resistivity of the selected materials in Table A is included in Table B. Specifications of this paper: National Fresh (CNS) A4 (21〇-36-297 ^ 7 1) Jul ----------- r ---- Order --------- (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 557286 A7 __ —_B7 V. Description of Invention
表B 無機固體材料 導熱度 電阻 莫氏硬度 (在 300K 之 IN/mK) (微歐姆-公分) (原始尺度) 氮化硼 20032 1.7 X 1〇1933 234 磷化硼 35035 9.536 磷化鋁 13037 _ - 氮化鋁 20038 大於1〇1939 940 氮化鎵 17041 _ - 磷化鎵 10042 一 碳化矽 27043 4 X 105 至 1 X 1〇644 大於945 氮化矽 3046 1〇19至1〇2〇47 948 氧化鋇 24049 - 950 32 G. Slack, "Nonmetallic Crystals with High Thermal Conductivity, J. Phvs· Chem. Solids Π 973、第 34 卷,第 322 頁,其在此併 入作爲參考。 33 A· Weimer (編者),Carbide, Nitride and Boride MaterialsTable B Thermal conductivity of inorganic solid materials Mohs hardness (IN / mK at 300K) (microohm-cm) (original scale) Boron nitride 20032 1.7 X 1〇1933 234 Boron phosphide 35035 9.536 Aluminum phosphide 13037 _- Aluminium nitride 20033 greater than 1019939 940 gallium nitride 17041 _-gallium phosphide 10042-silicon carbide 27043 4 X 105 to 1 X 1〇644 greater than 945 silicon nitride 3046 1109 to 102047 948 barium oxide 24049-950 32 G. Slack, " Nonmetallic Crystals with High Thermal Conductivity, J. Phvs. Chem. Solids Π 973, Vol. 34, p. 322, which is incorporated herein by reference. 33 A · Weimer (editor), Carbide, Nitride and Boride Materials
Synthesis and Processing,(1997)第 654 頁0 34 Friction,Wear,Lubrication 第 27 頁。 35 G. Slack, "Nonmetallic Crystals with High Thermal Conductivity, J. Phvs. Chem. Solids (1973^ 第 34 卷,第 325 頁,其在此併 入作爲參考。 36 R. Lewis, Sr., Hawley^ Condensed Chemical Dictionary.(第 12版1993 )第104頁,其在此併入作爲參考。 -37- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)Synthesis and Processing, (1997) p. 654 0 34 Friction, Wear, Lubrication p. 27. 35 G. Slack, " Nonmetallic Crystals with High Thermal Conductivity, J. Phvs. Chem. Solids (1973 ^ Vol. 34, p. 325, which is incorporated herein by reference. 36 R. Lewis, Sr., Hawley ^ Condensed Chemical Dictionary. (12th edition 1993) p. 104, which is incorporated herein by reference. -37- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)
ItlhJtL----------^----訂---------線 (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7 五、發明說明(35 ) 37 G. Slack, "Nonmetallic Crystals with High Thermal Conductivity, J. Phvs· Chem. Solids Π973、第 34 卷,第 333 頁,其在此併 入作爲參考。 38 G. Slack, "Nonmetallic Crystals with High Thermal Conductivity, J. Phvs. Chem. Solids (1973)第 34 卷,第 329 頁,其在此併 入作爲參考。 ^ Q · A· Weimer (編者),Carbide,Nitride and Boride Materials Synthesis and Processing, (1997)第 654 頁0 40 Friction, Wear, Lubrication H 27 頁。 41 G. Slack,"Nonmetallic Crystals with High Thermal Conductivity, J. Phvs. Chem. Solids 0973^ 第 34 卷,第 333 頁。 42 G. Slack, "Nonmetallic Crystals with High Thermal Conductivity, J. Phvs· Chem· Solids Π973、第 34 卷,第 321 頁,其在此併 入作爲參考。 43 Microelectronics Packaging Handbook 第 3ό 頁,其在此併入 作爲參考。 44 A. Weimer (編者),Carbide, Nitride and Boride Materials Synthesis and Processing,(1997)第 653 頁,其在此併入作爲 參考。 45 Friction. Wear. Lubrication 第 27 頁。 46 Microelectronics Packaging Handbook H 3ό 頁,其在此併入 作爲參考。 47 A. Weimer (編者),Carbide,Nitride and Boride Materials Synthesis and Processing,(1997)第 654 頁0 -38- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -—ill·!訂!! 線一 經濟部智慧財產局員工消費合作社印製 557286 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(36 ) 48 Friction, Wear, Lubrication 第 27 頁 〇 49 Microelectronics Packaging Handbook 第 905 頁,其在此併 入作爲參考。 50 Hawlev’s Condensed Chemical Dictionary·(第 12 版 1993 )第 Ml頁,其在此併入作爲參考。 表B (續) 無機固體材料 導熱度 電阻 莫氏硬度 (在 300K 之 IN/mK) (微歐姆-公分) (原始尺度) 氧化鋅 26 4.551 硫化鋅 2552 2·7 X 105 至 1·2 X 101253 3.5-454 鑽石 230055 2.7 X 105 55 1057 矽 8458 10.059 j60 石墨 達 200061 10062 0·5·163 鉬 13864 5.265 5·566 鉑 6967 10.668 4·369 1巴 7〇70 10.871 4.872 鎢 20073 5.574 7·575 51 Friction, Wear. Lubrication 第 27 頁。 52 Handbook of Chemistry and Physics, CRC Press (1975)第 12-54頁。 53 Handbook of Chemistry and Physics· CRC Press (第 71 版 199〇)第12_63頁,其在此併入作爲參考。 -39- 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) -----------r-- 丨訂---------線 (請先閱讀背面之注音?事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 557286 A7 B7 五、發明說明(37 ) 54 Handbook of Chemistry and Physics, CRC Press (第 71 版 1990)第4-158頁,其在此併入作爲參考。 55 Microelectronics Packaging Handbook 第 3ό 頁。 56 Handbook of Chemistry and Physics· CRC Press (第 71 版 1990)第12-63頁,其在此併入作爲參考。 57 Handbook of Chemistry and Physics,第 F-22 頁。 58 Microelectronics Packaging Handbook 第 174 頁。 59 Handbook of Chemistry and Physics.第 F-166 頁,其在此併 入作爲參考。 60 Friction,Wear,Lubrication 第 27 頁。 61 G. Slack, "Nonmetallic Crystals with High Thermal Conductivity, J. Phvs. Chem. Solids (1973、第 34 卷,第 322 頁,其在此併 入作爲參考。 62 See W. Callister, Materials Science and Engineering An Introduction,(第2版1"1)第637頁,其在此併入作爲參 考0 63 Handbook of Chemistry and Physics·第 F_22 頁。 64 Microelectronics Packaging Handbook 第 174 頁。 65 Microelectronics Packaging Handbook 第 37 頁。 66 依照"Web Elements" http://www.shef· ac.uk/〜chem/web-elents/nofr-image-l/hardness-minerals-l.html ( 1998 年 2 月 26 曰)。 67 Microelectronics Packaging Handbook 第 174 頁。 68 Microelectronics Packaging Handbook 第 37 頁。 -40- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 11 卜 — — — I · I I I 卜 — — I — 1 — _ (請先閱讀背面之注音?事項再填寫本頁) 557286 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(38 ) 69 Handbook of Chemistry and Physics,第 F-22 頁。 70 Handbook of Chemistry and Physics.第 37 頁。 71 Microelectronics Packaging Handbook 第 37 頁。 72 Handbook of Chemistry and Physics·第 F-22 頁。 73 Handbook of Chemistry and Physics·第 37 頁。 74 Microelectronics Packaging Handbook 第 37 頁。 75 依照"Web Elements” http://www.shef. ac.uk/〜chem/web· elents/nofr-image-l/hardness-minerals-l.html ( 1998 年 2 月 26 曰)0 表B (續) 無機固體材料 導熱度 (在 300K 之 W/mK) 電阻 (微歐姆-公分) 莫氏硬度 (原始尺度) 鎳 9276 6.877 578 鋁 20579 4.380 2。581 鉻 6682 2083 9.084 銅 39885 1.786 2.5-387 金 29788 2.289 2.5-390 鐵 74.591 992 4_593 銀 41894 1.695 2.5-496 76 Microelectronics Packaging Handbook 第 174 頁。 77 Microelectronics Packaging Handbook 第 37 頁。 78 Handbook of Chemistry and Physics.第 F-22 頁。 -41· — — — — — I I I l· I--— — — — — — — II (請先閱讀背面之注意事項再填寫本頁) 格 規 A4 s) N (c 準 標 家 國 國 中 用 適 度 尺 張 紙 本 210 χ 297 公釐) 經濟部智慧財產局員工消費合作社印製 557286 A7 B7 五、發明說明(39 ) 79 Microelectronics Packaging Handbook 第 174 頁。 80 Microelectronics Packaging Handbook 第 37 頁。 81 Friction, Wear, Lubrication 第 27 頁。 O f\ItlhJtL ---------- ^ ---- Order --------- line (please read the notes on the back before filling this page) 557286 A7 B7 V. Description of the invention 37 G. Slack, " Nonmetallic Crystals with High Thermal Conductivity, J. Phvs. Chem. Solids Π973, Vol. 34, p. 333, which is incorporated herein by reference. 38 G. Slack, " Nonmetallic Crystals with High Thermal Conductivity, J. Phvs. Chem. Solids (1973) Vol. 34, p. 329, which is incorporated herein by reference. ^ Q · Weimer (editor), Carbide, Nitride and Boride Materials Synthesis and Processing, (1997) p. 654 0 40 Friction, Wear, Lubrication H 27. 41 G. Slack, " Nonmetallic Crystals with High Thermal Conductivity, J. Phvs. Chem. Solids 0973 ^ Vol. 34, p. 333. 42 G. Slack, " Nonmetallic Crystals with High Thermal Conductivity, J. Phvs. Chem. Solids Π973, Vol. 34, p. 321, which is incorporated herein by reference. 43 Microelectronics Packaging Handbook page 3, which is incorporated herein by reference. 44 A. Weimer (ed.), Carbide, Nitride and Boride Materials Synthesis and Processing, (1997) p. 653, which is incorporated herein by reference. 45 Friction. Wear. Lubrication p. 27. 46 Microelectronics Packaging Handbook H 3ό page, which is incorporated herein by reference. 47 A. Weimer (editor), Carbide, Nitride and Boride Materials Synthesis and Processing, (1997) page 654 0 -38- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (please first Read the notes on the back and fill out this page)--ill! Order! !! Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (36) 48 Friction, Wear, Lubrication, page 27, 49 Microelectronics Packaging Handbook page 905, It is incorporated herein by reference. 50 Hawlev's Condensed Chemical Dictionary, (12th edition 1993) page M1, which is incorporated herein by reference. Table B (continued) Thermal conductivity of inorganic solid materials Mohs hardness (IN / mK at 300K) (microohm-cm) (original scale) Zinc oxide 26 4.551 Zinc sulfide 2552 2 · 7 X 105 to 1.2 X 101253 3.5-454 diamond 230055 2.7 X 105 55 1057 silicon 8458 10.059 j60 graphite up to 200061 10062 0.55163 molybdenum 13864 5.265 5.566 platinum 6967 10.668 4 · 369 1 bar 7070 10.871 4.872 tungsten 20073 5.574 7.575 51 Friction , Wear. Lubrication p. 27. 52 Handbook of Chemistry and Physics, CRC Press (1975) pp. 12-54. 53 Handbook of Chemistry and Physics · CRC Press (71st Edition 199〇), pages 12_63, which are incorporated herein by reference. -39- This paper size is applicable to China National Standard (CNS) A4 specification (210 χ 297 mm) ----------- r-- 丨 order --------- line (please First read the phonetic on the back? Matters and then fill out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 B7 V. Description of the Invention (37) 54 Handbook of Chemistry and Physics, CRC Press (71st Edition 1990) Section 4- Page 158, which is incorporated herein by reference. 55 Microelectronics Packaging Handbook page 3. 56 Handbook of Chemistry and Physics · CRC Press (71st Edition 1990) pages 12-63, which are incorporated herein by reference. 57 Handbook of Chemistry and Physics, page F-22. 58 Microelectronics Packaging Handbook p. 174. 59 Handbook of Chemistry and Physics. Page F-166, which is incorporated herein by reference. 60 Friction, Wear, Lubrication p. 27. 61 G. Slack, " Nonmetallic Crystals with High Thermal Conductivity, J. Phvs. Chem. Solids (1973, Vol. 34, p. 322, which is incorporated herein by reference. 62 See W. Callister, Materials Science and Engineering An Introduction, (Second Edition 1 " 1), page 637, which is incorporated herein by reference. 63 Handbook of Chemistry and Physics, page F_22. 64 Microelectronics Packaging Handbook, page 174. 65 Microelectronics Packaging Handbook, page 37. 66 According to " Web Elements " http: //www.shef·ac.uk/~chem/web-elents/nofr-image-l/hardness-minerals-l.html (February 26, 1998). 67 Microelectronics Packaging Handbook, page 174. 68 Microelectronics Packaging Handbook, page 37. -40- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 11 BU — — — I · III BU — — I — 1 — _ (Please read the note on the back? Matters before filling out this page) 557286 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (38) 69 Handbook of Chemistry and Physics, page F-22. 70 Handbook of Chemistry and Physics. Page 37. 71 Microelectronics Packaging Handbook page 37. 72 Handbook of Chemistry and Physics. Page F-22. 73 Handbook of Chemistry and Physics. Page 37. 74 Microelectronics Packaging Handbook p. 37. 75 According to "Web Elements" http: //www.shef. Ac.uk/~chem/web·elents/nofr-image-l/hardness-minerals-l.html (February 26, 1998) 0 Table B (Continued) Thermal conductivity of inorganic solid materials (W / mK at 300K) Resistance (microohm-cm) Mohs hardness (original scale) Nickel 9276 6.877 578 Aluminum 20579 4.380 2.581 Chrome 6682 2083 9.084 Copper 39885 1.786 2.5-387 Gold 29788 2.289 2.5-390 Iron 74.591 992 4_593 Silver 41894 1.695 2.5-496 76 Microelectronics Packaging Handbook page 174. 77 Microelectronics Packaging Handbook page 37. 78 Handbook of Chemistry and Physics. Page F-22. -41 · — — — — — III l · I --— — — — — — — II (Please read the precautions on the back before filling out this page) Code A4 s) N (c Appropriate rule paper for standard national and national schools 210 χ 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 B7 V. Description of Invention (39) 79 Microelectronics Packaging Handbook page 174. 80 Microelectronics Packaging Handbook page 37. 81 F riction, Wear, Lubrication page 27. O f \
Microelectronics Packaging Handbook 第 37 頁。 83 Microelectronics Packaging Handbook 第 37 頁。 84 Handbook of Chemistry and Physics.第 F_22 頁。 85 Microelectronics Packaging Handbook 第 174 頁。 〇 zrMicroelectronics Packaging Handbook p. 37. 83 Microelectronics Packaging Handbook p. 37. 84 Handbook of Chemistry and Physics. Page F_22. 85 Microelectronics Packaging Handbook p. 174. 〇 zr
Microelectronics Packaging Handbook M 37 頁。 87 Handbook of Chemistry and Physics·第 F-22 頁。 88 Microelectronics Packaging Handbook 第 174 頁。 89 Microelectronics Packaging Handbook M 37 頁。 90 Handbook of Chemistry and Physics·第 F_22 頁。 91 Microelectronics Packaging Handbook 第 174 頁。 92 Handbook of Chemistry and Physics. CRC Press (1975)第 D-171頁,其在此併入作爲參考。 93 Handbook of Chemistry and Physics,第 F-22 頁。 94 Microelectronics Packaging Handbook 第 174 頁。 95 Microelectronics Packaging Handbook 第 37 頁。 96 Handbook of Chemistry and Physics·第 F-22 頁。 熟悉此技藝者應了解,本發明塗層組合物之顆粒18可 包括以上討論之顆粒18之任何組合或混合物。更特別 地,而且不限制本發明,顆粒18可包括由任何上述材料 製造之額外顆粒之任何組合。因此,所有之顆粒18不必 爲相同的;其可化學地不同及/或化學地相同但是組態或 -42- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 1 Ί l· Ji If L-----------^----訂---------線 (請先閱讀背面之注咅?事項再填寫本頁) 557286Microelectronics Packaging Handbook M 37 pages. 87 Handbook of Chemistry and Physics, page F-22. 88 Microelectronics Packaging Handbook p. 174. 89 Microelectronics Packaging Handbook M 37 pages. 90 Handbook of Chemistry and Physics, page F_22. 91 Microelectronics Packaging Handbook p. 174. 92 Handbook of Chemistry and Physics. CRC Press (1975) at page D-171, which is incorporated herein by reference. 93 Handbook of Chemistry and Physics, page F-22. 94 Microelectronics Packaging Handbook p. 174. 95 Microelectronics Packaging Handbook p. 37. 96 Handbook of Chemistry and Physics, page F-22. Those skilled in the art will appreciate that the particles 18 of the coating composition of the present invention may include any combination or mixture of particles 18 discussed above. More particularly, and without limiting the invention, the particles 18 may include any combination of additional particles made from any of the foregoing materials. Therefore, all the particles 18 need not be the same; they may be chemically different and / or chemically the same but the configuration or -42- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1 Ί l · Ji If L ----------- ^ ---- Order --------- line (Please read the note on the back? Matters before filling out this page) 557286
經濟部智慧財產局員工消費合作社印製 性質相同。額外之顆粒通常包含至多顆粒18之一半,較 佳爲至多顆粒18之15%。 在具體實施例中,顆粒18包含基於總固體爲塗層組合 物之0.001至99重量%,較佳爲50至99重量%,而且更 佳爲75至99重量%。在此具體實施例中,特佳之塗層包 括但不限於:〇包含有機成分及具有在3〇〇κ之溫度爲每 米κ至少1瓦之導熱度之薄平顆粒之塗層;u)包含有機 成分及不可水合薄平顆粒之塗層;出)包含至少一種具有 在300K之溫度爲每米K至少〗瓦之導熱度之無硼薄平顆 粒之塗層;iv)包含具有在300K之溫度爲每米κ至少ι瓦 之導熱度之薄平顆粒(即,纖維上之薄平顆粒)之水性組合 物殘渣;及ν)包含具有在30〇κ之溫度爲每米κ至少i瓦 之導熱度之無銘不可水合顆粒(即,纖維上之無鋁不可水 合顆粒)之水性組合物殘渣。 在另一具體實施例中,顆粒18包含基於總固體爲塗層 組合物之0.001至99重量%,較佳爲i至80重量%,而且 更佳爲1至40重量%。此外,在其中顆粒μ爲不可水合 無機顆粒之特定具體實施例中,顆粒較佳爲包含基於總固 體爲塗層組合物之1至50重量%,而且更佳爲至多25重 量%。 在另一具體實施例中,顆粒18包含基於總固體爲大於 20重量%,較佳爲範圍爲20至99重量%,更佳爲範圍爲 25至80重量%,而且最佳爲範圍爲50至60重量%。在 此具體實施例中,特佳之塗層包括樹脂相容塗層組合物, -43- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) — — — — · I---r - I - 11111111 (請先閲讀背面之注意事項再填寫本頁} 557286 A7 B7 五、發明說明(4!) 其包含基於總固體爲大於2〇重量% 顆粒、有機中空顆粒及複合顆粒之顆粒,I至少=無機 :有不超過至少—個破璃纖維之莫氏硬度値之莫氏= :另一個具體實施例中,顆粒18包含 至80重量%,妨# g , χ M 為1 佳為1至60重量%。在具體實 ==物含基於總固體爲20至60重量%之==且 义馬35至55重量%,而且更佳爲30至50重#% 具體實施例之更佳塗層包含樹脂相容塗層,其包含❶ 個由選自不可熱膨脹有機材料、無機聚合材料、不可裁= 脹複=材料及其混合物之材料形成之不連續顆粒,此顆粒 有典而外來之熱應用而足以使股濕潤之平均粒度;(匕) 至少一種異於該多個不連續顆粒之潤滑材料;及⑷至少 一種膜形成材料。除了顆粒,塗層組合物較佳爲包含一或 更多種膜形成材料,如有機、無機及天然聚合材料。可用 之有機材料包括但不限於選自合成聚合材料、半合成聚合 材料、天然聚合材料、及以上任何之混合物之聚合材料。 經濟部智慧財產局員工消費合作社印製 合成聚合材料包括但不限於熱塑性材料及熱固性材料。較 佳爲,在塗佈於玻璃纖維之表面16時,聚合膜形成材料 形成大致連續膜。 通常’膜形成材料之量範園爲基於總固體爲塗層組合物 之1至99重量%。在具體實施例中,膜形成材料之量較 佳爲1至50重量%,而且更佳爲1至25重量%。在另一 個具體實施例中,膜形成材料之量範圍爲2〇至99重量 -44- 本紙張尺度翻巾國國家標準(CNS)A4規格(210 X 297公愛) 557286 A7 B7 五 、發明說明(42 %,而且更佳爲6〇至8〇重量%。 在另一個具體實施例中,膜形成材料之量較佳爲範圍爲 *基:總固體爲塗層組合物之2〇至75重量%,而且更佳爲 4〇至50重量%。在此具體實施例中,特佳之塗層包含膜 形成材料’其包含基於總固體爲大於20重量%之至少一 個選自無機顆粒、有機中空顆粒及複合顆粒之顆粒,此至 ^個顆粒具有不超過至少一個玻璃纖維之莫氏硬度値之 莫氏硬度値。 在另一個具體實施例中,聚合膜形成材料之量範圍爲基 於總固體爲塗層組合物之i至6〇重量%,較佳爲5至5〇 重量/❶,而且更佳爲1〇至3〇重量%。此具體實施例之更 佳塗層包括樹脂相容塗層,其包含⑷多個由選自不可熱 膨脹有機材料、播機聚合材料、不可熱膨脹複合材料及其 混合物之材料形成之不連續顆粒,此顆粒具有無需外來之 熱應用而足以使股濕潤之平均粒度;(1?)至少一種異於該 多個不連續顆粒之潤滑材料;及⑷至少一種膜形成材 料。 在本發明之非限制具體實施例中,熱固性聚合膜形成材 料爲用於塗覆玻璃纖維股之塗層組合物之較佳聚合膜形成 材料。此種材料與作爲印刷電路板之層合物之熱固性基質 材料相容,如FR-4環氧樹脂,其爲多官能基環氧樹脂, 而且在本發明之特定具體實施例中爲二官能基溴化環氧樹 脂。參見 Electronic Materials Handbook™ ASM Intematicmal (1989)第534-537頁,其特別地在此併入作爲參考。 •45- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) 1 Ί r 11 μ------0Μ--------^--------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 557286 A7 B7 五、發明說明(43 ) 可用之熱固性材料包括熱固性聚酯、環氧材料、乙烯 酯、酚系、胺基塑料、熱固性聚胺基甲酸酯、及以上任何 之混合物。適合之熱固性聚酯包括STYPOL聚酯,其商業 得自密蘇里州 Kansas 市之 Cook Composites and Polymers 公 司,及NEOXIL聚酯,其商業得自義大利Como之DSM Β· V· 公司。 熱固性聚合材料之非限制實例爲環氧材料。可用之環氧 材料在一個分子含至少一個環氧基或環氧乙烷基,如多羥 基醇或硫醇之聚縮水甘油醚。適合之環氧基膜形成聚合物 之實例包括ΕΡΟΝ® 826與ΕΡΟΝ® 880環氧樹脂,其商業得 自德州 Houston 之 Shell Chemical 公司。 可用之熱塑性聚合材料包括乙烯聚合物、熱塑性聚酯、 聚烯烴、聚醯胺(例如,脂族聚醯胺或如芳族醯胺之芳族 聚醯胺)、熱塑性聚胺基甲酸酯、丙烯聚合物(如聚丙烯 酸)、及以上任何之混合物。 在本發明之另一個非限制具體實施例中,較佳之聚合膜 形成材料爲乙烯聚合物。本發明之可用乙烯聚合物包括但 不限於聚乙烯基吡咯啶酮,如PVP K-15 、PVP K_30 、 PVP Κ-60與PVP Κ_90,其各商業得自紐澤西州Wayne之 International Specialty Products Chemicals 公司。其他適合之 乙烯聚合物包括RESYN 2828及RESYN 1037乙酸乙烯酯共 聚物乳液,其商業得自紐澤西州Bridgewater之National Starch and Chemical公司,其他之聚乙酸乙烯酯,如商業得 自 H. B_ Fuller 公司與賓州 Allentown 之 Air Products and -46- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) Ί Ί Γ 1---Γ-------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7 五、發明說明(44 )Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The extra particles usually comprise at most one-half of the particles 18, preferably 15% of the particles at most. In a specific embodiment, the particles 18 comprise 0.001 to 99% by weight, preferably 50 to 99% by weight, and more preferably 75 to 99% by weight based on the total solids of the coating composition. In this specific embodiment, a particularly good coating includes, but is not limited to: 0 a coating containing organic components and thin flat particles having a thermal conductivity of at least 1 watt per meter k at a temperature of 300 k; u) containing Coating of organic ingredients and non-hydratable thin flat particles; Out) contains at least one boron-free thin flat particle having a thermal conductivity of at least watts per meter K at a temperature of 300K; iv) contains a temperature of 300K Aqueous composition residues of thin flat particles (ie, thin flat particles on fibers) having a thermal conductivity of at least 1 watt per meter of k; and v) comprising a thermal conductivity of at least 1 watt per meter of k at a temperature of 30 ° K Degrees of water-based composition residues of unnamed non-hydratable particles (ie, aluminum-free non-hydratable particles on fibers). In another specific embodiment, the particles 18 comprise 0.001 to 99% by weight, preferably i to 80% by weight, and more preferably 1 to 40% by weight based on the total solids of the coating composition. Further, in a specific embodiment in which the particles µ are non-hydratable inorganic particles, the particles preferably contain 1 to 50% by weight, and more preferably up to 25% by weight based on the total solids as the coating composition. In another specific embodiment, the particles 18 comprise greater than 20% by weight based on total solids, preferably in the range of 20 to 99% by weight, more preferably in the range of 25 to 80% by weight, and most preferably in the range of 50 to 60% by weight. In this specific embodiment, the particularly good coating includes a resin-compatible coating composition. -43- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) — — — — · I-- -r-I-11111111 (Please read the notes on the back before filling out this page} 557286 A7 B7 V. Description of the invention (4!) It contains more than 20% by weight of particles, organic hollow particles and composite particles based on total solids Granules, I at least = inorganic: Mohs hardness of not more than at least one glass-breaking fiber 値 Mohs = = In another specific embodiment, the granules 18 contain up to 80% by weight, and #g, χ M is preferably 1 It is 1 to 60% by weight. In the specific embodiment, == 20 to 60% by weight based on total solids == and 35 to 55% by weight of Yima, and more preferably 30 to 50% by weight. The good coating includes a resin compatible coating, which contains ❶ discontinuous particles formed of a material selected from the group consisting of non-thermally expandable organic materials, inorganic polymeric materials, non-cuttable = swell compound = materials and mixtures thereof. The average particle size of heat applied to wet the strands; (dagger) at least one A lubricating material different from the plurality of discontinuous particles; and at least one film-forming material. In addition to the particles, the coating composition preferably contains one or more film-forming materials, such as organic, inorganic, and natural polymeric materials. Available Organic materials include, but are not limited to, polymeric materials selected from synthetic polymeric materials, semi-synthetic polymeric materials, natural polymeric materials, and mixtures of any of the above. Synthetic polymeric materials printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs include but are not limited to thermoplastic And thermosetting materials. Preferably, the polymer film-forming material forms a substantially continuous film when coated on the surface 16 of the glass fiber. Usually, the amount of the film-forming material ranges from 1 to 99 based on the total solids of the coating composition. % By weight. In a specific embodiment, the amount of the film-forming material is preferably from 1 to 50% by weight, and more preferably from 1 to 25% by weight. In another specific embodiment, the amount of the film-forming material ranges from 20%. Weight to 99-44- National paper standard (CNS) A4 size (210 X 297 public love) of this paper size 557286 A7 B7 V. Description of invention (42%, and more It is preferably 60 to 80% by weight. In another embodiment, the amount of the film-forming material is preferably in the range of * based: the total solids are 20 to 75% by weight of the coating composition, and more preferably 40 to 50% by weight. In this specific embodiment, a particularly preferred coating includes a film-forming material, which includes at least one particle selected from inorganic particles, organic hollow particles, and composite particles based on a total solids content of greater than 20% by weight. The particles have a Mohs hardness 値 of at least one glass fiber. In another embodiment, the amount of the polymer film-forming material ranges from 1 to 1 based on the total solids of the coating composition. 60% by weight, preferably 5 to 50% by weight per ton, and more preferably 10 to 30% by weight. A better coating of this embodiment includes a resin-compatible coating comprising a plurality of discontinuous particles formed of a material selected from the group consisting of non-thermally expandable organic materials, drill polymer materials, non-thermally expandable composite materials, and mixtures thereof. The particles have an average particle size sufficient to wet the strand without external heat application; (1?) At least one lubricating material different from the plurality of discontinuous particles; and ⑷ at least one film-forming material. In a non-limiting embodiment of the present invention, the thermosetting polymer film-forming material is a preferred polymer film-forming material for coating a coating composition of glass fiber strands. This material is compatible with a thermosetting matrix material as a laminate of a printed circuit board, such as FR-4 epoxy resin, which is a multifunctional epoxy resin, and is a difunctional group in a specific embodiment of the present invention. Brominated epoxy resin. See Electronic Materials Handbook ™ ASM Intematicmal (1989) pages 534-537, which are specifically incorporated herein by reference. • 45- This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) 1 Ί r 11 μ ------ 0M -------- ^ ------- -(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives of the Ministry of Economic Affairs and Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperatives of the Ministry of Economic Affairs 557286 A7 B7 Thermosetting polyesters, epoxy materials, vinyl esters, phenolic, amine-based plastics, thermosetting polyurethanes, and mixtures of any of the above. Suitable thermosetting polyesters include STYPOL polyester, commercially available from Cook Composites and Polymers, Kansas, Missouri, and NEOXIL polyester, commercially available from DSM Β · V ·, Como, Italy. A non-limiting example of a thermosetting polymeric material is an epoxy material. Useful epoxy materials are polyglycidyl ethers containing at least one epoxy or ethylene oxide group, such as a polyhydric alcohol or thiol, in one molecule. Examples of suitable epoxy film-forming polymers include Epon® 826 and Epon® 880 epoxy resins, commercially available from Shell Chemical Company of Houston, Texas. Useful thermoplastic polymeric materials include ethylene polymers, thermoplastic polyesters, polyolefins, polyamides (e.g., aliphatic polyamides or aromatic polyamides such as aromatic polyamides), thermoplastic polyurethanes, A propylene polymer (such as polyacrylic acid), and a mixture of any of the above. In another non-limiting embodiment of the present invention, the preferred polymer film forming material is an ethylene polymer. Useful ethylene polymers of the present invention include, but are not limited to, polyvinylpyrrolidone, such as PVP K-15, PVP K_30, PVP K-60 and PVP K90, each commercially available from International Specialty Products Chemicals, Wayne, New Jersey the company. Other suitable ethylene polymers include RESYN 2828 and RESYN 1037 vinyl acetate copolymer emulsions, commercially available from National Starch and Chemical Company of Bridgewater, New Jersey, and other polyvinyl acetates, such as commercially available from H. B_ Fuller Air Products and -46-Allentown, Penn.- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) Ί Ί Γ 1 --- Γ ----------- --Order --------- line (please read the precautions on the back before filling this page) 557286 A7 B7 V. Description of the invention (44)
Chemicals公司者,及聚乙晞醇,其亦得自Air Products and Chemicals 公司0 用於本發明之熱塑性聚酯包括DESMOPHEN 2000及 DESMOPHEN 2001KS ,其均商業得自賓州Pittsburgh之 Bayer公司。較佳之聚酯包括RD-847A聚酯樹脂,其商業 得自俄亥俄州 Columbus之Borden Chemicals公司, DYNAKOLL Si 100經化學修改松脂,其商業得自瑞典之 Eka Chemicals AB公司。可用之聚醯胺包括VERSAMID產 品,其商業得自俄亥俄州Cincinnati之Cognis公司,及得 自比利時Ciba Geigy公司之EUREDOR產品。可用之熱塑 性聚胺基甲酸酯包括WITCOBOND® W-290H,其商業得自 康乃迪克州Greenwich之CK Witco公司,及RUCOTHANE⑧ 2011L聚胺基甲酸酯乳膠,其商業得自紐約州Hicksville之 Ruco Polymer 公司0 本發明之塗層組合物可包含一或更多種熱固性聚合材料 及一或更多種熱塑性聚合材料之混合物。在特別用於印刷 電路板之層合物之本發明非限制具體實施例中,水性上漿 組合物之聚合材料包括RD-847A聚酯樹脂、PVPK-30聚 乙烯基吡咯啶酮、DESMOPHEN 2000聚酯及VERSAMID聚 醯胺之混合物。在適合用於印刷電路板之層合物之替代非 限制具體實施例中,水性上漿組合物之聚合材料包含PVP K-30聚乙烯基吡咯啶酮,其視情況地組合EPON 826環氧 樹脂。 適合作爲聚合膜形成材料之半合成聚合材料包括但不限 -47- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ϋ 1 H ϋ ϋ ϋ ϋ ^ ί (請先閱讀背面之注意事項再填寫本頁)Chemicals, Inc., and polyethylene glycol, which are also available from Air Products and Chemicals. The thermoplastic polyesters used in the present invention include DESMOPHEN 2000 and DESMOPHEN 2001KS, all commercially available from Bayer, Pittsburgh, PA. Preferred polyesters include RD-847A polyester resin, commercially available from Borden Chemicals, Columbus, Ohio, and DYNAKOLL Si 100 chemically modified turpentine, commercially available from Eka Chemicals AB, Sweden. Useful polyamides include VERSAMID products, which are commercially available from Cognis, Inc. of Cincinnati, Ohio, and EUREDOR products, from Ciba Geigy, Belgium. Useful thermoplastic polyurethanes include WITCOBOND® W-290H, commercially available from CK Witco, Greenwich, Connecticut, and RUCOTHANE (R) 2011L polyurethane latex, commercially available from Ruco, Hicksville, New York Polymer Company 0 The coating composition of the present invention may comprise a mixture of one or more thermosetting polymeric materials and one or more thermoplastic polymeric materials. In a non-limiting embodiment of the present invention specifically for laminates for printed circuit boards, the polymeric material of the aqueous sizing composition includes RD-847A polyester resin, PVPK-30 polyvinylpyrrolidone, DESMOPHEN 2000 polymer Mixture of ester and VERSAMID polyamide. In alternative non-limiting specific embodiments suitable for laminates for printed circuit boards, the polymeric material of the aqueous sizing composition comprises PVP K-30 polyvinylpyrrolidone, optionally combined with EPON 826 epoxy resin . Semi-synthetic polymeric materials suitable as polymeric film-forming materials include, but are not limited to -47- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ϋ 1 H ϋ ϋ ϋ ϋ ^ (Please read first (Notes on the back then fill out this page)
-1 --! — ί 丨訂-!!! ·線 I 經濟部智慧財產局員工消費合作社印製 557286 五 經濟部智慧財產局員工消費合作社印製 A7 、發明說明(45 ) 於纖維素,如羥丙基纖維素,及經修改澱粉,如 KOLLOTEX 1250 (以環氧乙烷醚化之低黏度低直鏈澱粉馬 鈐薯片爲主澱粉),其商業得自荷蘭之AVEBE公司。 適合作爲聚合膜形成材料之天然聚合材料包括但不限於 由馬鈐薯、玉米、小麥、含蠟玉米、西米、稻米、蘆粟及 以上任何之混合物製備之澱粉。 應了解,視澱粉之本性而定,澱粉可作爲顆粒18及/或 膜形成材料。更特別地,一些澱粉完全溶於溶劑中,特別 疋水中,並且作爲膜形成材料,而其他則不完全溶解且維 持特定之粒度及作爲顆粒18 。雖然依照本發明可使用澱 粉(天然及半合成),本發明之塗層組合物較佳爲實質上無 澱粕材料。在此使用之名詞”實質上無澱粉材料,,表示塗層 組合物包含基於塗層組合物之總固體爲少於%重量%, 較佳爲少於35重量%之澱粉材料。更佳爲,本發明之。塗 層、、、&物本貧上操澱粉材料。在此使用之名詞,,本質上無 澱粉材料"表示塗層組合物包含基於塗層組合物之總固體 ^於20重量% ’較佳爲少於5重量%,而且更 粉材料。 π ”、、救 塗佈於加人印刷電路板之層合物之纖維股之典型含 上漿組合物並非樹脂相容性,而且必須在加入聚i基 =爲樹脂相容性,而且不須在織物處理前自纖 ’’除。更佳馬’本發明之塗層組合物與刷雷 路板之基質材科下討論)相容,_最佳爲環:=相電 ^ 尺度適 (請先閱讀背面之注意事項再填寫本頁)-1-! — Ί 丨 order-!!! · Line I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7, Invention Description (45) on cellulose, such as Hydroxypropyl cellulose, and modified starches such as KOLLOTEX 1250 (based on ethylene oxide etherified low viscosity and low amylose stable potato chips) are commercially available from AVEBE in the Netherlands. Natural polymeric materials suitable as polymeric film-forming materials include, but are not limited to, starches prepared from potato, corn, wheat, waxy corn, sago, rice, millet, and any mixtures thereof. It should be understood that depending on the nature of the starch, starch may be used as the granules 18 and / or the film-forming material. More specifically, some starches are completely soluble in solvents, especially mashed water, and serve as film-forming materials, while others are not completely dissolved and maintain a specific particle size and serve as granules 18. Although starch (natural and semi-synthetic) can be used in accordance with the present invention, the coating composition of the present invention is preferably substantially free of starch material. The term "substantially starch-free material" as used herein means that the coating composition contains less than% by weight, preferably less than 35% by weight, starch material based on the total solids of the coating composition. More preferably, In the present invention, the coating material is a starch material. The term used herein, essentially starch-free material, means that the coating composition contains a total solids based on the coating composition. % By weight 'preferably less than 5% by weight, and more powdery materials. Π', the typical sizing-containing composition of fiber strands coated on laminates added to printed circuit boards is not resin compatible, In addition, it must be added for the purpose of resin compatibility, and it is not necessary to remove the fiber before the fabric is processed. Better Jiama 'The coating composition of the present invention is compatible with the substrate material of the brushed road board, discussed below. _ The best is the ring: = phase electricity ^ appropriate size (please read the precautions on the back before filling this page) )
557286 經濟部智慧財產局員工消費合作社印製 A7 -----— B7 ▼ ^------- 五、發明說明(46 ) 容性。 聚合膜形成材料可爲水溶性、可乳化、可分散及/或可 硬化。在此使用之"水純"表μ合材㈣本質上均句地557286 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ------ B7 ▼ ^ ------- V. Description of Invention (46) Capacitive. The polymeric film-forming material may be water-soluble, emulsifiable, dispersible, and / or hardenable. The "water purity" used here is essentially syntactic
摻合及/或分子地或離子地分I 刀散於水中,以形成眞實溶 液。參見第1〇75 W,其特別地在此併入作爲參 考。"可乳化"表示聚合材料可在乳化劑之存在下,在水中 形成本質上安定混合物或懸浮。參見第461頁, 其特別地在此併入作爲參考。適合之乳化劑之非限制實例 敘述於下。"可分散"表*聚合材料之任何成分可如細微分 割顆粒分布於全部水中’如乳膠。參見^第435 頁,其特別地在此併入作爲參考。分散液之均句度可藉以 下討論之濕潤、分散或乳化劑(界面活性劑)之加成而增 加。可硬化"表7F聚合材料及上漿組合物之其他成分可聚 結成膜或彼此交聯而改變聚合材料之物理性質。參見 第331頁,其特別在此併入作爲參考。 除了或代替以上討論之膜形成材料,本發明之塗層組合 物較佳爲包含一或更多種玻璃纖維偶合劑,如有機矽烷偶 合劑、過渡金屬偶合劑、磷酸偶合劑、鋁偶合劑、含胺基 Werner偶合劑、及以上任何之混合物。這些偶合劑一般具 有雙重功能。各金屬或矽原子具有一或更多個基連接之, 其可直接反應或與纖維表面及/或樹脂基質之成分相容。 在此使用之名詞”相容,,表示基化學地連接(例如,藉極 性、濕潤或溶劑合力)但是不键結纖維表面及/或塗層組合 物之成分。在非限制具體實施例中,各金屬或矽原子具有 Ί Ί J--------1®^--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) -49- 557286 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(47 ) 一或更多個可使偶合劑反應玻璃纖維表面之可水解基,及 一或更多個可使偶合劑反應樹脂基質成分之官能基連接 之。可水解基之實例包括: Ο Η 0 R3Blended and / or molecularly or ionicly divided into knives and dispersed in water to form a solid solution. See No. 1075 W, which is specifically incorporated herein by reference. " Emulsifiable " means that a polymeric material can form an essentially stable mixture or suspension in water in the presence of an emulsifier. See page 461, which is specifically incorporated herein by reference. Non-limiting examples of suitable emulsifiers are described below. " Dispersible " Table * Any component of the polymeric material can be distributed as finely divided particles in all water 'such as latex. See ^ page 435, which is specifically incorporated herein by reference. The average degree of dispersion can be increased by the addition of wetting, dispersing or emulsifying agents (surfactants) as discussed below. Hardenable " Table 7F The polymer material and other ingredients of the sizing composition can be coalesced to form a film or cross-linked with each other to change the physical properties of the polymer material. See page 331, which is specifically incorporated herein by reference. In addition to or in place of the film-forming materials discussed above, the coating composition of the present invention preferably includes one or more glass fiber coupling agents, such as an organic silane coupling agent, a transition metal coupling agent, a phosphoric acid coupling agent, an aluminum coupling agent, Amine-containing Werner coupling agents, and mixtures of any of the above. These coupling agents generally have a dual function. Each metal or silicon atom has one or more radical linkages, which can react directly or be compatible with the components of the fiber surface and / or resin matrix. The term "compatible," as used herein, means that the radicals are chemically connected (eg, by polarity, wetting, or solvent) but do not bond the components of the fiber surface and / or the coating composition. In a non-limiting embodiment, Each metal or silicon atom has Ί Ί J -------- 1® ^ -------- order --------- line (please read the precautions on the back before filling in this Page) -49- 557286 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (47) One or more hydrolyzable groups that can react the coupling agent on the surface of glass fiber, and one or more hydrolyzable groups The coupling agent reacts the functional group of the resin matrix component to be connected. Examples of the hydrolyzable group include: 〇 Η 0 R3
II I II I -OR1,-0_C_R2, -N-_-C-R2, -〇-N=C-R4, -0_N=CR5,及 單羥基及/或1,2_或1,3-二醇之環形C2-C3殘基,其中R1爲 Ci-C3 ; R2爲Η或CVC4烷基;R3與R4獨立地選自 Η、Ci_C4燒基或C5-C6芳基;及R5爲C4_C7伸燒基。適合 之相容或官能基之實例包括環氧基、去水甘油基、氫硫 基、氰基、烯丙基、烷基、胺基甲酸基、_基、異氰酸 基、脲基、咪唑琳基、乙烯基、丙烯酸基、甲基丙烯酸 基、胺基或聚胺基。 官能基有機矽烷偶合劑用於本發明較佳。可用之官能有 機矽烷偶合劑之實例包括γ-胺基丙基三烷氧基矽烷、γ-異 氰酸基丙基三乙氧基矽烷、乙烯基三烷氧基矽烷、去水甘 油基丙基三烷氧基矽烷、及脲基丙基三烷氧基矽烷。較佳 之官能有機矽烷偶合劑包括Α-187 γ-去水甘油基丙基三甲 氧基矽烷、Α_174 γ-甲基丙烯氧基丙基三甲氧基矽烷、a-1100 γ-胺基丙基三乙氧基矽烷偶合劑、A-1108胺基矽烷偶 合劑、及Α-1160 γ-脲基丙基三乙氧基矽烷(其各商業得自 紐約州Tarrytown之CK Witco公司)。有機矽烷偶合劑可在 應用於纖維之前以水至少部份地水解,較佳爲1:1化學計 -50- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) Ί Ί r Ί 1 L---------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 557286 A7 B7 五、發明說明(48 ) 量比例,如果需要則或以未水解形式應用。水之pH可藉 酸或鹼之加成修改以引發或加速偶合劑之水解,如此技藝 所已知。 適合之過渡金屬偶合劑包括鈥、锆、氣及鉻偶合劑。適 合之鈦酸鹽偶合劑與錐酸鹽偶合劑商業得自 Kenrich Petrochemical公司。適合之鉻錯合物商業得自德拉瓦州 Wilmington 之 E.I. DuPont de Nemours 公司。含胺基 Werner 型偶合劑爲其中以具有胺基官能基之有機酸配位如鉻之三 價核原子之錯合物化合物。在此可使用熟悉此技藝者己知 之其他之金屬鉗合劑與配位型偶合劑。 偶合劑之量通常範圍基於總固體爲塗層組合物之1至 99重量%。在具體實施例中,偶合劑之量範圍基於總固體 爲塗層組合物之1至30重量%,較佳爲1至10重量%, 而且更佳爲2至8重量°/〇。 本發明之塗層組合物更可包含一或更多種軟化劑或界面 活性劑,其賦與纖維表面均勻之電荷,造成纖維彼此排斥 及減少纖維間之磨擦,以作用如潤滑劑。雖然並非必要, 較佳爲,軟化劑爲化學地異於塗層組合物之其他成分。此 種軟化劑包括陽離子性、非離子性或陰離子性軟化劑及其 混合物,如脂膀酸之胺鹽、燒基咪峻淋衍生物(如CATION X,其商業得自紐澤西州Princeton之Rhone Poulenc/Rhodia 公司)、溶解酸之脂肪酸醯胺、脂肪酸與聚伸乙二亞胺及 經醯胺取代聚伸乙二亞胺(如EMERY® 6717,部份醯胺化 聚伸乙二亞胺,其商業得自俄亥俄州Cincinnati之Cognis -51- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) Ί Ί ui 11 -------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 557286 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(49 ) 公司)< 縮合物。雖然塗層組合物可包含達6〇重量%之軟 化劑,較佳爲,塗層組合物包含少於2〇重量%而且更佳 爲少於5重量%之軟化劑。更多軟化劑之資訊參見a尸 Hall 之 第 2 版(1957)第 1〇8115 頁其特 別地在此併入作爲參考。 本發明之塗層組合物更可包括一或更多種化學地異於以 上討論之聚合物材料與軟化劑之潤滑材料,以在織動時賦 與纖維股所需之處理特徵。適合之潤滑材料可選自油、 壌、脂、及以上任何之混合物。用於本發明之蠘材料之非 限制實例包括水溶性、可乳化或可分散蠟材料,如蔬菜、 動物、礦物、合成或石油蠟,例如,鏈烷烴。用於本發明 之油包括天然油、半合成油及合成油。通常,蠟或其他潤 滑材料之量範圍基於總固體爲上漿組合物之〇至80重量 0/〇,較佳爲1至50重量%,更佳爲20至4〇重量。/。,而且 最佳爲25至35重量〇/〇。II I II I -OR1, -0_C_R2, -N -_- C-R2, -〇-N = C-R4, -0_N = CR5, and monohydroxyl and / or 1,2_ or 1,3-diol A circular C2-C3 residue, wherein R1 is Ci-C3; R2 is fluorene or CVC4 alkyl; R3 and R4 are independently selected from fluorene, Ci_C4 alkyl or C5-C6 aryl; and R5 is C4_C7 alkyl. Examples of suitable compatible or functional groups include epoxy, dehydroglyceryl, hydrothio, cyano, allyl, alkyl, carbamate, phenyl, isocyanate, urea, imidazole Linyl, vinyl, acrylic, methacrylic, amine or polyamine. Functional organosilane coupling agents are preferred for use in the present invention. Examples of useful functional organic silane coupling agents include γ-aminopropyltrialkoxysilane, γ-isocyanatopropyltriethoxysilane, vinyltrialkoxysilane, dehydrated glycerylpropyl Trialkoxysilanes and ureidopropyltrialkoxysilanes. Preferred functional organic silane coupling agents include A-187 γ-dehydrated glycerylpropyltrimethoxysilane, A-174 γ-methacryloxypropyltrimethoxysilane, a-1100 γ-aminopropyltriethyl Oxysilane coupling agent, A-1108 amine silane coupling agent, and A-1160 γ-ureidopropyltriethoxysilane (each commercially available from CK Witco, Tarrytown, NY). The organic silane coupling agent can be hydrolyzed at least partially with water before being applied to the fiber, preferably 1: 1 stoichiometry -50-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Ί Ί r Ί 1 L --------------- Order --------- line (please read the precautions on the back before filling out this page) Staff Consumption of Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative 557286 A7 B7 V. Description of the invention (48) Amount ratio, if required, or applied in unhydrolyzed form. The pH of water can be modified by addition of acid or base to initiate or accelerate the hydrolysis of the coupling agent, as is known in the art. Suitable transition metal coupling agents include “zirconium, gas, and chromium coupling agents. Suitable titanate coupling agents and caperate coupling agents are commercially available from Kenrich Petrochemical. A suitable chromium complex is commercially available from E.I. DuPont de Nemours, Wilmington, Delaware. The amine-containing Werner type coupling agent is a complex compound in which an organic acid having an amine functional group is coordinated, such as a trivalent nuclear atom of chromium. Other metal clamps and coordination type coupling agents known to those skilled in the art can be used here. The amount of coupling agent usually ranges from 1 to 99% by weight based on the total solids of the coating composition. In a specific embodiment, the amount of the coupling agent ranges from 1 to 30% by weight based on the total solids of the coating composition, preferably from 1 to 10% by weight, and more preferably from 2 to 8% by weight. The coating composition of the present invention may further include one or more softeners or surfactants, which impart a uniform charge to the surface of the fibers, causing the fibers to repel each other and reducing friction between the fibers to act as a lubricant. Although not necessary, it is preferred that the softener is other ingredients that are chemically different from the coating composition. Such softeners include cationic, non-ionic or anionic softeners and mixtures thereof, such as amine salts of fatty acids, and calcined derivatives such as CATION X, commercially available from Princeton, New Jersey Rhone Poulenc / Rhodia), acid-dissolved fatty acid amidine, fatty acids and polyethyleneimine, and ammonium substituted polyethyleneimine (such as EMERY® 6717, some ammonium-polyethyleneimine Cognis -51, commercially available from Cincinnati, Ohio. This paper is sized for China National Standard (CNS) A4 (210 X 297 mm). Ί Ί ui 11 ------------- Order --------- Line (Please read the notes on the back before filling out this page) 557286 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Invention Description (49) Company) < Condensate. Although the coating composition may contain up to 60% by weight of the softener, preferably, the coating composition contains less than 20% by weight and more preferably less than 5% by weight of the softener. For more information on softeners, see Hall 2nd Edition (1957), page 1081115, which is specifically incorporated herein by reference. The coating composition of the present invention may further include one or more lubricating materials that are chemically different from the polymer materials and softeners discussed above to impart the desired processing characteristics to the fiber strands during weaving. Suitable lubricating materials may be selected from the group consisting of oil, grease, grease, and mixtures of any of the foregoing. Non-limiting examples of the hafnium material used in the present invention include water-soluble, emulsifiable or dispersible wax materials such as vegetable, animal, mineral, synthetic or petroleum waxes, such as paraffins. The oils used in the present invention include natural oils, semi-synthetic oils and synthetic oils. Generally, the amount of wax or other lubricating material ranges from 0 to 80% by weight based on the total solids of the sizing composition, preferably from 1 to 50% by weight, and more preferably from 20 to 40% by weight. /. And more preferably 25 to 35 weight 0 / 〇.
較佳之潤滑材料包括具有極性特徵之蟻及油,而且更佳 爲包括具有極性特徵及高於35 t而且更佳爲高於45 t之 溶點之高結晶蠟。比較塗覆含不具有極性特徵之蠟及油之 上漿組合物之纖維股,此種材料據信改良塗覆含此種極性 材料之上漿組合物之纖維股上極性樹脂之濕潤及濕透。較 佳之具有極性特徵之潤滑材料包括由反應以下形成之酯: (1)單羧酸及(2)單羥基醇。此種用於本發明之脂肪酸酯之 非限制實例包括較佳之棕搁酸鯨蠟酯(如得自紐澤西州 Maywood 之 Stepan 公司之 KESSCO 653 或 STEPANTEX -Ί.— Ί 1 --— I — i — !· — — 訂 _ — !!線 (請先閱讀背面之注意事項再填寫本頁)Preferred lubricating materials include ants and oils with polar characteristics, and more preferably include high crystalline waxes with polar characteristics and melting points higher than 35 t and more preferably higher than 45 t. Comparing fiber strands coated with a sizing composition containing waxes and oils having no polar characteristics, this material is believed to improve the wetting and penetration of polar resins on fiber strands coated with a size composition containing such a polar material. Preferred polar lubricating materials include esters formed by reacting: (1) monocarboxylic acids and (2) monohydroxy alcohols. Non-limiting examples of such fatty acid esters for use in the present invention include the preferred cetyl palmitate (eg, KESSCO 653 or STEPANTEX from Stepan Company, Maywood, New Jersey -Ί.—Ί 1 --- I — I —! · — — Order _ — !! (Please read the precautions on the back before filling this page)
557286 A7 經濟部智慧財產局員工消費合作社印製 _B7___五、發明說明(5〇 ) 653 )、肉豆蔻酸鯨蠟酯(亦得自Stepan公司之STEPANLUBE 654 )、月桂酸鯨蠟酯、月桂酸十八酯、肉豆蔻酸十八酯、 棕櫚酸十八酯、及硬脂酸十八酯。用於本發明之其他脂肪 酸酯、潤滑材料包括三羥甲基丙烷三壬酸酯、天然鯨蠟及 三甘油酯,例如但不限於大豆油、亞麻油、環氧化大豆 油、及環氧化亞麻油。 潤滑材料亦可包括水溶性聚合材料。可用材料之非限制 實例包括聚伸烷多元醇及聚氧化伸烷多元醇,如MACOL E-300,其商業得自紐澤西州Parsippany之BASF公司,及 CARBOWAX 300與CARBOWAX 400,其商業得自康乃迪克 州Danbury之Union Carbide公司。可用潤滑材料之其他非 限制實例爲POLYOX WSR 301 ,其爲商業得自康乃迪克州 Danbury之Union Carbide公司之聚(環氧乙燒)0 代替或除了以上討論之潤滑材料,本發明之塗層組合物 可另外包括一或更多種其他之潤滑材料,如非極性石油 蠟。非極性石油蠟之非限制實例包括MICHEM® LUBE 296 微晶蠟、POLYMEKON® SPP-W 微晶蠟、及 PETROLITE 75 微晶蟻,其各商業得自俄亥俄州Cincinnai之Michelman公 司,及喬治亞州Cumming之Baker Petrolite公司,聚合物分 部。通常,此型蠟之量爲上漿組合物總固體之至多10重 量%。 本發明之塗層組合物亦可包括樹脂反應性稀釋劑,以藉 由在此製造操作中降低細毛、孔環與破裂纖絲之可能性, 同時維持樹脂相容性,而進一步改良本發明經塗覆纖維股 -53- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 先 閱 讀 背 面 之 注 項 再 填 寫 本 頁 I I I I I 訂 ▲ 557286 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(Μ ) 之潤滑,及在織動與針織提供良好之處理力。在此使用之 ••樹脂反應性稀釋劑"表示稀釋劑包括可化學地反應與塗層 組合物相容之相同樹脂之官能基。稀釋劑可爲任何具有一 或更多個可與樹脂系統反應之官能基之潤滑材料,較佳爲 反應裱氧樹脂系統之官能基,而且更佳爲反應FR_4環氧 樹脂系統之官能基。適合之潤滑劑之非限制實例包括具有 胺基、醇基、酐基、酸基或環氧基之潤滑劑。具有胺基之 潤滑劑之非限制實例爲修改聚乙二胺,例如,emery 6717 ’其爲商業得自俄亥俄州cincinnati之c〇gnis公司之 部份地醯胺化聚伸乙二亞胺。具有醇基之潤滑劑之非限制 實例爲聚乙二醇,例如,CARBOWAX 3〇〇,其爲商業得自 康乃迪克州Danbury之Union Carbide公司之聚乙二醇。具 有酸基之潤滑劑之非限制實例爲脂防酸,例如,硬脂酸及 硬脂酸之鹽。具有環氧基之潤滑劑之非限制實例包括環氧 化大旦油與環氧化亞麻油,例如,FLEX〇L L〇E,其爲環 氧化亞麻油,及FLEXOL EPO ,其爲環氧化大豆油,其均 商業侍自康乃迪克州Danbury之Union Carbide公司,及LE-9300環氧化聚矽氧乳液,其商業得自紐約州Tarryt〇wn之 CK Witco公司。雖然在本發明中不限制,上漿組合物可包 括基於總固體爲上漿組合物之至多15重量%之量之以上 討論之樹脂反應性稀釋劑。 塗層組合物可另外包括一或更多種乳化劑以乳化或分散 塗層組合物之成分,如顆粒18及/或潤滑材料。適合之乳 化劑或界面活性劑之非限制實例包括聚氧化伸烷基嵌段共 -54- 私紙張尺度適用中國國家標準(CNS)A4規格(21〇 x 297公爱) ϋ ϋ ϋ ϋ ϋ ϋ ^1 ϋ ^ ^ ^1 Ί 1— F I I I I I - ^1 ^1 I ϋ ^ ^1 I I 1 ^ ^ ϋ ϋ ^ ^ I A (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7 五、發明說明(52 ) 聚物(如PLURONIC™ F-108聚氧化丙烯-聚氧化乙烯共聚 物,其商業得自紐澤西州 Parsippany之BASF公司 (PLURONIC™ F-108共聚物在歐洲以商標名SYNPERONIC F-108得到)、乙氧化烷酚(如IGEPAL CA-630乙氧化辛基苯 氧基乙醇,其商業得自紐澤西州Wayne之GAF公司)、聚 氧化乙烯辛基苯基乙二醇乙醚、花楸醇酯之環氧乙烷衍生 物(如TMAZ 81,其商業得自紐澤西州Parsippany之BASF 公司)、聚氧化乙烯化蔬菜油(如ALKAMULS EL-719 ,其 商業得自 Rhone-Poulenc/Rhodia公司)、乙氧化坑g分(如 MACOL OP-10 SP ,其亦商業得自BASF公司)、及壬酚界 面活性劑(如MACOL NP-6與ICONOL NP-6,其亦商業得自 BASF公司,及SERMUL EN 668 ,其商業得自CON BEA, Benelux )。通常,乳化劑之量範圍基於總固體爲塗層組合 物之1至30重量%,較佳爲1至15重量%。 交聯材料,如三聚氰胺甲醛,及塑性劑,如酞酸酯、偏 苯三甲酸酯與己二酯,亦可包括於塗層組合物中。交聯劑 或塑性劑之量範圍基於總固體爲塗層組合物之1至5重量 % 〇 其他之添加物可包括於塗層組合物中,如聚碎氧、殺眞 菌劑、殺菌劑及防沫材料,其通常爲少於5重量%之量。 足以提供塗層組合物2至10之pH之有機及/或無機酸或 鹼亦可包括於塗層組合物中。適合之聚矽氧乳液之非限制 實例爲LE-9300環氧化聚矽氧乳液,其商業得自紐約州 Tarrytown之CK Witco公司。適合之殺菌劑之實例爲 -55- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -½¾--------訂---------線* 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 557286 A7557286 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs_B7___ V. Invention Description (50) 653), Cetyl Myristate (also available from STEPANLUBE 654 from Stepan), Cetyl Laurate, Laurel Stearyl stearate, stearyl myristate, stearyl palmitate, and stearyl stearate. Other fatty acid esters and lubricating materials used in the present invention include trimethylolpropane trinonanoate, natural cetyl wax and triglycerides, such as, but not limited to, soybean oil, linseed oil, epoxidized soybean oil, and epoxidized sesame oil. Lubricating materials may also include water-soluble polymeric materials. Non-limiting examples of useful materials include polyalkylene polyols and polyoxyalkylene polyols such as MACOL E-300, commercially available from BASF Corporation, Parsippany, New Jersey, and CARBOWAX 300 and CARBOWAX 400, commercially available Union Carbide, Danbury, Connecticut. Other non-limiting examples of useful lubricating materials are POLYOX WSR 301, which is commercially available from Union Carbide of Danbury, Connecticut (Ethylene Oxide). Instead of or in addition to the lubricating materials discussed above, the coatings of the present invention The composition may additionally include one or more other lubricating materials, such as non-polar petroleum wax. Non-limiting examples of non-polar petroleum waxes include MICHEM® LUBE 296 microcrystalline wax, POLYMEKON® SPP-W microcrystalline wax, and PETROLITE 75 microcrystalline ants, each commercially available from Michelman Corporation of Cincinnai, Ohio, and Cumming, Georgia Baker Petrolite, Polymer Division. Generally, the amount of this type of wax is up to 10% by weight of the total solids of the sizing composition. The coating composition of the present invention may also include a resin-reactive diluent to further improve the process of the present invention by reducing the possibility of fine hairs, rings, and broken filaments in this manufacturing operation, while maintaining resin compatibility. Coated Fiber Stock -53- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) Read the notes on the back before filling out this page IIIII Order ▲ 557286 Printed by the Employees ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Lubrication of the invention (M), and provide good processing power in weaving and knitting. As used herein • Resin Reactive Diluent " means that the diluent includes functional groups that chemically react with the same resin that is compatible with the coating composition. The diluent may be any lubricating material having one or more functional groups capable of reacting with the resin system, preferably the functional group of the reactive oxygen resin system, and more preferably the functional group of the FR_4 epoxy resin system. Non-limiting examples of suitable lubricants include lubricants having amine, alcohol, anhydride, acid or epoxy groups. A non-limiting example of an amine-based lubricant is a modified polyethylene diamine, for example, emery 6717 ', which is a partially aminated poly (ethylene diimide) commercially available from the Cognis Company of Cincinati, Ohio. A non-limiting example of an alcohol-based lubricant is polyethylene glycol, such as CARBOWAX 300, which is a polyethylene glycol commercially available from Union Carbide, Danbury, Connecticut. Non-limiting examples of acid-based lubricants are fatty acids, such as stearic acid and salts of stearic acid. Non-limiting examples of lubricants having epoxy groups include epoxidized big oil and epoxidized linseed oil, for example, FLEXOLOE, which is an epoxidized linseed oil, and FLEXOL EPO, which is an epoxidized soybean oil, which Both are commercially available from Union Carbide, Danbury, Connecticut, and LE-9300 epoxidized polysiloxane emulsion, commercially available from CK Witco, Tarry Town, NY. Although not limiting in the present invention, the sizing composition may include the resin reactive diluent discussed above based on the total solids in an amount of up to 15% by weight of the sizing composition. The coating composition may additionally include one or more emulsifiers to emulsify or disperse ingredients of the coating composition, such as particles 18 and / or lubricating materials. Non-limiting examples of suitable emulsifiers or surfactants include polyoxyalkylene block co-54- private paper sizes Applicable to China National Standard (CNS) A4 specifications (21〇x 297 public love) ϋ ϋ ϋ ϋ ϋ ϋ ^ 1 ϋ ^ ^ ^ 1 Ί 1— FIIIII-^ 1 ^ 1 I ϋ ^ ^ 1 II 1 ^ ^ ϋ ϋ ^ ^ IA (Please read the notes on the back before filling out this page) 557286 A7 B7 V. Description of the invention (52) Polymers (such as PLURONIC ™ F-108 polyoxypropylene-polyethylene oxide copolymer, which is commercially available from BASF Corporation, Parsippany, New Jersey (PLURONIC ™ F-108 copolymer in Europe under the trade name SYNPERONIC F- 108)), ethoxylated alkylphenols (such as IGEPA CA-630 ethoxylated octylphenoxyethanol, commercially available from GAF Company, Wayne, New Jersey), polyethylene oxide octylphenyl glycol ether, flowers Ethylene oxide derivatives of methyl alcohol esters (such as TMAZ 81, commercially available from BASF, Parsippany, New Jersey), and polyoxyethylene vegetable oils (such as ALKAMULS EL-719, commercially available from Rhone-Poulenc / Rhodia company), acetic acid pits (such as MACOL OP-10 SP, which is also commercially available from BASF company ), And nonanol surfactants (such as MACOL NP-6 and ICONOL NP-6, which are also commercially available from BASF, and SERMUL EN 668, which are commercially available from CON BEA, Benelux). Generally, the amount of emulsifier ranges 1 to 30% by weight, preferably 1 to 15% by weight, based on the total solids of the coating composition. Crosslinked materials, such as melamine formaldehyde, and plasticizers, such as phthalates, trimellits, and adipates It can also be included in the coating composition. The amount of the cross-linking agent or plasticizer ranges from 1 to 5% by weight based on the total solids. Other additives can be included in the coating composition, such as polymer Broken oxygen, fungicides, bactericides and anti-foaming materials, usually in an amount of less than 5% by weight. Organic and / or inorganic acids or bases sufficient to provide the pH of the coating composition 2 to 10 may also be included in In a coating composition, a non-limiting example of a suitable silicone emulsion is LE-9300 epoxidized silicone emulsion, which is commercially available from CK Witco, Tarrytown, NY. An example of a suitable biocide is -55- Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (please first Read the notes on the back and fill out this page) -½¾ -------- Order --------- line * Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives Printed 557286 A7
五、發明說明(53 ) BIOMET66抗微生物化合物,其商業得自紐澤西州Rahway 之Μ & T Chemicals公司。適合之防沫材料之實例爲SAG 材料,其商業得自康乃迪克州Greenwich之CK Witco公 司,及MAZU DF-136,其商業得自紐澤西州parsippany之 BASF公司。如果需要,可將氳氧化銨加入塗層組合物以 安定塗層。較佳爲,水,而且更佳爲去離子水,以足以利 於在股上塗佈大致均勻塗層之量包括於塗層組合物中。塗 層組合物之固體重量%通常範園爲1至20重量0/〇。 在具體實施例中’本發明之塗層組合物實質上無玻璃材 料。在此使用之”實質上無玻璃材料”表示塗層組合物包含 少於50體積%之形成玻璃複合物之玻璃基質材料,較佳 爲少於35體積%。在更佳具體實施例中,本發明之塗層 組合物本質上無玻璃材料。在此使用之,,本質上無玻璃材 料π表示塗層組合物包含少於20體積%之形成玻璃複合物 之玻璃基質材料,較佳爲少於5體積%,而且更佳爲無玻 璃材料。此種玻璃基質材料之實例包括黑玻璃陶瓷基質材 料或鋁矽酸鹽基質材料,如熟悉此技藝者所已知。 在本發明之具體實施例中,包含多個纖維之纖維股以包 含有機成分及具有在300Κ之溫度爲每米Κ至少1瓦之導 熱度之薄平顆粒之塗層至少部份地塗覆。在另一個具體實 施例中,包含多個纖維之纖維股以包含有機成分及不可水 合薄平顆粒之塗覆至少部份地塗覆。在這些具體實施例 中’有機成分及薄平顆粒可選自以上討論之塗層成分。有 機成分及薄平顆粒可爲相同或不同,而且塗層可爲水性塗 -56- 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 χ 297公釐) 1 Ί h 11 L.--------------訂---------線· (請先閱讀背面之注意事項再填寫本頁) 557286 五 A7 B7 、發明說明(54 ) 層組合物殘渣或粉狀塗層組合物。 在另一個具體實施例中,包含多個纖維之纖維股以包含 至少一個具有在300K之溫度爲每米K至少1瓦之導熱度 之無硼薄平顆粒之塗層至少部份地塗覆。在另一個具體實 施例中,包含多個纖維之纖維股以包含具有在300K之溫 度爲每米K至少1瓦之導熱度之無硼薄平顆粒之水性組合 物殘渣至少部份地塗覆。在另一個具體實施例中,包含多 個纖維之纖維股以包含具有在300K之溫度爲每米κ至少 1瓦之導熱度之無鋁不可水合顆粒之水性組合物殘逢至少 部份地塗覆。 這些具體實施例中之成分可選自以上討論之塗層成分, 而且另外之成分亦可選自上列者。 在本發明之另一個具體實施例中,包含多個纖維之纖維 股在該纖維至少之一之至少一部份表面上以樹脂相容塗層 組合物至少部份地塗覆,此樹脂相容塗層組合物包含:(a) 多個由選自不可熱膨脹有機材料、無機聚合材料、不可熱 膨服複合材料及其混合物之材料形成之不連續顆粒,此顆 粒具有足以使股濕潤之平均粒度;(b)至少一種異於該多 種不連續顆粒之潤滑材料;及⑷至少一種膜形成材料。 &些具體實施例中之成分可選自以上討論之塗層成分。在 另一個具體實施例中,多個不連續顆粒在該纖維至少之一 與至少一個相鄰纖維之間提供間隙空間。 在另一個具體實施例中,包含多個纖維之纖維股在該纖 維至少之—之至少一部份表面上以樹脂相容塗層組合物至 Ί .1 Γ Ί 1 l· I I I--in----訂------I--線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製5. Description of the invention (53) BIOMET66 antimicrobial compound, commercially available from M & T Chemicals, Rahway, New Jersey. Examples of suitable anti-foaming materials are SAG materials, commercially available from CK Witco, Greenwich, Connecticut, and MAZU DF-136, commercially available from BASF, Parsippany, New Jersey. If desired, ammonium osmium oxide can be added to the coating composition to stabilize the coating. Preferably, water, and more preferably deionized water, is included in the coating composition in an amount sufficient to facilitate application of a substantially uniform coating on the strand. The solids% by weight of the coating composition is usually from 1 to 20% by weight. In a specific embodiment ' the coating composition of the present invention is substantially free of glass material. As used herein, "substantially glass-free material" means that the coating composition contains less than 50% by volume of a glass composite-forming glass matrix material, preferably less than 35% by volume. In a more preferred embodiment, the coating composition of the present invention is essentially glass-free. As used herein, the essentially glass-free material π means that the coating composition contains less than 20% by volume of a glass composite-forming glass matrix material, preferably less than 5% by volume, and more preferably a glass-free material. Examples of such glass matrix materials include black glass ceramic matrix materials or aluminosilicate matrix materials, as known to those skilled in the art. In a specific embodiment of the present invention, a fiber strand comprising a plurality of fibers is at least partially coated with a coating containing organic components and thin flat particles having a thermal conductivity of at least 1 watt per meter K at a temperature of 300K. In another embodiment, a fiber strand comprising a plurality of fibers is at least partially coated with a coating comprising an organic component and non-hydratable thin flat particles. In these embodiments, the ' organic ingredients and thin flat particles may be selected from the coating ingredients discussed above. The organic composition and thin flat particles can be the same or different, and the coating can be water-based. -56- This paper size is applicable to China National Standard (CNS) A4 (21〇χ 297 mm) 1 Ί h 11 L .-- ------------ Order --------- Line · (Please read the precautions on the back before filling out this page) 557286 Five A7 B7, invention description (54) layer composition Residual or powdery coating composition. In another specific embodiment, a fiber strand comprising a plurality of fibers is at least partially coated with a coating comprising at least one boron-free thin flat particle having a thermal conductivity of at least 1 watt per meter K at a temperature of 300K. In another specific embodiment, a fiber strand comprising a plurality of fibers is at least partially coated with an aqueous composition residue comprising boron-free thin flat particles having a thermal conductivity of at least 1 watt per meter K at 300K. In another specific embodiment, a fiber strand comprising a plurality of fibers is at least partially coated with an aqueous composition comprising aluminum-free non-hydratable particles having a thermal conductivity of at least 1 watt per meter k at a temperature of 300K. . The components in these embodiments may be selected from the coating components discussed above, and other components may be selected from the above. In another specific embodiment of the present invention, a fiber strand comprising a plurality of fibers is at least partially coated with a resin-compatible coating composition on at least a portion of a surface of at least one of the fibers, the resin being compatible The coating composition includes: (a) a plurality of discontinuous particles formed of a material selected from the group consisting of non-thermally expandable organic materials, inorganic polymeric materials, non-thermally expandable composite materials and mixtures thereof, the particles having an average particle size sufficient to make the strands wet (B) at least one lubricating material different from the plurality of discontinuous particles; and ⑷ at least one film-forming material. & The ingredients in some embodiments may be selected from the coating ingredients discussed above. In another embodiment, a plurality of discontinuous particles provide an interstitial space between at least one of the fibers and at least one adjacent fiber. In another specific embodiment, a fiber strand comprising a plurality of fibers is coated with a resin compatible coating composition on at least a part of the surface of the fiber to Ί.1 Γ Ί 1 l · II I--in ---- Order ------ I--line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
X 297公釐) 557286 經濟部智慧財產局員工消費合作社印製 A7 >、發明說明(55 ) 少部份地塗覆,此樹脂相容 •立句本mI滑、、'且奋物包含··(a)多個顆 粒,、口 ^一個由有機材科形成之顆粒;及⑻至 少〆個由選自氮化硼、石黑人 、 1 至屬一硫族化合物之無機材 料形成(顆粒’其中多個顆 ”、、 …本# 顆▲具有足以使股濕潤之平均粒 度,(b)至v —種異於該多個不 至少-種膜形成材料。 _顆粒<潤滑材料;及⑷ 在另一個具體實施例中,由夕 ^ .、 匕。夕個纖維之纖維股在該纖 維至少心一 < 至少一部松矣 表面上以树脂相容塗層組合物至 少部:地塗覆,此樹脂相容塗層組合物包含:⑷多個由 選自有機材料、無機聚合材料、 ,丄、 復口材枓及其混合物之材 料=成t不連續顆粒,此顆粒具有依照雷射散射技術測量 範=0.1至5微米之平均粒度;(b)至少-種異於該多個 不連續顆粒之潤滑材料;及⑷至少—種膜形成材料。 在另一個具體實施例中,以上敘述之樹脂相容塗層組合 物含⑷基於總固體爲20至60重量%,較佳爲35至55重 量% ’而且更佳爲3〇至5〇重量%之多個不連續顆粒;⑼ 基於總固體爲〇至8〇重量%,較佳爲】至5〇重量。/。,而 且更佳爲20至40重量%之至少一種潤滑材料;及⑷基於 總固體爲1至60重量%,較佳爲5至 佳爲至%重量%之至少-種膜形成材料量/〇,而且更 在本發明之另-個具體實施例中,包含多個纖維之纖維 股在該纖維至^ ^ YyV ^ ^ m乍主/〈一之至少一部份表面上以樹脂相容塗層 ^合物至少部份地塗覆,此樹脂相容塗層組合物包含:⑷ 多個由選自有機材料、複合材料及其混合物之材料形成之 _ 58 _ 本紙張尺錢財規格⑽ X 297公釐) — — — — — · 11 — I I I I 訂 (請先閱讀背面之注意事項再填寫本頁) 五、發明說明(56 ) =㈣狀顆粒,此顆粒具有依照雷射散射技術測量範 :·至5微米之平均粒度;及⑼至少—種異於該多個 不連績顆粒之潤滑材料。 月^本Γ月之另—個具體實施例中’包含多個纖維之纖維 ’%至»之至少—部份表面上以樹脂相容塗層 至少邵份地塗覆,此樹脂相容塗層組合物包含基於 :固體爲大於20重量%之至少一個選自無機顆粒、有機 2顆粒及複合顆粒之顆粒,此至少一個顆粒具有不超過 至少一個該纖維之莫氏硬度値之莫氏硬度値。 2本發明(另—個具體實施例中’包含多個纖維之纖維 =該纖維至少之_之至少—部份表面上以樹脂相容塗層 、心物至少部份地塗覆,此樹脂相容塗層組合物包含:⑷ 至少—個具有不超過至少—個該纖維之莫氏硬度値之莫氏 硬度値m機顆粒;及(b)至少—種聚合材料。 ^本發明i額外具體實施例中,包含多個纖維之纖維股 在该纖維至少之一之至少一部份表面上以樹脂相容塗層组 合物至少部份地塗覆’此樹脂相容塗層組合物包含:⑷ 至少-個中空不可熱膨脹有機顆粒;及⑼至少—種異於 至少一個中空有機顆粒之潤滑材料。 各以上具體實施例中之成分選自以上討論之塗層成分, 而且另外之成分亦可選自上列者。 在本發明(具體實施例中,纖維塗覆包含有機成分及具 有在3·之溫度爲每米κ至少1瓦之導熱度之薄平顆粒 〈組口物。在另一個具體實施例中,纖維塗覆包含有機成 557286 A7 五、發明說明(57 ) 分及不可水合薄平顆粒之組合物。在另_個具體實施例 中,纖維塗覆包含至少-個具有在贿之溫度爲每米κ 至少1瓦之導熱度之無硼薄平顆粒之組合物。在另—個具 體實施例中’纖維塗覆包含具有在300Κ之溫度爲每米: 至少1瓦之導熱度之薄平顆粒之組合物。在另一個具體實 施例中’纖維塗覆包含具有在3〇οκ之溫度爲每米Κ至少 1瓦之導熱度之無鋁不可水合無機顆粒之組合物。 在本發明之另一個具體實施例中,纖維塗覆包含以下之 組合物:(a)多個由選自不可熱膨脹有機材料無機聚合 材料、不可熱膨脹複合材料及其混合物之材料形成之不= 續顆粒,此顆粒具有足以使股濕潤之平均粒度;(b)至少 一種異於該多個不連續顆粒之潤滑材料;及⑷至少一種 膜形成材料。在另一個具體實施例中,纖維塗覆包含以下 之組合物:⑷多個顆粒,其包含⑴至少—個由有機材料 形成之顆粒;及(ii)至少一個由選自氮化硼、石墨及金屬 二硫族化合物之無機材料形成之顆粒,其中多個顆粒具有 ^以使股濕潤之平均粒度;(b)至少—種異於該多個不連 續顆粒之潤滑材料;及(c)至少一種膜形成材料。 在另—個具體實施例中,纖維塗覆包含以下之組合物: (a)夕個由選自有機材料、無機聚合材料、複合材料及其 混合物之材料形成之不連續顆粒,此顆粒具有依照雷射散 射技術測量範圍爲0.1至5微米之平均粒度;及(b)至少一 種異於該多個不連續顆粒之潤滑材料;及(c)至少—種膜 形成材料。 -60- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐 (請先閱讀背面之注意事項再填寫本頁) ----------------9^------- —訂---------線* 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 557286 A7 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 五、發明說明(58 ) 在本發明心另一個具體實施例 組合物:(a)多個由選自有機材料、:人材:包含以下之 之材料形成之不連續非㈣㈣,及其混合物 射技術測量範園爲 0·1至^止、 有依照雷射散 種異於該多個不連續顆_ L〈平均粒度’·及(b)至少一 焉觸粒 < 潤滑材料。 例中,纖維塗覆包含樹旨 一個具體實施 脂相容塗層組合物包含基於她 <、、'且5物,此樹 丞於、,、心固體馬大於2〇 少一個選自無機顆粒、有 里❶<至 兮班^ 職中艾顆粒及複合顆粒之顆护, 4顆粒具有不超過該纖唯 上 在本發…/ 硬度値之莫氏硬度値。 在本發月4另一個具體實施例中,纖維塗覆包 組合物:(a)至少一個薄平Α^ 材料。在本發明之另一個且贿 ^" ,、實施例中,纖維塗覆包含以 下 < 組合物:(a)多個中命τ | U夕1U肀二不可熱膨脹有機顆粒·及 y —種異於至少一個中命古 、 甲工有機顆粒之聚合材料。在本發明 (額外具體實施例中,纖維塗覆樹脂相容塗層組合物,其 在該纖維之至少—部份表面上具有上漿组合物之第-塗 層’及包含水性塗層组合物殘遙之第二塗層,此組合物包 含多個塗佈於上漿組合物之第—塗層之至少一部份上之不 連續顆粒。 各以上具體實施例中之成分選自以上討論之塗層成分, 而且另外之成分亦可選自上列者。 在本發明之非限制具體實施例中,本發明纖維股之該纖 維至少之一之至少一部份塗佈包含p〇LARTHER]v^ 16〇氮 化爛粉末及/或BORON NITRIDE RELEASECOAT分散液、 ΊΊΓΊΙμ------ΦΜ--------訂---------線# (請先閱讀背面之注意事項再填寫本頁)X 297 mm) 557286 Printed by A7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the invention description (55) is partially coated. This resin is compatible. (A) a plurality of particles, one of which is formed of an organic material family; and at least one of which is formed of an inorganic material selected from the group consisting of boron nitride, black stone, and 1 to a monochalcogen compound (particles of which "Multiple particles" ,, ... This # ▲ has an average particle size sufficient to make the strand moist, (b) to v — different from the multiple not less than-film-forming materials. _Particles < lubricating materials; and In another specific embodiment, the fiber strands of the fiber are coated with a resin-compatible coating composition at least partially on the surface of the fiber The resin-compatible coating composition includes: ⑷ a plurality of materials selected from the group consisting of organic materials, inorganic polymeric materials, rhenium, composite materials, and mixtures thereof, which are discontinuous particles, and the particles have Measurement range = average particle size of 0.1 to 5 microns; (b) at least-species A lubricating material on the plurality of discontinuous particles; and at least one film-forming material. In another specific embodiment, the resin-compatible coating composition described above contains 20 to 60% by weight based on total solids, It is preferably 35 to 55% by weight, and more preferably 30 to 50% by weight of a plurality of discontinuous particles; 〇 0 to 80% by weight based on the total solids, more preferably] to 50% by weight. And more preferably 20 to 40% by weight of at least one lubricating material; and ⑷ based on the total solids of 1 to 60% by weight, preferably 5 to 5% to 5% by weight of at least-the amount of film-forming material / 〇, Furthermore, in another specific embodiment of the present invention, a fiber strand including a plurality of fibers is coated with a resin compatible coating on at least a part of the surface of the fiber to ^ ^ YyV ^ m / ^ The resin-compatible coating composition includes: ⑷ a plurality of materials selected from the group consisting of organic materials, composite materials, and mixtures thereof _ 58 _ paper rule money specification ⑽ X 297 mm ) — — — — — · · 11 — IIII Order (Please read the notes on the back first (Fill in this page again.) 5. Description of the invention (56) = ㈣-shaped particles, this particle has an average particle size according to the measurement range of laser scattering technology: · to 5 microns; and ⑼ at least-different from the plurality of non-continuous particles The lubricating material of this month. In another embodiment of the present invention, at least a portion of the "fibers containing a plurality of fibers"% to »is coated at least partly with a resin-compatible coating. This resin The compatible coating composition comprises at least one particle selected from the group consisting of inorganic particles, organic particles, and composite particles based on a solid content of more than 20% by weight, and the at least one particle has a Mohs hardness of at least one of the fibers. The hardness is 値. 2 The present invention (another embodiment of a 'fiber comprising a plurality of fibers = at least of the fibers-at least-part of the surface is coated with a resin compatible coating, the heart is at least partially coated, this resin phase The coating composition comprises: 至少 at least-having a Mohs hardness of the fiber 値 Mohs hardness 値 m machine particles; and (b) at least-a polymeric material. ^ Is an additional specific implementation of the present invention For example, a fiber strand comprising a plurality of fibers is at least partially coated with a resin-compatible coating composition on at least a portion of the surface of at least one of the fibers. 'This resin-compatible coating composition includes: 至少 at least -A hollow non-heat-expandable organic particle; and at least-a lubricating material different from at least one hollow organic particle. The components in each of the above specific embodiments are selected from the coating components discussed above, and other components may also be selected from the above. In the present invention (a specific embodiment, the fiber coating comprises an organic component and thin flat particles having a thermal conductivity of at least 1 watt per meter k at a temperature of 3 ° (group mouthpiece). In another specific embodiment Medium The coating contains an organic component 557286 A7 V. Composition of the invention (57) and non-hydratable thin flat particles. In another specific embodiment, the fiber coating contains at least one Composition of boron-free thin flat particles with a thermal conductivity of 1 watt. In another embodiment, a fiber coating composition comprising thin flat particles with a thermal conductivity of at least 1 watt per meter at a temperature of 300K: In another specific embodiment, the 'fiber coating comprises a composition of aluminum-free non-hydratable inorganic particles having a thermal conductivity of at least 1 watt per kilogram at a temperature of 30 ° K. In another specific embodiment of the present invention In the fiber coating, the following composition is included: (a) a plurality of non-continuous particles formed of a material selected from the group consisting of non-thermally expandable organic materials, inorganic polymer materials, non-thermally expandable composite materials, and mixtures thereof, the particles having sufficient moisture to make the strands moist Average particle size; (b) at least one lubricating material different from the plurality of discontinuous particles; and ⑷ at least one film forming material. In another specific embodiment, the fiber coating includes the following Composition: (i) a plurality of particles comprising: (ii) at least one particle formed from an organic material; and (ii) at least one particle formed from an inorganic material selected from the group consisting of boron nitride, graphite, and a metal dichalcogen compound, wherein Each particle has an average particle size to make the strand moist; (b) at least-a lubricating material different from the plurality of discontinuous particles; and (c) at least one film-forming material. In another embodiment, the fiber The coating comprises the following composition: (a) discontinuous particles formed of a material selected from the group consisting of organic materials, inorganic polymeric materials, composite materials and mixtures thereof, the particles having a measurement range of 0.1 to 5 according to laser scattering technology The average particle size of micrometers; and (b) at least one kind of lubricating material different from the plurality of discontinuous particles; and (c) at least-a film-forming material. -60- This paper size applies to China National Standard (CNS) A4 specifications ( 210 X 297 mm (Please read the notes on the back before filling this page) ---------------- 9 ^ ------- —Order ----- ---- Line * Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (58) Another specific embodiment of the composition of the present invention: (a) a plurality of materials selected from the group consisting of organic materials: human resources: Discontinuous and non-continuous, and the measurement range of its mixture shooting technique is from 0.1 to ^, and there are different discontinuous particles according to the laser scattering _ L <average particle size 'and (b) at least one contact Grain < Lubricant. In the example, the fiber coating contains a specific embodiment of the fat-compatible coating composition, which contains based on <,,,, and 5 substances. , There are ❶ 至 to Xiban ^ vocational secondary particles and composite particles of the protection, 4 particles have no more than the fiber in the hair ... / hardness 値 Mohs hardness 値. In another specific embodiment of the present invention, the fiber coating package composition: (a) at least one thin flat A ^ material. In another embodiment of the present invention, the fiber coating includes the following composition: (a) a plurality of hits τ | U 1 1 2 non-thermally expandable organic particles and y — species A polymeric material that is different from at least one Zhongguo, Jiagong organic particles. In the present invention (additional specific embodiments, a fiber-coated resin compatible coating composition having a first coating of a sizing composition on at least a portion of the surface of the fiber and comprising an aqueous coating composition Residual second coating, the composition includes a plurality of discontinuous particles coated on at least a part of the first coating of the sizing composition. The ingredients in each of the above specific embodiments are selected from the ones discussed above. The coating component, and other components may be selected from the above. In a non-limiting specific embodiment of the present invention, at least a part of at least one of the fibers of the fiber strand of the present invention is coated with pLARTHER] v ^ 16 ° Nitrided rot powder and / or BORON NITRIDE RELEASECOAT dispersion, ΊΊΓΊΙμ ------ ΦΜ -------- Order --------- line # (Please read the (Please fill in this page again)
經濟部智慧財產局員工消費合作社印製 557286 A7 B7 五、發明說明(59 ) EPON 826環氧基膜形成材料、PVP K-30聚乙烯基吡咯啶 酮、A-187環氧基官能基有機矽烷偶合劑、ALKAMULS EL-719聚氧化乙基化蔬菜油、IGEPAL CA-630乙氧化辛基 苯氧基乙醇、KESSCO PEG 600聚乙二醇單月桂酸酯(其商 業得自伊利諾州芝加哥之Stephan公司)、及EMERY® 6717 部份醯胺化聚伸乙二亞胺之水性塗層組合物。 在本發明另一個用於織布之非限制具體實施例中,本發 明纖維股之該纖維至少之一之至少一部份塗佈包含 POLARTHERM® 160 氮化硼粉末及 / 或 BORON NITRIDE RELEASECOAT 分散液、RD-847A 聚酯、PVP K-30 聚乙烯 基吡咯啶酮、DESMOPHEN 2000聚酯、A-174丙烯基官能 基有機矽烷偶合劑、與A-187環氧基官能基有機矽烷偶合 劑、PLURONIC F-108聚氧化丙烯-聚氧化乙烯共聚物、 MACOL NP-6 壬酚界面活性劑、VERS AMID 140、及 LE· 9300環氧化聚矽酮乳液之水性上漿組合物之乾燥殘渣。Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 B7 V. Description of the invention (59) EPON 826 epoxy-based film forming material, PVP K-30 polyvinyl pyrrolidone, A-187 epoxy-functional organosilane Coupling agent, ALKAMULS EL-719 polyoxyethylated vegetable oil, IGEPAL CA-630 ethoxylated octylphenoxyethanol, KESSCO PEG 600 polyethylene glycol monolaurate (commercially available from Stephan, Chicago, Illinois Co., Ltd.), and EMERY® 6717 Partially Aminated Polyethylene Diimide Aqueous Coating Composition. In another non-limiting embodiment of the present invention for weaving, at least a portion of at least one of the fibers of the fiber strand of the present invention is coated with a POLARHERM® 160 boron nitride powder and / or a BORON NITRIDE RELEASECOAT dispersion RD-847A Polyester, PVP K-30 Polyvinylpyrrolidone, DESMOPHEN 2000 Polyester, A-174 Acrylic Functional Organosilane Coupling Agent, A-187 Epoxy Functional Organosilane Coupling Agent, PLURONIC Dry residue of an aqueous sizing composition of F-108 polyoxypropylene-polyoxyethylene copolymer, MACOL NP-6 nonylphenol surfactant, VERS AMID 140, and LE · 9300 epoxy polysiloxane emulsion.
在本發明之另一個用於電子電路板之織物之非限制具體 實施例中,本發明纖維股之該纖維至少之一之至少一部份 塗佈包含P〇LARTHERM®PT160氮化硼粉末及/或ORPAC BORON NITRIDE RELEASECOAT-CONC 25 分散液、PVP K-30聚乙烯基吡咯啶酮、A-174丙烯基官能基有機矽烷偶合 劑、A-187環氧基官能基有機矽烷偶合劑、ALKAMULS EL-719聚氧化乙基化蔬菜油、EMERY® 6717部份醯胺化 聚伸乙二亞胺、RD-847A聚酯、DESMOPHEN 2000聚酯、 PLURONIC F-108聚氧化丙晞-聚氧化乙烯共聚物、ICONOL -62- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) ---------------訂---------線* 經濟部智慧財產局員工消費合作社印製 557286 Α7 Β7 五、發明說明(60 ) NP-6烷氧化壬酚、及SAG 10防沫材料之水性塗層組合 物。如果需要,此特定具體實施例可視情況地另外包括 ROPAQUE⑧ HP-1055 及 / 或 ROPAQUE®OP-96 苯乙烯丙烯 共聚物中空球粒。 在本發明之另一個用於電子電路板之織物之非限制具體 實施例中,本發明纖維股之該纖維至少之一之至少一部份 塗佈包含POLARTHERM® PT 160氮化硼粉末及/或ORPAC BORON NITRIDE RELEASECOAT-CONC 25 分散液、RD-847A聚酯、PVP K-30聚乙烯基吡咯啶酮、DESMOPHEN 2000聚酯、A-174丙烯基官能基有機矽烷偶合劑、A-187 環氧基官能基有機矽烷偶合劑、PLURONIC F_108聚氧化 丙烯·聚氧化乙烯共聚物、VERSAMID 140聚醯胺、及 MACOL NP-6壬酚之水性上漿組合物。如果需要,此特定 具體實施例可視情況地另外包括ROPAQUE® HP-1055及/ 或ROPAQUE® OP-96苯乙烯-丙烯共聚物中空球粒。 在本發明之另一個用於織動層合印刷電路板用織物之非 限制具體實施例中,本發明纖維股之該纖維至少之一之至 少一部份塗佈包含ROPAQUE® HP-1055及/或ROPAQUE® OP-96苯乙烯-丙烯共聚物中空球粒、PVP K-30聚乙烯基 吡咯啶酮、A-174丙晞基官能基有機矽烷偶合劑與A-187 環氧基官能基有機矽烷偶合劑、EMERY® 6717部份醯胺 化聚伸乙二亞胺、STEPANTEX 653棕櫚酸鯨蠟酯、TMAZ 81花楸醇酯之環氧乙烷衍生物、MACOL ΟΡ·10乙氧化烷 驗、及MAZU DF-136防末材料之水性第一塗層組合物殘 •63- >紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公 ^1 1 i^· I Ik I I ϋ ·ϋ ϋ 1 ϋ ^1 ϋ ϋ ^1 1 ^1 ϋ I -1 言 矣 (請先閱讀背面之注咅?事項再填寫本頁) 557286 A7 B7 五、發明說明(61 ) 渣。雖然並非必要,此特定具體實施例較佳爲更包括 POLARTHERM® PT 160 氮化硼粉末及 / 或 ORPAC BORON NITRIDE RELEASECOAT-CONC 25 分散液。 在本發明之另一個用於電子電路板之織物之非限制具體 實施例中,本發明纖維股之該纖維至少之一之至少一部份 塗佈包含DESMOPHEN 2000聚酯、A-174丙烯基官能基有 機矽烷偶合劑、A-187環氧基官能基有機矽烷偶合劑、 PLURONIC F-108聚氧化丙烯-聚氧化乙烯共聚物、 VERSAMID 140 聚醯胺、及 MACOL NP-6 壬酚、POLYOX WSR 301聚(環氧乙烷)、及DYNAKOLL Si 100松脂之水性 塗層組合物。此外,此特定具體實施例更包括 POLARTHERM® PT 160 氮化硼粉末及 / 或 ORPAC BORON NITRIDE RELEASECOAT-CONC 25 分散液。In another non-limiting embodiment of the fabric for electronic circuit boards of the present invention, at least a portion of at least one of the fibers of the fiber strands of the present invention is coated with POLARTHERM® PT160 boron nitride powder and / ORPAC BORON NITRIDE RELEASECOAT-CONC 25 dispersion, PVP K-30 polyvinylpyrrolidone, A-174 propenyl-functional organosilane coupling agent, A-187 epoxy-functional organosilane coupling agent, ALKAMULS EL- 719 Polyoxyethylated Vegetable Oil, EMERY® 6717 Partially Aminated Polyethylene Diimide, RD-847A Polyester, DESMOPHEN 2000 Polyester, PLURONIC F-108 Polypropylene Oxide-Polyethylene Oxide Copolymer, ICONOL -62- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------------- -Order --------- line * Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 Α7 Β7 V. Description of the invention (60) Water-based coating of NP-6 alkoxynonylphenol and SAG 10 antifoam material层 组合 物。 Layer composition. If desired, this particular embodiment may optionally include ROPAQUE (R) HP-1055 and / or ROPAQUE® OP-96 styrene-propylene copolymer hollow spheres. In another non-limiting embodiment of the fabric for electronic circuit boards of the present invention, at least a portion of at least one of the fibers of the fiber strands of the present invention is coated with POLARHERM® PT 160 boron nitride powder and / or ORPAC BORON NITRIDE RELEASECOAT-CONC 25 dispersion, RD-847A polyester, PVP K-30 polyvinylpyrrolidone, DESMOPHEN 2000 polyester, A-174 acrylic functional organosilane coupling agent, A-187 epoxy A functional sizing composition of a functional organosilane coupling agent, PLURONIC F_108 polyoxypropylene · polyoxyethylene copolymer, VERSAMID 140 polyamidamine, and MACOL NP-6 nonylphenol. If desired, this particular embodiment may optionally include ROPAQUE® HP-1055 and / or ROPAQUE® OP-96 styrene-propylene copolymer hollow pellets as appropriate. In another non-limiting embodiment of the present invention for weaving a fabric for a laminated printed circuit board, at least a portion of at least one of the fibers of the fiber strand of the present invention is coated with ROPAQUE® HP-1055 and / Or ROPAQUE® OP-96 styrene-propylene copolymer hollow pellets, PVP K-30 polyvinylpyrrolidone, A-174 propionyl functional organosilane coupling agent and A-187 epoxy functional organosilane Couplings, EMERY® 6717 Partially Aminated Polyethylene Diimide, STEPENTE 653 Cetyl Palmitate, TMAZ 81 Ethylene Oxide Derivatives of Anisocyanate, MACOL OP · 10 Ethoxylate Test, and MAZU DF-136 Residue of water-based first coating composition of anti-finishing material • 63- > Paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm ^ 1 1 i ^ · I Ik II ϋ · ϋ ϋ 1 ϋ ^ 1 ϋ ϋ ^ 1 1 ^ 1 ϋ I -1 (Please read the note on the back? Matters before filling out this page) 557286 A7 B7 V. Description of the invention (61) Slag. Although not necessary, this specific Specific embodiments preferably include POLARHERM® PT 160 boron nitride powder and / or ORPAC BORON NITRIDE RELEASECOAT-CONC 25 In another non-limiting embodiment of the fabric for electronic circuit boards of the present invention, at least a portion of at least one of the fibers of the fiber strands of the present invention is coated with DESMOPHEN 2000 polyester, A-174 Acryl-functional organosilane coupling agent, A-187 epoxy-functional organosilane coupling agent, PLURONIC F-108 polyoxypropylene-polyoxyethylene copolymer, VERSAMID 140 polyamide, and MACOL NP-6 nonylphenol, POLYOX WSR 301 poly (ethylene oxide) and DYNAKOLL Si 100 turpentine coating composition. In addition, this particular embodiment further includes POLARHERM® PT 160 boron nitride powder and / or ORPAC BORON NITRIDE RELEASECOAT-CONC 25 Dispersions.
在本發明之另一個用於電子電路板之織物之非限制具體 實施例中,本發明纖維股之該纖維至少之一之至少一部份 塗佈包含DESMOPHEN 2000聚酯、A-174丙烯基官能基有 機矽烷偶合劑、A-187環氧基官能基有機矽烷偶合劑、 SYNPERONIC F-108聚氧化丙烯-聚氧化乙烯共聚物、 EUREDUR 140 聚醯胺、MACOL ΝΡ·6 壬酚、SERMUL ΕΝ 668乙氧化壬酚、POLYOX WSR 301聚(環氧乙烷)、及 DYNAKOLL Si 100松月旨之水性塗層組合物。此外,此特定 具體實施例更包括ROPAQUE® HP_1055及/或ROPAQUE® OP-96苯乙烯·丙晞共聚物中空球粒,及/或 POLARTHERM® PT 160 氮化硼粉末及 / 或 ORPAC BORON -64- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) _ί-ί-ί·訂 ------線, 經濟部智慧財產局員工消費合作社印製 557286 A7 -—-----2Z___—— 五、發明說明(62 ) NITRIDE RELEASECOAT-CONC 25 分散液。 雖然不佳,依照本發明可製備具有類似上述之無顆粒 18之塗層組合物之纖維股。特別地,依照本發明意圖製 迨包括一或更多種膜形成材料,如ρνρ Κ·3〇聚乙烯吡咯 咯啶酮;一或更多種矽烷偶合劑,如Α_174丙烯基官能基 有機矽烷偶合劑與Α-187環氧基官能基有機矽烷偶合劑; 及基於總固體爲上漿組合物之至少25重量%之具有極性 特徵之潤滑材料,如STEPANTEX 653棕櫚酸鯨蠟酯之樹脂 相谷塗層組合物。熟悉此技藝者更應了解,依照本發明可 將具有無顆粒18之樹脂相容塗層組合物之纖維股紡織成 織物且製成電子撑體及電子電路板(如以下所述)。 本發明之塗層組合物可藉任何適合之方法製備,如熟悉 此技藝者已知之習知混合。較佳爲,以上討論之成分以水 稀釋以具有所需之固體重量%且混合在一起。顆粒18可 在混合塗層之其餘成分之前以水預混,乳化,或加入塗層 組合物之一或更多種成分。 依照本發明之塗層組合物可以許多方式塗佈,例如,以 輥或帶塗器接觸纖絲,噴灑或其他之工具。經塗覆纖維較 佳爲在室溫或高溫乾燥。乾燥器自纖維去除過量之水份, 而且如果存在,則將任何可硬化上漿組合物成分硬化。將 玻璃纖維乾燥之溫度及時間視如塗層組合物中之固體0/〇、 塗層組合物之成分及纖維型式之變數而定。 在此關於組合物而使用之名詞"硬化",如"硬化組合物 ”’表示將組合物之任何可交聯成分至少部份地交聯。在 -65- 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 X 297公釐) (請先閱讀背面之注音?事項再填寫本頁) -If 訂---------線· 經濟部智慧財產局員工消費合作社印製 557286In another non-limiting embodiment of the fabric for electronic circuit boards of the present invention, at least a portion of at least one of the fibers of the fiber strands of the present invention is coated with DESMOPHEN 2000 polyester, A-174 acrylic functionalities Organosilane coupling agent, A-187 epoxy-functional organosilane coupling agent, SYNPERONIC F-108 polyoxypropylene-polyoxyethylene copolymer, EUREDUR 140 polyamide, MACOL NP · 6 nonylphenol, SERMUL ENE 668 B An aqueous coating composition of nonoxynol, POLYOX WSR 301 poly (ethylene oxide), and DYNAKOLL Si 100 Matsuki. In addition, this specific embodiment further includes ROPAQUE® HP_1055 and / or ROPAQUE® OP-96 styrene-acrylic copolymer hollow pellets, and / or POLARHERM® PT 160 boron nitride powder and / or ORPAC BORON -64- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) _ί-ί-ί · Order ------ line, Ministry of Economic Affairs wisdom Printed by the Consumer Cooperative of the Property Bureau 557286 A7 -------- 2Z ___---- 5. Description of the invention (62) NITRIDE RELEASECOAT-CONC 25 dispersion. Although unsatisfactory, fiber strands having a coating composition similar to the particleless 18 described above can be prepared according to the present invention. In particular, it is intended according to the present invention to include one or more film-forming materials, such as ρνρ κ · 30 polyvinylpyrrolidone; one or more silane coupling agents, such as A_174 propenyl functional organosilane coupling Mixture with A-187 epoxy-functional organosilane coupling agent; and at least 25% by weight of the sizing composition based on the total solids of a lubricating material with polar characteristics, such as the resin phase coating of STEPANTEX 653 cetyl palmitate层 组合 物。 Layer composition. Those skilled in the art should further understand that according to the present invention, the fiber strands of the resin-compatible coating composition without particles 18 can be woven into fabrics and made into electronic supports and electronic circuit boards (as described below). The coating composition of the present invention may be prepared by any suitable method, such as mixing, as is known to those skilled in the art. Preferably, the ingredients discussed above are diluted with water to have the desired solids weight percent and mixed together. The particles 18 may be premixed with water, emulsified, or added to one or more of the components of the coating composition prior to mixing the remaining components of the coating. The coating composition according to the present invention can be applied in many ways, for example, by contacting the filaments with a roller or a belt applicator, spraying or other means. The coated fiber is preferably dried at room temperature or high temperature. The dryer removes excess water from the fibers and, if present, hardens any hardenable sizing composition ingredients. The temperature and time for drying the glass fibers depend on the solids in the coating composition, the components of the coating composition and the variables of the fiber type. The term "hardening" used herein with respect to the composition, such as "hardening composition" means to at least partially cross-link any crosslinkable components of the composition. At -65- This paper standard applies to China Standard (CNS) A4 Specification (21〇X 297 mm) (Please read the note on the back? Matters before filling out this page) -If Ordered --------- Line · Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative Print 557286
發明說明(64 ) 經濟部智慧財產局員工消費合作社印製 LOI=100 χ r(w^- w^/W 1Description of the Invention (64) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs LOI = 100 χ r (w ^-w ^ / W 1
Uw乾乾] (方程式〇Uw dry) (Equation 〇
其中w乾爲在220 T(約104 q之烤箱中乾燥6〇分鐘後之 纖維股重量加塗層組合物重量,及w裸爲纖維股在1150T (約621。〇之烤箱中加熱20分鐘且在乾燥器中冷卻至室 溫後之裸纖維股重量。 在塗佈第-上漿料之後,即,在纖維形成後首次塗佈上 衆料,將纖維聚集成每股具有2至15,〇〇(Μ固纖維之股,而 且較佳爲每股100至W00個纖維。 #第二塗層,组合物可以足以*覆或浸潰股部份之量塗佈於 第-上衆料’例如,藉由將經塗覆股浸於含第二塗層組合 物之浴中,將第二塗層組合物噴灑在經塗覆股上,或藉: 以以上討論之塗佈器接觸經塗覆股。經塗覆股可通過模以 自股去除過量塗層組合物及/或如以上所討論,乾燥足以 至少邵份地乾燥或硬化第二塗層組合物之時間。將第二塗 =組合物塗佈於股之方法及裝置部份地由股材料之組態決 疋。股較佳爲在塗佈第二塗層組合物後以此技藝已知之方 法乾燥。 適合之第二塗層組合物可包括一或更多種以上討論之膜 形成材料、潤滑劑、及其他添加劑。第二塗層較佳爲異於 第一上漿組合物,即,其⑴含至少一種化學地異於上漿 組合物之成分之成分;或(2)以異於上漿組合物中所含相 同成分之量之量含至少一種成分。包括聚胺基甲酸酯之 Ί M l· ί L.-----------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) -67- 經濟部智慧財產局員工消費合作社印製 557286 A7 _________B7___ 五、發明說明(65 ) —~ 合第二塗層組合物之非限制實例揭示於美國專利 4,762,751,其特別地在此併入作爲參考。 現在參考圖2,在依照本發明之替代具體實施例中,經 塗覆纖維股210之玻璃纖維212可塗佈第一上漿組合物2 第-層214,其以以上討論之量包括任何上聚成分。適合 之上漿組合物之實例敘述於箄237-291頁(第3 版,1993 )及美國專利4,390,647與4 795 678,其各特別地 在此併入作爲參考。第二塗層組合物之第二層215塗佈於 第一層214之至少一部份,而且較佳爲全部外表面。第二 塗層組合物包含一或更多型式之顆粒216,如以上顆粒18 所詳細討論。在具體實施例中,第二塗層爲在至少一部份 第一塗層上之水性第二塗層組合物殘渣,特別是包含薄平 顆粒之水性第二塗層組合物殘渣。在另一個具體實施例 中,第二塗層爲在至少一部份第一塗層上之粉狀塗層組合 物,特別是包含薄平顆粒之粉狀塗層組合物。 在替代具體實施例中,第二塗層組合物之顆粒包含在親 水性顆粒之間隙中吸收及保留水之親水性無機實心顆粒。 親水性播機實心顆粒在接觸水或參與水之化學反應時可吸 水或膨脹,例如,形成黏性膠狀溶液,其阻礙或抑制水進 入使用經塗覆玻璃纖維股強化之通訊電纜之間隙。在此使 用之”吸收"表示水穿透親水性材料之内部結構或間隙,而 且實質上保留在其中。參見Hawley^ Condensed Chemical DLctionary第3頁,其特別地在此併入作爲參考。"膨脹” 表示親水性顆粒之大小或體積膨脹。參見Webster^ New -68 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) Ί M l· i 11 -----r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 557286 A7 ----B7 五、發明說明(66 )Wherein dry is the weight of the fiber strands after drying in an oven at 220 T (about 104 q for 60 minutes plus the weight of the coating composition), and bare fiber is heated in an oven at 1150 T (about 621.0 for 20 minutes and The weight of the bare fiber strands after cooling to room temperature in a desiccator. After coating the first-size, that is, for the first time after the fiber is formed, the mass is aggregated into fibers having a weight per share of 2 to 15. 〇 (M solid fiber strands, and preferably 100 to W00 fibers per share. #Second coating, the composition can be coated on the first-most popular material in an amount sufficient to cover or impregnate the strand portion. , By immersing the coated strand in a bath containing the second coating composition, spraying the second coating composition on the coated strand, or by: contacting the coated strand with the applicator discussed above The coated strands can be removed from the excess coating composition by the die and / or as discussed above, for a time sufficient to at least dry or harden the second coating composition. The second coating = composition The method and device for coating the strands are determined in part by the configuration of the strand material. The strands are preferably after the second coating composition is applied This method is known to dry. Suitable second coating compositions may include one or more of the film-forming materials, lubricants, and other additives discussed above. The second coating is preferably different from the first sizing combination. That is, it contains at least one ingredient that is chemically different from the ingredients of the sizing composition; or (2) contains at least one ingredient in an amount different from the same ingredient contained in the sizing composition. Includes a polyamine group Formic acid ester M l · ί L .----------- r --- order --------- line (Please read the precautions on the back before filling this page) -67- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 _________B7___ V. Description of Invention (65) A non-limiting example of a second coating composition is disclosed in US Patent 4,762,751, which is specifically incorporated herein as Reference. Referring now to FIG. 2, in an alternative embodiment in accordance with the present invention, the glass fibers 212 of the coated fiber strands 210 may be coated with the first sizing composition 2 first-layer 214, including the amounts discussed above Any sizing composition. Examples of suitable sizing compositions are described on pages 237-291 (page 3 (1993) and U.S. Patent Nos. 4,390,647 and 4 795 678, each of which is specifically incorporated herein by reference. The second layer 215 of the second coating composition is coated on at least a portion of the first layer 214, and is preferably Is the entire outer surface. The second coating composition includes one or more types of particles 216, as discussed in detail above with particles 18. In a specific embodiment, the second coating is on at least a portion of the first coating Residues of aqueous second coating composition, especially residues of aqueous second coating composition containing thin flat particles. In another specific embodiment, the second coating is at least a portion of the first coating. Powdery coating compositions, especially powdery coating compositions comprising thin flat particles. In alternative embodiments, the particles of the second coating composition include hydrophilic inorganic solid particles that absorb and retain water in the interstices of the hydrophilic particles. Solid particles of hydrophilic seeders can absorb or swell when exposed to water or participate in chemical reactions with water, for example, forming a viscous colloidal solution that prevents or inhibits water from entering the gaps of communication cables reinforced with coated glass fiber strands. As used herein, "absorption" means that water penetrates the internal structure or interstices of a hydrophilic material and remains substantially within it. See Hawley ^ Condensed Chemical DLctionary, page 3, which is specifically incorporated herein by reference. &Quot; "Swelling" means that the size or volume of the hydrophilic particles is expanding. See Webster ^ New -68-This paper size is applicable to Chinese National Standard (CNS) A4 (210 χ 297 mm) Ί M l · i 11 ----- r --- Order -------- -Line (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 ---- B7 V. Description of Invention (66)
Collegiate Dictionary. (1977)第1178頁,其特別地在此併入作 爲參考。較佳爲,親水性顆粒在接觸水後膨脹至其原始乾 重之至少一倍半,而且更佳爲其原始乾重之二至六倍。膨 脹之親水性無機實心潤滑顆粒之非限制實例包括如蛭石與 微晶高嶺石之蒙脱石類,吸收性沸石及無機吸收性凝膠。 較佳爲,這些親水性顆粒以粉末形式塗佈於膠黏狀上漿料 或其他膠黏狀第二塗層材料。 在本發明之具體實施例中,包含多個纖維之纖維股在至 少一個纖維之至少一部份表面上至少部份地塗覆樹脂相容 塗層組合物,此樹脂相容塗層組合物在至少一個纖維之至 少一部份表面上具有上漿組合物之第一塗層,而且包含水 性塗層組合物殘渣(其包含至少一個不連續顆粒)之第二塗 層塗佈於上漿組合物之第一塗層上之至少一部份上。在較 佳具體實施例中,至少一個不連續顆粒選自在親水性顆粒 之間隙中吸收及保留水之親水性顆粒。 除了這些具體實施例,第二塗層組合物中顆粒之量範圍 基於總固體可爲1至99重量%,較佳爲20至90,更佳爲 25至80重量%,而且甚至更佳爲50至60重量%。 在圖3所示之替代具體實施例中,第三塗層組合物之第 三層320可塗佈於第二層312之至少一部份表面,而且較 佳爲全部表面,即,此纖維股312具有第一上漿料之第一 層314、第二塗層組合物之第二層315、及第三塗層組合 物之第三外層320。經塗覆纖維股310之第三塗層較佳爲 異於第一上漿組合物及第二塗層組合物,即,第三塗層組 -69- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ' Ί Ί l· Η- 1 L-----------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) 557286Collegiate Dictionary. (1977) p. 1178, which is specifically incorporated herein by reference. Preferably, the hydrophilic particles swell to at least one and a half times their original dry weight after contact with water, and more preferably two to six times their original dry weight. Non-limiting examples of the expanded hydrophilic inorganic solid lubricant particles include montmorillonites such as vermiculite and microcrystalline kaolinite, absorbent zeolites, and inorganic absorbent gels. Preferably, these hydrophilic particles are applied in powder form to a viscous sizing agent or other viscous second coating material. In a specific embodiment of the present invention, a fiber strand including a plurality of fibers is at least partially coated with a resin-compatible coating composition on at least a portion of a surface of at least one fiber. The resin-compatible coating composition is At least a portion of the at least one fiber has a first coating of the sizing composition on the surface, and a second coating comprising a residue of the aqueous coating composition (which includes at least one discontinuous particle) is applied to the sizing composition On at least a portion of the first coating. In a preferred embodiment, at least one discontinuous particle is selected from hydrophilic particles that absorb and retain water in the interstices of the hydrophilic particles. Except for these specific examples, the amount of particles in the second coating composition may range from 1 to 99% by weight, preferably 20 to 90, more preferably 25 to 80% by weight, and even more preferably 50 based on total solids. To 60% by weight. In the alternative embodiment shown in FIG. 3, the third layer 320 of the third coating composition may be applied to at least a part of the surface of the second layer 312, and preferably the entire surface, that is, the fiber strand 312 has a first layer 314 of a first sizing, a second layer 315 of a second coating composition, and a third outer layer 320 of a third coating composition. The third coating of the coated fiber strand 310 is preferably different from the first sizing composition and the second coating composition, that is, the third coating group -69- This paper size applies to the Chinese National Standard (CNS) A4 size (210 X 297 mm) 'Ί Ί l · Η-1 L ----------- r --- order --------- line (please read the first (Please fill in this page again)
:物(1)含至少一種化學地異於第一上漿料與第二塗層組 合物 < 成分之成分;或⑺以異於第一上漿料與第二塗層 組合物中所含相同成分之量之含至少一種成分。 經濟部智慧財產局員工消費合作社印製 在此具體實施例中,第二塗層組合物包含一或更多種以 上时論 < 聚合材料,如聚胺基甲酸酯,及第三粉狀塗層組 合物包含以上討論之實心顆粒,如POLARTHERM®氮化硼 顆粒,及中空顆粒,如R〇pAQUE⑧顏料。較佳爲,藉由使 塗佈之具有液態第二塗層組合物之股通過流體化床或噴灑 裝置,以將粉末顆粒黏附在膠黏狀第二塗層組合物而塗佈 粉狀塗層。或者,股可在塗佈第三塗層92〇之層之前組合 成纖物912,如圖9所示。組合織物912與樹脂914之複 合物或層合物910亦包括導電層922,其類似在以下更詳 細地讨論之圖8所示之構造。黏附於經塗覆纖維股31〇之 粉狀實心顆粒之重量%範圍可爲乾燥股總重量之〇1至75 重量%,而且較佳爲〇」至3〇重量%。 第三粉狀塗層亦可包括一或更多種以上討論之聚合材 料,如丙烯聚合物、環氧化物、或聚烯烴,此塗層技藝已 知之習知安定劑及其他修改劑,其較佳爲乾燥粉末形式。 在具體實施例中,包含多個纖維之纖維股至少部份地以 上漿組合物之第一塗層塗覆纖維至少之一之至少一部份表 面,以包含聚合材料之第二塗層組合物塗覆第一組合物之 至少一部份,及以包含不連續顆粒之第三塗層組合物塗覆 第二塗層之至少一部份。在另一個具體實施例中,包含多 個纖維之纖維股至少部份地以上漿組合物之第一塗層塗覆 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 17 — 1-----------r---訂---------線· (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7 五、發明說明(68 智 局 員 工 消 費 涊纖維至少之一之至少一 二塗層组合物塗费々/ 面,以包含聚合材料之第4= ί組合物之至少-部份,及以包含薄 粒…塗層组合物塗覆第二塗層之至少一部份。 :較佳具體實施例中,各以上具體實施例中之至少_種 眘層馬不同的。在另_個較佳具體實施例中,各以上 實施例中之至少兩種 八體 於狀、、…人4 塗層Α不同的。此外,第三塗層可 域塗層組合物之水性乳液殘逢。塗層組合物包含-或 夕種以上討論之塗層成分。 一 =上討論之經塗覆纖維股之各具體實施例可作爲連續月 或進一步處理成各種口 ㈣私… 切股、交織股、紡條及 :織::如織物、非織物(包括單相織物)、針織物與編 Η ’ “織物之經紗與緯紗(即,填紗)股之經塗 =維=可爲非交織(亦稱爲未交織或零交織),或 則交織,而且織物可包括交織與非交織經紗與緯紗股之各 種組合。 =明之較佳具體實施例包括至少部份地塗覆之織物, m至/自包含多個以上詳細討論之纖維之纖維股。 、,在本發明中意圖爲由各所揭示包含多個纖維之纖 版製造4至少料地塗覆之織物。例如,本發明之較佳 體實施例係關於至少部份地塗覆之織物,其包含至少_ 包含多個纖維之纖維股,其塗層包含有機成分及且有 3幡之溫度爲每米K至少丨瓦之導熱度之薄平顆粒、。 明之具體實施例中,將依照本發明之塗層組合物 佈;個別纖維。在另—個具體實施例中,將塗層塗佈於 爲 更 股 織 覆 維 具 個 在 •ΙΓ — ί ---------訂---------線·! (請先閱讀背面之注音?事項再填寫本頁) I-- - -71- 本紐尺度剌巾國國家標準(CNSM4規格(210 χ 297公髮: Object (1) contains at least one component that is chemically different from the ingredients of the first sizing agent and the second coating composition; or is different from that contained in the first sizing agent and the second coating composition. The amount of the ingredients contains at least one ingredient. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In this embodiment, the second coating composition contains one or more of the above-mentioned < polymer materials, such as polyurethane, and a third powder The coating composition comprises the solid particles discussed above, such as POLARTHERM® boron nitride particles, and hollow particles such as RopAQUE (R) pigments. Preferably, the powdery coating is applied by passing the coated strands having the liquid second coating composition through a fluidized bed or a spraying device to adhere the powder particles to the adhesive second coating composition. . Alternatively, the strands can be combined into a fibrous material 912 before coating the third coating layer 92, as shown in FIG. The composite or laminate 910 of the composite fabric 912 and the resin 914 also includes a conductive layer 922, which is similar to the structure shown in Figure 8 discussed in more detail below. The weight percentage of the powdery solid particles adhered to the coated fiber strands 31 may range from 0.01 to 75% by weight of the total weight of the dry strands, and is preferably 0 to 30% by weight. The third powder coating may also include one or more of the polymeric materials discussed above, such as propylene polymers, epoxides, or polyolefins. Conventional stabilizers and other modifiers known in this coating technology are It is preferably in the form of a dry powder. In a specific embodiment, a fiber strand comprising a plurality of fibers is at least partially coated on at least a portion of the surface of at least one of the first coating fibers of the sizing composition to a second coating composition comprising a polymeric material. Coating at least a portion of the first composition and coating at least a portion of the second coating with a third coating composition comprising discrete particles. In another specific embodiment, a fiber strand comprising a plurality of fibers is at least partially coated with a first coating of a sizing composition. The size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm). 17 — 1 ----------- r --- Order --------- Line · (Please read the notes on the back before filling out this page) 557286 A7 B7 V. Description of the invention ( 68 Intellectual staff consume at least one or two coating compositions of at least one of the fibers, including at least one part of the 4th composition of the polymer material, and at least one part of the composition, and the coating composition including thin particles ... At least a part of the second coating is applied to the substrate. In the preferred embodiment, at least one of the above embodiments is different. In the other preferred embodiment, each of the above is different. At least two octahedrons in the examples have different coatings A. In addition, the third coating may be an aqueous emulsion of the coating composition. The coating composition contains-or more The coating composition in question. One = The specific embodiments of the coated fiber strands discussed above can be treated as continuous months or further processed into various For private ... Cut, interlaced, spun, and: weaving: such as fabrics, non-wovens (including single-phase fabrics), knitted fabrics and braids Η "The warp and weft of fabrics = Dimensions can be non-interlaced (also known as non-interlaced or zero-interlaced), or interlaced, and the fabric can include various combinations of interlaced and non-interlaced warp and weft strands. = A preferred embodiment of the Ming includes at least partially Coated fabrics, m to / from fiber strands containing a plurality of fibers discussed in detail above. In the present invention, it is intended to make at least a materially coated fabric from each disclosed fiberboard containing a plurality of fibers. For example, The preferred embodiment of the present invention relates to a fabric that is at least partially coated, which comprises at least a fiber strand containing a plurality of fibers, the coating of which contains an organic component and has a temperature of at least 3 K per meter K丨 The thermal conductivity of the thin flat particles. In the specific embodiment of the invention, the coating composition cloth according to the present invention; individual fibers. In another specific embodiment, the coating is applied to a more woven fabric. Wei Wei has a place in ΙΓ — ί --- ------ Order --------- Line ·! (Please read the phonetic on the back? Matters before filling out this page) I----71- National Standard of National Standard (CNSM4) Specifications (210 x 297)
I 經濟部智慧財產局員工消費合作社印製 557286I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 557286
至少-個纖維股。在另__個具體實施例中,將依照本發明 之塗層組合物塗佈於織物。這些替代具體實施例在以下詳 細討論。 雖然以上之討論大致關於在纖維形成後將本發明之塗層 組合物直接塗佈在玻璃纖維上,繼而將纖維加入織物中, 本發明亦包括其中將本發明之塗層組合物塗佈於織物之具 體實施例。例如,藉由在製造織物前將塗層塗佈於纖維 月又或藉由在已使用此技藝已知之各種技術製造之後將塗 層塗佈於織物,而將塗層組合物塗佈於織物。視織物之處 理而定,本發明之塗層組合物可直接塗佈於織物中之玻璃 纖維或,或另一個已在玻璃纖維及/或織物上之塗層。例 如,玻璃纖維可在形成及紡織成織物之後塗覆習知澱粉_ 油上漿料。然後在塗佈本發明之塗層組合物之前處理織物 以去除澱粉-油上漿料。此上漿料去除可使用此技藝已知 之技術完成,如熱處理或清洗織物。在此情形中,塗層組 合物直接塗覆織物之纖維表面。如果在形成之後未去除起 初塗佈於破璃纖維上之任何上漿組合物部份,則本發明之 塗層組合物塗佈於上漿組合物之殘餘部份而非直接在纖維 表面上。 在本發明之另一個具體實施例中,可在形成後立即將本 發明塗層組合物之經選擇成分塗佈於玻璃纖維,而且可在 製造後將塗層組合物之其餘成分塗佈於織物。以類似以上 討論之方法,可在以其餘成分塗覆纖維及織物之前自玻璃 纖維去除一些或全部之經選擇成分。結果,其餘成分直接 -72-At least one fiber strand. In another embodiment, a coating composition according to the present invention is applied to a fabric. These alternative embodiments are discussed in detail below. Although the above discussion is generally about directly coating the coating composition of the present invention on glass fibers after fiber formation, and then adding the fibers to the fabric, the present invention also includes coating the coating composition of the present invention on the fabric. The specific embodiment. For example, the coating composition is applied to the fabric by applying the coating to the fiber before manufacturing the fabric, or by applying the coating to the fabric after manufacturing using various techniques already known in the art. Depending on the fabric, the coating composition of the present invention may be applied directly to glass fibers in the fabric or to another coating already on the glass fibers and / or fabric. For example, glass fibers can be coated with a conventional starch-on-oil slurry after being formed and woven into a fabric. The fabric is then treated to remove the starch-oil sizing before coating the coating composition of the present invention. This sizing removal can be accomplished using techniques known in the art, such as heat treating or cleaning the fabric. In this case, the coating composition directly coats the fiber surface of the fabric. If any part of the sizing composition originally applied to the broken glass fibers is not removed after formation, the coating composition of the present invention is applied to the remaining part of the sizing composition rather than directly on the fiber surface. In another embodiment of the present invention, the selected ingredients of the coating composition of the present invention can be applied to glass fibers immediately after formation, and the remaining ingredients of the coating composition can be applied to the fabric after manufacturing. . In a manner similar to that discussed above, some or all of the selected components may be removed from the glass fibers before coating the fibers and fabric with the remaining components. As a result, the remaining ingredients are directly -72-
上. ---------訂---------線 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 297公釐) 557286 經濟部智慧財產局員工消費合作社印製 A7 -----^ 五、發明說明(70 ) ' 〜 塗覆織物之纖維表面或塗覆未自纖維表面去除之經選 分0 在依照本發明之另一個具體實施例中,包含至 7 1固包 含多個纖維之股之織物至少部份地塗覆第一塗層,而且在 弟一塗層(至少一部份上塗覆第二塗層,第二塗層包含具 有在300K之溫度爲每米κ大於!瓦之導熱度之無機 顆粒。 在另一個具體實施例中,包含至少一個包含多個纖維之 股I織物至少部份地塗覆包含以下之塗層:(幻薄平無機 顆粒,其具有不超過至少一個玻璃纖維之莫氏硬度値之莫 氏硬度値;及(b)膜形成材料。 在另一個具體實施例中,包含至少一個包含多個纖維之 股之織物至少部份地塗覆包含以下之塗層··(a)金屬顆 粒’其具有不超過至少一個玻璃纖維之莫氏硬度値之莫氏 硬度値,此金屬顆粒選自銦、鉈、錫、金與銀,及(b)膜 形成材料。 在另一個具體實施例中,包含至少一個包含多個纖維股 之織物至少部份地塗覆第一塗層,而且在第一塗層之至少 一部份上塗覆第二塗層,第二塗層多個在親水性顆粒之間 隙中吸收及保留水之親水性顆粒。 在另一個具體實施例中,包含至少一個包含多個纖維之 股之織物在織物之至少一部份表面上具有樹脂相容塗層組 合物’此樹脂相容塗層組合物包含:(a)多個由選自不可 熱膨脹有機材料、無機聚合材料、不可熱膨脹複合材料及 _-73- ______ 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 x 297公釐) • Ί Ί l· T 1 1%-----------r---訂---------線# (請先閱讀背面之注意事項再填寫本頁) 557286 A7--------- Order --------- Line (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 specification (210 297 (Mm) 557286 Printed A7 by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ----- ^ V. Description of the invention (70) '~ The coated fiber surface or the selected points that have not been removed from the fiber surface According to another specific embodiment of the present invention, a fabric containing up to 71% of a plurality of fiber strands is at least partially coated with a first coating, and a first coating (at least a portion is coated with a second coating) Coating, the second coating comprises inorganic particles having a thermal conductivity of κ greater than watts per meter at a temperature of 300 K. In another specific embodiment, the at least one strand I fabric comprising a plurality of fibers is at least partially The coating comprises the following coating: (magic thin flat inorganic particles having a Mohs hardness 値 of at least one glass fiber; and (b) a film-forming material. In another embodiment, A fabric comprising at least one strand comprising a plurality of fibers is at least partially coated Contains the following coatings: (a) metal particles' having a Mohs hardness of at least one glass fiber, a Mohs hardness, of a metal particle selected from the group consisting of indium, thorium, tin, gold and silver, and (b ) A film-forming material. In another embodiment, a fabric comprising at least one fabric comprising a plurality of fiber strands is at least partially coated with a first coating, and at least a portion of the first coating is coated with a second coating Layer, the second coating, a plurality of hydrophilic particles that absorb and retain water in the gaps between the hydrophilic particles. In another embodiment, a fabric comprising at least one strand comprising a plurality of fibers is in at least a portion of the fabric A resin-compatible coating composition on the surface 'This resin-compatible coating composition contains: (a) a plurality of materials selected from the group consisting of non-thermally expandable organic materials, inorganic polymeric materials, non-thermally expandable composite materials, and _-73- ______ this paper Standards are applicable to China National Standard (CNS) A4 specifications (21 × 297 mm) • Ί Ί l · T 1 1% ----------- r --- order ------- -线 # (Please read the notes on the back before filling this page) 557286 A7
Ι Ί I Ί 1 I, -----r I--訂---------線· C請先閱讀背面之注意事項再填寫本頁) (C)滑動玻璃纖維股之至少一部份以接觸固體物件之表 面粗面,此表面粗面具有大於至少一個破璃纖維之硬度値 之硬度値,使得藉塗層組合物抑制至少一個玻璃纖維股之 至少一個玻璃纖維因接觸固體物件之表面粗面之磨耗。 如上,用於這些具體實施例之塗層成分可選自以上討論 之塗層成分,而且另外之成分亦可選自上列者。 經塗覆纖維股10,210,310及由其形成之產品,如上 列之經塗覆織物,可用於廣泛之應用中,但是較佳爲作爲 強化聚合基質材料412之強化物410而形成複合物414, 如圖4所示,其在以下詳細討論。此種應用包括但不限於 用於印刷電路板之層合物、用於通訊電纜之強化物、及各 種其他之複合物。 本發明之經塗覆股及織物較佳爲與用以製造電子撑體及 印刷電路板之典型聚合基質材料相容。此外,經塗覆=維 股適合用於常用以製造用於此種應用之強化織物之空氣喷 射織布機。塗佈於使用空氣噴射織布機紡織之纖維之習知 上漿組合物包括如澱粉及油之通常不與此種樹脂系統相容 之成分。已觀察到,塗覆包含依照本發明顆粒18之塗層 組合物之纖維股之織動特徵接近塗覆習知澱粉/油爲主上 漿組合物之纖維股之織動特徵’而且與FR_4環氧樹脂相 容。耗不表示受任何特定理論限制,據信本發明之顆米 18在處理及空氣噴射織動時,藉由提供空氣噴射織動操 作所需之纖維分離及空氣阻力,而以類似習知殿粉"由上 聚组合物之澱粉成分之方式作用,但是藉由提供與環 76- 本紐尺度適用中國國家標準(CNS)A4 i格(21G X 297公爱丁 557286 經濟部智慧財產局員工消費合作社印製 A7 ------2Z______ 五、發明說明(74 ) 脂系統之相容性而不以異於習知組合物之方式作用。例 如,顆粒18促進塗層類似澱粉塗層之乾燥潤滑特徵之乾 燥、粉末特徵。 在本發明之經塗覆股中,顆粒可有利地在股之纖維間提 供間隙,其利於其間基質材料更快速之流動及/或均勻地 濕潤及濕透股之纖維。此外,股較佳爲具有高股開放性 (以上討論),其亦利於基質材料在束中之流動。令人驚奇 地,在特足具體實施例中,顆粒量可超過塗佈於纖維之塗 層組合物總固體之20重量❶/。,卻仍適當地黏附於纖維及 提供具有至少可與無顆粒塗層之股比擬之處理特徵之股。 現在參考圖8,本發明經塗覆股之優點爲,由加入經塗 覆股之織物812製造之層合物810可在織物812與聚合基 質材料814之間之界面具有良好之偶合。良好之偶合可在 由層合物810製造之電子撑體818中提供良好之水解安定 力及對金屬移動之抗力(以上討論)。 在圖5所示之另一個非限制具體實施例中,依照本發明 製造之經塗覆股510可在針織或紡織織物512強化物中作 爲經紗及/或緯紗股514與516,較佳爲形成用於印刷電路 板之層合物(如圖7_9所示)。雖然並非必要,經紗股 可在使用前藉熟悉此技藝者已知之任何習知交織技術交 織。一種此種技術使用交織框以賦與股每英吋〇5至3圈 之交織。強化織物512較佳爲每公分包括5至1〇〇條經紗 股(每英忖約13至254條經紗股),而且較佳爲每公分: 有6至50條緯紗股(每英吋約15至約127條緯紗股)。織 Ί M l· Ί ---·-----------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) -77- 557286 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(75 ) 動構造亦可爲規則平織或格網(如圖5蛴一、 澈籴Φ壮蓺本口, 所不),雖然可使用 熟悉此技藝者已知之任何其他織動型. U h織織動或緞 在具體實施例中’適合之本發明織動強化織物512可藉 由使用熟悉此技藝者已知之任何習知織 曰 、W機形成,如織梭 織布機、空氣噴射織布機或劍杆織布機, . 、 化疋較佳爲使用 更氣噴射織布機形成。較佳之空氣噴射織布機商業得自曰 本 Tsudakoma 公司之型號 103、1〇31 、1〇33 或 Ζχ 驗er Ruti型號L_5000、L-5謂或L_52〇〇,其商業得自瑞 士 Zurich 之 Sulzer Brothers 大限公司;及 T〇y〇da 型號 JAT610 〇 如圖中所述,空氣喷射織動指使用空氣噴射織布機626 (織物織動型式(如圖6所示),其中如以上所討論,以來 自一或更多個空氣噴射噴嘴618之強壓縮空氣614將填紗 (緯紗)610插入經紗棚中(如圖6與圖6a所示)。填紗61〇 被壓縮空氣推動通過織物628之寬度624 (約1〇至約6〇 英吋),而且更佳爲0.91米(約36吋)。 2氣噴射充填系統可具有單一主噴嘴616,但較佳爲沿 經紗棚612亦具有多個輔助繼動噴嘴620以對填紗61〇提 供強輔助空氣622 ,而維持紗610橫越織物628之寬度 624所需之空氣壓力。供應至主空氣噴嘴616之空氣壓力 (量規)較佳爲範園爲103至413仟巴斯卡(kPa)(每平方英 吋約15至約60磅(psi)),而且更佳爲310 kPa (約45 Psi)。主空氣噴嘴616之較佳型式爲Sulzer Ruti針式空氣 78- 十··------费----l·——訂---------線· C請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 x 297公釐) 557286 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(76 ) 嘴射單位型號044 455 001 ,其具有2毫米直徑617及20 公分長度621之噴嘴出口管619之内空氣噴射槽(商業得 自北卡州Spartanburg之Sulzer Ruti公司)。較佳爲,空氣噴 射充填系統具有15至20個輔助空氣喷嘴620,其以填紗 610之橫向方向供應輔助空氣以幫助推動紗61〇橫越織布 機626。供應至各輔助空氣噴嘴62〇之空氣壓力(量規)較 佳爲範圍爲3至6巴。 藉進料系統632以每分鐘180至550米,而且較佳爲每 分鐘274米(約300碼)之進料速率,自供應包裝63〇抽取 填紗610。經夾板將填紗610進料至主噴嘴618中。強空 氣推動預定長度之紗(大約等於所需之織物寬度)通過管導 片導件。在完成插入時,以切割器634切割在主喷嘴618 末梢之紗端。 不同紗及空氣噴射織動過程之相容性及空氣動力性質可 由以下之方法決定,其大致在此稱爲”空氣噴射運輸阻力” 試驗法。使用空氣喷射運輸阻力測量在以空氣噴射之力將 紗拉至空氣噴射噴嘴中時,施加在紗上之吸引或拉動力(,, 阻力")。在此方法中,在310仟巴斯卡(每平方英吋約45 磅)量規之空氣壓力,以每分鐘274米(約300碼)之速率將 各紗樣品進料通過Sulzer Ruti針式空氣嘴射噴嘴單位型號 044 455 001 ’其具有2毫米直徑617及20公分長度621之 噴嘴出口管619之内空氣噴射槽(商業得自北卡州 Spartanburg之Sulzer Ruti公司)。張力計在紗進入空氣喷射 噴嘴之前之位置接觸紗。張力計提供紗被拉至空氣噴射噴 -79- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -*—「>: 11·-----------r---訂---------線· (請先閱讀背面之注音?事項再填寫本頁) 5 5 經濟部智慧財產局員工消費合作社印製 五Ι Ί I Ί 1 I, ----- r I--order --------- line · C Please read the precautions on the back before filling this page) (C) At least sliding glass fiber strands A part of the rough surface contacting the solid object, the rough surface having a hardness greater than the hardness 至少 of at least one glass breaking fiber, so that the coating composition inhibits at least one glass fiber of at least one glass fiber strand from contacting the solid. Wear of the rough surface of the object. As mentioned above, the coating ingredients used in these embodiments may be selected from the coating ingredients discussed above, and the other ingredients may be selected from those listed above. Coated fiber strands 10,210,310 and products formed therefrom, such as the coated fabrics listed above, can be used in a wide range of applications, but are preferably formed as composites as a reinforcement 410 to reinforce the polymeric matrix material 412 414, as shown in FIG. 4, which is discussed in detail below. Such applications include, but are not limited to, laminates for printed circuit boards, reinforcements for communication cables, and various other composites. The coated strands and fabrics of the present invention are preferably compatible with typical polymeric matrix materials used to make electronic supports and printed circuit boards. In addition, coated = strands are suitable for use in air-jet looms commonly used to make reinforced fabrics for such applications. Conventional coating of fibers spun using an air-jet loom. Sizing compositions include ingredients such as starch and oils that are generally not compatible with such resin systems. It has been observed that the weaving characteristics of the fiber strands coated with the coating composition according to the present invention, the particle composition 18 are close to the weaving characteristics of the fiber strands coated with the conventional starch / oil-based sizing composition 'and are similar to those of the FR_4 ring. Oxygen resin is compatible. Consumption does not mean that it is limited by any specific theory. It is believed that the rice 18 of the present invention is similar to the conventional powder by providing the fiber separation and air resistance required for the air jet weaving operation during processing and air jet weaving. " It acts by the starch component of the polymer composition, but by providing with the ring 76- this New Zealand standard applies the Chinese National Standard (CNS) A4 grid (21G X 297 public Eding 557286 employee consumption of Intellectual Property Bureau of the Ministry of Economic Affairs) Cooperative printed A7 ------ 2Z______ V. Description of the invention (74) The compatibility of the lipid system does not act in a manner different from the conventional composition. For example, granule 18 promotes the drying of the coating similar to a starch coating Dry, powdery characteristics of lubricating characteristics. In the coated strands of the present invention, the particles can advantageously provide gaps between the fibers of the strands, which facilitates faster flow of the matrix material and / or uniformly wets and wets the strands. In addition, the strands preferably have high strand openness (discussed above), which also facilitates the flow of the matrix material in the bundle. Surprisingly, in specific embodiments, the amount of particles can exceed the amount coated on the fibers 20% by weight of the total solids of the coating composition, while still properly adhering to the fibers and providing strands with processing characteristics that are at least comparable to those of particle-free coatings. Referring now to FIG. 8, the present invention is coated The advantage of the strands is that the laminate 810 made from the coated fabric 812 can have a good coupling at the interface between the fabric 812 and the polymeric matrix material 814. A good coupling can be made from the laminate 810 The electronic support 818 provides good hydrolytic stability and resistance to metal movement (discussed above). In another non-limiting embodiment shown in FIG. 5, the coated strand 510 made in accordance with the present invention may be knitted in Or woven fabric 512 reinforcement as warp and / or weft strands 514 and 516, preferably to form a laminate for printed circuit boards (as shown in Figure 7_9). Although not necessary, the warp strands can be borrowed before use. Any conventional weaving technique known to those skilled in the art of interweaving. One such technique uses an interweaving frame to impart interlacing of 5 to 3 turns per inch. The reinforcing fabric 512 preferably includes 5 to 100 per cm. Warp strands (each There are about 13 to 254 warp yarn strands in the English flag, and preferably each cm: 6 to 50 weft yarns (about 15 to about 127 weft yarns per inch). Woven reed M l · Ί --- ·- ---------- r --- Order --------- line (please read the notes on the back before filling out this page) -77- 557286 Employees' Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs A7 is printed. 5. Description of the invention (75) The dynamic structure can also be a regular plain weave or a grid (as shown in Figure 5), but it can be used for any other known to those skilled in the art. Weaving type. U h weaving or satin in a specific embodiment of the invention is suitable for weaving and strengthening the fabric 512 can be formed by using any conventional weaving machine, such as weaving weaving, Cloth looms, air jet looms, or rapier looms,.. And 疋 are preferably formed using more air jet looms. The preferred air jet loom is commercially available from Japanese Tsudakoma company model 103, 1031, 1033, or ZZ tester Ruti model L_5000, L-5 or L_52〇00, which is commercially available from Sulzer, Zurich, Switzerland. Brothers Limited; and TOYODA model JAT610 〇 As shown in the figure, air jet weaving refers to the use of air jet loom 626 (weaving type of fabric (as shown in Figure 6), as discussed above, The filling yarn (weft) 610 is inserted into the warp shed with strong compressed air 614 from one or more air jet nozzles 618 (as shown in FIGS. 6 and 6a). The filling yarn 61 is pushed through the fabric 628 by the compressed air. A width of 624 (about 10 to about 60 inches), and more preferably 0.91 meters (about 36 inches). The 2 gas jet filling system may have a single main nozzle 616, but preferably also has multiple along the warp shed 612 The auxiliary relay nozzle 620 provides strong auxiliary air 622 to the filling yarn 61 and maintains the air pressure required for the yarn 610 to cross the width 624 of the fabric 628. The air pressure (gauge) supplied to the main air nozzle 616 is preferably Fan Garden is 103 to 413 仟 Baska (kPa) (per square Inches from about 15 to about 60 pounds (psi)), and more preferably 310 kPa (about 45 Psi). The preferred type of main air nozzle 616 is Sulzer Ruti needle air 78-ten ... ---- l · ——Order --------- Line · C Please read the notes on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 specification (21〇x 297 557286 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7. V. Description of the invention (76) Mouth-shooting unit model 044 455 001, which has a nozzle outlet pipe 619 with a diameter of 617 mm and a diameter of 20 cm and a diameter of 621 mm Tank (commercially available from Sulzer Ruti, Spartanburg, NC). Preferably, the air-jet filling system has 15 to 20 auxiliary air nozzles 620 which supply auxiliary air in the transverse direction of the filling yarn 610 to help push the yarn 61 through the loom 626. The air pressure (gauge) supplied to each auxiliary air nozzle 62 is preferably in the range of 3 to 6 bar. The feeding system 632 draws the filling yarn 610 from the supply package 63 at a feed rate of 180 to 550 meters per minute, and preferably 274 meters (about 300 yards) per minute. The filler 610 is fed into the main nozzle 618 via a splint. Strong air forces a yarn of a predetermined length (approximately equal to the desired fabric width) through the tube guide. When the insertion is completed, the yarn end at the end of the main nozzle 618 is cut with a cutter 634. The compatibility and aerodynamic properties of different yarns and air jet weaving processes can be determined by the following methods, which are roughly referred to herein as the "air jet transport resistance" test method. Use air jet transport resistance to measure the force of attraction or pulling exerted on the yarn when pulling the yarn into the air jet nozzle with the force of air jet (,, resistance "). In this method, each yarn sample is fed through a Sulzer Ruti needle air nozzle at an air pressure of 310 仟 Baska (about 45 pounds per square inch) at a rate of 274 meters (about 300 yards) per minute. Jet Nozzle Unit Model No. 044 455 001 'It has an air jet groove inside a nozzle outlet pipe 619 with a diameter of 2 mm 617 and a length of 621 20 cm (commercially available from Sulzer Ruti, Spartanburg, NC). The tensiometer touches the yarn before it enters the air jet nozzle. The tensiometer provides the yarn is pulled to the air jet spray -79- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm)-* — ">: 11 · --------- --r --- Order --------- line · (Please read the note on the back? Matters before filling out this page) 5 5 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
發明說明(77 ) 嘴中時,空氣噴射施加在紗之克力(阻力)測量。 」 每單位質量之阻力可作爲紗樣品之相對比較之基礎。對 於相對比較,將通過1公分長度之紗之阻力測量標準化。 1公分長度之紗之克質量可依照方程式2測定: 克質量=(π((1/2)2)(Ν)(ρ _)(1公分長度之紗) (方程式2) 其中d爲紗束單一纖維之直徑,N爲紗束中之纖維數量, 及P朗爲玻璃在25 °C之密度(每立方公分約2.6克)。表C 列出許多種典型玻璃纖維紗產品之紗中之纖維直徑及教 量。Description of the invention (77) The measurement of the gram force (resistance) of the air jet applied to the yarn while in the mouth. The resistance per unit mass can be used as the basis for a relative comparison of yarn samples. For relative comparison, the resistance measurement through a yarn of 1 cm length is standardized. The gram mass of a yarn of 1 cm length can be determined according to Equation 2: gram mass = (π ((1/2) 2) (N) (ρ _) (yarn of 1 cm length) (Equation 2) where d is the yarn bundle The diameter of a single fiber, N is the number of fibers in the yarn bundle, and P is the density of glass at 25 ° C (approximately 2.6 grams per cubic centimeter). Table C lists the fibers in many typical glass fiber yarn products. Diameter and teaching volume.
例如,1公分長度之G75紗之克質量爲(π(9 χ ι〇·4/2)2)(4〇ο)(每立方公分2·6克)(ι公分長度之紗)=:6 62 χ 1〇_4克質量。對於D450紗,克質量爲1.34 X 10-4克質量。 藉由以張力計測定之阻力(克力)測量除以所試驗紗型式之 克質量,而計算每單位質量之相對阻力(”空氣噴射運輸阻 -80 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) (請先閱讀背面之注意事項再填寫本頁) -----»----訂---------線. 557286For example, the gram mass of a G75 yarn with a length of 1 cm is (π (9 χ ιο · 4/2) 2) (4〇ο) (2.6 grams per cubic centimeter) (ι cm of yarn) =: 6 62 x 10-4 g mass. For D450 yarn, the gram mass is 1.34 X 10-4 gram mass. Calculate the relative resistance per unit mass by measuring the resistance (gram force) measured by the tensiometer (gram force) divided by the gram mass of the tested yarn type ("Air Jet Transport Resistance -80-This paper standard applies to China National Standard (CNS) A4 Specifications (210 χ 297 mm) (Please read the notes on the back before filling this page) ----- »---- Order --------- line. 557286
經濟部智慧財產局員工消費合作社印製 五、發明說明(78 ) 力")。例如,對於G75紗,如果阻力之張力計測量爲 68·5,則每克質量之紗之空氣喷射運輸阻力等於68 5除以 6.62 X 1〇·4=ι〇3,474 克力。 依照以上討論之空氣噴射運輸阻力試驗方法測定,用以 形成依照本發明用於層合物之纺織織物之紗之空氣噴射運 輸阻力較佳爲每克質量之紗大於100,000克力,更佳爲範 園爲每克質量之紗100,000至400,000克力,而且甚至更佳 爲範圍爲每克質量之紗120,000至300,000克力。 本發明之織物較佳爲以適合用於電子撑體或印刷電路板 用層合物之型式纺織,如"Fabrics Around the World"所揭 示’其爲南卡州Anderson之Clark_Schwebel公司之技術公 告(1995),其特別地在此併入作爲參考。層合物可爲單向 層合物,其中各層織物中大部份之纖維、紗或股以相同之 方向定向。 例如,使用E225 E-玻璃纖維紗之非限制織物型式爲 2116型,其每5公分具有118條經紗及114條填紗(或緯 紗)(每英吋6〇條經紗及58條填紗);使用7 22 lx0 (E225 1/0)經紗及填紗,·具有0.094毫米(約0.037英忖)之公稱織 物厚度;及每平方米103.8克(每平方碼約3〇6盎司)之織 物重量(或基本重量)。使用G75 E-破璃纖維紗之織物型式 之非限制實例爲7628型,其每5公分具有87條經紗及 條填紗(每英吋44條經紗及31條填紗);使用9 68 1χ〇 1/0)經紗及填紗;具有0.173毫米(約〇〇〇68英忖)之公稱織 物厚度;及每平方米203.4克(每平方碼約6〇〇盎司)之'織 Ί l· Ί 11.-----------r---訂---------線· (請先閱讀背面之注意事項再填寫本頁) -81- 557286 經濟部智慧財產局員工消費合作社印製 A7 ——————— B7 五、發明說明(79 ) 物重量。使用D450 E-玻璃纖維紗之織物型式之非限制實 例爲1080型,其每5公分具有118條經紗及%條填紗(每 英吋60條經紗及47條填紗);使用5 u 1χ〇 (D45〇 "…經紗 及填紗;具有〇·()53毫米(約G_英忖)之公稱織物厚 度;及每平方米46.8克(每平方碼約138盎司)之織物重 量。使用D900 E·玻璃纖維紗之織物型式之非限制實例爲 106型,其每5公分具有11〇條經紗及11〇條填紗(每英吋 56條經紗及56條填紗);使用5 5 5 1χ〇 (D9〇〇 1/〇)經紗及 填紗;具有0.033毫米(約〇.〇13英吋)之公稱織物厚度;及 每平方米24·4克(每平方碼約〇72盎司)之織物重量。另 一種使用D900 Ε-玻璃纖維紗之織物型式之非限制實例爲 108型,其每5公分具有118條經紗及83條填紗(每英吋 60條經紗及47條填紗);使用5 5 5 1χ2 (D9〇〇 1/〇)經紗及 填紗;具有0.061毫米(約0.0024英吋)之公稱織物厚度; 及每平方米47.5克(每平方碼約14〇盎司)之織物重量。 使用D225與D450 E-玻璃纖維紗之織物型式之非限制實例 爲2113型,其每5公分具有118條經紗及11〇條填紗(每 英吋60條經紗及56條填紗);使用7 22 1χ〇 (D225 1/〇)經紗 及5 11 1x0 (D450 1/0)填紗;具有0 079毫米(約〇 〇〇31英忖) 之公稱織物厚度;及每平方米78.0克(每平方碼約23〇盎 司)之織物重量。使用G50與G75E-玻璃纖維紗之織物型 式之非限制實例爲7535型,其每5公分具有87條經紗及 57條填紗(每英吋44條經紗及29條填紗);使用9 68 1χ〇 (G75 1/0)經紗及9 99 1x0 (G50 1/0)填紗;具有〇 2〇1毫米 -82- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ' -- -VMLT1I.----------l·---訂---------線· (請先閱讀背面之注音?事項再填寫本頁) 557286 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(80 ) (約0.0079英吋)之公稱織物厚度;及每平方米232.3克(每 平方碼約6.85盎司)之織物重量。 這些及其他可用之織物型式规格示於IPC-EG-140 ,fSpecification for Finished Fabric Woven from Έ1 Glass for Printed Boards" , The Institute for Interconnecting and Packaging Electronic Circuits之刊物(1997年6月),其特別地在此併 入作爲參考。雖然上述織物型式使用交織紗,意圖依照本 發明製造這些或其他使用零交織紗或纺條結合或代替交織 紗之織物。 在本發明之具體實施例中,織物中之一些或全部經紗可 具有塗覆第一樹脂相容上漿組合物之纖維,而且一些或全 部填紗可具有塗覆異於第一組合物之第二樹脂相容塗層之 纖維,即,第二組合物(1)含至少一種化學地異於或在一 些形式異於第一上漿組合物之成分之成分;或(2)以異於 第一上漿組合物中所含相同成分之量之量含至少一種成 分0 現在參考圖7 ,藉由以基質材料塗覆及/或浸潰,較佳 爲聚合膜形成熱塑性或熱固性基質材料716,織物712可 用以形成複合物或層合物714。複合物或層合物714適合 作爲電子撑體。在此使用之”電子撑體”表示機械地支撑及 /或電交連元件之結構。實例包括但不限於,主動電子組 件、被動電子組件、印刷電路、積體電路、半導體裝置, 及其他結合此種元件之硬體,其包括但不限於,連接器、 插槽、扣夾及散熱器。 -83 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) Ί M l· T ^--·-----------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) /ΖδΟ Α7 Β7 五、發明說明() 本發明之較佳且體音益Α丨μ 少-w 關於強化複合物,其包含至 0n gj Λ ^ . 纖維I郅份塗覆纖維股。本發 明因此思圖馬由各所揭示句冬夕 >fP il ^ ^ 〇 >f,! 4 + 〇夕個纖維之纖維股製造之強 化複5物例如,本發明之較佳且體眚# 八铷 f4甘併 /、恤實施例係關於強化複 合物,其包含基質材料及至少一 薄嫉維FF甘冬a 個匕含夕個纖維之部份塗 覆纖維版,其塗層包含有機成 ^ . ^ ^ } t 乂刀及,、有在3〇〇K之溫度爲 每未K至少1瓦之導熱度之薄平顆粒。 本發明之另—個較佳具體實施例係關於強化複合物,其 包含⑷包含多個纖維之至少 1切地塗覆 < 纖維股,其塗 層包含至少一個薄平顆粒,及(b)基質材料。 本發明之另一個較佳具體實施例係關於強化複合物,其 包含⑷包含多個玻璃纖維之至少部份地塗覆之纖維股, 其塗層包含水性組合物殘渣,其包含⑴多個由選自有機材 料、無機聚合材料、複合材料及其混合物之材料形成之不 連續顆t,(11)至 > -種異於該多個不連續顆粒之潤滑材 料;及(iii)至少一種膜形成材料;及(b)基質材料。 本發明之另一個較佳具體實施例係關於強化複合物,其 包含至少一個纖維股及基質材料,其中強化複合物更包含 水性組合物殘渣,其包含(a)多個由選自有機材料、無機 聚合材料、複合材料及其混合物之材料形成之不連續顆 粒;(b)至少一種異於該多個不連續顆粒之潤滑材料;及(c) 至少一種膜形成材料。 本發明之另一個較佳具體實施例係關於強化複合物,其 包含⑷包含多個玻璃纖維之至少部份地塗覆之纖維股, 84- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) Ί M l· ,Ί ^--.-----------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 557286 經濟部智慧財產局員工消費合作社印製 A7 ----21____ 五、發明說明(82 ) 其塗層包含水性組合物殘渣,其包含基於總固體爲大於 2〇重量❶/。之不連續顆粒,此顆粒具有不超過至少一個該玻 璃纖維之莫氏硬度値之莫氏硬度値;及(b)基質材料。 本發明之另一個較佳具體實施例係關於強化複合物,其 包含至少一個包含多個玻璃纖維之纖維股及基質材料,其 中強化複合物更包含水性組合物殘渣,其包含基於總固體 爲大於20重量%之不連續顆粒,此顆粒具有不超過至少 —個該玻璃纖維之莫氏硬度値之莫氏硬度値。 本發明之額外具體實施例係關於強化複合物,其包含⑷ 至少一個包含多個玻璃纖維之纖維股,此股塗層包含多個 由選自有機材料、無機聚合材料、複合材料及其混^物之 材料形成I不連續顆粒之樹脂相容組合物,其中不連續顆 粒具有小於5微米之平均粒度;及⑻基質材料。特別 地,多個不連續顆粒由選自以上任何之不可熱膨脹有機材 料、無機聚合材料、不可熱膨脹複合材料、及其混合物之 材料形成。 用於以上有關強化複合物之具體實施例之塗層與樹脂相 容組合物之成分可選自以上討論之塗層成分,而且另外^ 成分亦可選自上列者。 用於本發明之較佳基質材料包括熱固性材料,如熱固性 聚酯、乙晞酯、環氧化物(在分子中含至少一個環氧基或 環氧乙烷基,如多羥基醇或硫醇之聚縮水甘油醚)、酚 系、胺基塑料、熱固性聚胺基甲酸酯、以上任何之衍生 物、及以上任何之混合物。形成用於印刷電路板之層合物 ^度適用中國國家標準(CNS)A4規格(210 X 297公髮)" ---------— (請先閱讀背面之注意事項再填寫本頁) ---I---- 訂--------線▲ 557286 A7 B7 五、發明說明(83 ) (請先閱讀背面之注意事項再填寫本頁) 之較佳基質材料爲FR-4環氧基樹脂(其爲如二官能基溴化 環氧樹脂多官能基環氧樹脂)、聚醯亞胺及液晶聚合物, 此種組合物對熟悉此技藝者爲已知的。如果需要有關此種 組合物之進一步資訊,參見 Electronic Materials Handbook™, ASM International (1989)第534-537頁,其特別在此併入作 爲參考。 適合之聚合熱塑性基質材料之非限制實例包括聚烯烴、 聚醯胺、熱塑性聚胺基甲酸酯與熱塑性聚酯、乙烯聚合 物、及以上任何之混合物。可用熱塑性材料之其他實例包 括聚醯亞胺、聚醚颯、聚苯基颯、聚醚酮、聚伸苯基氧化 物、聚伸苯基硫化物、聚縮醛、聚氣乙烯、及聚碳酸酯。 較佳之基質材料配方包括EPON 1120-A80環氧樹脂(商 業得自德州Houston之Shell Chemical公司)、二氰二酸胺、 2-甲基咪唑、及DOWANOL PM乙二醇乙醚(商業得自密西 根州 Midland 之 The Dow Chemical 公司)。 經濟部智慧財產局員工消費合作社印製 複合物中之聚合基質材料及強化材料可包括之其他成分 包括著色劑或顏料、潤滑劑或處理助劑、紫外光(UV)安定 劑、抗氧化劑、其他之填料及掺和劑。在較佳具體實施例 中,聚合基質材料包括無機材料。這些無機材料包括陶瓷 材料及金屬材料,而且可選自以上詳述之無機材料。 織物712可藉由將織物712浸於聚合基質材料716之浴 中而塗覆及浸潰,例如,如R. Tummala (編者)之 Microelectronics Packaging Handbook. (1989)第 895-896 頁所討 論,其特別地在此併入作爲參考。更常爲,以手或任合自 -86 - 尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 經濟部智慧財產局員工消費合作社印製 A7 五、發明說明(84 ) 動進料或混合裝置將短切或連續纖維股強化材料分散於基 資材料中’其將強化材料大致均句地分布於全部聚合基質 材料。例如,可藉由同時或循序地乾燥換合所有之成分, 而將強化材料分散於聚合基質材料。 視如所使職合基質材料之型式之因素而《,可藉許多 種万法將聚合基質材料716及股形成複合物或層合物 714 。例如,對熱固性基質材料,複合物可藉壓縮或注射 模塑、粉碎、纖絲捲繞、手動堆疊、噴灑、或藉板片模塑 或容積模塑繼而壓縮或注射模塑而形成。熱固性聚合基質 材料可藉由,例如,基質材料中包括交聯劑及/或應用熱 而硬化。用以交聯聚合基質材料之適合交聯劑如以上所討 論。熱固性聚合基質材料之溫度及硬化時間視例如但不限 於所使用聚合基質材料、基質系統中之其他添加劑、及複 合物厚度之因素而定。 對於熱塑性基質材料,形成複合物之適合方法包括直接 模塑或擠製複合繼而注射模塑。藉以上方法形成複合物之 方法及裝置討論於 I. Rubin 之 Handbook of Plastic Materials Sail^chnology mQO)竿 955-1062,1179-1215 及 1225-1271 頁,其特別地在此併入作爲參考。 本發明之額外具體實施例係關於適合用於電子撑體之強 化層合物,其包含至少部份地塗覆之織物,其包含至少一 個以上詳述之纖維股。因此,本發明意圖爲由各所揭示包 含至少一個纖維股之織物製造之適合用於電子撑體之強化 層合物。例如,本發明之較佳具體實施例係關於適合用於 -87 - 本、4張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) Ί. -ΊΊ 0M.--------訂---------線 j (請先閱讀背面之注意事項再填寫本頁) 557286 A7 ----—______ 五、發明說明(85 ) (請先閱讀背面之注意事項再填寫本頁) 電子撑體之強化層合物,其包含基質材料及至少一種包含 至少一個纖維股之部份地塗覆之織物,此塗層包含有機成 分及具有在300K之溫度爲每米K至少1瓦之導熱度之薄 平顆粒。在其他具體實施例中,塗層與適合用於電子撑體 之強化層合物中之基質材料相容。 本發明之額外具體實施例係關於適合用於電子撑體之強 化層合物,此層合物包含⑷基質材料,及⑻至少一種包 含至少一個纖維股之未脱脂織物,至少一種織物之至少一 郅份具有塗層,其與適合用於該電子撑體之該強化層合物 中之基質材料相容。本發明之另一個具體實施例係關於適 合用於電子撑體之強化層合物,此層合物包含⑷基質材 料,及(b)至少一種包含至少一個纖維股且在織物之至少 一邵份表面上具有未修整樹脂相容塗層組合物之織物。 經濟部智慧財產局員工消費合作社印製 在此使用之,,未脱脂織物”爲未進行自織物去除非樹脂相 容上漿材料之習知纖維處理之織物。如以上所討論,除了 洗滌,熱清除及水噴射清洗爲此種習知纖維處理之實例。 在此使用之未修整樹脂相容塗層組合物指未在習知纖維 修整過程中使用之以上討論之樹脂相容塗層組合物。例 如,未修整樹脂相容塗層組合物指以上討論之第一、第二 及/或第三塗層組合物,但是不指典型修整上衆料,例 如,㈣燒偶合劑與水所製造,並且在脱脂後塗佈於纖維 者。然而,本發明確實意圖使塗層包含具有修整上衆料塗 佈於塗層之依照本發明之樹脂相容塗層。 本發明之另一個具體實施例係關於形成用於電子撑體應 -88· 本紙張尺度適用中國國豕標4 (U%M4規格(21〇 X 297公£7 557286 A7Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of Invention (78) Power "). For example, for a G75 yarn, if the resistance tensiometer measures 68 · 5, the air jet transport resistance per gram of mass of yarn is equal to 68 5 divided by 6.62 X 10.4 · ι = 3,474 grams of force. Measured in accordance with the air jet transport resistance test method discussed above, the air jet transport resistance used to form the yarn for the textile fabric used in the laminate according to the present invention is preferably greater than 100,000 grams of force per gram of yarn, more preferably The circle is 100,000 to 400,000 gram-force per gram of yarn, and even more preferably ranges from 120,000 to 300,000 gram-force per gram of yarn. The fabric of the present invention is preferably woven with a type suitable for an electronic support or a laminate for a printed circuit board, as disclosed in "Fabrics Around the World", which is a technical bulletin of Clark_Schwebel Company of Anderson, South Carolina ( 1995), which is specifically incorporated herein by reference. The laminate may be a unidirectional laminate in which most of the fibers, yarns or strands in each layer of fabric are oriented in the same direction. For example, the unrestricted fabric type using E225 E-glass fiber yarn is type 2116, which has 118 warp yarns and 114 filling yarns (or weft yarns) every 5 cm (60 warp yarns and 58 filling yarns per inch); Using 7 22 lx0 (E225 1/0) warp and filling yarns, with a nominal fabric thickness of 0.094 mm (about 0.037 inches); and a fabric weight of 103.8 grams per square meter (about 3.06 ounces per square yard) ( Or basis weight). A non-limiting example of a fabric type using G75 E-broken fiber yarn is type 7628, which has 87 warp and fillets per 5 cm (44 warp and 31 fillets per inch); use 9 68 1χ〇 1/0) warp and filling yarn; a nominal fabric thickness of 0.173 mm (approximately 0.0068 inches); and a 'woven fabric l · Ί 11 of 203.4 grams per square meter (approximately 600 ounces per square yard) 11 .----------- r --- Order --------- Line · (Please read the notes on the back before filling this page) -81- 557286 Intellectual Property Bureau of the Ministry of Economic Affairs Printed by employee consumer cooperative A7 ——————— B7 V. Description of invention (79) Material weight. A non-limiting example of a fabric type using D450 E-glass fiber yarn is the 1080 type, which has 118 warp yarns and% fill yarns per 5 cm (60 warp yarns and 47 fill yarns per inch); use 5 u 1 × 〇 (D45〇 " ... warp and filling yarn; has a nominal fabric thickness of 53 mm (about G_English); and a fabric weight of 46.8 grams per square meter (about 138 ounces per square yard). Use D900 E. Non-limiting example of the fabric type of glass fiber yarn is 106 type, which has 110 warp yarns and 110 filling yarns every 5 cm (56 warp yarns and 56 filling yarns per inch); use 5 5 5 1χ 〇 (D9〇〇1 / 〇) warp and filling; a nominal fabric thickness of 0.033 mm (about 0.013 inches); and a fabric of 24.4 grams per square meter (about 72 ounces per square yard) Weight. Another non-limiting example of a fabric type using D900 E-glass fiber yarn is type 108, which has 118 warp yarns and 83 filling yarns per 5 cm (60 warp yarns and 47 filling yarns per inch); use 5 5 5 1χ2 (D9〇1 / 1 /) warp and filling yarn; has a nominal fabric thickness of 0.061 mm (about 0.0024 inches) And a fabric weight of 47.5 grams per square meter (approximately 14 ounces per square yard). A non-limiting example of a fabric type using D225 and D450 E-glass fiber yarn is type 2113, which has 118 warps and 11 per 5 cm. Filling yarn (60 warp yarns and 56 filling yarns per inch); filling with 7 22 1x〇 (D225 1 / 〇) warp and 5 11 1x0 (D450 1/0); with 0 079 mm (approximately 0.00) 〇31 inch) the nominal fabric thickness; and 78.0 grams per square meter (approximately 23 ounces per square yard) fabric weight. A non-limiting example of the fabric type using G50 and G75E-glass fiber yarn is 7535 type, each 5 cm with 87 warp yarns and 57 filling yarns (44 warp yarns and 29 filling yarns per inch); 9 68 1x〇 (G75 1/0) warp yarns and 9 99 1x0 (G50 1/0) yarn fillings; With 〇2〇1 mm-82- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) '--VMLT1I .---------- l · --- Order --------- Line · (Please read the note on the back? Matters before filling out this page) 557286 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (80) (about 0.0079 British ) The nominal fabric thickness; and 232.3 grams per square meter (approximately 6.85 ounces per square yard) fabric weight. These and other available fabric type specifications are shown in IPC-EG-140, fSpecification for Finished Fabric Woven from Έ1 Glass for Printed Boards ", The Institute for Interconnecting and Packaging Electronic Circuits (June 1997), which is specifically incorporated herein by reference. Although the above-mentioned fabric patterns use interlaced yarns, it is intended to make these or other fabrics that use zero-interlaced yarns or spunbonds to combine or replace interlaced yarns in accordance with the present invention. In a specific embodiment of the present invention, some or all of the warp yarns in the fabric may have fibers coated with the first resin-compatible sizing composition, and some or all of the filling yarns may have a coating different from the first composition. Two resin-compatible coating fibers, that is, the second composition (1) contains at least one component that is chemically different from or in some forms different from the first sizing composition; or (2) is different from the first composition The sizing composition contains at least one component in an amount equal to the amount of the same component. Referring now to FIG. 7, by coating and / or impregnating with a matrix material, preferably a polymeric film, a thermoplastic or thermosetting matrix material is formed. 712 may be used to form a composite or laminate 714. The complex or laminate 714 is suitable as an electron support. As used herein, "electronic support" refers to a structure that mechanically supports and / or electrically cross-links an element. Examples include, but are not limited to, active electronic components, passive electronic components, printed circuits, integrated circuits, semiconductor devices, and other hardware incorporating such components, including, but not limited to, connectors, sockets, clips, and heat sinks Device. -83-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Ί M l · T ^-· ----------- r --- order --- ------ Line (please read the precautions on the back before filling this page) / ZδΟ Α7 Β7 V. Description of the invention () The invention is better and the body sound benefits A 丨 μ less -w Regarding the strengthening compound, It contains up to 0n gj Λ ^. Fiber I coated fiber strands. Therefore, the present invention is therefore a reinforced compound made of the fiber strands of the disclosed winter eve > fP il ^ ^ ^ > f ,! 4 + 〇 eve fibers. For example, the present invention is better and the body # The Hachiman f4 Gan and / or shirt embodiment is about a reinforced composite, which includes a matrix material and at least one thin FF Gandong a coated portion containing fiber and a fiber plate, and the coating includes an organic compound ^. ^ ^} t trowel and thin flat particles with a thermal conductivity of at least 1 watt per K at a temperature of 300K. Another preferred embodiment of the present invention relates to a reinforced composite comprising at least one cut coated with a plurality of fibers and a fiber strand whose coating includes at least one thin flat particle, and (b) Matrix material. Another preferred embodiment of the present invention relates to a reinforced composite comprising at least partially coated fiber strands comprising a plurality of glass fibers, a coating comprising a residue of an aqueous composition comprising a plurality of Discontinuous particles t formed from materials selected from organic materials, inorganic polymeric materials, composite materials and mixtures thereof, (11) to >-a lubricating material different from the plurality of discontinuous particles; and (iii) at least one film Forming material; and (b) a matrix material. Another preferred embodiment of the present invention relates to a reinforced composite, which comprises at least one fiber strand and a matrix material, wherein the reinforced composite further comprises a residue of an aqueous composition, which comprises (a) a plurality of selected from organic materials, Discontinuous particles formed from materials of inorganic polymeric materials, composite materials, and mixtures thereof; (b) at least one lubricant material different from the plurality of discontinuous particles; and (c) at least one film-forming material. Another preferred embodiment of the present invention relates to a reinforced composite, which includes at least partially coated fiber strands containing a plurality of glass fibers. 84- This paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 public love) Ί M l ·, Ί ^ --.----------- r --- order --------- line (please read the precautions on the back first) Refill this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ---- 21____ V. Description of the Invention (82) The coating contains residues of water-based composition, which contains It is greater than 20% by weight based on total solids. Discontinuous particles, the particles having a Mohs hardness 値 of at least one of the glass fibers; and (b) a matrix material. Another preferred embodiment of the present invention relates to a reinforced composite comprising at least one fiber strand and a matrix material comprising a plurality of glass fibers, wherein the reinforced composite further comprises a residue of an aqueous composition, which comprises greater than 20% by weight of discontinuous particles, the particles having no more than at least one Mohs hardness 値 of the glass fiber. An additional specific embodiment of the present invention relates to a reinforced composite, which comprises: at least one fiber strand comprising a plurality of glass fibers, and the coating of the strand comprises a plurality of elements selected from the group consisting of organic materials, inorganic polymeric materials, composite materials, and mixtures thereof. The material of the material forms a resin compatible composition of discontinuous particles, wherein the discontinuous particles have an average particle size of less than 5 microns; and ⑻ matrix material. In particular, the plurality of discontinuous particles are formed of a material selected from any of the non-thermally expandable organic materials, inorganic polymeric materials, non-thermally expandable composite materials, and mixtures thereof. The components of the coating and resin-compatible composition used in the above specific embodiments of the reinforced composite may be selected from the coating components discussed above, and the components may also be selected from those listed above. Preferred matrix materials for use in the present invention include thermosetting materials such as thermosetting polyesters, acetoyl esters, epoxides (containing at least one epoxy or ethylene oxide group in the molecule, such as polyhydric alcohols or thiols). Polyglycidyl ether), phenolic, amino-based plastics, thermosetting polyurethanes, any of the above derivatives, and mixtures of any of the above. Form the laminate for printed circuit boards. Applicable to China National Standard (CNS) A4 specification (210 X 297). &Quot; ---------— (Please read the precautions on the back before filling This page) --- I ---- Order -------- Line ▲ 557286 A7 B7 V. Description of the invention (83) (Please read the precautions on the back before filling this page) It is FR-4 epoxy resin (which is a multifunctional epoxy resin such as a difunctional brominated epoxy resin), polyimide, and a liquid crystal polymer. Such compositions are known to those skilled in the art . If further information on such a composition is required, see Electronic Materials Handbook ™, ASM International (1989) pages 534-537, which are specifically incorporated herein by reference. Non-limiting examples of suitable polymeric thermoplastic matrix materials include polyolefins, polyamides, thermoplastic polyurethanes and thermoplastic polyesters, ethylene polymers, and mixtures of any of the foregoing. Other examples of useful thermoplastic materials include polyimide, polyether, polyphenylene, polyether ketone, polyphenylene oxide, polyphenylene sulfide, polyacetal, polyethylene gas, and polycarbonate. ester. Preferred matrix material formulations include EPON 1120-A80 epoxy resin (commercially available from Shell Chemical Company, Houston, Texas), dicyandiamide, 2-methylimidazole, and DOWANOL PM glycol ether (commercially available from Michigan) The Dow Chemical Company, Midland, PA). The polymer matrix materials and reinforcing materials in the printed consumer composites of the Intellectual Property Bureau of the Ministry of Economic Affairs may include other ingredients including colorants or pigments, lubricants or processing aids, ultraviolet stabilizers, antioxidants, other Fillers and admixtures. In a preferred embodiment, the polymeric matrix material includes an inorganic material. These inorganic materials include ceramic materials and metallic materials, and may be selected from the inorganic materials detailed above. Fabric 712 can be coated and impregnated by dipping fabric 712 in a bath of polymeric matrix material 716, for example, as discussed in Microelectronics Packaging Handbook. (1989) at R. Tummala (eds.), Pages 895-896, which Specifically incorporated herein by reference. More often, use hand or renhe from -86-the scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 557286 printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of invention (84) The feeding or mixing device disperses the chopped or continuous fiber strand reinforcement material in the base material, which distributes the reinforcement material substantially uniformly throughout the polymeric matrix material. For example, the reinforcing material can be dispersed in the polymeric matrix material by drying and compounding all the ingredients simultaneously or sequentially. Depending on the type of matrix material employed, the polymeric matrix material 716 and strands can be formed into a composite or laminate 714 by many methods. For example, for a thermoset matrix material, the composite may be formed by compression or injection molding, pulverization, filament winding, manual stacking, spraying, or by sheet molding or volume molding followed by compression or injection molding. The thermosetting polymeric matrix material can be hardened, for example, by including a cross-linking agent in the matrix material and / or applying heat. Suitable cross-linking agents for cross-linking polymeric matrix materials are discussed above. The temperature and curing time of the thermosetting polymeric matrix material will depend on factors such as, but not limited to, the polymeric matrix material used, other additives in the matrix system, and the thickness of the compound. For thermoplastic matrix materials, suitable methods for forming composites include direct molding or extrusion composites followed by injection molding. Methods and devices for forming composites by the above methods are discussed in I. Rubin's Handbook of Plastic Materials Sail ^ chnology mQO) rods 955-1062, 1179-1215, and 1225-1271, which are specifically incorporated herein by reference. An additional embodiment of the present invention pertains to a reinforced laminate suitable for use in an electronic support, which comprises an at least partially coated fabric, which comprises at least one fiber strand as detailed above. Accordingly, the present invention is intended to be a reinforced laminate suitable for an electronic support made from each of the disclosed fabrics containing at least one fiber strand. For example, the preferred embodiment of the present invention relates to -87-this, four-sheet scale applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Ί. -ΊΊ 0M .----- --- Order --------- line j (please read the notes on the back before filling out this page) 557286 A7 --------______ 5. Description of the invention (85) (Please read the notes on the back first Please fill in this page again) The reinforced laminate of electronic support, which contains matrix material and at least one partially coated fabric containing at least one fiber strand, this coating contains organic ingredients and has a temperature of 300K per Mi K is a thin flat particle with a thermal conductivity of at least 1 watt. In other embodiments, the coating is compatible with a matrix material suitable for use in a reinforcing laminate for an electronic support. An additional embodiment of the present invention relates to a reinforcing laminate suitable for use in an electronic support, the laminate comprising a rhenium matrix material, and at least one non-defatted fabric comprising at least one fiber strand, at least one of the at least one fabric The compound has a coating that is compatible with a matrix material in the reinforcing laminate suitable for the electronic support. Another embodiment of the present invention relates to a reinforcing laminate suitable for use in an electronic support, the laminate comprising a rhenium matrix material, and (b) at least one component comprising at least one fiber strand and at least one portion of the fabric Fabric with untrimmed resin compatible coating composition on the surface. Printed for use by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, “non-fat fabric” is a fabric that has not been treated with conventional fibers from non-resin-compatible sizing materials removed from the fabric. Removal and water jet cleaning are examples of such conventional fiber treatments. The untrimmed resin-compatible coating composition used herein refers to the resin-compatible coating composition discussed above that is not used in the conventional fiber conditioning process. For example, an untrimmed resin-compatible coating composition refers to the first, second, and / or third coating compositions discussed above, but does not refer to the typical trimming materials, such as those made with a calcined coupling agent and water, And it is applied to the fiber after degreasing. However, the present invention does intend to make the coating include a resin-compatible coating according to the present invention with a trimming material applied to the coating. Another embodiment of the present invention is About the formation of electronic support should be -88 · This paper size is applicable to China National Standard 4 (U% M4 specification (21〇X 297K £ 7 557286 A7)
五、發明說明(89 ) 經濟部智慧財產局員工消費合作社印製 一起而形成電子撑體。 在更佳具體實施例中’至少一種織物及至少一種基質在 電子撑體中形成第一複合物層。在另一個更佳具體實施例 中,電子撑體更包含異於第一複合物層之第二複合物層。 額外較佳具體實施例係關於電子電路板,其包含⑷電 子撑體’其包含⑴至少一種包含至少一個纖維股之未脱脂 織物,至少一種未脱脂織物之至少一部份具有基質材料相 容之塗層,及(ii)在電子撑體中至少一種織物之至少一部 份上<至少一種基質材料;及(b)導電層,撑體及導電層 含於電子電路板中。 額外較佳具體實施例係關於電子電路板,其包含(a)電 子撑體’其包含⑴至少一種包含至少一個纖維股且在纖物 之至少一部份表面上具有未修整樹脂相容塗層組合物之織 物’及(11)在電子撑體中至少一種織物之至少一部份上之 至少一種基質材料;及⑻導電層,撑體及導電層含於電 子電路板中。 在更佳具體實施例中,相鄰電子撑體之選擇部份安置導 電層。在另一個更佳具體實施例中,至少一種織物及至少 一種基質形成第一複合物層。在另一個具體實施例中,電 子撑體更包含異於第一複合物層之第二複合物層。較佳 爲,相鄰電子撑體之第一及/或第二複合物層之選擇部份 安置導電層〇 77 本發明之另一個具體實施例係關於形成印刷電路板之方 法’此方法包含步驟: 本紙週用中國國家標準(CNS)A4巧各⑽χ挪公$---- (請先閱讀背面之注意事項再填寫本頁} -L? 訂---------線- 557286 A7 五、發明說明(9〇 ) 至Γ1 藉:織動至少一個包含多個纖維之填紗而且在 ::個填紗之至少一部份上具有第一樹脂相容塗層,及 一二―個包含多個纖維之經紗而且在至少—個經紗之至少 -郅份上具有第二樹脂相容塗層,而形成之包本 :導電層及至少一種適合強化電子撑體之織物之電子撑 月这 , :將電子撑體之一或更多個導電層至少之—圖樣化以 形成印刷電路板。 用於以上關於電子撑體與電子電路板之具體實施例之塗 層之成分可選自以上討論之成分,而且另外之成分亦可選 自下列者。 如果需要,可藉此技藝已知之任何方便之方法,其包括 但不限於機械鑽洞與雷射鑽洞,在電子撑體中形成穿孔或 孔(吓稱爲”通路”),以使電子撑體相反表面之電路及/或 組件之間電交連。更特別地,參考圖10,穿孔1060延伸 通過本發明電子撑體1054之織物1012之至少一層1062。 織物1012包含經塗覆纖維股,其包含多個具有與各種聚 合基質材料相容之層之玻璃纖維,如在此所敎示。在形成 穿孔1060時,電子撑體ι〇54置於穿孔形成裝置中,如鑽 錐1064或雷射頭。藉由使用鑽錐1064或雷射形成通過織 物1012之至少一層1062之一部份1066之穿孔1060。 在較佳具體實施例中,在使用0.46毫米(0.018英吋)直 控碳化轉鑽頭,以每平方公分62個洞(每平方英吋400個 洞)之洞密度及〇 〇〇1之板片負載,通過3個層合物之堆疊 (請先閱讀背面之注意事項再填寫本頁)V. Description of Invention (89) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs to form an electronic support. In a more preferred embodiment, 'at least one fabric and at least one matrix form a first composite layer in an electronic support. In another preferred embodiment, the electronic support further includes a second composite layer different from the first composite layer. An additional preferred embodiment relates to an electronic circuit board, which includes an "electron support" that includes at least one non-defatted fabric containing at least one fiber strand, and at least a portion of the at least one non-defatted fabric has a matrix material compatible A coating, and (ii) < at least one matrix material on at least a portion of at least one fabric in the electronic support; and (b) a conductive layer, the support and the conductive layer being contained in an electronic circuit board. An additional preferred embodiment relates to an electronic circuit board that includes (a) an electronic support, which includes: at least one containing at least one fiber strand and having an unmodified resin compatible coating on at least a portion of the surface of the fiber The fabric of the composition 'and (11) at least one matrix material on at least a part of at least one of the fabrics in the electronic support; and ⑻ the conductive layer, the support and the conductive layer are contained in an electronic circuit board. In a more preferred embodiment, a conductive layer is disposed in a selected portion of an adjacent electronic support. In another more preferred embodiment, at least one fabric and at least one matrix form a first composite layer. In another embodiment, the electronic support further includes a second composite layer different from the first composite layer. Preferably, a conductive layer is disposed on a selected part of the first and / or second composite layer of the adjacent electronic support. Another specific embodiment of the present invention relates to a method for forming a printed circuit board. The method includes steps. : This paper uses Chinese National Standards (CNS) A4 for each week. $ ---- (Please read the precautions on the back before filling this page} -L? Order --------- line-557286 A7 V. Description of the invention (90) to Γ1 By: weaving at least one filling yarn containing a plurality of fibers and having a first resin-compatible coating on at least a part of the: filling yarns, and one or two- A warp yarn comprising a plurality of fibers and having a second resin-compatible coating on at least one part of at least one warp yarn, resulting in an envelope: a conductive layer and at least one electronic support for a fabric suitable for reinforcing an electronic support Here, at least one of the conductive layers of the electronic support is patterned to form a printed circuit board. The components of the coating used in the above specific embodiments of the electronic support and the electronic circuit board may be selected from the above The ingredients in question, and other ingredients can be selected from the following: If necessary, any convenient method known in the art can be used, including but not limited to mechanical drilling and laser drilling, to form a perforation or hole in the electronic support (scarcely called a "channel") to make the electronic support Electrical connections between circuits and / or components on opposite surfaces. More specifically, referring to FIG. 10, perforations 1060 extend through at least one layer 1062 of fabric 1012 of electronic support 1054 of the present invention. Fabric 1012 includes a coated fiber strand comprising Multiple glass fibers with layers compatible with various polymeric matrix materials, as shown here. When forming the perforation 1060, the electronic support ι54 is placed in a perforation forming device, such as a drill cone 1064 or a laser head By forming a perforation 1060 through a portion 1066 of at least one layer 1062 of the fabric 1012 by using a drill cone 1064 or laser. In a preferred embodiment, using a 0.46 mm (0.018 inch) direct-controlled carbonized drill bit With a hole density of 62 holes per square centimeter (400 holes per square inch) and a plate load of 001, pass through a stack of 3 laminates (please read the precautions on the back before filling this page)
-1®^--------訂---------線 I 經濟部智慧財產局員工消費合作社印製-1® ^ -------- Order --------- line I Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs
557286 A7 五、發明說明(91 鑽2000個孔之後,層合物具有不大於36微米之誤差距 離。在額外具體實施例中,在使用〇 46亳米(〇 〇18英吋) (請先閱讀背面之注意事項再填寫本頁) 直徑碳化鎢鑽頭,以每平方公分62個洞(每平方英吋4〇〇 個洞)之孔密度及〇·〇〇1之板片負載,通過3個層合物之堆 疊鑽2000個孔之後,層合物具有不大於32%之鑽具磨耗 % 〇 在其他具體實施例中,將包含無機潤滑劑之流體流分配 在牙孔形成裝置附近’使得無機潤滑劑接觸穿孔形成裝置 與電子撑體間之至少一部份界面。較佳爲,無機潤滑劑選 自以上詳述之無機潤滑劑。 本發明之另一個具體實施例係關於形成通過電子電路板 用電子系統撑體織物層之穿孔之方法,其包含: (1) 安置電子系統撑體,其包含織物層(其包含在織物之 至少一邵份表面上包含樹脂相容塗層組合物之經塗覆纖維 股)之一部份,其中以穿孔形成裝置形成穿孔;及 (2) 在織物之層部份形成穿孔。 經濟部智慧財產局員工消費合作社印製 在形成穿孔後,將一層導電材料沈積在穿孔壁或以導電 材料充填穿孔,以利於電子撑體1054表面上之一或更多 個導電層(在圖10中未示)間之所需電交連及/或熱散逸。 通路部份地通過或完全通過電子撑體及/或印刷電路板而 延伸’其可在電子撑體及/或印刷電路板之一或兩個表面 暴露,或者其可完全隱藏或含於電子撑體及/或印刷電路 板内("隱藏通路π )。 圖8所示之導電層82〇可藉熟悉此技藝者已知之任何方 •94- 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 χ 297公釐) 557286 A7 B7 五、發明說明(93 ) 層合物之樹脂含量較佳爲範圍爲35至80重量%,而且 更佳爲40至75重量%。層合物中之織物量較佳爲範園爲 20至65重量%,而且更佳爲25至60重量%。 對於由纺織E·玻璃織物及使用具有110 °C之最低玻璃轉 移溫度之FR-4環氧樹脂基質形成之層合物,依照IPC-4101 "Specification for Base Materials for Rigid and Multilayer Printed Boards"第 20 頁,The Institute for Interconnecting and Packaging Electronic Circuits 之刊物( 1997 年 12 月),橫越機 器或寬度方向(大致垂直織物之縱軸,即,在充填方向)之 較佳最小撓性強度大於3 X 107公斤/平方米,更佳爲大於 3.52 X 107公斤/平方米(約50 kpsi),而且甚至更佳爲大 於,4·9 X 107公斤/平方米(約70 kpsi)。IPC-4101特別地 在此併入作爲參考。在長度方向,在長度方向(大致平行 織物之縱軸,即,在經紗方向)之所需最小撓性強度較佳 爲大於4 X 107公斤/平方米,而且更佳爲大於4.23 X 107 公斤/平方米。撓性強度依照ASTM D-790及IPC-TM-650 Test Methods Manual of the Institute for Interconnecting and Packaging Electronic Circuits ( 1994 年 12 月)測量(其特別地 在此併入作爲參考),而且藉由依照IPC_4101之3.8.2.4部 份完全地去除金屬護面。本發明之電子撑體之優點包括高 撓性強度(張力及壓縮強度)及高模數,其可減少電路板 (包括層合物)之變形。 依照IPC試驗方法2.4.4.1 (其特別地在此併入作爲參 考),本發明之銅護面FR-4環氧基層合物形式之電子撑體 •96- 尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -1®^--------訂---------線▲ 經濟部智慧財產局員工消費合作社印製 557286 A7 B7_______ 五、發明說明(94 ) 較佳爲在層合物之ζ_方向("Z_CTE。,即,橫越層合物之厚 度’具有至5〇 °C至288 Ό爲0.01至5.0重量❶/。之熱膨脹係 數。各此種層合物較佳爲含八層7628型織物,雖然或可 使用例如但不限於1〇6、1〇8、1〇80、2113 、2116或 7535型織物之型式。此外,層合物可加入這些織物型式之 組合。具有低熱膨脹係數之層合物通常較不易膨脹及收縮 且可使板歪曲最小。 本發明更意圖爲多層層合物及電子電路板之製造,其包 括至少一個依照在此之敎示製造之複合物層,及至少一個 以異於在此敎示之複合物層之方法製造之複合物層,例 如’使用習知玻璃纖維複合物技術。更特別地及如熟悉此 技藝者所已知,傳統上,以包括部份或全部糊精化澱粉或 直鏈澱粉、氫化蔬菜油、陽離子性濕潤劑、乳化劑及水之 殿粉/油上衆料’其包括但不限於Loewenstein第237-244頁 (第3版,1993 )中所揭示者,其特別地在此併入作爲參 考’處理用於織動織物之連續玻璃纖維股中之纖維。然後 在織動前以溶液處理由這些股製造之經紗以保護股防止在 織動過程時磨損,例如,聚(乙晞醇),如美國專利 4,530,876第3欄,第67行至第4攔,第11行所揭示,其 特別地在此併入作爲參考。此操作通常稱爲漿紗。聚(乙 烯醇)及澱粉/油上漿料通常不與複合物製造者使用之聚合 基質材料相容,因此清除織物以在浸潰纺織織物之前自玻 璃纖維表面去除本質上所有之有機材料。其可以許多方式 完成,例如,藉由洗滌織物,或更常爲藉由以此技藝已知 •97- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) --------訂---------線一 經濟部智慧財產局員工消費合作社印製 557286 A7 五、發明說明(97 ) 法包含:⑴將至少-種以上詳細討論之第―、第二及/或 第三塗層組合物(其包含在股之相鄰纖維間提供間隙” 之顆粒)塗佈於纖維股強化材料,(2)乾燥塗層以在強化材 料上形成塗層;(3)組合強化材料與基質材料;及⑷至少 部份地硬化基質材料以提供強化複合物。雖然不限制本發 明,強化材料可組合聚合基質材料,例如,藉由將其分散 在基質材料中。較佳爲,塗層在乾燥時在強化材料上形成 實質上均勻塗層。在本發明之非限制具體實施例中,顆粒 包含基於總固體爲至少2〇重量%之上裝組合物。在另_ 個非限制具體實施例中,顆粒具有至少3微米,而且較佳 爲至少5微米之最小平均顆粒尺寸。在其他之非限制具 實施例中’顆粒具有小於任何含於纖維股之玻璃纖維之 氏硬度値之莫氏硬度値。 本發明亦包括抑制纖維股之相鄭纖維間之黏附之方法 其包含步驟:⑴將至少一種以上詳細討論之第一、第 及/或第三塗層組合物(其包含在股之相鄰纖維間提供間 空間之顆粒)塗佈於纖維股,⑺乾燥塗層以在纖維股之驟 維上形成塗層’使得抑制股之相鄰纖維間之黏附。較佳 爲,塗層在㈣時在強化材料上㈣實質上均勾塗層。 本發明之非限制具體實施例中,顆粒包含基於總固體爲 V 20重量/〇之上漿組合物。在另一個非限制具體實施 中,顆粒具有至少3微I,而且較佳爲i少$微米之最τ 平均顆粒尺寸。例如,在球形顆粒,最小平均顆粒尺寸相 ^於顆粒直徑。例如,在長方形顆粒,最小平均顆粒尺寸 扣平句顆粒之長度、寬度或咼度。在其他之非限制具體實 體 莫 隙 纖 在 至 例 小 (請先閱讀背面之注意事項再填寫本頁)557286 A7 V. Description of the invention (91 After 2000 holes are drilled, the laminate has an error distance of not more than 36 microns. In additional specific embodiments, when using 046 mm (0018 inches) (please read first Note on the back, please fill in this page again) Diameter tungsten carbide drill, pass through 3 layers with a hole density of 62 holes per square centimeter (400 holes per square inch) and a plate load of 0.001 After 2,000 holes are drilled in the stack of the composite, the laminate has a drill tool abrasion% of not more than 32%. In other specific embodiments, the fluid flow containing the inorganic lubricant is distributed near the perforation forming device. The agent contacts at least a part of the interface between the perforation forming device and the electronic support. Preferably, the inorganic lubricant is selected from the inorganic lubricants detailed above. Another embodiment of the present invention relates to the use of an electronic circuit board. A method of perforating a fabric layer of an electronic system support, comprising: (1) arranging an electronic system support including a fabric layer (which includes a coated coating comprising a resin-compatible coating composition on at least one surface of the fabric; Fiber-covered strands), in which perforations are formed by perforation forming devices; and (2) perforations are formed in the fabric layer. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs after the perforation is formed, a layer of conductive material is deposited The perforation wall or the perforation is filled with a conductive material to facilitate the required electrical cross-linking and / or heat dissipation between one or more conductive layers (not shown in Figure 10) on the surface of the electronic support 1054. The path is partially Extending through or completely through the electronic support and / or the printed circuit board 'it may be exposed on one or both surfaces of the electronic support and / or the printed circuit board, or it may be completely hidden or contained in the electronic support and / or Inside the printed circuit board (" hidden path π). The conductive layer 820 shown in Fig. 8 can be obtained by anyone who is familiar with this technique. 94- This paper size applies the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm) 557286 A7 B7 V. Description of the invention (93) The resin content of the laminate is preferably in the range of 35 to 80% by weight, and more preferably 40 to 75% by weight. The amount of fabric in the laminate is better For Fan Yuan is 20 to 65% by weight, It is more preferably 25 to 60% by weight. For a laminate formed of a woven E · glass fabric and a FR-4 epoxy resin matrix having a minimum glass transition temperature of 110 ° C, it is in accordance with IPC-4101 " Specification for Base Materials for Rigid and Multilayer Printed Boards " page 20, The Institute for Interconnecting and Packaging Electronic Circuits publication (December 1997), traversing the machine or width direction (generally vertical to the longitudinal axis of the fabric, i.e. in the filling direction) The preferred minimum flexural strength is greater than 3 X 107 kg / m2, more preferably greater than 3.52 X 107 kg / m2 (about 50 kpsi), and even more preferably greater than, 4 · 9 X 107 kg / m2 ( About 70 kpsi). IPC-4101 is specifically incorporated herein by reference. In the longitudinal direction, the required minimum flexural strength in the longitudinal direction (generally parallel to the longitudinal axis of the fabric, that is, in the warp direction) is preferably greater than 4 X 107 kg / m2, and more preferably greater than 4.23 X 107 kg / Square meters. Flexural strength is measured in accordance with ASTM D-790 and IPC-TM-650 Test Methods Manual of the Institute for Interconnecting and Packaging Electronic Circuits (December 1994) (which is specifically incorporated herein by reference), and by following IPC_4101 Section 3.8.2.4 completely removes the metal finish. The advantages of the electronic support of the present invention include high flexural strength (tensile and compressive strength) and high modulus, which can reduce the deformation of the circuit board (including the laminate). According to the IPC test method 2.4.4.1 (which is specifically incorporated herein by reference), the electronic support of the FR-4 epoxy-based laminate of the copper surface of the present invention is 96-scale applicable to China National Standard (CNS) A4 Specifications (210 X 297 mm) (Please read the precautions on the back before filling this page) -1® ^ -------- Order --------- line ▲ Intellectual Property Bureau, Ministry of Economic Affairs Printed by the employee consumer cooperative 557286 A7 B7_______ 5. The description of the invention (94) is preferably in the z_ direction of the laminate (" Z_CTE.), That is, the thickness across the laminate 'has to 50 ° C to 288 Ό is a thermal expansion coefficient of 0.01 to 5.0 weight ❶ /. Each such laminate is preferably a 7628 type fabric containing eight layers, although or can be used, for example but not limited to 106, 108, 1080, 2113 , 2116, or 7535 fabric types. In addition, laminates can be added to the combination of these fabric types. Laminates with a low thermal expansion coefficient are generally less susceptible to expansion and shrinkage and minimize board distortion. The present invention is more intended as a multilayer layer And electronic circuit boards, including at least one composite layer manufactured in accordance with the instructions herein, and A composite layer made in a method different from the composite layer shown here, such as' using conventional glass fiber composite technology. More specifically and as known to those skilled in the art, traditionally, Part or all of dextrinized starch or amylose, hydrogenated vegetable oil, cationic humectant, emulsifier, and water powder / oil on ingredients' which include but are not limited to Loewenstein pp. 237-244 (3rd edition, As disclosed in 1993), which is specifically incorporated herein by reference for the treatment of fibers in continuous glass fiber strands for weaving fabrics. Warp yarns made from these strands are then treated with a solution to protect the strands from weaving before weaving Wear during the weaving process, for example, poly (acetol), as disclosed in U.S. Patent 4,530,876, column 3, lines 67 through 4, and line 11, which is specifically incorporated herein by reference. This operation Commonly referred to as sizing. Poly (vinyl alcohol) and starch / oil sizing are generally not compatible with the polymeric matrix materials used by the composite maker, so the fabric is removed to remove essentially the surface of the glass fiber before impregnating the textile fabric all Organic materials. It can be done in many ways, for example, by washing fabrics, or more often by this technique. • 97- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) ( Please read the precautions on the back before filling this page) -------- Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 V. Description of Invention (97 The method includes: (i) coating at least one of the first, second, and / or third coating compositions discussed in detail above (which includes particles that provide gaps between adjacent fibers of the strand) to a fiber strand reinforcing material (2) drying the coating to form a coating on the reinforcing material; (3) combining the reinforcing material with a matrix material; and (ii) at least partially hardening the matrix material to provide a reinforced composite. Although not limiting the invention, the reinforcing material may be combined with a polymeric matrix material, for example, by dispersing it in the matrix material. Preferably, the coating forms a substantially uniform coating on the reinforcing material when dried. In a non-limiting specific embodiment of the present invention, the particles comprise at least 20% by weight of the coating composition based on total solids. In another non-limiting embodiment, the particles have a minimum average particle size of at least 3 microns, and preferably at least 5 microns. In other non-limiting examples, the particles have a Mohs hardness 小于 smaller than the hardness 値 of any glass fiber contained in the fiber strand. The present invention also includes a method for inhibiting adhesion between fiber strands and fibers. The method includes the steps of: ⑴ at least one of the first, first, and / or third coating compositions discussed in detail above, which are included in adjacent fibers of the strand Particles that provide interspaces) are applied to the fiber strands, and the coating is dried to form a coating on the fiber strand's dimension so as to inhibit adhesion between adjacent fibers of the strands. Preferably, the coating is substantially uniformly coated on the reinforcing material at the time of the coating. In a non-limiting specific embodiment of the present invention, the particles comprise a sizing composition of V 20 weight /% based on total solids. In another non-limiting embodiment, the particles have a minimum average particle size of at least 3 micrometers, and preferably i less than $ micrometers. For example, in spherical particles, the smallest average particle size is relative to the particle diameter. For example, in rectangular particles, the minimum average particle size is the length, width, or length of the particles. In other non-restricted concrete entities, Mo Gap fiber is small to small (please read the precautions on the back before filling this page)
--------訂---------線I L_______-loo- 本紙張尺度適用中關家標準(CNS)A4規格⑵G χ撕公羞y 五、發明說明(98 ) 施例中,顆粒具有小於任何含於纖維股之破璃纖維之莫氏 硬度値之莫氏硬度値。 本發明亦包括抑制纖維強化複合物之基質材料水解之方 法。此方法包含:(1)將至少一種以上詳細討論之第一、 第二及/或第三塗層組合物(其包含基於總固體爲大於20 重量%之不連續顆粒)塗佈於纖維股強化材料,(幻乾燥塗 層以在強化材料上形成塗層;(3)組合強化材料與基質材 料;及(4)至少部份地硬化基質材料以提供強化複合物。 較佳爲,塗層在乾燥時在強化材料上形成實質上均句塗 層。如以上所討論,強化材料可藉由,例如,將強化材料 分散於基質材料中而組合基質材料。 在本發明之非限制具體實施例中,織物較佳爲紡織成 7628型織物且具有每分鐘小於1〇立方英呎,而且更佳爲 每分鐘小於5立方英呎之透氣力,如ASTMD 737紡織織 物透氣力之標準試驗方法所測量。雖然在本發明中不限 制,比較使用漿紗經紗製造之多種習知織物,據信本發明 之經紗之伸長橫切面及高股開放性(以下詳細討論)降低本 發明織物之透氣力。 經濟部智慧財產局員工消費合作社印製 如前所討論,在電子撑體應用之習知織動操作中,經紗 一般在織動前塗覆漿紗上漿料,以助於防止經紗在織動過 程時黏附。漿紗上漿組合物一般藉由通過使經紗通過含漿 紗上漿料之浸盤或浴,然後通過一或更多組擠壓輥以去除 任何過量之材料,而塗佈於經紗。典型漿紗上漿組合物可 包括,例如,膜形成材料、塑性劑及潤滑劑。常用於漿紗 -101 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7-------- Order --------- Line I L _______- loo- This paper size is applicable to Zhongguanjia Standard (CNS) A4 specifications ⑵G χ tear public shame y 5. Description of the invention (98) In the embodiment, the particles have a Mohs hardness 小于 smaller than the Mohs hardness 値 of any glass-breaking fiber contained in the fiber strand. The invention also includes a method for inhibiting the hydrolysis of the matrix material of the fiber-reinforced composite. This method comprises: (1) applying at least one of the first, second, and / or third coating compositions discussed in detail above (which contains discontinuous particles greater than 20% by weight based on total solids) to fiber strand reinforcement (3) drying the coating to form a coating on the reinforcing material; (3) combining the reinforcing material with a matrix material; and (4) at least partially hardening the matrix material to provide a reinforcing composite. Preferably, the coating is on A substantially uniform coating is formed on the reinforcing material upon drying. As discussed above, the reinforcing material can be combined with the matrix material by, for example, dispersing the reinforcing material in the matrix material. In a non-limiting embodiment of the present invention The fabric is preferably woven into a 7628-type fabric and has an air permeability of less than 10 cubic feet per minute, and more preferably less than 5 cubic feet per minute, as measured by the ASTMD 737 standard test method for air permeability of textile fabrics. Although not limited in the present invention, comparing various conventional fabrics made using sizing warp yarns, it is believed that the elongation cross-section and high openness of the warp yarns of the present invention are reduced (discussed in detail below) The breathability of the fabric of the present invention. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. As previously discussed, in the conventional weaving operation of the electronic support application, the warp yarn is generally coated with sizing on the sizing yarn before weaving. Helps prevent warp yarns from sticking during weaving. Sizing sizing compositions typically remove any excess by passing the warp yarns through a dipping tray or bath containing the sizing of the sizing yarn and then through one or more sets of squeeze rollers And sizing. Typical sizing composition can include, for example, film-forming materials, plasticizers, and lubricants. Commonly used in sizing-101-This paper applies Chinese National Standard (CNS) A4 (210 X 297 mm) 557286 A7
五、發明說明(l〇1 ) 經濟部智慧財產局員工消費合作社印製 面”表示經紗具有大致平坦或橢圓形橫切面形狀。以上討 論之高股開放性指紗或股之個別纖維未緊密地保持在一 起,而且在一或更多個個別纖維間之開放空間利於基質材 料穿透至束中之特徵。漿紗之經紗(如以上所討論)通常具 有圓形橫切面及低股開放性,因此不利於此穿透。雖然在 本發明中不限制,據信藉由降低或排除水份進入層合物與 電子撑體中之路徑,在層合時良好之樹脂穿透至經紗束中 (即,良好之樹脂濕透)可改良依照本發明製造之層合物與 電子撑體之總水解安定力。其對於降低由此種層合物與電 子撑體製造之印刷電路板由於在暴露於潮濕條件時,在偏 壓下形成導電性陽極纖絲而呈現電短路失敗之趨勢,亦可 具有正面影響。 股之開放性程度可由F-指數試驗測量。在f-指數試驗 中’被測量之紗通過一系列垂直對齊之輥,而且相鄰包含 發光表面與相反之感光表面之水平配置感應裝置而安置, 使得紗之垂直軸大致平行對齊發光及感光表面。感應裝置 安裝在使其大約爲垂直對齊輥之間一半之垂直高度,而且 藉由朝向或離開感應裝置移動輥而控制紗與感應裝置之間 之水平距離。在紗通過輥時(一般爲每分鐘約3〇米),视 股之開放性而定,紗之一或更多個部份可遮蔽來自發光表 面之光之一部份,因而觸發感光裝置中之反應。然後對特 定紗長度(一般爲約10米)將遮蔽數量作表,而且生成比 例(即’每單位長度之遮蔽數量)視爲股開放性之測度。 據仏來自習知漿紗玻璃纖維紗之織物之緊密經紗結構 -1^ \ -----r---訂---------線 (請先閲讀背面之注意事項再填寫本頁) -104- 557286 A7 B7 五、發明說明(I〇2) : = 放性(如以上所討論),造成這些習知織物具 有比本發明較佳織物(較佳爲包括長 ' 〈經紗開放性)之透氣力古夕p丄 /濟切面及較呵 且體實施合I Φ j, ^透乳力。在本發明之非限制 物且有每^^ ASTMDW標準試驗方法所測量,織 ==方英…於10標準立― =….05標準立方米),更佳爲每 不大於5立方英吸(每分鐘每平方米152標準立方^ 分鐘每平方英…於3立方英吸(每分鐘每 且^施^1標準立方米)之透氣力。在本發明之另-個 二7 ==將織物纺織成型織物,而且如 D 737 &準試驗方法所測 訂 於H)炉進士、仗]量I有每分鐘每平方英吸不大 :w "尺’更佳爲每分鐘每平方英吸不大於5 最佳爲每分鐘每平方英^大於3立方英 、^然不表示受任何特定理論限制或以任何方式限制,兹 王張具有長形或平均橫切面之經紗亦 物製造之層合物中改良鐵鋼性能。更特別地,由二^ 2二織物中之經紗與填紗間交又點具有比加人 :^料切面經紗之習知織物低之外形,料織物之錯 七在鐵用時接觸極少之玻璃纖維,因而發生較少之 2前所討論’在本發明之具體實施财,較佳爲經紗與填 紗均具有在形成時塗佈之樹脂相容第—塗層組合物。塗佈 =紗之樹脂相容第-塗層組合物可與塗佈填紗之樹脂相 谷弟一塗層組合物相同,或者其可異於塗佈於填紗之樹脂 L______- 105 - 本紙張尺度適财關¥鮮(CNS)A4祕⑽ 557286 經濟部智慧財產局員工消費合作社印製 A7 —------sz________ 五、發明說明(103) "一"" — 相容第-塗層组合物。在此參考塗佈於經紗之樹脂相容第 -塗層組合物使用之名詞·,異於塗佈於填紗之樹脂相容第 -塗層組合物"表示,塗佈於經紗之第—塗層組合物之至 少一種成分以異於塗佈於填紗之第—塗層組合物之量存 在,或者塗佈於經紗之第一塗層组合物之至少一種成分不 存f於塗佈於填紗之第—塗層组合物中,或者塗佈於填紗 ^ m合物之至少-種成分不存在於塗佈於經紗之 第一塗層組合物中。 在本發明之另一個非限制具體實施例中,織物之紗之破 璃纖維爲具有每立方公分小於26〇克之密度之E_玻璃纖 維。在另-個非限制具體實施例中,在纺織成爲⑽型 織物時,E-玻璃纖維紗製造具有大於同型習知熱清除與 修整織物之強度(經紗方向)之平行經紗方向張力強度之織 物。在本發明之另一個非限制具體實施例中,較佳爲,^ 脂相容第一塗層組合物實質上無"膠黏狀"膜形成材料, 即,第一塗層組合物包含較佳爲基於總固體小於ι〇重量 % ’更佳爲基於總固體小於5重量%。 在較佳具體實施例中,樹脂相容第一塗層組合物本質上 無”膠黏狀”膜形成材料,即,第一塗層組合物包含較佳爲 基於總固體小於1重量%,更佳爲基於總固體小於〇5重 量%,而且最佳爲基於總固體小於〇1重量%之膠黏狀膜 形成材料。膠黏狀膜形成材料如因降低填紗之空氣噴射運 輸力及造成經紗彼此黏附,而對其所塗佈之紗之織動力爲 有害的。膠黏狀膜形成材料之特定非限制實例爲水溶性環 :丨--^ ,1,--,-----------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁} -106 - 557286 A7 B7 五、發明說明(106)V. Description of the Invention (101) The printed surface of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs "indicates that the warp yarn has a substantially flat or oval cross-section shape. The open fibers of the high-stranded yarns discussed above are not tightly individual fibers Keep together, and the open space between one or more individual fibers facilitates the penetration of the matrix material into the bundle. The warp of the sizing yarn (as discussed above) usually has a circular cross section and low openness, It is therefore not conducive to this penetration. Although not limited in the present invention, it is believed that by reducing or excluding the path of moisture entering the laminate and the electronic support, a good resin penetrates into the warp bundle during lamination ( That is, good resin penetration) can improve the total hydrolytic stability of the laminates and electronic supports manufactured in accordance with the present invention. It is useful for reducing the printed circuit boards manufactured from such laminates and electronic supports due to exposure to Under humid conditions, the formation of conductive anode filaments under a bias voltage and the tendency of electrical short circuit failure can also have a positive effect. The degree of openness of the strand can be measured by the F-index test. In the f-finger In the test, the yarn to be measured was placed through a series of vertically aligned rollers, and a horizontally arranged sensing device adjacent to the light emitting surface and the opposite photosensitive surface was arranged so that the vertical axis of the yarn was aligned substantially parallel to the light emitting and photosensitive surface. The horizontal distance between the yarn and the sensing device is controlled by making it approximately half the vertical height between the vertically aligned rollers, and by moving the roller toward or away from the sensing device. As the yarn passes through the roller (generally about 3 per minute) M), depending on the openness of the strand, one or more parts of the yarn can shield a part of the light from the light-emitting surface, thus triggering the reaction in the photosensitive device. Then for a specific yarn length (generally about 10 M) The number of masks is used as a table, and the generated ratio (ie, the number of masks per unit length) is regarded as a measure of the openness of the strand. According to the tight warp structure of the fabric from the conventional sizing glass fiber yarn-1 ^ \- ---- r --- order --------- line (please read the precautions on the back before filling this page) -104- 557286 A7 B7 V. Description of Invention (I〇2): = Put Sex (as discussed above), As a result, these conventional fabrics have better breathability than the fabrics of the present invention (preferably including long '<warp yarn openness), and good elasticity and permeability. In the non-restrictive material of the present invention and measured by the ASTMDW standard test method, weaving = = square British ... at 10 standard cubic-= ... .05 standard cubic meters), and more preferably not greater than 5 cubic cubic inches ( 152 standard cubic meters per square meter per minute ^ min per square inch ... breathability of 3 cubic meters per minute (^ 1 standard cubic meter per minute per minute). In another aspect of the present invention 7 == weaving fabric Molded fabric, and as measured by D 737 & quasi-test method set in H) furnace jinshi, war] the amount I has a small absorption per square inch per minute: w " ruler 'is better More than 5 The best is more than 3 cubic inches per square inch per minute. ^ However, it does not mean that it is limited by any particular theory or in any way. Wang Zhang has a long or average cross section of the warp yarn laminate. Improved iron steel performance. More specifically, the intersecting point between the warp yarns and the filling yarns in the two fabrics has a lower shape than that of the conventional fabrics: the material cuts the warp yarns with a cut surface, and the material fabrics have the least contact with glass when used in iron. The fiber, therefore, occurs less frequently as discussed in the foregoing. In the present invention, it is preferred that both the warp yarn and the filling yarn have a resin-compatible first coating composition applied during formation. The coating-compatible resin-coating composition of the yarn can be the same as the coating composition of the resin phase of the yarn filling, or it can be different from the resin of the yarn filling. L ______- 105-This paper Standards for Financial Affairs ¥ Fresh (CNS) A4 Secret 557286 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 —-------- sz________ V. Invention Description (103) " 一 " " — Compatible with -Coating composition. Reference is made here to the term used in the resin-compatible coating-coating composition coated on the warp yarn, which is different from the resin-compatible coating-coating composition coated on the warp yarn- " At least one component of the coating composition is present in an amount different from the first coating composition applied to the filling yarn, or at least one component of the first coating composition applied to the warp yarn is not present in the applied In the first coating composition of the yarn filling, or at least one component applied to the yarn filling composition is not present in the first coating composition applied to the warp yarn. In another non-limiting embodiment of the present invention, the glass fiber of the yarn of the fabric is an E-glass fiber having a density of less than 26 grams per cubic centimeter. In another non-limiting embodiment, when woven into a loop-type fabric, E-glass fiber yarns are made of fabrics having parallel warp direction tensile strength greater than the strength (warp direction) of conventional heat-clearing and trimming fabrics of the same type. In another non-limiting embodiment of the present invention, it is preferable that the fat-compatible first coating composition is substantially free of " adhesive " film-forming material, that is, the first coating composition includes It is preferably less than 10% by weight based on total solids, more preferably less than 5% by weight based on total solids. In a preferred embodiment, the resin-compatible first coating composition is essentially free of an "adhesive" film-forming material, that is, the first coating composition preferably contains less than 1% by weight based on total solids, more It is preferably less than 0.05% by weight based on total solids, and most preferably less than 0.01% by weight based on total solids. Adhesive film-forming materials are harmful to the weaving power of the coated yarns because they reduce the air jet transport force of the yarn filling and cause the warp yarns to stick to each other. A specific, non-limiting example of an adhesive film-forming material is a water-soluble ring: 丨-^, 1,-, ----------- r --- order -------- -Line (Please read the precautions on the back before filling this page} -106-557286 A7 B7 V. Description of the invention (106)
表1A 基於總固體之成分重量% 樣品 成分 A B C D E F RD-847A97 28.6 29.1 31.58 50.71 0 0 DESMOPHEN200098 43.7 39.1 0 0 0 0 EPI-REZ 3522-W-66" 0 0 21.05 0 0 0 EPON 826100 0 0 0 0 16.12 63.54 PVP-K30101 0 9.7 15.79 15.21 1.31 5.18 A-187102 2.3 2.3 8.42 8.11 3.17 12.51 A-174103 4.7 4.8 0 0 0 0 A-1100104 0 0 8.42 8.11 0 0 PLURONIC F-108105 10.7 5.6 0 0 0 0 IGEPAL CA-630106 0 0 4.74 6.39 1.63 6.44 VERSAMTD 140107 4.8 4.8 0 0 0 0 ALKAMULS EL-719108 0 0 0 0 1.63 6.44 KESSCO PEG 600109 0 0 0 0 0.79 3.11 MACOL NP-6110 3.6 3.6 4.74 6.39 0 0 RD-847A聚酯樹脂,其商業得自俄亥俄州Columbus之 (請先閱讀背面之注意事項再填寫本頁) 準 標 家 國 國 中 用 適 度 尺 張 紙 本 經濟部智慧財產局員工消費合作社印製Table 1A Ingredients% by weight based on total solids Sample composition ABCDEF RD-847A97 28.6 29.1 31.58 50.71 0 0 DESMOPHEN200098 43.7 39.1 0 0 0 0 EPI-REZ 3522-W-66 " 0 0 21.05 0 0 0 EPON 826100 0 0 0 0 16.12 63.54 PVP-K30101 0 9.7 15.79 15.21 1.31 5.18 A-187102 2.3 2.3 8.42 8.11 3.17 12.51 A-174103 4.7 4.8 0 0 0 0 A-1100104 0 0 8.42 8.11 0 0 PLURONIC F-108105 10.7 5.6 0 0 0 0 IGEPAL CA- 630106 0 0 4.74 6.39 1.63 6.44 VERSAMTD 140107 4.8 4.8 0 0 0 0 ALKAMULS EL-719108 0 0 0 0 1.63 6.44 KESSCO PEG 600109 0 0 0 0 0.79 3.11 MACOL NP-6110 3.6 3.6 4.74 6.39 0 0 RD-847A polyester resin , Its business was obtained from Columbus, Ohio (Please read the notes on the back before filling out this page) Printed on a moderately large piece of paper on a standard paper printed by the employee ’s consumer cooperative of the Ministry of Economy ’s Intellectual Property Bureau
Borden Chemicals 公司 0 98 DESMOPHEN 2000聚己二酸伸乙酯二醇,其商業得自賓州 Pittsburgh 之 Bayer 公司。 99 EPI-REZ 3522-W-66 其商業得自德州 Houston 之 Shell Chemical 公司0 -109 - 格 規 A4 S) (210 χ 297 公釐) 經濟部智慧財產局員工消費合作社印製 557286 A7 B7 五、發明說明(107) 100 EPON 826,其商業得自德州 Houston 之 Shell Chemical 公 司。 1G1 PVP-K30聚乙烯基吡咯啶酮,其商業得自紐澤西州 Wayne 之 ISP Chemicals 公司0 102 Α-187 γ-去水甘油基丙基三甲氧基矽烷,其商業得自紐約 州 Tarrytown 之 CK Witco 公司。 ιω Α-174 γ-甲基丙烯氧基丙基三甲氧基矽烷,其商業得自紐 約州 Tarrytown 之 CK Witco 公司。 1G4 A-1100胺基官能基有機矽烷偶合劑,其商業得自紐約州 Tarrytown 之 CK Witco 公司。 1G5 PLURONIC™ F-108聚氧化丙烯-聚氧化乙烯共聚物,其商 業得自紐澤西州Parsippany之BASF公司。 1G0 IGEPAL CA-630乙氧化辛基苯氧基乙醇,其商業得自紐澤 西州Wayne之GAF公司0 1G7 VERSAMID 140聚醯胺,其商業得自俄亥俄州Cincinnati之 Cognis 公司 ° 1G8 ALKAMULS EL-719聚氧化乙烯化蔬菜油,其商業得自 Phone_Poulenc 公司 〇 1G9KESSCO PEG 600聚乙二醇單月桂酸酯,其商業得自伊利锘 州芝加哥之Stepan公司。 11G MACOL NP_6壬酚界面活性劑,其商業得自紐澤西州 Parsippany 之 BASF 公司。 -no- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 一丨丨—-rul------------r---訂---------線# (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 557286 A7 B7 五、發明說明(108) 表1A (續) 莘於總固體之成分重量% 樣品 成分 A B c D E F EMERY 6717111 0 0 0 0 0.40 1.56 EMERY 6760112 0 0 4.21 4.06 0 0 POLYOX WSR-301113 0.6 0 0 0 0 0 POLARTHERM PT 160114 1.0 1.0 0 0 74.78 1.00 RELEASECOAT-CONC 25115 0 0 1.05 1.01 0 0 111 EMERY® 6717部分醯胺化聚伸乙二亞胺,其商業得自俄 亥俄州Cincinnati之Cognis公司。 112 EMERY® 6760潤滑劑,其商業得自俄亥俄州Cincinnati 之Cognis公司 。 113 POLYOX WSR-301聚(環氧乙烷),其商業得自康乃迪克 州 Danbury 之 Union Carbide 公司 0 114 POLARTHERM® PT 160氮化硼粉末顆粒,其商業得自俄 亥俄州 Lakewood 之 Advanced Ceramics 公司。 115 ORPAC BORON NITRIDE RELEASECOAT-CONC 25 氮化硼 顆粒於水性分散液中,其商業得自田納西州Oak Ridge之 ZYP Coatings 公司。 亦評估經商業產品631與633 D-450塗覆澱粉-油之紗; 經690與695塗覆澱粉·油之紗,及1383 G-75紗之比較性 樣品,其商業得自PPG Industries公司。此外,亦試驗各塗 覆以下表IB所述之相同水性形成組合物X之三個比較性 -111 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 丨 ^--\1,-------------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7 五、發明說明(1〇9) (請先閱讀背面之注意事項再填寫本頁) 樣品XI、X2與X3。比較性樣品XI具有2.5重量%之固 體。比較性樣品X2具有4.9重量%之固體並且在25 °C風 乾約8小時。比較性樣品X3具有4.6重量%之固體。Borden Chemicals Corporation 0 98 DESMOPHEN 2000 polyethylene adipate glycol, commercially available from Bayer Company, Pittsburgh, PA. 99 EPI-REZ 3522-W-66 Commercially available from Shell Chemical Company of Houston, Texas 0-109-G4 A4 S) (210 χ 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 B7 V. Description of the Invention (107) 100 EPON 826, commercially available from Shell Chemical, Houston, Texas. 1G1 PVP-K30 polyvinylpyrrolidone, commercially available from ISP Chemicals, Inc., Wayne, New Jersey 0 102 A-187 γ-dehydroglycerylpropyltrimethoxysilane, commercially available from Tarrytown, New York CK Witco. ιω A-174 γ-methacryloxypropyltrimethoxysilane, commercially available from CK Witco Corporation, Tarrytown, New York. 1G4 A-1100 amine-functional organosilane coupling agent, commercially available from CK Witco, Tarrytown, New York. 1G5 PLURONIC ™ F-108 polyoxypropylene-polyethylene oxide copolymer is commercially available from BASF Corporation, Parsippany, New Jersey. 1G0 IGEPAL CA-630 ethoxylated octylphenoxyethanol, commercially available from GAF Corporation of Wayne, New Jersey 0 1G7 VERSAMID 140 polyamine, commercially available from Cognis Corporation of Cincinnati, Ohio ° 1G8 ALKAMULS EL-719 Polyoxyethylated vegetable oil, which is commercially available from Phone_Poulenc, Inc. 01G9KESSCO PEG 600 polyethylene glycol monolaurate, and is commercially available from Stepan, Chicago, Ill. 11G MACOL NP_6 Nonyl Surfactant, commercially available from BASF Corporation, Parsippany, New Jersey. -no- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). 丨 丨 —-rul ------------ r --- order ----- ---- 线 # (Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 B7 V. Description of the invention (108) Table 1A (continued) Composition of total solids Weight% Sample Composition AB c DEF EMERY 6717111 0 0 0 0 0.40 1.56 EMERY 6760112 0 0 4.21 4.06 0 0 POLYOX WSR-301113 0.6 0 0 0 0 0 POLARTHERM PT 160114 1.0 1.0 0 0 74.78 1.00 RELEASECOAT-CONC 25115 0 0 1.05 1.01 0 0 111 EMERY® 6717 partially fluorinated poly (ethylene diimide), commercially available from Cognis Corporation of Cincinnati, Ohio. 112 EMERY® 6760 lubricant commercially available from Cognis Corporation of Cincinnati, Ohio. 113 POLYOX WSR-301 poly (ethylene oxide), commercially available from Union Carbide, Danbury, Connecticut 0 114 POLARTHERM® PT 160 boron nitride powder particles, commercially available from Advanced Ceramics, Lakewood, Ohio. 115 ORPAC BORON NITRIDE RELEASECOAT-CONC 25 Boron nitride particles in an aqueous dispersion commercially available from ZYP Coatings, Oak Ridge, Tennessee. Comparative samples of commercial products 631 and 633 D-450 coated starch-oil yarns; comparative samples of 690 and 695 coated starch-oil yarns, and comparative samples of 1383 G-75 yarns were also commercially available from PPG Industries. In addition, three comparisons of applying the same water-forming composition X described in Table IB below are also tested -111-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 丨 ^- \ 1, ------------- r --- Order --------- line (please read the notes on the back before filling this page) 557286 A7 B7 V. Invention Instructions (109) (Please read the notes on the back before filling out this page) Samples XI, X2 and X3. Comparative sample XI had a solids content of 2.5% by weight. Comparative sample X2 had 4.9% solids by weight and was air-dried at 25 ° C for about 8 hours. Comparative sample X3 had a solids of 4.6% by weight.
表1B 基於總固體之成分重量% 成分 樣品X RD-847A116 28.9 DESMOPHEN 2000117 44.1 A-187118 2.3 A-174119 4.8 PLURONIC F-108120 10.9 VERSAMID 140121 4.8 MACOL NP-6122 3.6 POLYOX WSR-301123 0.6 116 RD-847A聚酯樹脂,其商業得自俄亥俄州Columbus之 Borden Chemicals 公司。 經濟部智慧財產局員工消費合作社印製 117 DESMOPHEN 2000聚己二酸伸乙酯二醇,其商業得自賓 州 Pittsburgh 之 Bayer 公司。 118 Α-187 γ·去水甘油基丙基三甲氧基矽烷,其商業得自紐 約州 Tarrytown 之 CK Witco 公司。 119 Α-174 γ-甲基丙烯氧基丙基三甲氧基矽烷,其商業得自 紐約州Tarrytown之CK Witco公司0 12G PLURONIC™ F-108聚氧化丙烯聚氧化乙烯共聚物,其 商業得自紐澤西州Parsippany之BASF公司。 -112- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7 B7 五、發明說明(ill) 經濟部智慧財產局員工消費合作社印製 表1C 樣品號碼 紗型式 LOI (%) 阻力 (克力) 空氣噴射運輸阻力 (每克質量之克力) A G - 75 0.35 68.5 103,474 B G-75 0.30 84.9 128,248 Bvac G-75 0.35 95.0 143,587 C D-450 0.52 37.33 278,582 D D-450 0.40 47.1 351,493 E G-75 0.35 79.3 119,789 F G-75 0.35 83.2 125,680 比較性樣品 631* D-450 1.6 21.45 160,075 633* D-450 1.3 38.1 284,328 690* G-75 1.0 108.23 163,489 695* G-75 1.0 100.46 151,752 1383 G-75 0.75 14.47 21,858 XI G-75 0.33 36.4 54,985 X2 G-75 0.75 19.0 28,701 X3 D-450 1.37 12.04 89,851 Chi D-450 1.59 9.00 67,164 Cm D-450 1.66 10.43 77,836 塗覆澱粉-油之上漿配方。 如以上表1C所示,依照本發明各塗覆聚合基質材料相 -114- ------------------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7 B7 發明說明(113) 撓性強度 撓性模數 短束剪切強度 巴斯卡 psi 巴斯卡 psi 巴斯卡 psi Β 4.9 X 106 71534 2.4 X 1010 3465000 2.6 X 1〇7 3742 Bvac 5.0 X 106 72215 2.4 X 1010 3450600 2.5 X 1〇7 3647 695 4.3 X 106 62959 2.3 X 1010 3360800 2.3 X 1〇7 3264 (請先閱讀背面之注意事項再填寫本頁) liy π\ 小 '干又叫、议/双:復敬碼纖难 製備之層合物樣品時’依照本發明製備之層合物樣品B及 BVac具有較高之撓性強度與模數値及類似之短束剪切強 度。 亦藉由經一對習知張力測量裝置(其具有安裝在其間以 代替5公分來自張力測量裝置間直線路徑之約5公分(2英 吋)直徑之固定鉻柱)以每分鐘274米(300碼)之速率拉樣 ’對各紗樣品施加30克之張力,評估樣品A與B及比 較性樣品1383與XI之磨擦力。克力差敘述於以下表 IE。磨擦力試驗意圖模擬紗在織動操作時接受之磨擦力。 經濟部智慧財產局員工消費合作社印製 亦使用磨彳貝试驗器汗估樣品A與B及比較性樣品1383 與XI之破裂纖絲。在經磨損試驗裝置以每分鐘〇 46米 (18英吋)之速率拉各試驗樣品5分鐘時,對各試驗樣品施 加200克之張力,評估各樣品及比較性樣品之兩次試驗, 而且破裂纖絲數量之平均報告於以下表1E。磨損試驗器 :括兩個平行之鋼簧片歹,卜各列間隔1英吋。各試驗紗樣 品在第—歹,J簧片《兩個相鄰簧片間螺旋,然後在第二列簧 、兩個相鄰簧片間螺旋’但是在兩列簧片間位移半英吋 張 紙 本 -116- - 义適用 +^iST(CNS)A4 規格(210 X 297 公 557286 A7 B7 五、發明說明(114) 距離。簧片以每分鐘240 IS >、去f τ 蠖40圈心逮率,以平行紗橫越方向乏 i向’在4英寸長彦夹回仿孩 磨擦力(克數) 每碼之紗之破裂纖絲數哥 A B 比較性 ---^^j 比較性 樣品號碼1383 樣品號碼 24· 7 18.3 23.9 ----^ 38.1 2.0 1.0 _ 3.8 -------^ 1.0 如表1E所示,在比較比較性樣品時,依照本發明以包 含氮化硼之上漿組合物塗覆之樣品A與B具有較少之破 裂纖維及低磨擦力。 實例2 以類似以上討論之方法混合表2A中所述之量之各成 分,以形成依照本發明之上漿組合物G與S ’及比較性 樣品。在各組合物中包括基於總重量爲少於1重量%之乙 酸。 將表1A之實例1中水性形成上漿組合物E與F ’及表 2A之比較性樣品Y,塗覆於G-75 E-玻璃纖維股。各形成 上漿組合物具有6至25重量%之固體。 -—VI- -----r---訂---------線 ί請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -117- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) 557286 A7 B7 五、發明說明(ll5) 表2A 基於總固體之成分重量% 樣品 成分 G Η 比較性樣品Υ EPON 826124 16.12 63.54 60.98 PVP K-30125 1.31 5·18 4.97 ALKAMULS EL-719126 1.63 6.44 6.18 IGEPAL CA-630127 1.63 6.44 6.18 KESSCO PEG 600128 0.79 3.11 2.98 A-187129 3.17 12.51 12.00 EMERY 6717130 0.40 1.56 1.50 PROTOLUBE HD131 0 0 4.61 POLARTHERMPT 160132 0 0 0 RELEASECOAT-CONC 25133 74.78 1.00 0 (請先閱讀背面之注音?事項再填寫本頁) 124EPON 826,其商業得自德州 Houston 之 Shell Chemical 公 司0 經濟部智慧財產局員工消費合作社印製 in PVP K-30聚乙烯基吡咯啶酮,其商業得自紐澤西州 Wayne 之 ISP Chemicals 公司。 126 ALKAMULS EL_719聚氧化乙烯化蔬菜油,其商業得自 Rhone-Poulenc 公司 〇 127IGEPAL CA-630乙氧化辛基苯氧基乙醇,其商業得自紐 澤西州Wayne之GAF公司。 128 KESSCO PEG 600聚乙二醇單月桂酸酯,其商業得自伊利 #州芝加哥之Stepan公司。 • 118- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 557286 A7 B7 五、發明說明(116) 129 Α-187 γ-去水甘油基丙基三甲氧基矽烷,其商業得自紐 約州 Tarrytown 之 CK Witco 公司0 13Q EMERY® 6717部分醯胺化聚伸乙二亞胺,其商業得自俄 亥俄州Cincinnati之Cognis公司。 131 PROTOLUBE HD高密度聚乙烯乳液,其商業得自紐澤西 州 Birmingham 之 Sybron Chemicals 公司。 132 POLARTHERM® PT 160氮化硼粉末顆粒,其商業得自俄 亥俄州 Lakewood 之 Advanced Ceramics 公司。 133 ORPAC BORON NITRIDE RELEASECOAT-CONC 25 氮化硼 顆粒於水性分散液中,其商業得自田納西州Oak Ridge之 ZYP Coatings 公司。 交織各經塗覆玻璃纖維股以形成紗及使用習知交織裝置 以類似之方法捲繞在線軸上。樣品F與Η之紗在交織時呈 現最少之上漿料脱落,而且樣品Ε與G在交織時呈現嚴 重之上漿料脱落。 以類似以上實例1之方法評估樣品E-Η及比較性樣品Υ 之紗之空氣阻力,除了在表2Β所示之壓力測定兩個線軸 樣品之空氣阻力値。使用Shirley 84 041L型破裂纖絲偵測 器,其商業得自英國之SDL International公司,以每分鐘 200米評估各紗之每1200米之紗之平均破裂纖絲數量。這 些値表示在各紗之四個線軸上進行之測量之平均。由全部 線軸取得之部份(自線軸解下之136克(3/10磅)及272克 (6/10磅)之紗)報告破裂纖絲値。 亦評估各紗之閘張力,試驗敘述於以下表2B 。藉由以 -119- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 一---;--------------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7 五、發明說明(117) 200米/分鐘自線軸解下紗樣品,將紗螺旋通過一系列8個 平行陶资針,及使紗通過以上討論之Shirley破裂纖絲偵測 器以計算破裂纖絲數量,依照閘張力法測量破裂纖絲數 量° ---·;---.----------l·---訂---------線· (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -120- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7 B7 五、發明說明(118) 經濟部智慧財產局員工消費合作社印製 表2B 樣品 每米之紗之破裂纖絲數量 E F G Η 比較性樣品Υ 全部線軸 0.887 0.241 大於10 0.065 0.192 136 克(3/10 磅) 0.856 0.017 大於10 0.013 0.320 272 克(3/10 磅) 0〇676 0.030 大於10 0.101 0Λ92 閘張力(每米之髮數) 閘2 0.039 0.0235 0.721 閘3 _ 0.025 _ 0.028 0.571 閘4 0.0125 - 0.068 0.4795 閘5 0.015 0.093 0.85 閘6 - 0.0265 - 0.118 0.993 閘7 - 0.0695 一 0.31 1.0835 閘8 0.117 0.557 1.81 空氣阻力(克數) 25 psi 線軸1 10.420 10.860 11.610 線軸2 10.600 - 7.850 11.610 30 psi 線軸1 11.690 12.500 13.680 線軸2 12.200 8.540 13.850 35 psi 線軸1 13.490 14.030 15.880 線軸2 - 13.530 - 9.570 15.630 40 psi 線軸1 - 14.740 晴 14.110 17.560 線軸2 14.860 - 11.010 17.610 45 psi 線軸1 16.180 - 16.390 19.830 線轴2 16.680 12.700 18.950 50 psi 線軸1 17.510 晒 19.280 22.410 線軸2 17.730 - 14.000 20.310 55 psi 線軸1 - 19.570 - 23.350 29.350 線轴2 19.660 20.250 26.580 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) •121- -------------------r---訂---------線 i^w. (請先閱讀背面之注意事項再填寫本頁) 557286 A7 五、發明說明(119) 雖然表2B所示之試驗結果顯然顯示依照本發明之樣品 E-Η具有大致比比較品樣品γ高之耐磨損力,據信這些牡 果並非確定性的,因爲據信比較性樣品¥之聚乙缔乳液^ 分(在樣品E_H中不存在)有助於紗之磨損性質。 iiLi 混合表3A中所述之量之各成分,以形成依照本發明之 水性形成上漿組合物K至N。各水性形成上漿組合物以 類似以上討論之方法製備。在各組合物中包括基於總重量 爲少於1重量%之乙酸。 將表3A之各水性形成上漿組合物塗覆於2G-18 E_玻璃 纖維股。各形成上漿組合物具有1〇重量%之固體。 ----.--------------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -122- 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 X 297公釐) 557286 A7 B7 五、發明說明(121) 在270 °C以7 MPa (975 psi)擠製模塑48秒以製造254 X 254 X 3.175毫米(10 X 10 X 0.125英吋)之板。在以下指定之玻 璃含量評估各樣本之:依照ASTM方法D-638之張力強 度、張力伸長與張力模數;依照ASTM方法D-790之撓性 強度與能性模數;及依照ASTM方法D-256之缺口與無缺 口艾氏衝擊強度。 表3B提出在使用習知耐綸6,6基質樹脂形成之複合物 上進行之試驗結果。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 124- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7 B7 五、發明說明(122) 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 表3B 樣品 單位 K L M N 比較性樣品Z 張力強度 kpsi 27.1 27.6 27.3 27.4 26.2 MPa 186.9 190.34 188.27 188.96 180.68 張力伸長 % 3.32 3.37 3.36 3.42 3.32 張力模數 mpsi 1.48 1.55 1.47 1.44 1.51 GPa 10.2 10.7 10.1 9.9 10.4 撓性強度 kpsi 44.6 46.3 45.7 45.5 44.0 MPa 307.6 319.3 315.2 313.8 303.4 撓性模數 mpsi 1.52 1.56 1.54 1.54 1.5 GPa 10.5 10.7 10.6 10.6 10.6 缺口艾氏衝擊 ftlb/in 1.86 2.24 1.94 1.63 1.16 kJ/m2 7.89 9.50 8.23 6.91 4.92 無缺口艾氏衝擊 ft lb/in 21.8 22.9 21.1 20.5 22.0 kJ/m2 92.43 97.10 89.46 86.92 93.28 玻璃含量 _ % 32.9 32.6 32.4 32.3 32.4 如表3Β所示,在比較具有類似成分之比較性樣品(其在 ,-啊强化物中不含氮化硼)時,依照本發明以氮化硼顆 粒塗覆之破璃纖維股(樣品K-N)呈現改良之張力強度與缺 口艾氏衝擊性質,及類似之張力伸長與模數,撓性強度與 模數,及無缺口艾氏衝擊性質。在類似條件下使用耐綸 樹脂評估時,未觀察到張力強度及缺口艾氏衝擊性質 6 之改 (請先閱讀背面之注咅?事項再填寫本頁) ^紙張尺度適财目—⑽ -125- X 29「公釐)— 557286 A7 B7 五、發明說明(l23 ) 實例4 (請先閱讀背面之注意事項再填寫本頁) 混合表4A中所述之量之各成分,以形成依照本發明之 水性形成上漿組合物P至S。各水性形成上漿組合物以類 似以上討論之方法製備。在各組合物中包括基於總重量爲 少於1重量%之乙酸。 將表4A之各水性形成上漿組合物塗覆於G-31 E_玻璃纖 維股。各形成上漿組合物具有10重量%之固體。Table 1B Ingredients% by weight based on total solids Ingredient sample X RD-847A116 28.9 DESMOPHEN 2000117 44.1 A-187118 2.3 A-174119 4.8 PLURONIC F-108120 10.9 VERSAMID 140121 4.8 MACOL NP-6122 3.6 POLYOX WSR-301123 0.6 116 RD-847A polymer Ester resin, commercially available from Borden Chemicals, Columbus, Ohio. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 117 DESMOPHEN 2000 Polyethylene adipate, commercially available from Bayer Company, Pittsburgh, PA. 118 A-187 Glycerylpropyltrimethoxysilane, commercially available from CK Witco, Tarrytown, New York. 119 Α-174 γ-methacryloxypropyltrimethoxysilane, commercially available from CK Witco, Tarrytown, NY 0 12G PLURONIC ™ F-108 polyoxypropylene polyethylene oxide copolymer, commercially available from New Zealand BASF, Parsippany, Jersey. -112- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 557286 A7 B7 V. Description of Invention (ill) Printed on the 1C Sample Number Yarn Type LOI ( %) Resistance (gram force) Air jet transport resistance (gram force per gram of mass) AG-75 0.35 68.5 103,474 B G-75 0.30 84.9 128,248 Bvac G-75 0.35 95.0 143,587 C D-450 0.52 37.33 278,582 D D-450 0.40 47.1 351,493 E G-75 0.35 79.3 119,789 F G-75 0.35 83.2 125,680 Comparative sample 631 * D-450 1.6 21.45 160,075 633 * D-450 1.3 38.1 284,328 690 * G-75 1.0 108.23 163,489 695 * G-75 1.0 100.46 151,752 1383 G-75 0.75 14.47 21,858 XI G-75 0.33 36.4 54,85 X2 G-75 0.75 19.0 28,701 X3 D-450 1.37 12.04 89,851 Chi D-450 1.59 9.00 67,164 Cm D-450 1.66 10.43 77,836 coated with starch-oil Sizing formula. As shown in Table 1C above, each coated polymeric matrix material phase in accordance with the present invention is -114- ------------------ r --- order ------- --Line (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 557286 A7 B7 Description of invention (113) Flexural strength Flexural modulus Short Beam Shear Strength Baska psi Baska psi Baska psi Β 4.9 X 106 71534 2.4 X 1010 3465000 2.6 X 1〇7 3742 Bvac 5.0 X 106 72215 2.4 X 1010 3450600 2.5 X 1〇7 3647 695 4.3 X 106 62959 2.3 X 1010 3360 800 2.3 X 1〇7 3264 (please read the precautions on the back before filling this page) liy π \ Xiao'gan, also called / double / double: when it comes to the laminate sample that is difficult to prepare 'Laminate samples B and BVac prepared according to the present invention have higher flexural strength and modulus 値 and similar short beam shear strength. Also by passing a pair of conventional tension measuring devices with fixed chromium posts of about 5 cm (2 inches) in diameter installed in place of 5 cm from a straight path between the tension measuring devices at a distance of 274 meters (300 Code) Rate Pull Sample 'A tension of 30 grams was applied to each yarn sample, and the frictional forces of samples A and B and comparative samples 1383 and XI were evaluated. The acrylic force difference is described in Table IE below. The friction force test is intended to simulate the friction force that the yarn receives during weaving operations. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Also used the Moulin tester to estimate the broken filaments of samples A and B and comparative samples 1383 and XI. When each test sample was pulled at a rate of 046 meters (18 inches) per minute for 5 minutes through a wear test device, a tension of 200 g was applied to each test sample, and two tests of each sample and comparative samples were evaluated, and the fibers were broken. The average number of filaments is reported in Table 1E below. Wear tester: Includes two parallel steel reeds 歹, each row is 1 inch apart. Samples of each test yarn were spiraled between the first and second reeds, and then spiraled between the second row of springs and the two adjacent reeds, but shifted by half an inch between the two rows of reeds. Paper -116--Meaning + ^ iST (CNS) A4 specification (210 X 297 male 557286 A7 B7 V. Description of the invention (114) Distance. Reed 240 IS > per minute, go to f τ 蠖 40 circles Catch rate, in parallel to the transverse direction of the yarn, the direction of the imitated child friction force in grams of 4 inches long Yan (grams) the number of broken filaments per yard of yarn AB comparative --- ^^ j comparative sample number 1383 Sample No. 24 · 7 18.3 23.9 ---- ^ 38.1 2.0 1.0 _ 3.8 ------- ^ 1.0 As shown in Table 1E, when comparing comparative samples, according to the present invention to include boron nitride above Samples A and B coated with the pulp composition had fewer broken fibers and low friction. Example 2 A method similar to that discussed above was used to mix the ingredients in amounts described in Table 2A to form a size composition in accordance with the present invention G and S 'and comparative samples. In each composition, less than 1% by weight of acetic acid was included based on the total weight. Sizing compositions E and F 'and comparative sample Y of Table 2A were coated on G-75 E-glass fiber strands. Each sizing composition had 6 to 25% by weight solids.--VI-- ---- r --- Order --------- Line ί Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -117- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 public love) 557286 A7 B7 V. Description of invention (ll5) Table 2A Based on the total solids content by weight% Sample composition G Η Comparative sample Υ EPON 826124 16.12 63.54 60.98 PVP K-30125 1.31 5.18 4.97 ALKAMULS EL-719126 1.63 6.44 6.18 IGEPAL CA-630127 1.63 6.44 6.18 KESSCO PEG 600128 0.79 3.11 2.98 A-187129 3.17 12.51 12.00 EMERY 6717130 0.40 1.56 1.50 PROTOLUBE HD131 0 0 4.61 POLARTHERMPT 160132 0 0 RELEASECOAT- 74.78 1.00 0 (Please read the Zhuyin on the back? Please fill in this page again) 124EPON 826, commercially available from Shell Chemical Company of Houston, Texas 0 Printed by PVP K-30 Polyvinylpyrrolidone in Intellectual Property Bureau Employee Consumer Cooperative, Ministry of Economy, commercially available from New Jersey Wayne's ISP Chemicals. 126 ALKAMULS EL_719 polyoxyethylated vegetable oil, commercially available from Rhone-Poulenc Company 127 IGEPAL CA-630 ethoxylated octylphenoxyethanol, commercially available from GAF Company, Wayne, New Jersey. 128 KESSCO PEG 600 polyethylene glycol monolaurate, commercially available from Stepan Company, Chicago, Erie #. • 118- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 557286 A7 B7. 5. Description of the invention (116) 129 Α-187 γ-water removal Glycerylpropyltrimethoxysilane, which is commercially available from CK Witco, Inc. of Tarrytown, New York, 0 13Q EMERY® 6717 Partially Aminated Polyethylene Diimide, and is commercially available from Cognis, Inc. of Cincinnati, Ohio. 131 PROTOLUBE HD high density polyethylene emulsion, commercially available from Sybron Chemicals, Birmingham, New Jersey. 132 POLARTHERM® PT 160 boron nitride powder granules, commercially available from Advanced Ceramics, Lakewood, Ohio. 133 ORPAC BORON NITRIDE RELEASECOAT-CONC 25 Boron nitride particles in an aqueous dispersion, commercially available from ZYP Coatings, Oak Ridge, Tennessee. Each coated glass fiber strand is interlaced to form a yarn and wound on a bobbin in a similar manner using a conventional interlacing device. Samples F and Yarn showed minimal slurry shedding when interlaced, and samples E and G exhibited serious pulp shedding when interlaced. The air resistance of the yarns of Sample E-Η and Comparative Sample Υ was evaluated in a similar manner to Example 1 above, except that the air resistance 値 of the two bobbin samples was measured at the pressure shown in Table 2B. A Shirley 84 041L broken filament detector, commercially available from SDL International, UK, was used to evaluate the average number of broken filaments per 1200 meters of yarn at 200 meters per minute. These marks represent the average of the measurements made on the four spools of each yarn. Fractured filaments were reported from the entire spool (136 g (3/10 lb) and 272 g (6/10 lb) of yarn unwound from the spool). The brake tension of each yarn was also evaluated. The tests are described in Table 2B below. By using -119- this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1 -----; -------------- r --- order- -------- Thread (please read the precautions on the back before filling this page) 557286 A7 B7 V. Description of the invention (117) Untwist the yarn sample from the bobbin at 200 m / min, and pass the yarn spiral through a series of 8 Two parallel ceramic needles, and passing the yarn through the Shirley broken filament detector discussed above to calculate the number of broken filaments, and measure the number of broken filaments according to the brake tension method ° --- ·; ---.---- ------ l · --- Order --------- Line · (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -120- This Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 557286 A7 B7 V. Description of invention (118) Table 2B printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs per sample of broken filaments per meter of yarn EFG Η Comparative samples Υ All spools 0.887 0.241 greater than 10 0.065 0.192 136 grams (3/10 pounds) 0.856 0.017 greater than 10 0.013 0.320 272 grams (3/10 pounds) 0〇676 0.030 greater than 10 0.101 0 Λ92 Gate tension (rounds per meter) Gate 2 0.039 0.0235 0.721 Gate 3 _ 0.025 _ 0.028 0.571 Gate 4 0.0125-0.068 0.4795 Gate 5 0.015 0.093 0.85 Gate 6-0.0265-0.118 0.993 Gate 7-0.0695-0.31 1.0835 Gate 8 0.117 0.557 1.81 Air resistance (grams) 25 psi spool 1 10.420 10.860 11.610 spool 2 10.600-7.850 11.610 30 psi spool 1 11.690 12.500 13.680 spool 2 12.200 8.540 13.850 35 psi spool 1 13.490 14.030 15.880 spool 2-13.530-9.570 15.630 40 psi spool 1-14.740 Clear 14.110 17.560 Spool 2 14.860-11.010 17.610 45 psi Spool 1 16.180-16.390 19.830 Spool 2 16.680 12.700 18.950 50 psi Spool 1 17.510 Sun 19.280 22.410 Spool 2 17.730-14.000 20.310 55 psi Spool 1-19.570-23.350 29.350 Spool Axis 2 19.660 20.250 26.580 This paper size applies to China National Standard (CNS) A4 (210 χ 297 mm) • 121- ------------------- r --- Order --------- line i ^ w. (Please read the notes on the back before filling this page) 557286 A7 V. Description of the invention (119) Although The test results shown in Table 2B clearly show that the sample E-Η according to the present invention has approximately higher abrasion resistance than the comparative sample γ. It is believed that these fruits are not deterministic because it is believed that the comparative sample ¥ Ethylene emulsion ^ (not present in sample E_H) contributes to the abrasive properties of the yarn. iiLi mixes the ingredients in the amounts described in Table 3A to form the aqueous sizing compositions K to N according to the present invention. Each aqueous sizing composition is prepared in a manner similar to that discussed above. Acetic acid is included in each composition at less than 1% by weight based on the total weight. Each of the aqueous sizing compositions of Table 3A was applied to 2G-18 E_glass fiber strands. Each sizing-forming composition has 10% by weight solids. ----.-------------- r --- order --------- line (please read the notes on the back before filling this page) Printed by the Bureau of Property and Consumer Cooperatives -122- This paper size is applicable to the Chinese National Standard (CNS) A4 (21 × 297 mm) 557286 A7 B7 V. Description of the invention (121) at 270 ° C at 7 MPa (975 psi ) Extrusion molding for 48 seconds to make a 254 X 254 X 3.175 mm (10 X 10 X 0.125 inch) board. Each sample was evaluated at the glass content specified below: tensile strength, tensile elongation, and tensile modulus in accordance with ASTM method D-638; flexible strength and functional modulus in accordance with ASTM method D-790; and in accordance with ASTM method D- Notched and unnotched Izod impact strength of 256. Table 3B presents the results of tests performed on composites formed using conventional nylon 6,6 matrix resins. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 124- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 557286 A7 B7 V. Invention Explanation (122) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 3B Sample unit KLMN Comparative sample Z Tensile strength kpsi 27.1 27.6 27.3 27.4 MPa 186.9 190.34 188.27 188.96 180.68 Tensile elongation 3.32 3.37 3.36 3.42 3.32 Tensile modulus mpsi 1.48 1.55 1.47 1.44 1.51 GPa 10.2 10.7 10.1 9.9 10.4 Flexural strength kpsi 44.6 46.3 45.7 45.5 44.0 MPa 307.6 319.3 315.2 313.8 303.4 Flexible modulus mpsi 1.52 1.56 1.54 1.54 1.5 GPa 10.5 10.7 10.6 10.6 10.6 Notched Izod impact ftlb / in 1.86 2.24 2.24 1.94 1.63 1.16 kJ / m2 7.89 9.50 8.23 6.91 4.92 Unnotched Izod impact ft lb / in 21.8 22.9 21.1 20.5 22.0 kJ / m2 92.43 97.10 89.46 86.92 93.28 Glass content_% 32.9 32.6 32.4 32.3 32.4 As shown in Table 3B, in comparison Comparative samples with similar composition (which is,- When the reinforcement does not contain boron nitride, the glass-breaking fiber strand (sample KN) coated with boron nitride particles according to the present invention exhibits improved tensile strength and notched Izod impact properties, and similar tensile elongation and modulus. , Flexible strength and modulus, and notched Izod impact properties. When using nylon resin under similar conditions to evaluate, no change in tensile strength and notched Izod impact properties 6 was observed (please read the note on the back? Matters before filling out this page) ^ Paper size suitable financial item-⑽ -125 -X 29 "mm" — 557286 A7 B7 V. Description of the Invention (l23) Example 4 (Please read the notes on the back before filling out this page) Mix the ingredients in the amounts described in Table 4A to form the product according to the invention The aqueous forming sizing compositions P to S. Each aqueous forming sizing composition was prepared in a manner similar to that discussed above. Included in each composition was acetic acid based on the total weight of less than 1% by weight. The sizing compositions were coated on G-31 E-glass fiber strands. Each sizing composition had a solids content of 10% by weight.
表4A 基於總固體之成分重量% 樣品 成分 Ρ Q R S 熱塑性聚胺基甲酸酯膜形成聚合物137 23 28.75 28.75 23 熱塑性聚胺基甲酸酯膜形成聚合物138 34.45 43.1 43.1 34.45 聚氧化伸烷基多元醇共聚物 0.22 0.27 0.27 0.22 環氧化聚酯潤滑劑 4.8 6.0 6.0 4.8 γ-胺基丙基三乙氧基石夕烷偶合劑 1.84 2.3 2.3 1.84 γ·膽基丙基三乙氧基石夕烷偶合劑 2.22 2.78 2.78 2.22 胺基官能基有機矽烷偶合劑 0.1 0.12 0.12 0.1 POLARTHERMPT 160139 33.3 16.7 0 0 經濟部智慧財產局員工消費合作社印製 137熱塑性聚酯爲主聚胺基甲酸酯水性乳液,其具有65固 體%,陰離子性顆粒電荷,約2微米之粒度,7.5之pH, 及在25 °C爲400厘泊之黏度(Brookfield LVF)。 138熱塑性聚酯爲主聚胺基甲酸酯水性乳液,其具有62固 體%,約10之pH ,及範圍爲約0.8至約2.5微米之粒 -126- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)Table 4A Ingredients% by weight based on total solids Sample composition P QRS Thermoplastic polyurethane film-forming polymer 137 23 28.75 28.75 23 Thermoplastic polyurethane film-forming polymer 138 34.45 43.1 43.1 34.45 Polyoxyalkylene Polyol copolymer 0.22 0.27 0.27 0.22 Epoxidized polyester lubricant 4.8 6.0 6.0 4.8 γ-aminopropyltriethoxy petrolatum coupling agent 1.84 2.3 2.3 1.84 γ · cholylpropyl triethoxy petrolatum coupling agent 2.22 2.78 2.78 2.22 Amine-functional organosilane coupling agent 0.1 0.12 0.12 0.1 POLARTHERMPT 160 139 33.3 16.7 0 0 Printed by the Consumer Property Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs 137 thermoplastic polyester-based polyurethane emulsion, which has 65 % Solids, anionic particle charge, particle size of about 2 microns, pH of 7.5, and viscosity of 400 centipoise at 25 ° C (Brookfield LVF). 138 thermoplastic polyester-based polyurethane aqueous emulsion, which has 62% solids, a pH of about 10, and granules ranging from about 0.8 to about 2.5 microns -126- This paper size applies to Chinese National Standards (CNS) A4 size (210 X 297 mm)
557286 五、發明說明(125) 磨損材料(經研磨胡桃木樹皮顆粒6/10號,其商業得自 Hamm〇nProducts公司)、及習知泡沫型抗靜電乾燥劑片封 閉在4公升不銹鋼燒杯中,並使用Red Devil塗料搖動器 5400E3型振動6分鐘。使用5號及6號美國標準試驗筛筛 選經振動材料。以下報告在篩網上收集之細毛材料之重量 %如原始樣品之百分比。 表4B提出在使用樣品Ρ-S及比較性樣品z使用耐論6,6 基質樹脂形成之複合物上進行之試驗結果。 ---1------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製557286 5. Description of the invention (125) Abrasive material (ground walnut bark particles No. 6/10, which is commercially available from Hammon Products), and the conventional foam-type antistatic desiccant sheet are enclosed in a 4 liter stainless steel beaker, And use Red Devil paint shaker Model 5400E3 for 6 minutes. Use No. 5 and No. 6 American standard test sieve to select the vibrating material. The following reports the weight% of fine wool material collected on the screen as a percentage of the original sample. Table 4B presents the results of tests performed on composites formed using Samples P-S and Comparative Samples z using a 6,6 matrix resin. --- 1 ------------------ Order --------- line (Please read the notes on the back before filling this page) Intellectual Property of the Ministry of Economic Affairs Printed by Bureau Consumers Cooperative
557286 A7 B7 五、發明說明(ιπ) 實例5 混合表5中所述之量之各成分,以形成依照本發明之水 性形成上漿組合物Τ與U。各水性形成上漿組合物以類 似以上討論之方法製備。在各組合物中包括基於總重量爲 少於1重量%之乙酸。表5 Α提出在使用樣品Τ、U及比 較性樣品Z (如實例3之表3A中所討論且在以下重複)使 用耐綸6,6基質樹脂形成之複合物上進行之白化及黃化試 驗結果。使用Hunter比色計D25-PC2A型在具有3.175毫米 (1/8英吋)厚度及76.2毫米(3英吋)直徑之複合物上實行 顏色試驗。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 表5 基於總固體之成分重量% 樣品 成分 Τ U 比較性樣品Ζ 熱塑性聚胺基甲酸酯膜形成聚合物141 31.35 28.75 34.5 熱塑性聚胺基甲酸酯膜形成聚合物142 46.9 43.1 51.7 聚氧化伸烷基多元醇共聚物 0.3 0.27 0.3 環氧化聚酯潤滑劑 6.55 6.0 7.22 γ-胺基丙基三乙氧基秒烷偶合劑 2.5 2.3 2.76 γ-月尿基丙基三乙氧基石夕院偶合劑 3.0 2.78 3.34 胺基官能基有機矽烷偶合劑 0.1 0.12 0.14 RELEASECOAT-CONC 25143 9.1 16.7 0 白化指數 -16.3 -15.0 -20.7 黃化指數 39.3 38.1 42.7 -130- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 557286 Α7 Β7 五、發明說明(128) 141熱塑性聚酯爲主聚胺基甲酸酯水性乳液,其具有65固 體%,陰離子性顆粒電荷,約2微米之粒度,7.5之pH, 及在25 °C爲400厘泊之黏度(Brookfield LVF)。 I42熱塑性聚酯爲主聚胺基甲酸酯水性乳液,其具有62固 體%,約1〇之pH ,及範圍爲約0.8至約2.5微米之粒 度。 143 呈水性分散物之 ORPAC BORON NITRIDE RELEASECOAT-CONC 25氮化硼顆粒,其可自ZYP Coatings公司(Oak Ridge. 田納西)取得。 如表5所示,樣品T與U,其各塗覆依照本發明之含氮 化硼顆粒之上漿組合物,在耐綸6,6具有比比較性樣品Z 之類似配方(其不包括氮化硼)低之白化指數。 實例6 堆疊五層之ADFLO-C™針狀短切玻璃纖維網,其商業得 自PPG Industries公司,以形成具有每平方米爲4614克(每 平方英吋約15盎司)之表面重量之網。各樣品之厚度爲25 毫米(約1英吋)。將此網之四個8英吋平方樣品加熱至 649 °C (約1200 °F )之溫度以自樣品去除本質上所有之上漿 成分。 使用2個未塗覆樣品作爲比較性樣品(”比較性樣品”)。 將其他2個樣品(樣品X ’’)浸在包括1150毫升之ORPAC BORON NITRIDE RELEASECOAT-CONC ( 25 重量 % 之氮化硼 顆粒於水中之分散液)及150毫升之Α-187γ-去水甘油基丙 基三甲氧基石夕燒之5重量%水溶液之水性塗層組合物浴中 -131- 本紙張尺度適用中國國家標準(CNS)A4規格(210 Χ 297公釐) ---.--------------r---訂---------線 (請先閱讀背面之注音?事項再填寫本頁) 557286 A7 B7 五、發明說明(129) (請先閱讀背面之注意事項再填寫本頁) 且飽和。水性塗層組合物之總固體爲18.5重量%。塗佈於 各網樣品之氮化硼顆粒之量爲120克。經塗覆網樣品在25 °C之溫度在空氣中乾燥過夜,並且在150 °C之烤箱中加熱 3小時。 依照ASTM方法C-177,其特別地在此併入作爲參考, 評估各組樣品在300K (約70 °F)之溫度之導熱度及耐熱 性。各樣品之導熱度及耐熱性之値敘述於以下表6。 表6 樣品 X 比較性樣品 厚度(忖) 1.09 1.0 (公分) 2.77 2.54 溫度(°F) 75.62 74.14 (°C) 24.23 23.41 導熱度 每小時平方英呎°FiBtu英吋 0.373 0.282 每米K之瓦數 0.054 0.041 耐熱性 每BTU之小時平方英呎 2.92 3.66 每瓦之平方米K 0.515 0.626 經濟部智慧財產局員工消費合作社印製 參考表6 ,依照本發明塗覆氮化硼顆粒之試驗樣品在 300K之溫度之導熱度大於未塗覆氮化棚顆粒之比較性樣 品之導熱度。 -132- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 557286 A7 B7 五、發明說明(130) 實例7 由塗覆以上實例2之上漿料G之G-75紗及商業得自 PPG Industries公司之1062玻璃纖維紗之樣品,製備捲繞纖 絲之圓柱形複合物。藉由自紗供應抽取8個紗末端,以以 下所述之基質材料塗覆紗,及使用習知纖絲捲繞裝置將紗 纖絲捲繞成圓柱形形狀,而製備圓柱體。各圓柱體爲12.7 公分(5英吋)高,具有14.6公分(5.75英吋)之内徑,及 0.635公分(0.25英吋)之壁厚。 基質材料爲100份之EPON 800樹脂(商業得自德州 Houston 之 Shell Chemical 公司)、80 份之 AC-220J 甲基四氫 酉太酸酐(商業得自紐澤西州Newark之Anhydrides and Chemicals公司)、及1份之ARALDITE® DY 062苄基二甲胺 加速劑(商業得自Ciba-Geigy公司)之混合物。纖絲捲繞圓 柱體在100 °C硬化2小時然後在150 °C 3小時。 藉由將樣品圓柱體壁之一側暴露於6.4什焦耳閃光燈, 並且使用CCD陣列紅外線照相機以每秒達2000張之速率 偵測相反側之溫度變化,而測定各試驗樣品在空氣中之徑 向熱擴散度(導熱度/(熱容量X密度))。亦沿紗之長度(圓 周)及沿圓柱體之長度或高度(軸向)測定熱擴散度値。試 驗結果敘述於以下表7。 -133- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---、--------------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) 557286 A7 五、發明說明(m)557286 A7 B7 V. Description of the Invention (ιπ) Example 5 The ingredients in the amounts described in Table 5 were mixed to form the aqueous sizing compositions T and U according to the present invention. Each aqueous sizing composition is prepared in a manner similar to that discussed above. Acetic acid is included in each composition at less than 1% by weight based on the total weight. Table 5 A proposes whitening and yellowing tests on composites formed using nylon 6,6 matrix resin using samples T, U and comparative samples Z (as discussed in Table 3A of Example 3 and repeated below) result. The color test was performed on a compound having a thickness of 3.175 mm (1/8 inch) and a diameter of 76.2 mm (3 inch) using a Hunter colorimeter D25-PC2A. (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employee Consumption Cooperatives Table 5 Based on the total solids content% by weight Sample composition T U Comparative sample Z Thermoplastic polyurethane film formation polymerization 141 31.35 28.75 34.5 Thermoplastic polyurethane film-forming polymer 142 46.9 43.1 51.7 Polyoxyalkylene polyol copolymer 0.3 0.27 0.3 Epoxidized polyester lubricant 6.55 6.0 7.22 γ-aminopropyltriethoxy Glycosane coupling agent 2.5 2.3 2.76 γ-lunyl propyl triethoxy stone cocoon coupling agent 3.0 2.78 3.34 Amine functional organosilane coupling agent 0.1 0.12 0.14 RELEASECOAT-CONC 25143 9.1 16.7 0 Whitening index -16.3 -15.0 -20.7 Yellowing index 39.3 38.1 42.7 -130- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 Α7 Β7 V. Description of the invention (128) 141 thermoplastic polyester based polyurethane aqueous emulsion, which has 65% solids, anionic particle charge, particle size of about 2 microns, pH of 7.5, and 25 ° C, a viscosity of 400 centipoise (Brookfield LVF). The I42 thermoplastic polyester is a main polyurethane aqueous emulsion having a solids content of 62%, a pH of about 10, and a particle size ranging from about 0.8 to about 2.5 microns. 143 ORPAC BORON NITRIDE RELEASECOAT-CONC 25 boron nitride particles in an aqueous dispersion are available from ZYP Coatings (Oak Ridge. Tennessee). As shown in Table 5, samples T and U, each of which was coated with a boron nitride-containing particle size composition according to the present invention, had similar formulations in nylon 6,6 than comparative sample Z (which does not include nitrogen Boron) low whitening index. Example 6 A five-ply ADFLO-C ™ needle-like chopped glass fiber web, commercially available from PPG Industries, to form a web having a surface weight of 4,614 grams per square meter (about 15 ounces per square inch). The thickness of each sample was 25 mm (about 1 inch). Four 8-inch square samples of this mesh were heated to a temperature of 649 ° C (about 1200 ° F) to remove essentially all sizing components from the sample. Two uncoated samples were used as comparative samples ("comparative samples"). The other 2 samples (Sample X '') were immersed in 1150 ml of ORPAC BORON NITRIDE RELEASECOAT-CONC (a dispersion of 25% by weight of boron nitride particles in water) and 150 ml of A-187γ-dehydrated glycerol Propyltrimethoxy stone yakaya in a 5% by weight aqueous solution of an aqueous coating composition bath -131- This paper size applies to China National Standard (CNS) A4 specification (210 x 297 mm) ---.---- ---------- r --- Order --------- line (please read the note on the back? Matters before filling out this page) 557286 A7 B7 V. Description of the invention (129) ( Please read the notes on the back before filling out this page) and saturated. The total solids of the aqueous coating composition was 18.5% by weight. The amount of boron nitride particles coated on each mesh sample was 120 g. The coated mesh samples were dried in air at 25 ° C overnight and heated in an oven at 150 ° C for 3 hours. According to ASTM method C-177, which is specifically incorporated herein by reference, the thermal conductivity and heat resistance of each group of samples at a temperature of 300K (about 70 ° F) were evaluated. The thermal conductivity and heat resistance of each sample are described in Table 6 below. Table 6 Sample X Comparative sample thickness (忖) 1.09 1.0 (cm) 2.77 2.54 Temperature (° F) 75.62 74.14 (° C) 24.23 23.41 Thermal conductivity square foot per hour ° Fibtu inches 0.373 0.282 Watts per meter K 0.054 0.041 Heat resistance square feet per BTU 2.92 3.66 square meters per watt K 0.515 0.626 Reference Table 6 printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the test samples for coating boron nitride particles according to the present invention are at 300K The thermal conductivity at temperature is greater than the thermal conductivity of a comparative sample that is not coated with nitriding shed particles. -132- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 B7 V. Description of the invention (130) Example 7 A G-75 yarn of size G and a sample of 1062 glass fiber yarn commercially available from PPG Industries were used to prepare a cylindrical composite of wound filaments. A cylinder was prepared by extracting 8 yarn ends from a yarn supply, coating the yarn with a matrix material described below, and winding the yarn filaments into a cylindrical shape using a conventional filament winding device. Each cylinder is 12.7 cm (5 inches) tall, has an inner diameter of 14.6 cm (5.75 inches), and a wall thickness of 0.635 cm (0.25 inches). The matrix material was 100 parts of EPON 800 resin (commercially available from Shell Chemical, Houston, Texas), 80 parts of AC-220J methyltetrahydroacetic anhydride (commercially available from Anhydrides and Chemicals, Newark, New Jersey), and 1 part mixture of ARALDITE® DY 062 benzyldimethylamine accelerator (commercially available from Ciba-Geigy). The filament winding cylinder was hardened at 100 ° C for 2 hours and then at 150 ° C for 3 hours. The radial direction of each test sample in the air was measured by exposing one side of the cylinder wall of the sample to a 6.4 ShJ flash, and using a CCD array infrared camera to detect temperature changes on the opposite side at a rate of 2000 frames per second. Thermal diffusivity (thermal conductivity / (heat capacity X density)). The thermal diffusivity 値 is also measured along the length (circle) of the yarn and along the length or height (axial) of the cylinder. The test results are described in Table 7 below. -133- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ---, -------------- r --- order ----- ---- Line (please read the notes on the back before filling this page) 557286 A7 V. Description of the invention (m)
參考表7,試驗樣品(其塗覆少量之氮化侧)之熱擴散度 之値小於未塗覆氮化硼之比較性樣品。纖絲捲繞圓柱體之 氣洞及小試驗樣品面積爲影響這些結果之因素。 實例8 對各含8層由經Β_塗覆紗(實例i中所討論)及經 澱粉·油塗覆紗(實例1中所討論)(對照)之樣品製備之 7628型織物之層合物樣品,評估層合物^方向(即,橫越 層合物之厚度)之熱膨脹係數("Z-CTE’,)。使用實例1中所 时論之FR-4 ί衣氧樹脂製備層合物,並且依照IPC試驗法 2.4.41 ’其特別地在此併入作爲參考,以銅護面。依照 IPC試驗法2.4.41評估各層合物樣品在288 t之ζ-方向熱 膨脹係數。評估結果示於以下表8。 ---」--------- 11--r I--訂 ---ml— i^w. (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -134· 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7 經濟部智慧財產局員工消費合作社印製Referring to Table 7, the thermal diffusivity of the test sample (which is coated with a small amount of the nitrided side) is smaller than that of the uncoated boron nitride comparative sample. Air holes in the filament winding cylinder and small test sample area are factors that affect these results. Example 8 Laminates of type 7628 fabrics prepared from samples containing 8 layers of B_coated yarn (discussed in Example i) and starch / oil-coated yarn (discussed in Example 1) (control) Sample, and evaluate the thermal expansion coefficient (" Z-CTE ',) in the direction of the laminate (ie, across the thickness of the laminate). The laminate was prepared using FR-4 oxycoated resin as discussed in Example 1 and was specifically incorporated herein by reference in accordance with the IPC test method 2.4.41 ', with a copper finish. The thermal expansion coefficient of each laminate sample in the zeta-direction of 288 t was evaluated according to the IPC test method 2.4.41. The evaluation results are shown in Table 8 below. ---''--------- 11--r I--order --- ml-- i ^ w. (Please read the precautions on the back before filling out this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative -134 · This paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 557286 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
五、發明說明(132) 如表8所示,對於依照本發明之層合物 、 口 leA3,層合物 < z-万向熱膨脹係數小於由經695澱粉 仍/由塗覆紗製備之 對照樣品1與2。 實例9 混合表9A中所述之量之各成分,以形成你 a々成依本發明之水 性第一上漿組合物AA、BB與CC。各水性第一上聚組合 物以類似以上討論之方法製備。在各組合物中包括基於總 重量爲少於1重量%之乙酸。將表9A之各水性上漿組合 物塗覆於G-75 E-玻璃纖維股上。 將各經塗覆纖維股乾燥,使用習知交織裝以類似之方法 交織以形成紗,及捲繞在線軸上。塗覆上漿組合物之紗在 交織時呈現最少之上漿料脱落。 -135- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---^--------------:----訂---------線 (請先閱讀背面之注意事項再填寫本頁) 557286 A7B7 五、發明說明(133) 表9A 基於總固體之成分重量% 樣品 成分 AA BB CC PVP K-30144 14.7 14.7 13.4 STEPANTEX 653145 30.0 29.9 27.3 Α·187146 1.8 1.8 1.6 Α_174147 3.7 3.7 3.3 EMERY 6717148 2.4 2.4 2.2 MACOL OP-10149 1.6 1.6 1.5 TMAZ-81150 3.3 3.3 3.0 MAZUDF-136151 0.2 0.2 0.2 ROPAQUE HP-1055152 0 42.4 0 ROPAQUE OP-96153 42.3 0 38.6 REKEASECIAT-CONC 25154 0 0 6.3 POLARTHERMPT 160155 0 0 2.6 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 144 PVP K-30聚乙烯基吡咯啶酮,其商業得自紐澤西州 Wayne 之 ISP Chemicals 公司0 145 STEPANTEX 653,其商業得自紐澤西州Maywood之Stepan 公司。 146 A-187 γ-去水甘油基丙基三甲氧基矽烷,其商業得自紐約 州 Tarrytown 之 CK Witco 公司。 147 Α-174 γ-甲基丙晞氧基丙基三甲氧基矽烷,其商業得自紐 約州 Tarrytown 之 CK Witco 公司0 -136- 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) 經濟部智慧財產局員工消費合作社印製 557286 A7 B7 五、發明說明(134) 148 EMERY® 6717部分醯胺化聚伸乙二亞胺,其商業得自俄 亥俄州Cincinnati之Cognis公司。 149 MACOL OP-10乙氧化烷酚;此材料類似MACOL ΟΡ·10 SP ,除了 MACOL OP-10 SP接受後處理以去除觸媒; MACOL ΟΡ-10不再商業可得。 15G TMAZ-81花揪醇酯之環氣乙烷衍生物,其商業得自紐澤 西州Parsippany之BASF公司0 151 MAZU DF-136防沫劑,其商業得自紐澤西州Parsippany之 BASF公司。 152ROPAQUE® HP-1055 ,1.0微米顆粒分散液,其商業得自 賓州費城之Rohm and Haas公司。 153ROPAQUE® ΟΡ·96,0.55微米顆粒分散液,其商業得自賓 州費城之Rohm and Haas公司。 154 ORPAC BORON NITRIDE RELEASECOAT-CONC 25 氮化硼分散 液,其商業得自田納西州Oak Ridge之ZYP Coatings公司。 155POLARTHERM™ PT 160氮化硼粉末顆粒,其商業得自俄亥 俄州 Lakewood 之 Advanced Ceramics 公司 0 在使用Sulzer Ruti 5200型空氣噴射織布機織動7628型織 物時,使用以各上漿組合物(AA、BB與CC )上漿之紗作 爲填紗。經爲纖維塗覆不同之樹脂相容上漿組合物之交織 G-75 E-玻璃纖維股156。織物繼而以具有140 X:之Tg之 FR-4環氧樹脂(加州Anaheim之Nelco International公司之代 號4000-2樹脂)預浸。在預浸之前未自織物去除上漿組合 物。藉由在2層1盎司銅之間堆疊8層之預浸材料,並且 -137- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -----------------r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7 五、發明說明(135) (請先閱讀背面之注意事項再填寫本頁) 在355 °F (約179 °C)之溫度,每平方英吋300磅(約2·1百 萬巴斯卡)之壓力,將其層合在一起159分鐘(總循環時間) 而製備層合物。層合物無銅之厚度範圍爲0.043英吋(約 0.11公分)至0.050英吋(約0.13公分)。 在形成後,如以下表9Β所示試驗層合物(依照製造其之 纖維股稱爲ΑΑ、ΒΒ與CC)。在試驗時,在由玻璃纖維 紗製造之第一層合物塗覆上漿組合物樣品ΑΑ (以下稱爲 層合物樣品ΑΑ1 )時,同時試驗層合物ΒΒ。稍後,在由玻 璃纖維紗製造之第二層合物塗覆上漿组合物樣品CC (以 下稱爲層合物樣品ΑΑ2 )時,同時試驗層合物CC。 表9Β 層合物樣品 試驗 單位 AA11 BB1 AA22 CC2 平均厚度 英吋 0.048 0.048 0.053-0.055 0.053-0.055 焊錫浮動 秒數 409 386 235 253 焊錫浸潰 秒數 320 203 243 242 撓性強度經紗方向157 kpsi 99 102 91 90 撓性強度緯紗方向158 kpsi 86 81 73 72 經濟部智慧財產局員工消費合作社印製 1 基於2個樣品。 2 基於3個樣品。 156此經紗爲PPG Industries公司之商業可得纖維玻璃紗產 品,代號G-75玻璃纖維紗,其塗覆PPG Industries公司黏 合劑。 157 Per IPC-TM-650 "Flexural Strength of Laminates (At Ambient -138 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286V. Description of the invention (132) As shown in Table 8, for the laminate according to the present invention, mouth LeA3, the laminate < z-universal thermal expansion coefficient is less than the control made from 695 starch still / coated yarn Samples 1 and 2. Example 9 The ingredients are mixed in the amounts described in Table 9A to form a first aqueous sizing composition AA, BB and CC according to the present invention. Each aqueous first polymerization composition was prepared in a manner similar to that discussed above. Acetic acid is included in each composition at less than 1% by weight based on the total weight. Each of the aqueous sizing compositions of Table 9A was coated on G-75 E-glass fiber strands. Each coated fiber strand was dried, interlaced in a similar manner using conventional interlacing equipment to form a yarn, and wound on a bobbin. The sizing composition-coated yarns exhibited minimal slipping when interlaced. -135- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --- ^ --------------: ---- Order ---- ----- Line (please read the precautions on the back before filling this page) 557286 A7B7 V. Description of the invention (133) Table 9A Based on the total solid content by weight% Sample composition AA BB CC PVP K-30144 14.7 14.7 13.4 STEPANTEX 653145 30.0 29.9 27.3 Α187146 1.8 1.8 1.6 Α_174147 3.7 3.7 3.3 EMERY 6717148 2.4 2.4 2.2 MACOL OP-10149 1.6 1.6 1.5 TMAZ-81150 3.3 3.3 3.0 MAZUDF-136151 0.2 0.2 0.2 ROPAQUE HP-1055152 0 42.4 0 ROPAQUE OP-96153 42.3 0 38.6 REKEASECIAT-CONC 25154 0 0 6.3 POLARTHERMPT 160155 0 0 2.6 (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 144 PVP K-30 polyvinylpyrrolidone, which Commercially available from ISP Chemicals Corporation 0 145 STEPANTEX 653, Wayne, New Jersey, commercially available from Stepan Corporation, Maywood, New Jersey. 146 A-187 Glycerylpropyltrimethoxysilane, commercially available from CK Witco, Tarrytown, New York. 147 Α-174 γ-methylpropionyloxypropyltrimethoxysilane, commercially available from CK Witco, Tarrytown, NY 0 -136- This paper is sized to the Chinese National Standard (CNS) A4 (210 χ 297) (Mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 B7 V. Description of the invention (134) 148 EMERY® 6717 Partially aminated poly (ethylene diimide), commercially available from Cognis, Inc. of Cincinnati, Ohio. 149 MACOL OP-10 ethoxylated alkylphenol; this material is similar to MACOL OP-10 SP, except that MACOL OP-10 SP is subjected to post-treatment to remove the catalyst; MACOL OP-10 is no longer commercially available. 15G TMAZ-81 Anisocyanate derivative of anisocyanate, commercially available from BASF, Parsippany, New Jersey 0 151 MAZU DF-136 antifoam, commercially available from BASF, Parsippany, New Jersey . 152ROPAQUE® HP-1055, a 1.0 micron particle dispersion, commercially available from Rohm and Haas, Philadelphia, PA. 153ROPAQUE® OP · 96, 0.55 micron particle dispersion, commercially available from Rohm and Haas, Philadelphia, PA. 154 ORPAC BORON NITRIDE RELEASECOAT-CONC 25 Boron nitride dispersion, commercially available from ZYP Coatings, Oak Ridge, Tennessee. 155POLARTHERM ™ PT 160 boron nitride powder granules, commercially available from Advanced Ceramics, Lakewood, Ohio. When using a Sulzer Ruti Model 5200 air jet loom to weave a Model 7628 fabric, various sizing compositions (AA, BB With CC) sizing yarn as filling yarn. Interlaced G-75 E-glass fiber strands 156 coated with different resin-compatible sizing compositions for the fibers. The fabric was then pre-impregnated with a FR-4 epoxy resin (codename 4000-2 resin from Nelco International, Inc., Anaheim, CA) with a Tg of 140 X :. The sizing composition was not removed from the fabric before prepreg. By stacking 8 layers of prepreg between 2 layers of 1 ounce copper, and -137- this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) --------- -------- r --- order --------- line (please read the precautions on the back before filling this page) 557286 A7 B7 V. Invention Description (135) (Please read first Note on the back, fill in this page again) Laminate them together at a temperature of 355 ° F (approximately 179 ° C) at a pressure of 300 pounds per square inch (approximately 2.1 million bska) (Total cycle time) and a laminate is prepared. The thickness of the laminate without copper ranges from 0.043 inches (about 0.11 cm) to 0.050 inches (about 0.13 cm). After formation, the laminate was tested as shown in Table 9B below (the fiber strands from which it is made are referred to as AA, BB, and CC). At the time of the test, when the first laminate made of glass fiber yarn was coated with a sizing composition sample AAA (hereinafter referred to as a laminate sample AAA1), the laminate KB was simultaneously tested. Later, when the second laminate made of glass fiber yarn was coated with a sizing composition sample CC (hereinafter referred to as laminate sample AAA2), the laminate CC was simultaneously tested. Table 9B Laminate sample test unit AA11 BB1 AA22 CC2 average thickness inch 0.048 0.048 0.053-0.055 0.053-0.055 solder float seconds 409 386 235 253 solder immersion seconds 320 203 243 242 flexural strength warp yarn direction 157 kpsi 99 102 91 90 Flexural weft direction 158 kpsi 86 81 73 72 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 Based on 2 samples. 2 Based on 3 samples. 156 This warp yarn is a commercially available fiberglass yarn product of PPG Industries, code G-75 glass fiber yarn, which is coated with a PPG Industries adhesive. 157 Per IPC-TM-650 " Flexural Strength of Laminates (At Ambient -138-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 557286
經濟部智慧財產局員工消費合作社印製 五、發明說明(136)Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (136)
Temperature)”,12/94,修正 B 版。 158同一章節。 藉由將4英吋乘4英吋平方(1〇· 16公分乘ι〇16公分)之 銅護面層合物浮在550 T(約288。〇之共熔鉛·錫焊錫浴 中’直到觀察到起泡或分離,而進行焊錫浮動試驗。然後 記錄直到第一次起泡或分離之時間秒數。 藉由切割層合物之樣品,藉蝕刻自樣品去除銅,藉拋光 使樣品之切緣光滑,及將樣品置於250下(約121 X:)及每 平方英吋15磅(約0.1百萬巴斯卡)之壓力鍋中6〇分鐘, 而進行焊錫浸潰試驗。此試驗爲下表所稱之壓力鍋試驗。 在暴露60分鐘後,自壓力鍋去除樣品,拍乾且浸入55〇 F (約288 C )之共熔鉛-錫焊錫浴中,直到觀察到起泡或 分離。然後記錄直到第一次起泡或分離之時間秒數。 依照所示之IPC標準進行撓性試驗。 使用各以上漿組合物AA、BB與CC上之纖維股製造之 層合物AA、BB與CC具有作爲印刷電路板用電子撑體之 可接受性質(如表9B所示)。 亦對樣品AA、BB與CC實行以下之試驗,並且敘述於 表 9C 〇 、 ^ I -----r---訂---------線 (請先閱讀背面之注意事項再填寫本頁) -139- 557286 A7 五、發明說明(137) 樣品 試驗 單位 AA BB CC Tg by DSC 0/30/60 min °C 141/140/139 140/141/141 138/140/139 壓力鍋 吸水〇/〇 0.37 037 0.38 防水性159 重量增加% 0.12 0.09 0.09 DMF抗力 重量增加°/〇 0.35 0.27 0.29 MeC12 抗生 16C} 重量增加% 0.77 0.82 0.68 銅剝除強度161 (經紗/填紗) 磅數 11.8/11.0 12.1/11.1 11.2/11.4 層間黏合強度102 每英吋之碡數 12.8 14.2 15.4 (請先閱讀背面之注意事項再填寫本頁) 依照 IPC-TM-650,No. 2·6·2·1, "Water Absorption,Metal Clad Plastic Laminates",5/86,修正 A 版。 160 依照 IPC-TM-650,No· 2.3.4.3. "Chemical Resistance of Core Materials to Methylene Chloride,,,5/86·Temperature) ", 12/94, Revised Version B. 158 Same chapter. By floating 4 inches by 4 inches square (10.6 cm by ι 16 cm) of copper finish laminate at 550 T (Approximately 288. 0 in the eutectic lead · tin solder bath 'until a blistering or separation is observed, a solder float test is performed. Then the time in seconds until the first blistering or separation is recorded. By cutting the laminate For the sample, remove copper from the sample by etching, smooth the cut edge of the sample by polishing, and place the sample in a pressure cooker at 250 (about 121 X :) and 15 pounds per square inch (about 0.1 million Baska). After 60 minutes, the solder immersion test was performed. This test is the pressure cooker test described in the table below. After 60 minutes of exposure, the sample was removed from the pressure cooker, patted dry and immersed in 55F (about 288 C) eutectic lead. -In a solder bath until foaming or separation is observed. Then record the time in seconds until the first foaming or separation. Flexibility test is performed according to the IPC standard shown. Use each of the above slurry compositions AA, BB and Laminates AA, BB, and CC made of fiber strands on CC are used as printed circuit boards Acceptable properties of electronic supports (as shown in Table 9B). The following tests were also performed on samples AA, BB and CC, and are described in Table 9C 〇, ^ I ----- r --- order --- ------ Line (Please read the precautions on the back before filling this page) -139- 557286 A7 V. Description of the invention (137) Sample test unit AA BB CC Tg by DSC 0/30/60 min ° C 141 / 140/139 140/141/141 138/140/139 Pressure cooker absorbs water 〇 / 〇0.37 037 0.38 Water resistance 159 Weight increase 0.12 0.09 0.09 DMF resistance weight increase ° / 〇0.35 0.27 0.29 MeC12 Antibiotic 16C} Weight increase 0.77 0.82 0.68 Copper peel strength 161 (warp / filled yarn) lbs 11.8 / 11.0 12.1 / 11.1 11.2 / 11.4 Adhesive strength between layers 102 102 每 12.8 14.2 15.4 (Please read the precautions on the back before filling this page) According to IPC-TM-650, No. 2 · 6 · 2 · 1, " Water Absorption, Metal Clad Plastic Laminates ", 5/86, Rev. A. 160 According to IPC-TM-650, No. 2.3.4.3. &Quot; Chemical Resistance of Core Materials to Methylene Chloride ,,, 5/86 ·
161 依照 IPC-TM-650,No. 2.4.8,"Peel Strength: As Received, After Thermal Stress,After Process Chemicals”,1/86,修正 B 版0 經濟部智慧財產局員工消費合作社印製 162 依照 IPC-TM-650,No. 2.4.40,"Inner Layer Bond Strength of Multilayer Printed Circuit Boards·',10/87 o 實例10 混合表10中所述之量之各成分,以形成依照本發明之 水性上漿組合物DD、EE與FF。在各組合物中包括基於 總重量爲少於0.5重量%之乙酸。 -140- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7B7 五、發明說明(138) 表10 基於總固體之成分重量% 樣品 成分 DD EE FF PVP Κ-30163 12.3 11.7 12.3 STEPANTEX 653164 25.0 23.9 25.0 ΤΜΑΖ81165 3.5 3.9 2.7 MACOL ΟΡ-10166 1.8 2.0 1.4 POLARTHERMPT 160167 2.4 2.3 2.4 EMERY 6717168 2.0 2.0 2.0 A-174169 3.1 2.9 3.1 A-187170 1.5 1.4 1.5 RELEASECOAT-CONC 25171 5.7 5.5 5.6 MAZUDF-136172 0.2 0.2 0.2 ROPAQUE OP-96173 35.2 33.7 35.3 FLEXOL LOE174 7.3 10.5 0 FLEXOL EPO175 0 0 7.3 ---^--------------^----訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 163PVP Κ_30聚乙晞基吡咯啶酮,其商業得自紐澤西州 Wayne 之 ISP Chemicals 公司0 164STEPANTEX 653 ,其商業得自伊利諾州芝加哥之Stepan 公司。 165TMAZ 81花揪醇酯之環氧乙貌衍生物,其商業得自紐澤 西州Parsippany之BASF公司0 166MACOL OP-10乙氧化烷酚;此材料類似MACOL OP-10 -141- 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) 557286 A7 B7 五、發明說明(139) SP ,除了 MACOL OP_10 SP接受後處理以去除觸媒; MACOL OP_10不再商業可得。 (請先閱讀背面之注意事項再填寫本頁) 167POLARTHERM® PT 160氮化硼粉末顆粒,其商業得自俄 亥俄州 Lakewood 之 Advanced Ceramics 公司。 168EMERY® 6717部分醯胺化聚伸乙二亞胺,其商業得自俄 亥俄州Cincinnati之Cognis公司。 1ό9Α-174 γ-甲基丙烯氧基丙基三甲氧基矽烷,其商業得自 紐約州Tarrytown之CK Witco公司0 17GA-187 γ-去水甘油基丙基三甲氧基矽烷,其商業得自紐 約州 Tarrytown 之 CK Witco 公司。 171ORPAC BORON NITRIDE RELEASECOAT-CONC 25 氮化硼分散 液,其爲約25重量%氮化硼顆粒於水中之分散液,其商 業得自田納西州Oak Ridge之ZYP Coatings公司。 172MAZU DF-136 P方沫劑,其商業得自紐澤西州Parsippany 之BASF公司。 173ROPAQUE® OP-96,0.55微米顆粒分散液,其商業得自 賓州費城之Rohm and Haas公司。 經濟部智慧財產局員工消費合作社印製 174FLEXOL LOE環氧化亞麻油,其商業得自康乃迪克州 Danbury 之 Union Carbide 公司 0 175FLEXOL EPO環氧化大豆油,其商業得自康乃迪克州 Danbury 之 Union Carbide 公司 0 -142- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286161 According to IPC-TM-650, No. 2.4.8, " Peel Strength: As Received, After Thermal Stress, After Process Chemicals '', 1/86, Rev. B 0 Printed by Employee Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 162 In accordance with IPC-TM-650, No. 2.4.40, " Inner Layer Bond Strength of Multilayer Printed Circuit Boards · ', 10/87 o Example 10 The ingredients in the amounts described in Table 10 were mixed to form a composition according to the present invention Aqueous sizing composition DD, EE and FF. Included in each composition is acetic acid based on the total weight of less than 0.5% by weight. -140- This paper size applies to China National Standard (CNS) A4 (210 X 297) %) 557286 A7B7 V. Description of the invention (138) Table 10 Based on the total solids content by weight% Sample composition DD EE FF PVP K-30163 12.3 11.7 12.3 STEPANTEX 653164 25.0 23.9 25.0 ΤΑΑ81165 3.5 3.9 2.7 MACOL ΟΡ-10166 1.8 2.0 1.4 POLARTHERMPT 160167 2.4 2.3 2.4 EMERY 6717168 2.0 2.0 2.0 A-174169 3.1 2.9 3.1 A-187170 1.5 1.4 1.5 RELEASECOAT-CONC 25171 5.7 5.5 5.6 MAZUDF-136172 0.2 0.2 0.2 ROPAQUE OP-96173 35.2 3 3.7 35.3 FLEXOL LOE174 7.3 10.5 0 FLEXOL EPO175 0 0 7.3 --- ^ -------------- ^ ---- order --------- line (please read first Note on the back, please fill in this page again.) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 163PVP κ_30 polyethylpyrrolidone, commercially available from ISP Chemicals Company, Wayne, New Jersey, 0164STEPANTEX 653, commercially available from Stepan Company, Chicago, Illinois. 165TMAZ 81 Ethylene oxide derivative of anisocyanate, commercially available from BASF Corporation, Parsippany, New Jersey. 0 166 MACOL OP-10 ethoxylated phenol; this material is similar to MACOL OP- 10 -141- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 χ 297 mm) 557286 A7 B7 V. Description of the invention (139) SP, except for MACOL OP_10 SP which undergoes post-processing to remove catalyst; MACOL OP_10 does not Commercially available. (Please read the notes on the back before filling out this page.) 167POLARTHERM® PT 160 boron nitride powder particles are commercially available from Advanced Ceramics, Lakewood, Ohio. 168EMERY® 6717 partially fluorinated poly (ethylene diimide) is commercially available from Cognis Corporation of Cincinnati, Ohio. 1ό9Α-174 γ-methacryloxypropyltrimethoxysilane, commercially available from CK Witco, Tarrytown, NY 0 17GA-187 γ-dehydrated glycerylpropyltrimethoxysilane, commercially available from New York CK Witco Corporation of Tarrytown. 171ORPAC BORON NITRIDE RELEASECOAT-CONC 25 Boron nitride dispersion, which is a dispersion of about 25% by weight of boron nitride particles in water, is commercially available from ZYP Coatings, Oak Ridge, Tennessee. 172 MAZU DF-136 P square foam, commercially available from BASF Corporation, Parsippany, New Jersey. 173ROPAQUE® OP-96, a 0.55 micron particle dispersion, commercially available from Rohm and Haas, Philadelphia, PA. 174FLEXOL LOE Epoxidized Linseed Oil, printed by 174FLEXOL LOE epoxidized linseed oil, commercially available from Union Carbide, Danbury, Connecticut. 175FLEXOL EPO epoxidized soybean oil, commercially available from Union Carbide, Danbury, Connecticut. Company 0 -142- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 557286
A7 五、發明說明(140) 表10 (續) 基於總固體之成分重量% 樣品 成分 DD EE FF 固體重量% 3.4 3.5 3.4 LOI 0.42 0.39 0.30 使用表10之各水性上漿組合物塗覆玻璃纖維而形成G_ 75 Ε-玻璃纖維股·將各經塗覆玻璃纖維股乾燥,使用習知 交織裝置以類似之方法交織以形成紗,及捲繞在線軸上。 藉由比較此經塗覆紗與以類似樣品DD但無環氧化亞麻 油之上漿組合物塗覆之紗(以下稱爲”比較性樣品i "),而 評估樣品DD之紗。此比較包括目視檢視空氣喷射織布機 纺織之7628型織物之外觀。纺織之織物使用樣品DD作爲 填紗,纖維以不同之樹脂相容上漿組合物塗覆之交織G-75 E-玻璃纖維股170作爲經紗。在比較塗覆比較性樣品1之 紗纺織之織物時,觀察到以塗覆樣品DD之紗纺織之織物 在織物上呈現較少之鬆弛細毛,及在織布機上之接觸點收 集到較少之細毛,特別是在蓄紗器。因爲在織布機上觀察 到之細毛高起始量,無織物使用加入塗覆樣品EE或FF之 纖維之紗紡織。據信此情況爲比防止過量毛形成所需爲低 之LOI程度之結果。在本發明中,預期以上討論之上漿組 合物需要至少0.40之LOI,以在織動時減少細毛形成。 170此經紗爲PPG Industries公司之商業可得纖維玻璃紗產 品,代號G_75玻璃纖維紗,其塗覆PPG Industries公司之 -143- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) )----l· I--I-------I l· I — I ^---------線 (請先閱讀背面之注意事項再填寫本頁} 經濟部智慧財產局員工消費合作社印製 557286 A7 、發明說明(142) AA3、AA4與BB爲2.8重量%之固體。樣品CC爲3·1重量 °/〇之固體。比較性樣品2爲5.9重量%之固體。 經濟部智慧財產局員工消費合作社印製 ---- 丄口口 兴n兴喟q興讨 較性樣品2 (澱粉/油黏合劑)比擬之空氣阻力。此外,卷 比較比較性樣品2時,樣品ΑΑ、ΒΒ與CC之較低磨擦尤 表示在織動時紗較易自織布機蓄紗器去除。 實例12 以類似以上實例η之方法評估樣品ΑΑ、ΒΒ與cc及 比較性樣品2之空氣阻力,除了在表12所示之壓力測定 線軸樣品之空氣阻力値。 亦使用Shirley 84 041L型破裂纖絲偵測器,其商業得自 英國之SDL ―細丨嶋〗公司,以每分鐘米評估各紗之 每1200米之紗之平均破裂纖絲數量(在表12中示爲試驗 1)。破裂纖、絲値以自線柏去除227克(〇 5旬之紗後之線 軸及自線抽去除4540克(1G碡)之紗後之線轴,由全部線 軸取得之部份報告。進-步評估各紗在增加張力及磨損程 度時之破裂纖絲數量(在表12中示爲試驗2)。 2 中,以200米/分鐘自線軸解下紗, 在均勻張力控制裝置 __-145· 度適用中國國家標準(CNS)A4 &格(21〇 X 297公£ f請先閱讀背面之注意事項再填寫本頁} ---------tl---------線. 557286 A7 五、發明說明(⑷) (有時稱爲閘張力裝置)上以蛇形通過一系列8個陶瓷針, 及通過Shirley破裂纖絲偵測器以計算破裂纖絲數量。使用 不同之針盤設定改變張力裝置上之針之間隔,以對紗提供 不同之張力程度。使此特定試驗使用商業得自南卡州之 Steel Heddle公司之UTC_2003型張力裝置。破裂纖絲以每 米之紗之破裂纖絲數量報告。 樣品AA、BB與CC及比較性樣品2之試驗結果敘述於 以下表12。以類似以上實例n討論之方法,在第一份之 玻璃纖維紗塗覆上漿组合物樣品AA (以下稱爲樣品AA5) 時,同時試驗樣品BB及比較性樣品2,而且在稍後,在 第二份之玻璃纖維紗塗覆上漿组合物樣品AA (以下稱爲 樣品AA6 )時,同時試驗樣品cc。 146- 本紙張尺度適用中_家標準(CNS)A4規格(210 X 297公爱) 557286 A7 B7 五、發明說明(144) 經濟部智慧財產局員工消費合作社印製 表12 樣品 ΑΑ5 ΒΒ 2 ΑΑ6 CC 空氣阻力(克數) 15psi 46.10 42.50 42.23 47.47 42.33 20 psi 56.20 51.20 52.94 58.84 53,18 25 psi 67.33 60.30 64.13 69.45 67.66 30 psi 77.34 70.84 75.74 75.29 77.63 35 psi 89.42 89.96 85.96 83.70 82.74 40 psi 104.97 101.21 98.48 87.23 92.18 45 psi 113.41 107.74 110.34 99.91 102.91 試驗1 全部線軸 0.170 0.882 0.032 1.735 0.066 227 克(0.5 磅) 0.160 0.648 0.041 0.904 0.075 4540 克(10 磅) 0.098 1.348 0.008 0.518 0.022 試驗2 設定2 0.683 5.017 0.119 0.372 0.011 設定3 0.753 4.772 0.083 0.450 0.017 設定4 0.713 3.753 0.147 0.367 0.017 設定5 1.267 4.025 0.150 0.811 0.061 設定6 1.608 8.383 0.322 0.286 0.044 設定7 4.128 6.517 0.611 0.403 0.058 設定8 4.472 14.800 0.978 0.406 0.128 -147- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 557286 A7 __ B7__ 五、發明說明(146) 179DESMOPHEN 2000聚己二酸伸乙酯二醇,其商業得自賓 州 Pittsburgh 之 Bayer 公司0 ΐ8〇ρνΡ κ-30聚乙烯基吡咯啶酮,其商業得自紐澤西州 Wayne 之 ISP Chemicals 公司0 181Α-187 γ-去水甘油基丙基三甲氧基矽烷,其商業得自紐 約州 Tarrytown 之 CK Witco 公司0 182Α-174 γ-甲基丙烯氧基丙基三甲氧基矽烷,其商業得自 紐約州Tarrytown之CK Witco公司0 表13A (續) 成分 樣品HH PLURONIC F-108183 9.0 VERS AMID 140184 4.4 MACOL NP-6185 5.4 POLARTHERM PT 160186 0.9 RELEASECOAT-CONC 25187 1.5 乙酸 <0.1 183PLURONIC™ F-108聚氫化丙烯·聚氫化乙嬌其聚物, 商業得自紐澤西州Parsippany之BASF公司0 184 VERS AMID 140聚醯胺,其商業得自俄亥俄州Cincinnati 之Cognis公司 〇 185MACOL NP-6壬酚界面活性劑,其商業得自紐澤西州 Parsippany 之 BASF 公司0 186POLARTHERM PT 160氮化硼粉末顆粒,其商業得自俄亥 俄州 Lakewood 之 Advanced Ceramics 公司。 -149- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---^--------------^----訂---------線"^^· (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7A7 V. Description of the invention (140) Table 10 (continued) Based on the total solids content% by weight Sample composition DD EE FF solids% by weight 3.4 3.5 3.4 LOI 0.42 0.39 0.30 The glass fiber is coated with each of the aqueous sizing compositions of Table 10 Formation of G_75E-glass fiber strands. Each coated glass fiber strand was dried, interwoven in a similar manner using a conventional interlacing device to form a yarn, and wound on a bobbin. The yarn of sample DD was evaluated by comparing this coated yarn with a yarn coated with a similar sample DD but without epoxidized linseed sizing composition (hereinafter referred to as "comparative sample i "). This comparison Includes visual inspection of the appearance of Type 7628 fabric woven by air jet loom. The textile fabric uses sample DD as the filling yarn and interlaced G-75 E-glass fiber strand 170 coated with different resin compatible sizing compositions. As warp yarns. When comparing fabrics woven with the yarn coated with Comparative Sample 1, it was observed that the fabrics woven with the yarn coated with Sample DD showed less loose hairs on the fabric and collected at the contact points on the loom. Fewer fine hairs, especially in yarn accumulators. Because of the high starting amount of fine hairs observed on the loom, non-woven fabrics are woven using yarns with fibers coated with samples EE or FF. It is believed that this situation is better than The result is a low degree of LOI required to prevent excessive hair formation. In the present invention, it is expected that the sizing composition discussed above requires a LOI of at least 0.40 to reduce fine hair formation during weaving. 170 This warp yarn is a product of PPG Industries Commercially available Glass fiber yarn product, code G_75 glass fiber yarn, which is coated with -143- of PPG Industries. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). ---- l · I-- I ------- I l · I — I ^ --------- line (Please read the precautions on the back before filling out this page} Printed by the Intellectual Property Bureau Employee Consumer Cooperatives, Ministry of Economic Affairs 557286 A7 Explanation of the invention (142) AA3, AA4 and BB are 2.8% by weight solids. Sample CC is 3.1% by weight ° / 0 solids. Comparative sample 2 is 5.9% by weight solids. Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs Printing ---- Xingkoukou Xing n Xing Q q Comparative air resistance compared to comparative sample 2 (starch / oil adhesive). In addition, when comparing volume with comparative sample 2, the comparison of samples ΑΑ, ΒΒ and CC Low friction especially indicates that the yarn is easier to remove from the loom accumulator when weaving. Example 12 The air resistance of samples AA, BB, and cc and comparative sample 2 was evaluated in a similar manner to that of Example η above, except as shown in Table 12. The pressure shown is used to measure the air resistance of the bobbin sample. Shirley 84 041L broken filament detector is also used. From the UK's SDL ―Fine 丨 嶋〗 company, the average number of broken filaments per 1200 meters of yarn per meter is evaluated in meters per minute (shown as Test 1 in Table 12). The broken fibers and filaments are made from silk cypress Spools after removing 227 grams of yarn and yarn spools after removing 4,540 grams (1G 碡) of yarn from the thread, part of the report obtained from all the spools. Further evaluation of each yarn's increasing tension and wear The number of broken filaments at the time (shown as Test 2 in Table 12). In 2, the yarn was unwound from the bobbin at 200 meters / minute, and the Chinese National Standard (CNS) was applied in the uniform tension control device __145. A4 & (21〇X 297) f Please read the notes on the back before filling out this page} --------- tl --------- line. 557286 A7 V. Invention Explanation (⑷) (sometimes referred to as the brake tension device) is passed through a series of 8 ceramic needles in a serpentine shape and passed through the Shirley Rupture Filament Detector to calculate the number of broken filaments. Use different needle dial settings to change the needle interval on the tension device to provide different degrees of tension to the yarn. This particular test was made using a UTC_2003 tension device commercially available from Steel Heddle Corporation of South Carolina. Broken filaments are reported as the number of broken filaments per meter of yarn. The test results of samples AA, BB and CC and comparative sample 2 are described in Table 12 below. In a method similar to that discussed in Example n above, when the first portion of the glass fiber yarn coated sizing composition sample AA (hereinafter referred to as sample AA5) was tested at the same time, Sample BB and Comparative Sample 2 were tested at the same time. When the second portion of the glass fiber yarn coated sizing composition sample AA (hereinafter referred to as sample AA6), the sample cc was simultaneously tested. 146- The paper size is applicable _ Home Standard (CNS) A4 (210 X 297 public love) 557286 A7 B7 V. Description of the invention (144) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 12 Sample ΑΑ5 ΒΒ 2 ΑΑ6 CC Air Resistance (grams) 15psi 46.10 42.50 42.23 47.47 42.33 20 psi 56.20 51.20 52.94 58.84 53,18 25 psi 67.33 60.30 64.13 69.45 67.66 30 psi 77.34 70.84 75.74 75.29 75.29 77.63 35 psi 89.42 89.96 85.96 83.70 82.74 101.97 101.74 40.74 101. psi 113.41 107.74 110.34 99.91 102.91 Test 1 All spools 0.170 0.882 0.032 1.735 0.066 227 grams (0.5 pounds) 0.160 0.648 0.041 0.904 0.075 4540 grams (10 pounds) 0.098 1.348 0.008 0.518 0.022 Test 2 settings 2 0.683 5.017 0.119 0.372 0.011 settings 3 0.753 4.772 0.083 0.450 0.017 Setting 4 0.713 3.753 0.147 0.367 0.017 Setting 5 1.267 4.025 0.150 0.811 0.061 Setting 6 1.608 8.383 0.322 0.286 0.044 Setting 7 4.128 6.517 0.611 0.403 0.058 Setting 8 4.472 14.800 0.978 0.406 0.128 -147- (Please read the precautions on the back first fill (This page) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 557286 A7 __ B7__ V. Description of the invention (146) 179DESMOPHEN 2000 Polyadipate Ethyl diol, which is commercially available from Bayer, Pittsburgh, PA 0-880ρνρ κ-30 polyvinylpyrrolidone, and is commercially available from ISP Chemicals, Wayne, New Jersey 0 181A-187 γ-dewater Glycerylpropyltrimethoxysilane, commercially available from CK Witco, Tarrytown, NY 0 182A-174 γ-methacryloxypropyltrimethoxysilane, commercially available from CK Witco, Tarrytown, NY 0 Table 13A (continued) Composition sample HH PLURONIC F-108183 9.0 VERS AMID 140184 4.4 MACOL NP-6185 5.4 POLARTHERM PT 160186 0.9 RELEASECOAT-CONC 25187 1.5 Acetic acid < 0.1 183PLURONIC ™ F-108 polyhydrogenated polyethylenic acid polymer Property, commercially available from BASF, Parsippany, New Jersey, 0 184 VERS AMID 140 polyamid, commercially available from Cognis, Cincinnati, Ohio, 185 MACOL NP-6 nonylphenol interface Active agent, commercially available from BASF Company 0 186POLARTHERM PT 160 boron nitride powder particles in Parsippany, New Jersey, commercially available from Advanced Ceramics Company, Lakewood, Ohio. -149- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --- ^ -------------- ^ ---- Order ---- ----- line " ^^ · (Please read the precautions on the back before filling this page) 557286 A7 B7
II ---------tr---------_ (請先閱讀背面之注意事項再填寫本頁) 187 ORPAC BORON NITRIDE RELEASECOAT-CONC 25 氮化硼 分散液’其爲約25重量%氮化硼顆粒於水中之分散液, 其商業得自田納西州Oak Ridge之ZYP Coatings公司。 以手積程序製備預侵紗,其係採刷塗方式將標準fr_4 環氧樹脂(EPON 1120-A8〇樹脂,可自shell化學公司取得) 施用於織物上。該樹脂飽和織物立即在163 t (約325 τ) 之通入熱空氣之烘箱中"乾燥”及B階段,直到達到在 171 °C (約340 °F )之所要膠化時間爲124秒爲止。將預侵 紗修飾成46公分X 46公分(18英吋χ 18英吋)部分,秤 重以決定樹脂含量。只有樹脂含量爲44±2%之預侵紗才可 用於後續積層程序。 將預侵紗堆成8層高,於177 χ:(35〇 τ)及345牛頓/公 分2 (5〇OpSi)之Wabash輾壓中模製。所有積層板均在沒有 銅箔層之下模製的。積層板顯示各種空氣捕捉量。據信在 積層期間缺少眞空及溫度增減變化下對此條件有益。 工具磨耗分析 進行第一系列之試驗之評估鑽頭之磨耗。鑽頭磨耗以使 用下式計算之”鑽頭磨耗百分比”: 鑽頭磨耗百分比=100 X 其中Pi =第一切緣之起初寬度II --------- tr ---------_ (Please read the precautions on the back before filling this page) 187 ORPAC BORON NITRIDE RELEASECOAT-CONC 25 Boron Nitride Dispersion 'It is A dispersion of about 25% by weight of boron nitride particles in water is commercially available from ZYP Coatings, Oak Ridge, Tennessee. The pre-infiltrated yarn was prepared by a hand product procedure, and the standard fr_4 epoxy resin (EPON 1120-A80 resin, available from Shell Chemical Company) was applied to the fabric by brush coating. The resin-saturated fabric was immediately dried in a 163 t (approximately 325 τ) oven with hot air " drying " and stage B until the desired gelation time at 171 ° C (approximately 340 ° F) was 124 seconds .Modify the pre-infiltrated yarn into 46 cm x 46 cm (18 inches x 18 inches) and weigh to determine the resin content. Only pre-infiltrated yarns with a resin content of 44 ± 2% can be used in subsequent lamination procedures. The pre-infiltrated yarn was stacked in 8 layers and molded in Wabash rolling of 177 x: (35〇τ) and 345 Newtons / cm 2 (50OpSi). All laminated boards were molded without copper foil The laminated board shows various air capture amounts. It is believed that this condition is beneficial in the absence of airspace and temperature changes during lamination. Tool wear analysis Performs the first series of tests to evaluate the wear of the drill. The wear of the drill is calculated using the following formula "Drill wear percentage": Drill wear percentage = 100 X where Pi = initial width of the first cutting edge
Pf -在鑽分配孔後之第一切緣之寬度 參考圖11,在鑽頭周圍邊緣測量鑽1174之第一切緣1172 之寬度117〇。 使用單頭鑽頭機進行鑽銅。鑽洞在具有0·203毫米 -150· •本紙張尺度適用中®Ϊ家標準(CNS)A4規格(il〇 χ 297公羞「 557286 A7 五、發明說明(l48) (請先閱讀背面之注意事項再填寫本頁) (0.008英吋)厚鋁入口及L88 €米(0 074英吋)厚紙核經酚 塗覆襯蟄之3個層合物之高堆疊(以上討論)上實行。測定 兩個鑽頭直徑之鑽頭磨耗% : 〇35毫米(〇〇138英吋)及 0.46毫米(0·018英忖)。兩個鑽頭均爲得自加州以此也之 Tulon公司之508系列碳化鎢鑽頭。在鑽洞時之板片負載 對各工具彳呆持岐在Ο.,。在此使用之"板片負載,,表示 以每分鐘英吋測量鑽頭插入速率對以每分鐘圈數⑽以)測 量之心軸速度之比例。對於〇35毫米鑽頭,心軸速度爲 100,000 rpm及插入速率爲每分鐘1〇〇英吋(254公分)。對 於0.46毫米鑽頭,心軸速度爲8〇,〇〇〇 rpm及插入速率爲每 分鐘80英吋(203公分)。對各工具直徑保持固定在每分鐘 2.54米( 1000英吋)之收縮速率及165毫米(〇〇65英吋)之 上鑽頭限制。在此使用之,,鑽頭限制,,表示在層合物上表面 上抽回鑽*頭之距離。 基於圖12所示之500孔鑽洞圖案測定鑽頭磨耗%,其包 括391個在0.635公分乘10.16公分(0 25英吋乘4英吋)之 經濟部智慧財產局員工消費合作社印製 區(邵份1280 )鑽洞之孔’繼而爲1 〇〇個在丨〇乘丨〇孔圖案 (邵伤1282 )之孔’繼而爲9個在3乘3孔圖案(部份1284) 之孔。各邵份中之孔以每平方公分62個孔(每平方英忖 400個孔)之孔密度鑽洞。圖案重複另外三次而總共爲 2000個孔。使用Uniline 2000單頭鑽洞機完成試驗1及2 之鑽洞,及使用CNC-7單頭鑽洞機完成試驗3之鑽洞。兩 種機器均得自華盛頓州Bellevue之Esterline Technologies公 司。 -151- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 6- 8 72 五 經濟部智慧財產局員工消費合作社印製 A7 ______________ 發明說明(l49) 表13B顯tf 〇·35與〇 46毫米直徑鑽頭以以上討論之圖 案對對照GG與樣品ΗΗ鑽2〇〇〇個孔之後之鑽頭磨耗%。 各試驗以新鑽錐開始。 表13Β 對照GG 樣品ΗΗ 試驗1 工具數量 3 3 〇·35毫米直徑鑽頭 平均鑽頭磨耗% 28.8 22.2 試驗2 工具數量 20 20 〇·46毫米直徑鑽頭 平均鑽頭磨耗% 34.0 24。4 試驗3 工具數量 10 10 〇·46毫米直徑鑽頭 平均鑽頭磨耗% 30.8 29.3 如表13Β所見到,試驗1及2之樣品ηη (其包括塗覆 在此敎示與層合物基質樹脂相容之上漿料之玻璃纖維纖絲) 在2000個孔之後呈現遠比對照GG (其包括必須在塗覆含 碎規修整上漿料之前熱清除之玻璃纖維纖絲)小之鑽頭磨 耗%。試驗3顯示在鑽頭磨耗。/❶僅有些微之改良,但是據 信其乃由於用於此試驗之CNC-7鑽洞機較老舊,而且對鑽 洞試驗提供比用於試驗1及2之Uniline 2000鑽洞機少之 控制之事實所造成。 位置正確性 用以評定層合物之鑽洞性能之常見基質爲孔位置正確 性。此試驗測量實際孔位置對其意圖位置之距離之偏誤。 此測量取自3個層合物堆疊之下層合物之下表面,鑽頭離 開層合物堆疊之處,因爲預期此孔位置距意圖或”眞正"孔 -152- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) - I I--訂--丨! ί!線· 557286 經濟部智慧財產局員工消費合作社印製 A7 一 _B7_____ 五、發明說明(150) 位置具有最大差異。此差異以”偏誤距離"評定,即,鑽孔 在層合物表面上之實際眞正中心至孔之意圖眞正中心之距 離。偏誤距離在以上討論之500個孔序列重複4次之後測 量,即,在各工具鑽總共2000個孔之後。對最後鑽的1〇〇 個孔圖案測量偏誤距離,即,最後鑽的部份582。使用以 上討論型式之得自Tulon公司之0.46毫米(0.018英吋)直徑 508系列鑽孔。如同在工具磨耗試驗中所使用,對於o.ooi 之板片負載,鑽頭之心軸速度爲80,000 rpm,及插入速率 爲每分鐘80英吋。對各對照GG及樣品HH,試驗重複8, 次,各試驗以新鑽頭開始。 表13C顯示對照GG及樣品HH在經鑽孔2000個後之位 置準確度試驗之結果。Pf-the width of the first cutting edge after drilling the distribution hole With reference to FIG. 11, the width 1117 of the first cutting edge 1172 of the drill 1174 is measured around the edge of the drill. Use a single-head drill to drill copper. Drilling holes in the range of 0 · 203mm-150 · • This paper size is applicable ® Family Standard (CNS) A4 specification (il0χ 297 public shame "557286 A7 V. Description of the invention (l48) (Please read the note on the back first Please fill in this page again) (0.008 inches) thick aluminum inlet and L88 € m (0 074 inches) thick paper cores are implemented on a high stack of 3 laminates (discussed above) coated with phenol. Bit abrasion of drill bit diameter%: 0.35 mm (0.0138 inches) and 0.46 mm (0.018 inches). Both drill bits are 508 series tungsten carbide drill bits from Tulon Company of California. The plate load when drilling a hole is different from each tool. The "plate load" used here means that the drill bit insertion rate is measured in inches per minute and the number of turns per minute is less than 1) Measured mandrel speed ratio. For a 35 mm drill bit, the mandrel speed is 100,000 rpm and the insertion rate is 100 inches (254 cm) per minute. For a 0.46 mm drill bit, the mandrel speed is 80,000. 〇rpm and insertion rate is 80 inches per minute (203 cm). Keep the tool diameter constant The drill bit limit is above a contraction rate of 2.54 meters (1000 inches) per minute and 165 mm (0065 inches). Used here, the drill bit limit, means to withdraw the drill on the upper surface of the laminate * The distance of the head is determined based on the 500-hole drilling pattern shown in Figure 12. The drill bit abrasion% includes 391 stamps printed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs at 0.635 cm by 10.16 cm (0 25 inches by 4 inches). Production area (Shaofen 1280) drilled holes 'then 100 holes in the 丨 〇 by 丨 0 hole pattern (Shao 1282)' and then 9 holes in the 3 by 3 hole pattern (part 1284) Holes. The holes in each Shaofen were drilled at a density of 62 holes per square centimeter (400 holes per square inch). The pattern was repeated three more times for a total of 2000 holes. Uniline 2000 single-head drilling machine Drilling holes for Tests 1 and 2 and drilling holes for Test 3 using a CNC-7 single-head drilling machine. Both machines were obtained from Esterline Technologies, Bellevue, Washington. -151- This paper size applies to Chinese national standards ( CNS) A4 size (210 X 297 mm) 6- 8 72 Wisdom of the Ministry of Economic Affairs Printed by the Consumer Bureau of the Production Bureau A7 ______________ Description of the invention (l49) Table 13B shows tf 〇35 and 〇46 mm diameter drill bits in the pattern discussed above for the control GG and the sample after boring 2000 holes in% Each test starts with a new drill cone. Table 13B Control GG sample ΗΗ Test 1 Number of tools 3 3 0 · 35 mm diameter drill bit average wear of the drill 28.8 22.2 Test 2 Number of tools 20 20 0 · 46 mm diameter drill bit wear of the average drill 3% 24.4 Test 3 Number of tools 10 10 0.46 mm diameter drill bit average drill wear% 30.8 29.3 As seen in Table 13B, the samples ηη of tests 1 and 2 (which includes coatings shown here with the laminate matrix resin phase The glass fiber filaments of the above size) after 2000 holes showed a much smaller wear of the drill than the control GG (which includes glass fiber filaments that must be thermally cleared before coating with a size-adjusted upper size slurry). Test 3 showed wear on the bit. / ❶ There are only minor improvements, but it is believed to be due to the older CNC-7 drilling rig used for this test, and it provides less drilling test than the Uniline 2000 drilling rig used for tests 1 and 2. Caused by facts of control. Location Correctness A common matrix used to evaluate the drilling performance of laminates is hole location accuracy. This test measures the deviation of the actual hole position from its intended position. This measurement is taken from the lower surface of the laminate under the three laminate stacks, and the drill bit leaves the laminate stack because it is expected that the location of this hole is from the intended or "眞 正" hole -152- This paper size is applicable to the country of China Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page)-I I--Order-丨! Ί! 557286 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs System A7 _B7_____ V. Description of the invention (150) The position has the largest difference. This difference is evaluated by "deviation distance", that is, the actual center of the hole drilled on the surface of the laminate to the center of the hole's intended center Distance. The error distance was measured after the 500 hole sequence discussed above was repeated 4 times, that is, after each tool drilled a total of 2000 holes. The deviation distance was measured on the last drilled 100 hole pattern, that is, the last drilled portion 582. Use the 0.46 mm (0.018 inch) diameter 508 series bores from Tulon Corporation discussed above. As used in the tool abrasion test, the spindle speed of the drill was 80,000 rpm and the insertion rate was 80 inches per minute for a plate load of o.ooi. The test was repeated 8 times for each control GG and sample HH, and each test was started with a new drill. Table 13C shows the results of the position accuracy test of the control GG and the sample HH after 2,000 holes were drilled.
表13C 對照GG 樣品ΗΗ 鑽洞次數 8 8 平均偏誤距離(微米) 38 28 如所見到’樣品HH呈現比對照GG低之偏誤距離,其 在使用層合物作爲加入大量孔與電路之電子撑體時特別重 要。其與以上表13B所示之鑽頭磨耗❶/❶數據一致。更特別 地,預期呈現較低鑽頭磨耗%之層合物亦呈現較小之偏誤 距離’因爲在大量鑽洞之後,鑽頭較尖銳。 實例 。在實例14中,進行另外之鑽具磨耗百分比試驗。試驗 電子級層合物對照;j及如前所述加人雇型織物 品 _____ _153_ 本紙張尺度適用中國國家標準(CNS)A4規格(21〇 χ 297公釐) —''--------------^----訂丨———線 i^w. (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7 五、發明說明(151) AA、BB與KK之鑽具磨耗%。對照JJ中之織物爲得自 Clark_Schwebel 公司之 7628-718 織物。樣品 AA、BB 與 KK 中之織物由包含各塗覆實例9之表9A及以下表14所敎示 之樹脂相容上漿料之玻璃纖維之填紗,及具有塗覆不同聚 合基質材料相容塗層組合物188之玻璃纖維之經紗纺織。 188此經紗爲PPG Industries公司之商業可得纖維玻璃紗產 品,代號G_75玻璃纖維紗,其塗覆PPG Industries公司黏 合劑。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -154- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(152)Table 13C Control GG sample 次数 Number of holes 8 8 Average deviation distance (micron) 38 28 As you can see, the sample HH exhibits a lower deviation distance than the control GG. It uses a laminate as an electron that adds a large number of holes and circuits. This is particularly important when supporting a body. It is consistent with the drill wear ❶ / ❶ data shown in Table 13B above. More specifically, it is expected that laminates exhibiting a lower bit wear% will also exhibit smaller bias distances' because after a large number of holes, the bit is sharper. Examples. In Example 14, another drill wear percentage test was performed. Test electronic-grade laminate comparison; j and the employment-added fabric product as described above _____ _153_ This paper size is applicable to China National Standard (CNS) A4 (21〇χ 297 mm) —''---- ---------- ^ ---- Order 丨 ———— line i ^ w. (Please read the notes on the back before filling out this page) 557286 A7 B7 V. Description of the invention (151) AA, Wear of BB and KK drills. The fabric in Control JJ was a 7628-718 fabric available from Clark_Schwebel. The fabrics in samples AA, BB, and KK were filled with glass fibers containing resin-compatible sizing as shown in Table 9A and Table 14 below for each coating example 9, and compatible with coatings with different polymeric matrix materials Warp spinning of glass fiber of coating composition 188. 188 This warp yarn is a commercially available fiberglass yarn product of PPG Industries, code G_75 glass fiber yarn, which is coated with an adhesive from PPG Industries. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -154- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 557286 Intellectual Property of the Ministry of Economic Affairs A7 B7 printed by the Bureau's Consumer Cooperatives V. Invention Description (152)
表14A 用於樣品KK之上漿料基於總固體之成分重量% 基於總固體之成分重量% 樣品 成分 KK PVP K-30189 13.4 A-187190 1.9 A-174191 3·8 EMERY 6717192 1.9 SAG 10193 0.2 RELEASECOAT-CONC 25194 3.8 POLARTHERM PT 160195 5.9 RD-847A196 23.0 DESMOPHEN 2000197 31.0 PLURONIC F-108198 8.4 ALKAMULS EL-7191" 2.5 ICONOL NP-6200 4.2 LOI (%) 0.35 189PVP K-30聚乙烯基吡咯啶酮,其商業得自紐澤西州 Wayne 之 ISP Chemicals 公司0 19GA-187 γ-去水甘油基丙基三甲氧基矽烷,其商業得自紐 約州 Tarrytown 之 CK Witco 公司0 191Α-174 γ-甲基丙晞氧基丙基三甲氧基矽烷,其商業得自 -155- ---^--------------r---訂---------線 —.^w. (請先閱讀背面之注音2事項再填寫本頁) X 10 (2 格 規 Α4黯 (C 準 標 家 國 國祕 度 尺 張 紙 本 297公釐) 557286 A7 Β7 五、發明說明(157) 實例15 (請先閱讀背面之注意事項再填寫本頁) 以下表15中之樣品表示本發明之額外具體實施例。製 造但未試驗塗層樣品LL。尚未製造塗層樣品MM_QQ。 表15 基於總固體之成分重量% 樣品 成分 LL MM NN 00 PP QQ POLYOX WSR301201 0.56 0.55 0.61 0.43 0.47 0.34 A_174202 3.68 4.31 4.74 3.32 3.68 2.61 A-187203 1.74 2.08 2.29 1.60 1.78 1.26 DYNAKOLL SI ΙΟΟ204 26.60 26.58 - 20.46 - 16.08 SERMULEN668205 3.33 - _ _ DESMOPHEN 2000206 40.58 39.93 43.92 30.75 34.14 24.15 SYNPERONIC F-108207 9.98 - _ 一 - POLARTHERMPT 160208 5.46 5.45 - 6.00 6.00 EUREDUR 140209 4.43 - PLURONIC F-108210 - 9.83 10.81 7.56 8.40 5.94 MACOL NP-6211 一 3.28 3.60 2.52 2.80 1.98 VERSAMED 140212 - 4.36 4.80 3.36 3.73 2.64 201POLYOX WSR 301聚(環氧乙烷),其商業得自康乃迪克州 Danbury 之 Union Carbide 公司 ° 經濟部智慧財產局員工消費合作社印製 2G2A-174 γ-甲基丙烯氧基丙基三甲氧基矽烷,其商業得自 紐約州Tarrytown之CK Witco公司。 2G3A_187 γ-去水甘油基丙基三甲氧基矽烷,其商業得自紐 -160- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7 B7 五、發明說明(158) 約州 Tarrytown 之 CK Witco 公司。 (請先閱讀背面之注意事項再填寫本頁) 2G4DYNAKOLL SI 100松脂,其商業得自瑞典之Eka Chemicals AB公司。 205SERMUL ΕΝ 668乙氧化壬酚,其商業得自 CON ΒΕΑ, Benelux ° 2G6DESMOPHEN 2000聚己二酸伸乙酯二醇,其商業得自賓州 Pittsburgh 之 Bayer 公司。 2G7SYNPERONIC F-108聚氧化丙烯-聚氧化乙烯共聚物,其爲 PLURONIC F-108之歐洲配對物。 2G8POLARTHERM PT 160氮化硼粉末顆粒,其商業得自俄亥俄 州 Lakewood 之 Advanced Ceramics 公司。 2G9EUREDUR 140爲聚醯胺樹脂,其商業得自比利時之Ciba Geigy公司0 21GPLURONIC F-108聚氧化丙烯-聚氧化乙烯共聚物,其商業 得自紐澤西州Parsippany之BASF公司。 211MACOL NP-6壬酚界面活性劑,其商業得自紐澤西州 Parsippany 之 BASF 公司。 經濟部智慧財產局員工消費合作社印製 212VERSAMID 140聚醯胺,其商業得自俄亥俄州Cincinnati之 Cognis 公司 ° -161- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7 B7 五、發明說明(l59) 表15 (續) 基於總固體之成分重量% 樣品 成分 LL MM NN 00 PP QQ RELEASECOAT-CONC 25213 3.64 3.63 - 4.00 4.00 ROPAQUE OP-96214 - 29.23 30.00 35.00 35.00 塗層中之估計固體% 5.4 5.6 5.1 7.3 6.5 9.3 213ORPAC BORON NITRIDE RELEASECOAT-CONC 25 氮化硼分散 液,其爲約25重量%氮化硼顆粒於水中之分散液,其商 業得自田納西州Oak Ridge之ZYP Coatings公司。 214ROPAQUE® OP-96,0.55微米顆粒分散液,其商業得自賓 州費城之Rohm and Haas公司。 實例16 以實例9所述之材料及方法製造未護面層合物,除了在 層合時未使用銅。然後將各未護面層合物切割成52個1 英吋X 1/2英吋(約2.54公分X約1.27公分)長方形片。約 一半之片以平行經紗方向切割,而且約一半之片以平行填 紗方向切割。然後將26個得自各層合物之長方形(13個平 行經紗方向切割及13個平行填紗方向切割)置於有水之回 流裝置中,而且使水沸騰。使水沸騰24小時。在24小時 後,自水去除片且擦乾。其餘來自各層合物之26片並未 沸騰。亦製造以如以上實例9製造試驗層合物之相同方 法,使用習知熱清除及修整織物製造之未護面對照層合 物,並且依照以上之步驟試驗。 -162- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注音?事項再填寫本頁) ------^----訂---------線· 經濟部智慧財產局員工消費合作社印製 557286 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(m) 然後依照ASTM D 2344-84測量經滞騰及未 剪切強度。試驗結果示於表9,其中未護面樣品^束 BB與CC相當於使用各具有以上衆組合物Μ U 上漿之纖維之織物(敘述於實例9)製造之層合物。如以上 所討論,對照樣品使用習知之熱清除及修整織物製造。試 驗層合物(未護面樣品AA 、BB與cc)之厚度範園爲 0·〇5〇英忖(約0.127公分)至〇 〇63英忖(約〇⑽公分)。試 驗時’跨距長度對樣品厚度之比例爲5。 -163- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 557286 A7 B7 五、發明說明(⑹) 表16 試驗 單位 AA BB CC 對照 短束剪切強度,未 每平方英吋之碎 7787 8477 7769 7382 沸騰經紗方向 數(百萬巴斯卡) (54) (56) (54) (51) 樣品厚度N=13 英忖 0.060 0.050 0.056 0.055 (公分) (0.152) (0.127) (0.142) (0.140) 短束剪切強度,未 每平方英吋之镑 6626 7594 7118 5506 沸騰填紗方向 數(百萬巴斯卡) (46) (52) (49) (38) 樣品厚度N=13 英吋 0.061 0.050 0.060 0.055 (公分) (0.155) (0.127) (0.152) (0.140) 短束剪切強度24 每平方英吋之碡 5695 6522 5081 4929 小時沸騰經紗方向 數(百萬巴斯卡) (39) (45) (35) (34) 樣品厚度N=13 英吋 0.061 0.051 0.057 0.057 (公分) (0.155) (0.130) (0.145) (0.145) 短束剪切強度24 每平方英忖之镑 5266 5832 5179 4116 小時沸騰填紗方向 數(百萬巴斯卡) (36) (40) (36) (28) 樣品厚度N=13 英吋 0.063 0.051 0.062 0.056 (公分) (0.160) (0.130) (0.157) (0.142) 在此試驗中,試驗層合物(未護面樣品AA、BB與CC ) 在經紗與緯紗方向之短束剪切強度,在水沸騰之前與之後 均觀察到比對照樣品高。 實例17 將由塗覆實例9之表9A所示上漿組合物CC之E·玻璃 纖維股製造之填紗,及由PPG Industries公司之1383商業 -164- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) —:--------------:----訂---------線 i^w. (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7 五、發明說明(l62) 可得纖維玻璃紗產品製造之經紗,使用空氣噴射織布機紡 織成7628型織物。織物繼而預浸及層合以形成銅護面層 合物,如以上實例9所述。 繼而將銅護面層合物CC (如以上實例9所述)處理 (即,鑽洞、電鍍及圖案化)成爲具有多個試驗圖案之試驗 板,以試驗金屬移動性能。更特別地,各板包括三組七層 電路圖案1310 ,如圖13所示。一組圖案沿板之X-軸定 向’另一組沿板之Y-軸,及第三組沿橫越板之45。。各電 路圖案1310包括50列五個鑽孔1312,其各具有13.5 mil 之直徑,及範圍爲40至54.7 mil之相鄰列之孔間中心對中 心間隔。在鑽這些孔時,將兩個板堆疊在一起,使得在單 一鑽洞操作中將其鑽洞。各圖案中交錯列之孔沿板之第一 主要表面以匯流排1314及引線1316互連,如圖13所示。 將引線焊在各匯流排以連接電源。各電路更包括1K歐姆 表面電阻1322 ,以確定如果一個電路板損壞則仍維持對 其餘電路之電源。將各板浸於76.7 °C ( 170 T )去離子水10 分鐘以去除任何焊錫助熔劑殘渣及乾燥。然後將板置於 85 C (185 °F)及85%相對濕度之槽中,並且對圖案連續地 施加13.5伏特之DC電流。每200小時將槽關閉,打開槽 門以使圖案安定至周圍實驗室溫度,及測量各圖案之絕緣 電阻。 在此有兩個樣品CC及兩個對照板。對照板以如樣品 CC之相同方式製造,但是使用習知之熱清除及修整織 物。各板包括21個電路圖案(即,三組七層電路圖案), -165- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公f ) (請先閱讀背面之注意事項再填寫本頁) ------Γ---訂---------線· 經濟部智慧財產局員工消費合作社印製 557286 ----~_SI___五、發明說明(163) —- 樣品CC及對照板均試驗總共42個電路。以下表η顯示 200 400及100〇小時之結果,其中表列値爲具有指定電 阻之圖案數量。 表17 絕緣電阻 --- 樣品CC 對,昭 OHMS 200 Hrs 400 Hrs 1000 hrs 400 Hrs 短路 0 1 7 42 105 1 4 2 〇 106 1 1 1 0 107 0 2 0 0 108 1 0 1 0 109 3 2 1 0 >1010 36 32 30 0 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 樣品CC板在暴露200小時後具有比對照板少之短路。 在暴露400小時後,所有之對照板圖案損壞。爲了此試驗 樣品之目的,"短路"指小於1〇5歐姆之絕緣電阻値。 實例18 混合表18A中所述之量之各成分,以形成依照本發明之 水性樹脂相容第一上漿樣品RR。在組合物中包括基於總 重量爲少於1重量%之乙酸。將樣品RR塗覆於形成G_75 E-玻璃纖維股之玻璃纖維。使用習知交織裝置以類似之方 法將經塗覆玻璃纖維股交織以形成交織紗,並且捲繞在線 軸上。經塗覆紗具有0.35%之LOI。 -166- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 A7B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(164)Table 14A Ingredient weight% based on total solids of the slurry used for sample KK Sample ingredients KK PVP K-30189 13.4 A-187190 1.9 A-174191 3 · 8 EMERY 6717192 1.9 SAG 10193 0.2 RELEASECOAT- CONC 25194 3.8 POLARTHERM PT 160195 5.9 RD-847A196 23.0 DESMOPHEN 2000197 31.0 PLURONIC F-108198 8.4 ALKAMULS EL-7191 " 2.5 ICONOL NP-6200 4.2 LOI (%) 0.35 189 PVP K-30 polyvinylpyrrolidone, which is commercially available ISP Chemicals, Inc., Wayne, New Jersey 0 19GA-187 γ-desglycerylpropyltrimethoxysilane, commercially available from CK Witco, Tarrytown, NY 0 191A-174 γ-methylpropanyloxypropane Trimethoxysilane, which is commercially available from -155- --- ^ ---------- r --- order --------- line-. ^ W (Please read the note 2 on the back before filling in this page) X 10 (2 grid rule A4 dark (C quasi standard home country secret rule paper 297 mm) 557286 A7 Β7 V. Description of the invention (157) Example 15 (Please read the notes on the back before filling out this page) The samples in Table 15 below represent additional aspects of the invention Specific examples. The coating sample LL is manufactured but not tested. The coating sample MM_QQ has not been manufactured. Table 15 Composition weight% based on total solids Sample composition LL MM NN 00 PP QQ POLYOX WSR301201 0.56 0.55 0.61 0.43 0.47 0.34 A_174202 3.68 4.31 4.74 3.32 3.68 2.61 A-187203 1.74 2.08 2.29 1.60 1.78 1.26 DYNAKOLL SI ΙΟ204 204.60 26.58-20.46-16.08 SERMULEN668205 3.33-_ _ DESMOPHEN 2000206 40.58 39.93 43.92 30.75 34.14 24.15 SYNPERONIC F-108207 9.98-_6.00-6.00-4.6-6.00-6.00 140209 4.43-PLURONIC F-108210-9.83 10.81 7.56 8.40 5.94 MACOL NP-6211-3.28 3.60 2.52 2.80 1.98 VERSAMED 140212-4.36 4.80 3.36 3.73 2.64 201POLYOX WSR 301 Poly (ethylene oxide), commercially available from Connecticut Union Carbide Corporation of Danbury ° Printed 2G2A-174 γ-methacryloxypropyltrimethoxysilane produced by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy, commercially available from CK Witco, Tarrytown, New York. 2G3A_187 γ-dehydrated glycerylpropyltrimethoxysilane, which is commercially available from New-160- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 557286 A7 B7 V. Description of the invention (158 ) CK Witco, Tarrytown, Ill. (Please read the notes on the back before filling this page) 2G4DYNAKOLL SI 100 turpentine, which is commercially available from Eka Chemicals AB, Sweden. 205SERMUL EN 668 ethoxylated nonylphenol, commercially available from CON ΒΕΑ, Benelux ° 2G6DESMOPHEN 2000 polyethylene adipate glycol, commercially available from Bayer, Pittsburgh, PA. 2G7SYNPERONIC F-108 polyoxypropylene-polyethylene oxide copolymer, which is the European counterpart of PLURONIC F-108. 2G8POLARTHERM PT 160 boron nitride powder particles are commercially available from Advanced Ceramics Corporation of Lakewood, Ohio. 2G9EUREDUR 140 is a polyamide resin commercially available from Ciba Geigy, Belgium, 21 GLURONIC F-108 polyoxypropylene-polyethylene oxide copolymer, and commercially available from BASF, Parsippany, New Jersey. 211MACOL NP-6 nonanol surfactant, commercially available from BASF Corporation, Parsippany, New Jersey. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy, 212VERSAMID 140 Polyamide, which is commercially available from Cognis, Inc. of Cincinnati, Ohio ° -161- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 557286 A7 B7 V. Description of the invention (l59) Table 15 (continued) Based on the total solids content by weight% Sample composition LL MM NN 00 PP QQ RELEASECOAT-CONC 25213 3.64 3.63-4.00 4.00 ROPAQUE OP-96214-29.23 30.00 35.00 35.00 In the coating Estimated% solids 5.4 5.6 5.1 7.3 6.5 9.3 213 ORPAC BORON NITRIDE RELEASECOAT-CONC 25 Boron Nitride Dispersion, which is a dispersion of approximately 25% by weight of boron nitride particles in water, commercially available from ZYP Coatings, Oak Ridge, Tennessee the company. 214ROPAQUE® OP-96, a 0.55 micron particle dispersion, commercially available from Rohm and Haas, Philadelphia, PA. Example 16 An unprotected laminate was prepared using the materials and methods described in Example 9, except that copper was not used in the lamination. Each unfaced laminate was then cut into 52 1-inch X 1 / 2-inch (about 2.54 cm x about 1.27 cm) rectangular pieces. About half of the pieces are cut parallel to the warp direction, and about half of the pieces are cut parallel to the filling direction. Then, 26 rectangles (13 parallel warp direction cuts and 13 parallel fill direction cuts) obtained from each laminate were placed in a water recirculation device and the water was boiled. Boil water for 24 hours. After 24 hours, the tablets were removed from water and wiped dry. The remaining 26 tablets from each laminate did not boil. An unprotected control laminate made from the conventional heat-clearing and trimming fabric was also manufactured in the same manner as the test laminate as in Example 9 above, and tested in accordance with the above steps. -162- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) ------ ^ ---- Order-- ------- Line · Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (m) Then measure the stagnation according to ASTM D 2344-84 And unshear strength. The test results are shown in Table 9, where the uncovered samples BB and CC correspond to laminates made using fabrics (described in Example 9) each having fibers sized above the composition MU. As discussed above, the control samples were made using conventional heat removal and conditioning fabrics. The thickness of the test laminates (unfaced samples AA, BB, and cc) ranged from 0.050 cm (about 0.127 cm) to 0.063 cm (about 0 cm). In the test, the ratio of the span length to the thickness of the sample was 5. -163- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 A7 B7 V. Description of the invention (⑹) Table 16 Test unit AA BB CC Control Short beam shear strength, not broken per square inch 7787 8477 7769 7382 Boiling warp yarn direction (million basca) (54) (56) (54) (51) Sample thickness N = 13 Inches 0.060 0.050 0.056 0.055 (cm) (0.152) (0.127) (0.142) (0.140) Short beam shear strength, not pounds per square inch 6626 7594 7118 5506 Number of boiling filling yarn directions (million basca) (46) (52 ) (49) (38) Sample thickness N = 13 inches 0.061 0.050 0.060 0.055 (cm) (0.155) (0.127) (0.152) (0.140) Short beam shear strength 24 碡 5695 6522 5081 4929 hours per square inch Number of boiling warp threads (million basca) (39) (45) (35) (34) Sample thickness N = 13 inches 0.061 0.051 0.057 0.057 (cm) (0.155) (0.130) (0.145) (0.145) short Beam Shear Strength 24 pounds per square inch 5266 5832 5179 4116 hours boiling filling direction (million basca) (36) (40) (36) (28) Sample thickness N = 13 inches 0.063 0.051 0.062 0.056 (cm) (0.160) (0.130) (0.157) (0.142) In this test, the test laminate (unprotected For the surface samples AA, BB and CC), the short beam shear strength in the warp and weft directions was observed to be higher than that of the control sample before and after water boiling. Example 17 A gauze made from E · glass fiber strands coated with the sizing composition CC shown in Table 9A of Example 9 was applied, and 1383 Commercial-164 by PPG Industries was used. This paper size applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) —: --------------: ---- Order --------- line i ^ w. (Please read the first Note: Please fill in this page again.) 557286 A7 B7 V. Description of the invention (l62) The warp yarns made from fiberglass yarn products can be woven with air jet loom into 7628 type fabric. The fabric is then prepreged and laminated to form a copper facing laminate, as described in Example 9 above. The copper finish laminate CC (as described in Example 9 above) was then processed (i.e., drilled, plated, and patterned) into a test plate with multiple test patterns to test metal migration performance. More specifically, each board includes three groups of seven-layer circuit patterns 1310, as shown in FIG. One set of patterns is oriented along the X-axis of the board ', the other set is along the Y-axis of the board, and the third set is across 45 of the board. . Each circuit pattern 1310 includes 50 rows of five drill holes 1312, each of which has a diameter of 13.5 mil, and the center-to-center spacing between adjacent rows of holes ranging from 40 to 54.7 mil. When drilling these holes, the two plates are stacked together so that they are drilled in a single drilling operation. The staggered rows of holes in each pattern are interconnected along the first major surface of the board by bus bars 1314 and leads 1316, as shown in FIG. Solder leads to each bus to connect to a power source. Each circuit also includes 1K ohm surface resistance 1322 to ensure that if one circuit board is damaged, power to the remaining circuits is maintained. Immerse each plate in 76.7 ° C (170 T) deionized water for 10 minutes to remove any solder flux residue and dry. The plate was then placed in a tank at 85 C (185 ° F) and 85% relative humidity, and a DC current of 13.5 volts was continuously applied to the pattern. Close the slot every 200 hours, open the slot door to stabilize the pattern to the surrounding laboratory temperature, and measure the insulation resistance of each pattern. There are two sample CCs and two control plates. The control panel was made in the same manner as Sample CC, but the fabric was cleaned and trimmed using conventional heat. Each board includes 21 circuit patterns (that is, three groups of seven-layer circuit patterns), -165- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 male f) (Please read the precautions on the back before filling (This page) ------ Γ --- Order --------- Line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 557286 ---- ~ _SI ___ V. Description of the Invention (163) —- A total of 42 circuits were tested on the sample CC and the control board. Table η below shows the results for 200, 400 and 100 hours, where Table 値 is the number of patterns with the specified resistance. Table 17 Insulation resistance --- sample CC pair, OHMS 200 Hrs 400 Hrs 1000 hrs 400 Hrs short circuit 0 1 7 42 105 1 4 2 〇 106 1 1 1 0 107 0 2 0 0 108 1 0 1 0 109 3 2 1 0 > 1010 36 32 30 0 (Please read the precautions on the back before filling this page) The sample CC board printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has less short circuits than the control board after 200 hours of exposure. After 400 hours of exposure, all control plate patterns were damaged. For the purpose of this test sample, " short circuit " refers to an insulation resistance of less than 105 ohms. Example 18 The ingredients were mixed in the amounts described in Table 18A to form an aqueous resin compatible first sizing sample RR according to the present invention. Acetic acid is included in the composition at less than 1% by weight based on the total weight. Sample RR was coated on glass fibers forming a G_75 E-glass fiber strand. The coated glass fiber strands were interwoven in a similar manner using a conventional interlacing device to form an interlaced yarn, and wound on a bobbin. The coated yarn had a LOI of 0.35%. -166- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 557286 A7B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (164)
表18A 樣品RR上漿料基於總固體之成分重量% 成分 樣品RR RD-847A215 27.0 DESMOPHEN 2000216 36.2 PVP K-30217 9.0 A-187218 2.1 A-174219 4.4 PLURONIC F-108220 9.0 VERS AMID 140221 4.4 MACOL NP-6222 5.4 POLARTHERM PT 160223 0.9 RELEASECOAT-CONC 25224 1.5 乙酸 <0.1 215RD-847A聚酯樹脂,其商業得自俄亥俄州Columbus之Table 18A Ingredients% by weight based on total solids of sample RR Ingredient sample RR RD-847A215 27.0 DESMOPHEN 2000216 36.2 PVP K-30217 9.0 A-187218 2.1 A-174219 4.4 PLURONIC F-108220 9.0 VERS AMID 140221 4.4 MACOL NP-6222 5.4 POLARTHERM PT 160223 0.9 RELEASECOAT-CONC 25224 1.5 Acetic acid < 0.1 215RD-847A polyester resin, commercially available from Columbus, Ohio
Borden Chemicals 公司 〇 216DESMOPHEN 2000聚己二酸伸乙酯二醇,其商業得自賓 州 Pittsburgh 之 Bayer 公司0 217PVP K-30聚乙烯基吡咯啶酮,其商業得自紐澤西州 Wayne 之 ISP Chemicals 公司0 218Α-187 γ_去水甘油基丙基三甲氧基矽烷,其商業得自紐 約州 Tarrytown 之 OSi Specialties 公司0 219A-174 γ-甲基丙晞氧基丙基三甲氧基矽烷,其商業得自 紐約州 Tarrytown 之 OSi Specialties 公司。 • 167- 本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) —h--------------^----訂---------線 i^w. (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7 五、發明說明(165 ) 22GPLURONIC F-108聚氧化丙烯-聚氧化乙烯共聚物,其商 業得自紐澤西州Parsippany之BASF公司。 221 VERS AMID 140 聚醯胺,其商業得自 General Mills Chemicals 公司 〇 222MACOL NP-6壬酚界面活性劑,其商業得自紐澤西州 Parsippany 之 BASF 公司。 223POLARTHERM⑧PT 160氮化硼粉末顆粒,其商業得自俄 亥俄州 Lakewood 之 Advanced Ceramics 公司。 224ORPAC BORON NITRIDE RELEASECOAT-CONC 25 氮化硼 分散液,其爲約25重量%氮化硼顆粒於水中之分散液, 其商業得自田納西州Oak Ridge之ZYP Coatings公司。 混合表18B中所述之量之各成分,以形成依照本發明之 水性樹脂相容第一上漿樣品SS。將樣品SS塗覆於形成G-75 E-玻璃纖維股纖維之玻璃纖維,而且未將股交織。經 塗覆之未交織紗具有0.7%之LOI。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -168 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 557286 A7 ___B7 五、發明說明(166)Borden Chemicals Corporation 216 DESMOPHEN 2000 Polyethylene Adipate Glycol, commercially available from Bayer Corporation Pittsburgh, PA 0 217 PVP K-30 polyvinyl pyrrolidone, commercially available from ISP Chemicals, Wayne, New Jersey Company 0 218A-187 γ-Glycerylpropyltrimethoxysilane, commercially available from OSi Specialties, Tarrytown, New York Company 0 219A-174 γ-methylpropanyloxypropyltrimethoxysilane, commercially available Available from OSi Specialties, Tarrytown, New York. • 167- This paper size applies to China National Standard (CNS) A4 (210 χ 297 mm) —h -------------- ^ ---- Order ------ --- line i ^ w. (Please read the notes on the back before filling out this page) 557286 A7 B7 V. Description of the invention (165) 22GPLURONIC F-108 Polypropylene oxide-polyethylene oxide copolymer, commercially available from New Zealand BASF, Parsippany, Jersey. 221 VERS AMID 140 Polyamine, commercially available from General Mills Chemicals. 222MACOL NP-6 nonyl surfactant, commercially available from BASF, Parsippany, New Jersey. 223POLARTHERM⑧PT 160 boron nitride powder particles are commercially available from Advanced Ceramics, Lakewood, Ohio. 224ORPAC BORON NITRIDE RELEASECOAT-CONC 25 Boron nitride dispersion, which is a dispersion of about 25% by weight of boron nitride particles in water, is commercially available from ZYP Coatings, Oak Ridge, Tennessee. The ingredients are mixed in the amounts described in Table 18B to form an aqueous resin compatible first sizing sample SS according to the present invention. Sample SS was coated on glass fibers forming G-75 E-glass fiber strand fibers, and the strands were not interwoven. The coated uninterlaced yarn had a LOI of 0.7%. (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs's Consumer Cooperatives -168-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Employee Consumer Cooperative 557286 A7 ___B7 V. Description of Invention (166)
表18B 每100加侖樣品SS上漿料之成分磅數 成分 樣品SS MAPEG 600 DOT225 9.24 ALUBRASPIN 226226 1.9 A-174227 10.9 A-187228 5.45 A-1 10229 2.41 EPON 880230 91.1 PLURONIC F-108231 9.11 ALKAMULS EL-719232 9.11 MACOL OP-10-SP233 4.57 EPIREZ 3522234 20.9 乙酸 2.6 225爲得自BASF公司之乙氧化二牛脂。 226ALUBRASPIN 226部分醯胺化聚伸乙二亞胺,其商業得自 紐澤西州Parsippany之BASF公司0 227Α-174 γ-甲基丙烯氧基丙基三甲氧基矽烷,其商業得自 紐約州Tarrytown之CK Witco公司0 228Α-187 γ-去水甘油基丙基三甲氧基矽烷,其商業得自紐 約州 Tarrytown 之 CK Witco 公司。 229Α·1100胺基官能基有機矽烷偶合劑,其商業得自紐約州 Tarrytown 之 CK Witco 公司0 230EPON 880環氧樹脂,其商業得自德州Houston之Shell 169- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -----------------^----訂---------線 (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7 五、發明說明(167)Table 18B Per pound composition of SS on 100 gallon samples SS MAPEG 600 DOT225 9.24 ALUBRASPIN 226226 1.9 A-174227 10.9 A-187228 5.45 A-1 10229 2.41 EPON 880230 91.1 PLURONIC F-108231 9.11 ALKAMULS EL-719232 9.11 MACOL OP-10-SP233 4.57 EPIREZ 3522234 20.9 Acetic acid 2.6 225 is ethoxylated ditallow obtained from BASF. 226ALUBRASPIN 226 partially fluorinated poly (ethylene diimide), commercially available from BASF Corporation, Parsippany, New Jersey 0 227A-174 γ-methacryloxypropyltrimethoxysilane, commercially available from Tarrytown, New York CK Witco, Inc. 0 228A-187 γ-desglycerylpropyltrimethoxysilane, commercially available from CK Witco, Tarrytown, NY. 229A · 1100 Amine functional organosilane coupling agent, which is commercially available from CK Witco Company, Tarrytown, New York, 0 230EPON 880 epoxy resin, which is commercially available from Houston, Texas, Shell 169- This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----------------- ^ ---- order --------- line (Please read the precautions on the back first (Fill in this page again) 557286 A7 B7 V. Description of Invention (167)
Chemical 公司0 (請先閱讀背面之注意事項再填寫本頁) 231PLURONIC™ F-108聚氧化丙烯-聚氧化乙烯共聚物,其 商業得自紐澤西州Parsippany之BASF公司。 232ALKAMULS EL-719聚氧化乙晞化蔬菜油,其商業得自 Rhone-Poulenc 公司 〇 233MACOL OP-10 SP乙氧化烷酚,其商業得自紐澤西州 Parsippany 之 BASF 公司0 234EPIREZ 3522固態聯酚A二縮水甘油醚環氧樹脂之分散 液,其商業得自德州Houston之Sell Chemical公司。 使用以樣品RR與SS上漿之紗作爲經紗及填紗(或緯 紗),並且紡織成7628型織物。亦將對照紗纺織成7628型 織物,其爲具有塗層PPG 695上漿料之纖維且得自賓州 Pittsburgh之PPG Industries公司之商業可得G_75 E·交織 紗。上漿之經紗與填紗對照紗具有1%之LOI 。在織動 前,以聚乙烯醇組合物將經紗開縫,其將經紗之LOI增至 約2至約2.5%。生成織物具有範圍爲1.6至1.9%之LOI。 經濟部智慧財產局員工消費合作社印製 依照ASTM D 737纺織織物透氣力之標準試驗方法試驗 各織物之透氣力。織物纺織之平均透氣力示於以下表 18C 。 -170- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 557286 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(168 )Chemical Company 0 (Please read the notes on the back before filling this page) 231PLURONIC ™ F-108 Polyoxypropylene-Polyethylene Oxide Copolymer, commercially available from BASF Corporation, Parsippany, New Jersey. 232ALKAMULS EL-719 polyoxyacetic acid vegetable oil, commercially available from Rhone-Poulenc Company 233 MACOL OP-10 SP ethoxylated phenol, commercially available from BASF Company Parsippany, New Jersey 0 234EPIREZ 3522 solid biphenol A A dispersion of diglycidyl ether epoxy resin is commercially available from Sell Chemical Company of Houston, Texas. The sizing yarns of samples RR and SS were used as warp and filling yarns (or weft yarns), and woven into 7628 type fabrics. The control yarn was also woven into a Type 7628 fabric, which is a fiber with a coated PPG 695 sizing and is commercially available from PPG Industries of Pittsburgh, PA. The sizing warp yarn and the filling yarn have a LOI of 1%. Before weaving, the warp yarn is slit with a polyvinyl alcohol composition, which increases the LOI of the warp yarn to about 2 to about 2.5%. The resulting fabric has a LOI in the range of 1.6 to 1.9%. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Test the air permeability of each fabric in accordance with ASTM D 737 standard test method for air permeability of textile fabrics. The average air permeability of the fabrics is shown in Table 18C below. -170- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 557286 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (168)
表18C 透氣力 (每分鐘每平方英呎之標準立方英呎) 對照樣品 41 樣品RR 2.8 樣品SS 1.6 如由表18C所見到,加入樣品A與B之纺織織物之透 氣力遠低於以對照樣品纺織之織物。 實例19 表19包括塗佈於玻璃纖維(繼而將其纺織成織物)之額 外非限制上漿配方。各組合物中包括少於1重量%之乙 酸0 表19 基於總固體之成分重量% 成分 樣品TT 樣品UU 樣品XX 樣品YY PVP K-30235 13.7 13.5 15.3 14.7 STEPANTEX 653236 27.9 13.6 A-187237 1.7 1.9 1.9 1.8 235 PVP K-30聚乙烯基吡咯啶酮,其商業得自紐澤西州 Wayne 之 ISP Chemicals 公司0 236 STEPANTEX 653 ,其商業得自紐澤西州Maywood之 Stepan 公司。 237 A-187 r·去水甘油基丙基三甲氧基矽烷,其商業得自紐 約州 Tarrytown 之 CK Witco 公司0 -171- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) —^--------------^----訂---------線 i^v. (請先閱讀背面之注意事項再填寫本頁) 557286 A7 B7 五、發明說明(169) 表19 (續) 成分 樣品TT 樣品UU 樣品XX 樣品YY A-174238 3.4 3.8 3.8 3.7 EMERY 6717239 2.3 1.9 2.5 2.4 MACOL ΟΡ-ΙΟ240 1.5 1.7 1.6 TMAZ-81241 3.0 3.4 3.3 MAZU DF-136242 0.2 0.3 0.2 ROPAQUE OP-96243 39.3 43.9 42.3 RELEASECOAT-CONC 25244 4.2 6.4 POLARTHERMPT 160245 2.7 2.6 SAG 10246 0.2 RD-847A247 23.2 DESMOPHEN2000248 31.2 PLURONIC F-108249 8.5 238 A-174 r -甲基丙烯氧基丙基三甲氧基矽烷,其商業得自 紐約州Tarrytown之CK Witco公司0 -----------------=----訂---------線 i^w. (請先閱讀背面之注意事項再填寫本頁) 用 適 度 尺 張 紙 本 經濟部智慧財產局員工消費合作社印製 239 EMERY® 6717部份醯胺化聚伸乙二亞胺,其商業得自俄 亥俄州Cincinnati之Cognis公司。 240 MACOL OP-10乙氧化烷酚;此材料類似MACOL OP-10 SP ,除了 MACOL OP-10 SP接受後處理以去除觸媒; MACOL OP_10不再商業可得。 241 TMAZ-81花楸醇酯之環氧乙烷衍生物,其商業得自紐澤 西州Parsippany之BASF公司。 242 MAZU DF-136防沫劑,其商業得自紐澤西州Parsippany之 172-中國國家標準(CNS)A4規格(210 χ 297公釐) 557286 表19 (續) A7 B7 五、發明說明(170) BASF公司。 243 ROPAQUE® OP_96,0.55微米顆粒分散液,其商業得自賓 州費城之Rohm and Haas公司。 244 ORPAC BORON NITRIDE RELEASECOAT_CONC 25 氮化硼分散 液,其爲約25重量%氮化硼顆粒於水中之分散液,其商 業得自田納西州Oak Ridge之ZYP Coatings公司。 245 POLARTHERM PT® 160氮化硼粉末顆粒,其商業得自俄亥 俄州 Lakewood 之 Advanced Ceramics 公司。 240 SAG 10防沫材料,其商業得自康乃迪克州Greenwich之 CK Witco 公司。 247 RD-847A聚酯樹脂,其商業得自俄亥俄州Columbus之 Borden Chemicals 公司 〇 248DESMOPHEN 2000聚己二酸伸乙酯二醇,其商業得自賓州 Pittsburgh 之 Bayer 公司。 249PLURONIC™ F-108聚氧化丙烯聚氧化乙烯共聚物,其商 業得自紐澤西州Parsippany之BASF公司0 成分 樣品TT 樣品UU 樣品XX 樣品YY ALKAMULS EL-719250 3.4 ICONOL NP-6251 3.4 FLEXOL ΕΡ0252 13.6 30.0 謂ALKAMULS EL-719聚氧化乙烯化蔬菜油,其商業得自 Rhone-Poulenc 公司 ° ICONOL NP-6烷氧化壬酚,其商業得自紐澤西州 -173- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---:--------------r---訂---------線 (請先閱讀背面之注音?事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製Table 18C Air permeability (standard cubic feet per square foot per minute) Control sample 41 Sample RR 2.8 Sample SS 1.6 As seen in Table 18C, the air permeability of the textile fabrics added with samples A and B is much lower than that of the control sample Textile fabric. Example 19 Table 19 includes additional non-limiting sizing formulations coated on glass fibers, which are then woven into a fabric. Each composition includes less than 1% by weight of acetic acid. Table 19 Ingredients% by weight based on total solids Ingredient Sample TT Sample UU Sample XX Sample YY PVP K-30235 13.7 13.5 15.3 14.7 STEPANTEX 653236 27.9 13.6 A-187237 1.7 1.9 1.9 1.8 235 PVP K-30 polyvinylpyrrolidone, commercially available from ISP Chemicals Corporation 0236 STEPANTEX 653, Wayne, New Jersey, and commercially available from Stepan Corporation, Maywood, New Jersey. 237 A-187 r · Dehydrated glycerylpropyltrimethoxysilane, commercially available from CK Witco, Tarrytown, New York 0 -171- This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm) ) — ^ ---------------------- Order --------- line i ^ v. (Please read the notes on the back before filling this page) 557286 A7 B7 V. Description of the invention (169) Table 19 (continued) Composition sample TT sample UU sample XX sample YY A-174238 3.4 3.8 3.8 3.7 EMERY 6717239 2.3 1.9 2.5 2.4 MACOL ΟΡ-ΙΟ240 1.5 1.7 1.6 TMAZ-81241 3.0 3.4 3.3 MAZU DF-136242 0.2 0.3 0.2 ROPAQUE OP-96243 39.3 43.9 42.3 RELEASECOAT-CONC 25244 4.2 6.4 POLARTHERMPT 160245 2.7 2.6 SAG 10246 0.2 RD-847A247 23.2 DESMOPHEN2000248 31.2 PLURONIC F-108249 8.5 238 A-174 r -methacryloxypropyl Trimethoxysilane, commercially available from CK Witco, Tarrytown, NY 0 ----------------- = ---- Order --------- Line i ^ w. (Please read the precautions on the back before filling out this page) Printed on a moderately large piece of paper Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 239 EMERY® 6717 partially fluorinated poly (ethylene diimide), commercially available from Cognis Corporation of Cincinnati, Ohio. 240 MACOL OP-10 ethoxylated alkylphenol; this material is similar to MACOL OP-10 SP, except that MACOL OP-10 SP is subjected to post-treatment to remove the catalyst; MACOL OP_10 is no longer commercially available. An ethylene oxide derivative of 241 TMAZ-81 anisolate, commercially available from BASF Corporation, Parsippany, New Jersey. 242 MAZU DF-136 Antifoam, commercially available from Parsippany, New Jersey, 172-Chinese National Standard (CNS) A4 Specification (210 x 297 mm) 557286 Table 19 (continued) A7 B7 V. Description of the Invention (170 ) BASF Company. 243 ROPAQUE® OP_96, 0.55 micron particle dispersion, commercially available from Rohm and Haas, Philadelphia, PA. 244 ORPAC BORON NITRIDE RELEASECOAT_CONC 25 Boron nitride dispersion, which is a dispersion of about 25% by weight of boron nitride particles in water. It is commercially available from ZYP Coatings, Oak Ridge, Tennessee. 245 POLARTHERM PT® 160 boron nitride powder particles are commercially available from Advanced Ceramics, Lakewood, Ohio. 240 SAG 10 antifoam material commercially available from CK Witco, Greenwich, Connecticut. 247 RD-847A polyester resin, commercially available from Borden Chemicals, Columbus, Ohio. 248DESMOPHEN 2000 polyethylene adipate glycol, commercially available from Bayer, Pittsburgh, PA. 249PLURONIC ™ F-108 Polyoxypropylene Polyethylene Oxide Copolymer, commercially available from BASF Corporation, Parsippany, New Jersey 0 Ingredient Sample TT Sample UU Sample XX Sample YY ALKAMULS EL-719250 3.4 ICONOL NP-6251 3.4 FLEXOL ΕΡ0252 13.6 30.0 Referred to as ALKAMULS EL-719 polyethylene oxide vegetable oil, it is commercially available from Rhone-Poulenc Company ° ICONOL NP-6 alkoxylated nonylphenol, and it is commercially available from New Jersey -173- This paper size applies to Chinese national standards (CNS ) A4 size (210 X 297 mm) ---: -------------- r --- order --------- line (please read the note on the back first) ? Please fill out this page again) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
Claims (1)
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14633799P | 1999-07-30 | 1999-07-30 | |
US14660599P | 1999-07-30 | 1999-07-30 | |
US14686299P | 1999-08-03 | 1999-08-03 | |
US18356200P | 2000-02-18 | 2000-02-18 | |
US52703400A | 2000-03-16 | 2000-03-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
TW557286B true TW557286B (en) | 2003-10-11 |
Family
ID=32303811
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW89115361A TWI230698B (en) | 1999-07-30 | 2000-07-29 | Impregnated glass fiber strands and products including the same |
TW89115359A TW557286B (en) | 1999-07-30 | 2000-07-29 | Impregnated glass fiber strands and products including the same |
TW89115360A TWI283255B (en) | 1999-07-30 | 2000-11-14 | Impregnated glass fiber strands and products including the same |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW89115361A TWI230698B (en) | 1999-07-30 | 2000-07-29 | Impregnated glass fiber strands and products including the same |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW89115360A TWI283255B (en) | 1999-07-30 | 2000-11-14 | Impregnated glass fiber strands and products including the same |
Country Status (1)
Country | Link |
---|---|
TW (3) | TWI230698B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI585315B (en) * | 2012-10-22 | 2017-06-01 | Hef公司 | Self-lubricating joint element operating under high loads in dynamic state |
-
2000
- 2000-07-29 TW TW89115361A patent/TWI230698B/en not_active IP Right Cessation
- 2000-07-29 TW TW89115359A patent/TW557286B/en not_active IP Right Cessation
- 2000-11-14 TW TW89115360A patent/TWI283255B/en not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI585315B (en) * | 2012-10-22 | 2017-06-01 | Hef公司 | Self-lubricating joint element operating under high loads in dynamic state |
Also Published As
Publication number | Publication date |
---|---|
TWI230698B (en) | 2005-04-11 |
TWI283255B (en) | 2007-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6593255B1 (en) | Impregnated glass fiber strands and products including the same | |
US6419981B1 (en) | Impregnated glass fiber strands and products including the same | |
US6809046B2 (en) | Non-heat cleaned fabrics and products including the same | |
US8105690B2 (en) | Fiber product coated with particles to adjust the friction of the coating and the interfilament bonding | |
US6949289B1 (en) | Impregnated glass fiber strands and products including the same | |
MXPA01003656A (en) | Preimpregnates reinforced with glass fiber, laminated, electronic circuit plates and methods to mount a t | |
US20020193027A1 (en) | Coating solubility of impregnated glass fiber strands | |
US20020086598A1 (en) | Fabrics comprising resin compatible yarn with defined shape factor | |
WO2001068749A1 (en) | Impregnated glass fiber strands and products including the same | |
CN100366563C (en) | Impregnated glass fibre strands and products including same | |
CN100387642C (en) | Impregnated glass fiber strands and products including same | |
CN100475882C (en) | Impregnated glass fiber strands and products including the same | |
US20020058449A1 (en) | Articles having defined surface profiles formed from fabrics comprising resin compatible yarn | |
WO2001009226A1 (en) | Impregnated glass fiber strands and products including the same | |
TW557286B (en) | Impregnated glass fiber strands and products including the same | |
TWI228520B (en) | Glass fiber-reinforced prepregs, laminates, electronic circuit boards and methods for assembling a fabric | |
WO2001068753A1 (en) | Impregnated glass fiber strands and products including the same | |
WO2001068755A1 (en) | Impregnated glass fiber strands and products including the same | |
CA2380594A1 (en) | Impregnated glass fiber strands and products including the same | |
WO2001068751A1 (en) | Impregnated glass fiber strands and products including the same | |
WO2001068748A1 (en) | Impregnated glass fiber strands and products including the same | |
WO2001068750A1 (en) | Impregnated glass fiber strands and products including the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
GD4A | Issue of patent certificate for granted invention patent | ||
MM4A | Annulment or lapse of patent due to non-payment of fees |