201026780 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種印刷電路基板製造步驟中之穿孔加 工步驟（Drilling)中所使用之潤滑片及該潤滑片形成用組成 物。 . 【先前技術】 印刷電路基板之製造步驟，例如，電腦數値控制穿孔 參步驟（CNC Drillingg)係於基板形成導通孔（Via Hole)、通孔 (Through Hole)，並藉由内部鍍敷等形成電氣電路。 近年來，隨著印刷電路基板的小型化、薄膜化及高密 度化演進’係要求穿孔開口的小徑化及高密度化。一般來 說，當對於玻璃纖維含浸有環氧基等之印刷電路基板進行 穿孔開口加工的情況時，鑽頭（Drill bit)與印刷電路基板會 產生摩擦熱’因此錄頭熱變形造成之鑽孔位置準確度會變 差，且會發生鑽頭折損等破損。又，由該加工步驟所加工 ® 而成之鑽孔的内壁會有印刷電路基板樹脂熔附，或鑽孔表 面均勻性會降低’或於樹脂層與玻璃纖維發生因剝離所造 " 成之不均的鏟敷。 為了解決該問題’係於鑽頭徑〇.3mm以下之小孔開口 處使用潤滑性片。潤滑性片不僅使鑽頭表面潤滑性增大， 提升穿孔加工步驟時鑽孔的位置準確度、鍍敷時内壁之品 質及物性改善，更可藉由1次穿孔時之多層積層所需之製 造步驟花費降低、及防止鑽頭破損來謀求製造花費降低。 201026780 此種潤滑性片之製造方法有：如美國發明專利第 4风495號公報、第4,929,370號公報等所揭示之製造將包 含水溶性潤滑劑及合成蝶、界面活性劑耸 , 劑等之潤滑性樹脂含 浸於紙等所成之片之方法，但是穿孔拄 牙孔時鑽頭的發熱抑制 差，樹脂含浸困難，故有片表面會黏著之缺點。 為了改善此點，有人提出一種使用有熱傳導性及發散 力優異之鋁或銅金屬薄膜之潤滑性片的製造方法，此種方 法中提出大致分為包含水溶性潤滑樹脂層之穿孔片與包 含非水溶性潤滑樹脂層之穿孔片。 水溶性之满滑性片係揭示於韓國專利公開第 1992-0005676號公報、專利公開第2〇〇2 〇〇18984號公報、 專利公開第2003-0036041號公報、專利公開第 2006-0006681號公報、專利公開第2〇〇7_〇1 15732號公報、 及專利公開第2003-0036770號公報、登錄專利第〇672775 號公報、登錄專利第0615132號公報、登錄專利第〇654552 號公報等。 韓國專利公開第1992-0005676號公報及專利公開第 2002-0018984號公報係包含聚乙二醇、聚酯衍生物及液體 水溶性潤滑劑者，該等樹脂於樹脂層潤滑性方面雖優異， 但高速穿孔等鑽頭的發熱增加時，會發生樹脂卷附到鑽頭 周邊之現象，故孔位置準確度變差，會發生鑽頭折損現象。 為了改善此點’藉由於樹脂層添加水不溶性潤滑劑之醯胺 系化合物、脂肪酸化合物、脂肪酸酯系化合物來改善樹脂 卷附至錢頭周邊之現象之韓國專利公開第2〇〇3_〇〇36〇41號 201026780 公報所揭示之發明，因使用低溫下會溶解 宵+鮮之非水溶性活化 劑’而於鐵孔内壁穿孔時所炼融之非水溶性活化劑會殘 存，故於鍍敷時可能會誘發品質降低。韓國專利公開第 2006-006681號公報所揭示之發明，其特徵在於，為了區分 潤滑劑片的表/裏面而將潤滑劑層加以著色，與潤滑性片的 - 特性無關。 • * 又’韓國專利公開第2007_0115732號公報中雖揭示藉 由潤滑層的表面平滑度與氣泡的減少所進行之塗佈法但 傪於水溶性塗料混合物使用有醇系等有機溶劑之氣泡防止效 果（小泡效果）、及以表面張力控制來賦予表面平坦性只不過 是一般塗料製造步驟中廣泛使用之習知方法。 韓國登錄專利第0654552號公報所揭示之發明係由含 有聚乙二醇、聚乙浠基醇及聚乙二醇之酯化合物及無機填 充劑中之至少3種以上之樹脂組成物所構成。該專利因使 用了低分子量的聚乙二醇化合物，故長期間保存時表面會 有發生黏著之虞，認為有因所添加之無機填充劑誘發鑽頭 先端摩耗之問題點。 韓國登錄專利第0615132號公報之發明係於鋁基板上 積層聚乙稀（PE)、聚丙烯（PP)等鑄膜後，於其上層使用水溶 性潤滑層者。_般來說有機樹脂膜係熱傳導性低之物質， 因此該鎮膜有抑制熱分散至鋁與水溶性潤滑層及空氣層之 虞。又’為了増大鑄膜之熱分散力，所添加之氧化鋁、氧 化猛、氣化爛等熱傳導性無機粒子會誘發鑽頭的摩耗及於 鍍敷步驟時殘存而品質不良。 201026780 另一方面，非水溶性潤滑劑片之韓國專利公開第 2001-01 10645號公報、登錄專利第〇657427號公報、登錄 專利第062861 1號公報等所揭示之發明雖有改善了水溶性 樹脂層保存性（耐濕性、保存容易性）之優點，但樹脂層的熔 點高，且樹脂層所致之熱發散效果低，故有發生pCB樹脂 基板熔附之鑽污（smear)現象之虞，鑽頭的溫度上昇時潤滑 樹脂會熔融而殘存於孔内壁，此種殘存潤滑樹脂以水洗步 驟除去困難’故有鍍敷時發生不良之問題。 因此，為了解決根本之問題，必須為於鑽孔時對潤滑 片形成用組成物之效率性增加之構成。 【發明内容】 本發明所欲解決之第1課題係提供一種不含非水溶性 樹脂及有機樹脂粒子、或無機樹脂粒子，且抑制屑卷附至 穿孔時鑽頭周邊，同時鑽頭之發熱抑制效果優異之水溶性 潤滑片。 本發明所欲解決之第2課題係提出一種含有對水之溶 解度相異之第1水溶性樹脂與第2水溶性樹脂及使相分離 均勻化之乳化劑之混合物作為具有適於印刷電路基板穿孔 用潤滑片t造之剪切黏度之材料，#此大幅增#穿孔加工 步驟之效率性。 為了達成該第1課題，本發明係一種潤滑片，其係具 備形成於基材上之潤滑樹脂層者；該潤滑樹脂層係包含對 水之’合解度相異之2種以上之水溶性樹脂且微細相分離而 201026780 成者，該潤滑片樹脂層在15 0 °C溶融狀態下之黏度具有在剪 切速度條件100mm/sec下為5xl04〜lxl〇5cp範圍的値。 本發明之一實施例係，該水溶性樹脂係包含對水之溶 解度為40%以下之第1水溶性樹脂及對水之溶解度為4〇% 以上的第2水溶性樹脂。 本發明之一實施例係，該第i水溶性樹脂可使用選自 •由聚乙烯基°比咯烷酮系樹脂、聚乙烯基醇系樹脂、分子量 萬以上之聚乙二醇系樹脂、該等之衍生物及該等之氣化 物所構成群中之一者以上。 本發明之一實施例係，該第2水溶性樹脂可使用選自 刀子量5萬以下之聚乙二醇系樹脂、聚酯系樹脂、該等 之衍生物及該等之氣化物所構成群之一者以上。 本發明之-實施例係，該第！水溶性樹脂及第2水溶 陡樹月曰之重量比較佳為2 : 8〜8 : 2，更佳為4 : 6〜6 : 4。[Technical Field] The present invention relates to a lubricating sheet used in a piercing processing step (Drilling) in a manufacturing process of a printed circuit board, and a composition for forming the same. [Prior Art] The manufacturing steps of the printed circuit board, for example, the CNC Drillingg step is to form a Via Hole, a Through Hole, and the like by internal plating. Form an electrical circuit. In recent years, with the miniaturization, thinning, and high density of printed circuit boards, it has been required to reduce the diameter and density of the perforation openings. In general, when a perforated opening process is performed on a printed circuit board in which a glass fiber is impregnated with an epoxy group or the like, a Drill bit and a printed circuit board generate frictional heat, and thus the drilling position caused by thermal deformation of the head is generated. The accuracy will be deteriorated, and damage such as bit breakage will occur. Moreover, the inner wall of the drilled hole formed by the processing step may have a printed circuit board resin fused, or the uniformity of the surface of the drilled surface may be reduced, or the resin layer and the glass fiber may be formed by peeling off. Uneven shovel. In order to solve this problem, a lubricative sheet is used at a small hole opening of a drill diameter of 3 mm or less. The lubricious sheet not only increases the lubricity of the drill surface, but also improves the positional accuracy of the drilling during the perforation processing step, the quality and physical properties of the inner wall during plating, and the manufacturing steps required for the multi-layer lamination in one perforation. The cost is reduced and the drill bit is prevented from being damaged to reduce the manufacturing cost. 201026780 The manufacturing method of such a lubricative sheet is as follows: manufacturing of a water-soluble lubricant, a synthetic butterfly, a surfactant, a lubricant, etc., as disclosed in U.S. Patent No. 4, 495, and No. 4,929,370. The resin is impregnated with a sheet formed of paper or the like, but the heat generation of the drill bit is poorly suppressed when the perforated hole is punched, and the impregnation of the resin is difficult, so that the surface of the sheet adheres. In order to improve this, there has been proposed a method for producing a lubricative sheet using an aluminum or copper metal film having excellent thermal conductivity and divergence, and in this method, it is proposed to be roughly classified into a perforated sheet containing a water-soluble lubricating resin layer and containing non- A perforated sheet of a water-soluble lubricating resin layer. The water-soluble full-slip film is disclosed in Korean Patent Publication No. 1992-0005676, Patent Publication No. 2, No. 2, 1984, No. 1, 1984, No. 2003-0036041, and Patent Publication No. 2006-0006681 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Korean Patent Publication No. 1992-0005676 and Patent Publication No. 2002-0018984 are those containing polyethylene glycol, a polyester derivative, and a liquid water-soluble lubricant, which are excellent in lubricity of a resin layer, but When the heat of the drill such as the high-speed perforation increases, the phenomenon that the resin roll is attached to the periphery of the drill bit occurs, so that the accuracy of the hole position is deteriorated, and the bit breakage phenomenon occurs. In order to improve this, the Korean Patent Publication No. 2 〇〇 3_〇 by the addition of a hydrazine-based compound, a fatty acid compound, or a fatty acid ester-based compound of a water-insoluble lubricant to a resin layer to improve the periphery of the resin roll to the periphery of the head is disclosed.发明36〇41# 201026780 The invention disclosed in the publication, the water-insoluble activator which is fused during perforation of the inner wall of the iron hole will remain due to the use of a non-water-soluble activator which dissolves the 宵+ fresh water at low temperature, so plating is performed. A decrease in quality may be induced during application. The invention disclosed in Korean Patent Publication No. 2006-006681 is characterized in that the lubricant layer is colored in order to distinguish the surface/inside of the lubricant sheet, regardless of the characteristics of the lubricative sheet. In the Korean Patent Publication No. 2007_0115732, the coating method by the surface smoothness of the lubricating layer and the reduction of the bubbles is disclosed, but the bubble preventing effect of the organic solvent such as an alcohol is used for the water-soluble coating mixture. (Small bubble effect) and surface flatness control by surface tension control are merely conventional methods widely used in general paint manufacturing steps. The invention disclosed in Japanese Patent Publication No. 0654552 is composed of at least three or more resin compositions containing an ester compound of polyethylene glycol, polyethylene glycol, and polyethylene glycol, and an inorganic filler. Since this patent uses a low-molecular-weight polyethylene glycol compound, it is likely to adhere to the surface during long-term storage, and it is considered that the inorganic filler added causes the problem of the tip end wear. The invention of the Japanese Patent Publication No. 0615132 discloses a method of laminating a cast film such as polyethylene (PE) or polypropylene (PP) on an aluminum substrate, and then using a water-soluble lubricating layer on the upper layer. In general, the organic resin film is a substance having low heat conductivity, and therefore the film has a tendency to suppress heat dispersion to aluminum and a water-soluble lubricating layer and an air layer. Further, in order to increase the heat dispersing power of the cast film, the thermally conductive inorganic particles such as alumina, oxidized, and gasified are added to induce wear of the drill and remain in the plating step and are inferior in quality. In addition, the invention disclosed in the Korean Patent Publication No. 2001-01 10645, the registered patent No. 657 427, the registered patent No. 062861, and the like, has improved the water-soluble resin. The layer has the advantages of preservability (moisture resistance, ease of storage), but the melting point of the resin layer is high, and the heat dissipation effect by the resin layer is low, so there is a smear phenomenon in which the pCB resin substrate is fused. When the temperature of the drill bit rises, the lubricating resin melts and remains on the inner wall of the hole. This residual lubricating resin is difficult to remove by the water washing step, so that there is a problem that plating occurs when plating occurs. Therefore, in order to solve the fundamental problem, it is necessary to increase the efficiency of the composition for forming a lubricant sheet during drilling. SUMMARY OF THE INVENTION The first problem to be solved by the present invention is to provide a non-water-soluble resin, an organic resin particle, or an inorganic resin particle, and to suppress the periphery of the drill when the chip is attached to the perforation, and the heat generation suppressing effect of the drill is excellent. Water soluble lubricating sheet. A second object to be solved by the present invention is to provide a mixture containing a first water-soluble resin having a solubility in water and a second water-soluble resin and an emulsifier which is uniform in phase separation as having a perforation suitable for a printed circuit board. The material of the shear viscosity made with the lubricating sheet t, this greatly increases the efficiency of the perforation processing step. In order to achieve the first problem, the present invention is a lubricating sheet comprising a lubricating resin layer formed on a substrate; the lubricating resin layer containing two or more kinds of water-soluble having different degrees of water compatibility Resin and fine phase separation, 201026780, the viscosity of the lubricating resin layer in the molten state at 150 ° C has a enthalpy in the range of 5 x 10 4 l l l 〇 5 cp at a shear rate condition of 100 mm / sec. According to an embodiment of the present invention, the water-soluble resin comprises a first water-soluble resin having a solubility in water of 40% or less and a second water-soluble resin having a solubility in water of 4% by weight or more. According to an embodiment of the present invention, the ith water-soluble resin may be selected from the group consisting of a polyvinylpyrrolidone resin, a polyvinyl alcohol resin, and a polyethylene glycol resin having a molecular weight of 10,000 or more. One or more of the constituents of the derivatives and the vapors of the above. According to an embodiment of the present invention, the second water-soluble resin may be a group of polyethylene glycol-based resins selected from the group consisting of knives of 50,000 or less, polyester-based resins, derivatives thereof, and the like. More than one. The embodiment of the invention, the first! The weight of the water-soluble resin and the second water-soluble steep tree sorghum is preferably 2: 8 to 8: 2, more preferably 4: 6 to 6: 4.
為了達成該第2課題’本發明係提供—種潤滑片形成 用組成物，其包含： 含水之溶劑100重量份、對水之溶解度相異之2種以 上之水溶性樹月旨5〜60重量份、微細相形成用乳化劑 0·〇1〜2.5重量份；且 …::::範狀:度…速度條"。—“ 該溶劑可使用水或水與有機溶 本發明之一實施例係 劑之現合溶劑。 本發明係提供一 種利用具有特定黏度條件之潤滑樹脂 7 201026780 層的微細好離現象，來改U相至㈣之現象及防止 樹脂卷附至鑽頭周邊’鑽孔位置準確度高且鑽頭不會折 損，再者所穿孔之鑽孔内部的鍍敷特性優異之潤滑片及該 潤滑片形成用組成物。 又，藉由排除使用醯胺系樹脂等之非水溶性樹脂、有 機樹脂（PE Wax等）或無機粒子，來抑制㈣時水洗步驟後 於穿孔洞（hole)内壁有殘存物殘留之情形，故鍍敷均勻之品 質性及不良可受到抑制，且藉由抑制既存之低分子量的水 溶性樹脂之使用’而使用高分子量之水溶性樹脂，來彌補 製品保存時空氣中的濕氣等造成製品表面發生黏著之缺點 而可增加製品的保存安定性。 又，該潤滑片形成用組成物係一種混合物係含有對水 之溶解度相異之第1水溶性樹脂、與第2水溶性樹脂 '及 使樹脂層之微細相分離均勻化之乳化劑；於製造印刷電路 基板穿孔用潤滑片時，藉由將在常溫下含溶劑之組成物的 液狀黏度限定為既定範圍，可大幅增加穿孔加工步驟之效 率性。 【實施方式】 本發明之潤滑片係具備形成於基材上之潤滑樹脂層， 該潤滑樹脂層係將相異特性之樹脂2種以上混合所得，藉 由此所得之樹脂塗膜的微細相分離來調節該潤滑樹脂層之 勤性，因而潤滑性優異且可抑制穿孔時樹脂卷附至鑽頭周 邊。 201026780 尤其’該樹脂較佳為炼點在1 5 〇 °C以下，且水溶性者。 一般來說’溶解於溶劑中之樹脂在溶劑乾燥後固化 時、因對該溶劑之個別的溶解度差及樹脂層本身之極性 (Dipole)差會誘發微細相分離現象，此一般稱為海（sea)/島 (island)構造’將各個樹脂層特性相異之樹脂加以混合，並 以混合比來控制物性。 -. 例如，調節樹脂之混合比而可決定主樹脂（Sea部樹脂） 之特性，且調解此所得之補助樹脂（Island部樹脂）之混合比 ❹而可調節總體樹脂層之物性。舉例而言，藉由將韌性優異 之主樹脂層與易破裂特性之補助樹脂之含量加以調節可 控制總體之樹脂的機械物性（相反的情況亦同）。又，不僅是 此種樹脂之混合比，亦可藉由控制補助樹脂（Island)之尺 寸、粗密度等來控制物性。 本發明中，藉由控制此種微細相分離而成之樹脂構 造，同時賦予既定範圍之熔融黏度，即使沒有非水溶性添 φ 加劑亦可除去潤滑樹脂層所造成之屑卷附至鑽頭周邊的現 •象，因此可製造潤滑性優異且鑽孔位置準確度及鍍敷時鑽 孔内部的品質優異之潤滑片。 般來說，鑽孔過程中之鑽頭的旋轉數為15萬〜3〇萬 rpm左右的高剪切條件，鑽頭進入潤滑片之速度為 l.Om/min〜3.〇m/min，鑽頭接觸於潤滑片之時間極短。因此， 右依剪切速度提議適當的熔融黏度，則潤滑片樹脂層所具 有之潤滑性與切削屬的排出變得容易，在電路線寬窄之高 密度鐵頭加工中，可防止鑽頭的折損，增加洞的平滑性與 9 201026780 位置準確度經提升之鑽頭加工的效率性。 本發明之該潤滑片所具備之該潤滑樹脂層於經過乾燥 步驟後幾乎不含溶劑，在15(TC熔融之狀態下的剪切黏度具 有在剪切速度條件l〇〇mm/sec下為5Χι〇4〜ixi〇5cpp範圍的 值，在4,000mm/sec之高剪切速度下熔融黏度可具有2χ 102〜2xl03cp之範圍的值。 該熔融黏度若過高，則會產生切削屑易殘存而洞位置 準確度會變差’且鑽頭的折損變大、鑽頭加工的效率性降 低之問題。相反地，熔融黏度若過低，則洞加工結束後移 ❹ 動至下一個洞加工時，潤滑片組成物有落在潤滑片上之 虞’故不佳。此會引起洞位置準確度不良與鑽頭折損之致 命問題。 前述本發明之潤滑樹脂層係將相異特性之樹脂2種以 上混合所得，例如，可包含對水之溶解度為4〇%以下之第ι 水溶性樹脂及對水之溶解度為40%以上的第2水溶性樹脂。 該第1水溶性樹脂及第2水溶性樹脂較佳為一般市售 之熔點15(TC以下之水溶性樹脂，尤其熔點3(rc以下之樹 ❹ 脂乾燥時塗佈膜會黏著，故較佳為熔點及軟化點為3〇它以 -上' 150。(：以下之水溶性樹脂。 . 該第1水溶性樹脂對水之溶解度為4〇%以下，較低且 含韌性及機械特性優異之高分子量樹脂，故塗佈於基材薄 膜時會提升塗佈膜之機械物性及附著力等，塗佈層扮演使 不會因外部衝擊發生破裂或剥離的角色。又，對水之溶解 度相對較低，故會提升對水之耐濕性’即使放置於高溫多 201026780 濕之條件下亦具有經提升之耐濕性。 該第1水溶性樹脂對水之溶解度為4 〇 %以下，較佳為 30%以下，該溶解度若超過40%,則有不會引起良好相分離 之問題，故不佳。 此種第1水溶性樹脂例如可使用選自由聚乙烯基咄咯 烷酮系樹脂、聚乙烯基醇系樹脂、分子量1〇萬以上之聚乙 . 二醇系樹脂、該等之衍生物及該等之氣化物所構成群之一 者以上。較佳為乙烯基<7比洛烧_與乙烯基乙酸醋之共聚物 ^ (聚乙烯基β比咯烷酮之衍生物）之部分加水分解所得之樹 脂、加水分解度為75〜90%之聚乙烯基醇與其之衍生物、或 分子量100,000以上之線形聚乙二醇與其之衍生物。 該第1水溶性樹脂中之聚乙烯基醇及其之衍生物的情 況時，因聚乙烯基醇的分子量與加水分解程度（鹼化度）的差 造成對水之溶解度改變；而聚乙烯基吡咯烷酮及其之衍生 物的情況時’藉由分子量與交聯度及共聚物之乙酸酯基的 ❹ 含量、鹼化率可調節對水之溶解度；聚環氧乙烷化合物的 情況時，因分子量造成對水之溶解度改變。因此，較佳係 以此種特性適當調節溶解度使用。 該第1水溶性樹脂’分子量為3〇,〇〇〇以上，較佳為 100,000以上，可維持樹脂層機械強度者較佳。 該第2水溶性樹脂係對水之溶解度為以上之水溶 性樹脂，為了改善高分子量樹脂之韌性所造成之卷附至鑽 頭周邊之現象，係使用易因外部衝擊而破裂，且受熱嫁融 時樹脂之熔融黏度低之相較低分子量的樹脂來增大切削屑 11 201026780 的飛散效果’且會減少熔融時之樹脂層的黏著，抑制屑卷 附至鑽頭周邊。 此種第2水溶性樹脂可使用分子量5萬以下之聚乙二 醇系樹脂、聚酯系樹脂與其之共聚物及該等之衍生物所構 成群之一者以上’其分子量只要滿足樹脂之溶解度即無特 別限定’但特徵在於樹脂層的機械強度低，且因外部衝擊 而易於破裂’且熔融時黏度低、不會發生樹脂卷附至鑽頭 周邊現象者較佳。 該第1水溶性樹脂及第2水溶性樹脂之含量比較佳為 2 : 8〜8 : 2 ’更佳為4 : 6〜6 : 4 »該第1水溶性樹脂之含量 比未滿2時’樹脂層易於破裂而所塗佈之樹脂層機械強度 低，故使用困難，含量比超過8時，樹脂層韌性高，鑽頭 的發熱造成樹脂層熔融時黏度高而切削樹脂有附於鑽頭之 虞，故不佳。 上述這樣的潤滑性樹脂層係形成於基材上以構成潤滑 片’而此基材可使用鋁片或銅片。該鋁片係產業上可利用 之純度99%以上之熱發散優異之鋁或複合材，係使用厚度 為50〜200μιη範圍内者，但無特別限定。一般來說，鋁片係 使用壓延後進行了熱處理、平坦化處理步驟者，可因應錢 頭直徑及穿孔作業條件使用各種厚度的鋁。 又’本發明中’為了提升潤滑樹脂層與鋁基材之基材 密合力，可具備接著力增大層。此種接著力増大層，為了 抑制鑽頭發熱所造成之樹脂熔融、此所致之洞内部樹脂殘 存’係使用熱硬化性樹脂，可使用具代表性的環氧基系、 201026780In order to achieve the second problem, the present invention provides a composition for forming a lubricating sheet comprising: 100 parts by weight of a solvent containing water, and two or more kinds of water-soluble trees having different solubility in water; Parts, fine phase forming emulsifier 0·〇1~2.5 parts by weight; and...::::norm: degree...speed bar". - "The solvent can use water or water and organic solvent to dissolve the present invention." The present invention provides a fine separation phenomenon using a lubricating resin 7 201026780 layer having a specific viscosity condition. The phenomenon of the phase to the (4) and the prevention of the resin roll attached to the periphery of the drill bit. The drilling position is high and the drill bit is not damaged, and the lubricating sheet having excellent plating characteristics inside the drilled hole and the lubricant forming composition are Further, by using a water-insoluble resin such as a guanamine-based resin or an organic resin (such as PE Wax) or inorganic particles, it is possible to suppress the residual residue on the inner wall of the hole after the water washing step. Therefore, the quality and the poorness of the plating can be suppressed, and the high molecular weight water-soluble resin can be used to suppress the moisture in the air during storage of the product by suppressing the use of the existing low molecular weight water-soluble resin. The disadvantage of adhesion on the surface can increase the preservation stability of the product. Moreover, the composition for forming the lubricating sheet is a mixture containing different solubility to water. The first water-soluble resin, the second water-soluble resin, and the emulsifier which separates and separates the fine phase of the resin layer; and when the lubricant sheet for perforating a printed circuit board is produced, the composition containing the solvent at normal temperature is used. The liquid viscosity is limited to a predetermined range, and the efficiency of the perforation processing step can be greatly increased. [Embodiment] The lubricating sheet of the present invention comprises a lubricating resin layer formed on a substrate, the lubricating resin layer being a resin having a different characteristic When the two or more types are mixed, the fine phase separation of the resin coating film obtained thereby adjusts the workability of the lubricating resin layer, so that the lubricity is excellent and the resin is wound around the periphery of the drill when the perforation is suppressed. Preferably, the melting point is below 15 °C, and it is water-soluble. Generally, the resin dissolved in the solvent is cured after the solvent is dried, due to the difference in solubility of the solvent and the polarity of the resin layer itself. Dipole) difference induces fine phase separation, which is generally called sea/island structure. The resin with different resin layer characteristics is mixed and mixed. For example, adjusting the mixing ratio of the resin determines the characteristics of the main resin (Sea part resin), and adjusts the mixing ratio of the obtained auxiliary resin (Island part resin) to adjust the physical properties of the entire resin layer. For example, by adjusting the content of the main resin layer excellent in toughness and the content of the auxiliary resin which is easy to be broken, the mechanical properties of the overall resin can be controlled (the reverse is also the case). Moreover, not only the mixing ratio of the resin The physical properties can also be controlled by controlling the size, the coarse density, etc. of the auxiliary resin. In the present invention, by controlling the resin structure formed by separating such fine phases, the melt viscosity of a predetermined range is imparted, even if there is no The water-soluble φ addition agent can also remove the swarf caused by the lubricating resin layer and attach it to the periphery of the drill bit. Therefore, it can produce lubrication with excellent lubricity, accurate drilling position and excellent quality inside the drilled hole during plating. sheet. Generally speaking, the number of rotations of the drill bit during the drilling process is a high shear condition of about 150,000 to 30,000 rpm, and the speed at which the drill enters the lubricating sheet is 1.0 m/min to 3. 〇m/min, and the drill bit is in contact. The time for the lubricant is extremely short. Therefore, when the right melt viscosity is proposed by the shear rate, the lubricity of the lubricated sheet resin layer and the discharge of the cutting genus are facilitated, and the breakage of the drill bit can be prevented in the high-density iron head processing in which the circuit line width is narrow. Increased hole smoothness and 9 201026780 Position accuracy improved efficiency of bit machining. The lubricating resin layer provided in the lubricating sheet of the present invention contains almost no solvent after the drying step, and has a shear viscosity at 15 (TC melting state of 5 Χ at a shear rate condition of 10 mm/sec). The value of the range of 〇4~ixi〇5cpp, the melt viscosity at a high shear rate of 4,000 mm/sec may have a value in the range of 2χ102~2xl03cp. If the melt viscosity is too high, the chips may be liable to remain. The accuracy of the position will deteriorate, and the breakage of the drill will become larger, and the efficiency of the drill processing will be reduced. Conversely, if the melt viscosity is too low, the lubricant will be formed when the hole is processed and moved to the next hole. It is not preferable that the object falls on the lubricating sheet. This causes a fatal problem of poor hole position accuracy and bit breakage. The lubricating resin layer of the present invention is obtained by mixing two or more kinds of resins having different characteristics, for example, The first water-soluble resin having a solubility in water of 4% by weight or less and the second water-soluble resin having a solubility in water of 40% or more may be contained. The first water-soluble resin and the second water-soluble resin are preferably general cities. Melting point 15 (water-soluble resin below TC, especially melting point 3 (the coating film will adhere when the resin is below rc, so it is preferable that the melting point and softening point are 3 〇 it is -1'. (: the following water-soluble Resin resin. The first water-soluble resin has a solubility in water of 4% by weight or less, and is high in molecular weight resin having excellent toughness and mechanical properties. Therefore, when applied to a base film, the mechanical properties of the coating film are improved. And adhesion, etc., the coating layer acts as a role that does not cause cracking or peeling due to external impact. Moreover, the solubility in water is relatively low, so it will improve the moisture resistance to water' even if it is placed at high temperature, 201026780 Wet The moisture resistance of the first water-soluble resin to water is 4% by mole or less, preferably 30% or less, and if the solubility exceeds 40%, it does not cause good phase separation. The first water-soluble resin may be, for example, a polyethylene glycol-based resin selected from the group consisting of a polyvinylpyrrolidone resin, a polyvinyl alcohol resin, and a molecular weight of 1,000,000 or more. a derivative of such a derivative and a group of such vapors One or more. It is preferably a resin obtained by hydrolysis of a part of a vinyl <7 piroxime _ with a copolymer of vinyl acetate vinegar (a derivative of polyvinyl β pyrrolidone), and the degree of hydrolysis is 75 to 90% of a polyvinyl alcohol and a derivative thereof, or a linear polyethylene glycol having a molecular weight of 100,000 or more and a derivative thereof. In the case of the polyvinyl alcohol and the derivative thereof in the first water-soluble resin, The solubility in water is changed by the difference between the molecular weight of polyvinyl alcohol and the degree of hydrolysis (basicity); in the case of polyvinylpyrrolidone and its derivatives, 'by molecular weight and degree of crosslinking and copolymer The hydrazine content and alkalization rate of the acetate group can adjust the solubility to water; in the case of the polyethylene oxide compound, the solubility in water changes due to the molecular weight. Therefore, it is preferred to appropriately adjust the solubility using such characteristics. The first water-soluble resin has a molecular weight of 3 Å or more, preferably 100,000 or more, and is preferable because the mechanical strength of the resin layer can be maintained. The second water-soluble resin is a water-soluble resin having a solubility in water of more than the water-soluble resin, and is used to improve the toughness of the high-molecular-weight resin, and is attached to the periphery of the drill bit, and is easily broken by an external impact, and is subjected to heat-gathering. The lower molecular weight resin with a lower melt viscosity of the resin increases the scattering effect of the chip 11 201026780' and reduces the adhesion of the resin layer during melting, and suppresses the attachment of the chip to the periphery of the bit. As the second water-soluble resin, a polyethylene glycol-based resin having a molecular weight of 50,000 or less, a copolymer of a polyester-based resin, and a group of such a derivative can be used. The molecular weight thereof satisfies the solubility of the resin. That is, it is not particularly limited, but it is characterized in that the mechanical strength of the resin layer is low, and it is easy to be broken by external impact, and the viscosity at the time of melting is low, and the phenomenon that the resin is not attached to the periphery of the drill does not occur. The content of the first water-soluble resin and the second water-soluble resin is preferably 2: 8 to 8: 2 'more preferably 4: 6 to 6: 4 » when the content of the first water-soluble resin is less than 2' The resin layer is easily broken and the applied resin layer has low mechanical strength, so that it is difficult to use. When the content ratio exceeds 8, the resin layer has high toughness, and when the heat of the drill bit causes the viscosity of the resin layer to be melted, the cutting resin is attached to the drill bit. It is not good. The above-mentioned lubricating resin layer is formed on a substrate to constitute a lubricating sheet', and an aluminum sheet or a copper sheet can be used as the substrate. The aluminum sheet is an aluminum or composite material which is excellent in heat dissipation of 99% or more in purity and is used in the range of 50 to 200 μm in thickness, but is not particularly limited. In general, aluminum sheets are heat-treated and flattened after rolling, and various thicknesses of aluminum can be used depending on the diameter of the head and the perforation conditions. Further, in the present invention, in order to increase the adhesion between the lubricating resin layer and the substrate of the aluminum substrate, an adhesion-enhancing layer may be provided. In order to suppress the melting of the resin caused by the heat generated by the drill, and to prevent the resin from remaining inside the hole, the thermosetting resin is used to make the representative epoxy group, 201026780
果降低。 形成用 上述那樣的满滑片係藉由於基材上塗佈潤滑片 組成物並乾燥以形成潤滑樹脂層來製造。If it is lowered. The above-described full-slip sheet is produced by applying a lubricant sheet composition to a substrate and drying it to form a lubricating resin layer.
該潤滑片形成用組成物係包含：含水之溶劑H 份、對水之溶解度相異之2種以上之水溶性樹脂5〜 構成此種潤滑樹脂層之水溶性樹脂可使用上述那樣的 對水之溶解度相異之第丨水溶性樹脂及第2水溶性樹脂， 尤其於熔點為150。〇以下之樹脂中，為了將對水具有相異之 溶解度的2種以上化合物溶解於溶劑後，於乾燥時誘發微 細相分離，該溶劑亦可單獨使用水，而為了調節樹脂層的 溶解度’可添加與水之相溶性優異之有機溶劑。 該?合劑雖使用水’但為了調g卩樹脂層之溶解度及相溶 性可混合與水混合容易之有機溶劑。此種溶劑可使用破數5 個以下之1次醇系溶劑（甲醇、乙醇、異丙醇等）或乙基赛珞 蘇、曱基赛路蘇這樣的醇系溶劑。溶劑的沸點為了樹脂層 的順利乾燥較佳為20CTC以下之製品。 該溶劑係與水一起使用有機溶劑的情況時，有機溶劑 的含量為總體溶劑中的10〜60重量份範圍。有機溶劑的含 量超過總體溶劑重量的6〇重量份時，樹脂不會完全溶解， 13 201026780 若未滿Η)重量份，則乾燥速度慢而生產性降低，且有時乾 燥時相分離現象無法順利地進行。 該溶劑可於可使該水溶性樹脂完全溶解的範圍内選 擇。一般來說，以該溶劑100重量份作為基準，將溶劑含 量調節成水溶性樹脂之含量為5〜6〇重量份之範圍較佳。該 樹脂之含量若未滿5重量份’則樹脂含量低時溶劑的乾燥 困難，因作業性降低而製造花費提高、變得難以厚厚地被 覆樹脂。相反地，樹脂含量若為6G重量份以上，則樹脂不 會完全溶解而塗佈液安定性降低，故會誘發所塗佈之樹月旨❿ 層的品質不良。 尤其，為了調節該微細相分離度，將乳化劑添加於該 組成物’-般而言’相分離時相分離的大小及組成密度可 :對樹脂之溶劑的組合來調節，但亦可以該乳化劑來調 節。為了調節在相異特性之樹脂層界面樹脂層對溶劑之相 溶度，:般而言，藉由乳化劑添加時可獲得較小之微細相。 該乳化劑係用以調節樹脂層及溶劑之相溶度，只要是 般所用之陰離子性 '陽離子性、非離子性乳化劑巾與樹❹ 脂相溶性優異之製品即無特別限定。例如，可添加縮聚物- 末端為錄離子、績酸基、幾酸之金屬鹽形態的離子性界面 活性劑及聚乙二醇與護酸的縮聚物即醋系非離子性系界面 活性劑全體。 以/合劑100重量份作為基準可使用〇 〇2〜2 5重量份。 右使用該乳化劑未滿〇 〇2重量份，則相分離時之分離相的 表面均勻度低且表面會變粗，相反地若使用超㉟2.5重量 14 201026780 伤，與濕氣接觸時表面會有黏著之虞， 穿孔時切削屑會附於鑽頭而使物性降低 且樹脂層或變脆 9 本發明中於基材形成潤滑性樹脂層之方法只要是以溶 劑型樹脂塗佈方法進行商用化之方法即無特別限定。可使 用例如’點塗法、模具塗佈法、親塗法、喷塗法簾塗（咖麻 coat)法、流塗法等。 ’但本發明並不限 以實施例與比較例詳細說明本發明 定於該等。 ΟThe lubricant sheet forming composition contains two or more kinds of water-soluble resins 5 to which the solubility of water is different, and the water-soluble resin constituting the lubricating resin layer can be used as described above. The second water-soluble resin and the second water-soluble resin having different solubility have a melting point of 150. In the following resins, in order to dissolve two or more kinds of compounds having different solubility in water, the fine phase separation is induced during drying, and the solvent may be used alone to adjust the solubility of the resin layer. An organic solvent excellent in compatibility with water is added. Although the water is used in the mixture, the organic solvent which is easily mixed with water can be mixed in order to adjust the solubility and compatibility of the resin layer. As such a solvent, an alcohol solvent such as an alcohol solvent (methanol, ethanol, isopropanol or the like) having a minimum of 5 or less, or an alcohol solvent such as ethyl cyproterone or thiopyrrolidine can be used. The boiling point of the solvent is preferably 20 CTC or less for smooth drying of the resin layer. When the solvent is an organic solvent together with water, the content of the organic solvent is in the range of 10 to 60 parts by weight in the total solvent. When the content of the organic solvent exceeds 6 parts by weight of the total solvent weight, the resin does not completely dissolve. 13 201026780 If it is less than 5% by weight, the drying speed is slow and the productivity is lowered, and sometimes the phase separation phenomenon during drying is not smooth. Conducted. The solvent can be selected within a range in which the water-soluble resin can be completely dissolved. In general, it is preferred to adjust the solvent content so that the content of the water-soluble resin is 5 to 6 parts by weight based on 100 parts by weight of the solvent. When the content of the resin is less than 5 parts by weight, the solvent is difficult to dry when the resin content is low, and the production cost is lowered due to the decrease in workability, so that it is difficult to coat the resin thickly. On the other hand, when the resin content is 6 parts by weight or more, the resin is not completely dissolved and the stability of the coating liquid is lowered, so that the quality of the coated layer is deteriorated. In particular, in order to adjust the degree of separation of the fine phase, the size and compositional density of the phase separation when the emulsifier is added to the composition in a 'generally' phase separation may be adjusted for the combination of the solvent of the resin, but the emulsification may also be carried out. To adjust. In order to adjust the solubility of the resin layer to the solvent at the resin layer interface of different characteristics, in general, a small fine phase can be obtained by the addition of an emulsifier. The emulsifier is used to adjust the compatibility of the resin layer and the solvent, and is not particularly limited as long as it is an anionic 'cationic, nonionic emulsifier towel which is excellent in compatibility with a tree gum. For example, a polycondensate may be added - an ionic surfactant in the form of a metal salt of a recording ion, a acid group or a few acid, and a polycondensate of a polyethylene glycol and an acid-protecting agent, that is, a vinegar-based nonionic surfactant. . 〇 2 to 2 5 parts by weight can be used based on 100 parts by weight of the mixture. When the emulsifier is used up to 2 parts by weight, the surface uniformity of the separated phase at the time of phase separation is low and the surface becomes thick. Conversely, if the surface is damaged by using 352.5 weight 14 201026780, the surface is in contact with moisture. In the case of adhesion, the chips may be attached to the drill to reduce the physical properties and the resin layer may become brittle. 9 In the present invention, the method of forming the lubricating resin layer on the substrate is preferably commercialized by a solvent-based resin coating method. The method is not particularly limited. For example, a 'dot coating method, a die coating method, a pro-coating method, a spray coating method, a flow coating method, or the like can be used. The present invention is not limited to the details of the embodiments and the comparative examples. Ο
(實施例1) 首先，將2液型聚胺酯樹脂棒塗佈於12〇μιη的鋁片以 導入5μιη的接著増大層。 接著，將線形聚乙二醇（MEISEI公司ALKOX R-400、 分子量18萬〜25萬）50g與線形聚乙二醇（GREEN s〇FT CEM 公司KONIONPEG-20000F、分子量2萬）50g溶解於水7〇〇g 與醇300g後’添加非離子性界面活性劑peg(4〇〇)變性酿 5g以製造塗佈液。使用可調節厚度之刮刀（doct〇r blade)塗 佈法，將該塗佈液塗佈於形成有該接著增大層之120μιη的 鋁片（純度99%以上）以形成樹脂層。塗佈後將塗佈試驗片置 入90°C之熱循環乾燥烘箱使溶劑揮發，藉此製作乾燥塗膜 厚度為40μιη之潤滑性片。 (實施例2) 將線形聚乙二醇（MEISEI公司ALKOX R-150、分子量 10萬〜17萬）50g與計算分子量為1〇萬之變性聚乙二醇（將 分子量6000之聚乙二醇在多元烷基羧酸與酸觸媒下加以縮 15 201026780 聚合，以合成分子鏈中具有取代有酯之官能基之樹脂。所 合成之樹脂之溶解度對水在常溫為60%以上）50g溶解於水 700g與醇300g後，添加非離子性界面活性劑PEG(400)變 性酯7g以製造塗佈液。使用所生成之塗佈液以與實施例1 相同之方法製造潤滑片。 (實施例3) 前述實施例2中非離子性界面活性劑PEG(400)變性酯 的含量變更為20g(相對於固形粉的含量為20重量％)以製造 塗佈液，以與前述實施例2相同之方法製造潤滑片。 (實施例4) 前述實施例2中非離子性界面活性劑PEG(400)變性酯 的含量變更為25g(相對於固形粉的含量為25重量％)以製造 塗佈液，以與前述實施例2相同之方法製造潤滑片。 (實施例5) 前述實施例2中非離子性界面活性劑PEG(400)變性酯 的含量變更為lg(相對於固形粉的含量為1重量％)以製造塗 佈液，以與前述實施例2相同之方法製造潤滑片。 (比較例1) 將線形聚乙二醇（MEISEI公司ALKOX R-400、分子量 18萬〜25萬）50g與線形聚乙二醇（GREEN SOFT CEM公司 KONION PEG-20000F、分子量2萬）50g溶解於水700g與醇 300g以製造塗佈液。將所生成之塗佈液以與實施例1相同 之方法製造潤滑片。 (比較例2) 201026780 將乙烯基吡咯烷酮與乙烯基乙酸酯之共聚物即BASF 公司之Luviskol(乙烯基吡咯烷酮/乙烯基乙酸酯的含量= 6/4) VA64粉末40g與GREEN SOFT CEM公司之線形聚乙 二醇KONION PEG-6000 60g —點一點地添加於水700g與 乙醇300g之混合溶劑使之完全溶解，藉此除了使用具黏度 之均勻塗佈液以外，進行與前述實施例1相同之過程以製 作乾燥塗膜厚度為40μιη之满滑性片。 (比較例3) ®.. 乙烯基吡咯烷酮與乙烯基乙酸酯之共聚物即BASF公 司之Luviskol(乙稀基》比洛烧嗣/乙稀基乙酸醋的含量= 6/4) VA64粉末40g與GREEN SOFT CEM公司之線形聚乙二醇 KONION PEG-6000 60g —點一點地添加於水700g與乙醇 300g之混合溶劑使之完全溶解，藉此除了使用具黏度之均 勻塗佈液以外，進行與前述實施例1相同之過程以製作乾 燥塗膜厚度為40μιη之潤滑性片。 (比較例4) w 將線形聚乙二醇（MEISEI公司ALKOX R-400、分子量 18萬〜25萬）50g溶解於水500g以製造塗佈液，使用其以與 實施例1相同之方法製造潤滑片。 (實驗例1) 將前述比較例1、2、3及4所製造之試驗片安裝於具 有120,000rpm速度之CNC穿孔機械，使用0.25mm徑之鑽 頭進行穿孔。穿孔時，PCB基板係積層FR-4材質且0.2T 厚度之基板5層，穿孔次數為進行1〇〇〇次。穿孔後觀察鑽 17 201026780 頭折損與切削屑卷附至鑽頭周邊之現象’將其結果表示於 下述表1 » 表1 區分 比較例1 比較例2 比較例3 比較例4 鑽頭的切削 屑卷附 發生一些 發生一些 發生一些 大量發生 鑽頭的 鑾曲 發生一些 發生一些 發生一些 大量發生 (實驗例2) 將前述比較例1、4及實施例1、2所製造之試驗片安 裝於具有120,000rpm速度之CNC穿孔機械，使用〇.25mm 徑之鑽頭進行穿孔。穿孔時，PCB基板係積層FR-4材質且 〇·2T厚度之基板5層，穿孔次數為進行1 〇〇〇次。穿孔後判 定鑽頭狀態及折損程度。所穿孔之洞位置準確度以在誤差 範圍±50μηι基準時之步驟變數（Cpk)來表示。品質基準方 面’最下方之板的PCB基板的位置準確度定為Cpk=1.33 以上。又，將所穿孔之試驗片洗淨後進行銅鍍敷，並將洞 部位顯微切片（MiCrosection)，觀察洞截面的内面平坦度（若 為2〇μΐη以下則OK)、對樹脂層之浸潤（Wicking，若為5〇μιη 以下則οκ)、樹脂層之剝離所致之不良（Nail Head，若為 200%以下則OK)及PCB樹脂層熔融所致之鑽污（smear)現 象，將其結果表示於下述表2。又’評估穿孔加工步驟中之 洞位置準確度錢敷後之洞的顯微切片、、洞内壁的品質並 表示於圖1及圖h 18 201026780 表2 項目 樹脂之 卷附 鑽頭的 蠻曲 C成 洞之 平坦度 浸潤 剝離 鑽污 比較例1 發生一些 發生一些 0.89 0K QK 0K 4fff 比較例4 大量發生 大量發生 0.7 NG 0K 0K m /iw 霣施例1 無 無 1.35 0K 0K 0K 4Tff /s\\ 實施例2 無 無 1.55 0K 0K 0K 卜無 (實驗例3) φ 對於前述比較例4及實施例2所得之試驗片，使用光 學顯微鏡觀察乾燥時樹脂層的表面特性及粗縫度等並表示 於圖3及圖5,為了比較微細相分離係以光學顯微鏡觀察前 述實施例5之樹脂層表面並表示於圖4。 如圖3所示，未添加非離子性界面活性劑pEG(4〇〇)變 性酯之比較例4的情況時，樹脂對溶劑之溶解度低，故因 所產生之多數個泥裂（mud crack)與鑽孔時鑽頭切削屑的卷 附，而發生洞位置準確度（Cpk)變差之現象。 ® 圖4可了解到·微細相形成用乳化劑的含量低時，不 會引起良好之相分離，雖鑽頭的折損及穿孔洞的位置準確 . 度獲得改善，但塗佈層之樹脂狀的相分離部分不均勻。為 了於樹脂層得到均勻微尺寸之微細相分離，投入相對於固 形粉100重量份為7重量份之微細相形成用乳化劑所得之 實施例2係如圖5所示，了解到其可獲得均勻的微細相分 離，因此洞位置準確度等方面非常優異。 刀 (實驗例4) 又，在低剪切條件下以旋轉流變計（RMS)測定前述比較 19 201026780 例1、實施例2、3及4所製造之塗佈液的黏度並表示於圖 6 〇 由圖6可確認到：未添加非離子性界面活性劑PEG(400) 變性酯的情況與有添加的情況時，確認到添加含量造成黏 度的減少。因此了解到：若於高分子樹脂添加pEG(400)變 性酯，則樹脂分子間結合力變弱而黏度降低，並於樹脂分 子間有潤滑油這樣的功能，而付與柔軟性。 另一方面，了解到非離子性界面活性劑pEG(4〇〇)變性 S旨的含量超過25g(相對於固形粉1〇〇重量份為25重量份）Θ 時，如圖6所示，潤滑組成物有變得不安定之虞，且接觸 濕、氣時表面有黏著之虞。又’ 了解到會使樹脂層變脆且塗 佈樹脂層的機械強度降低，鑽頭穿孔時削屑會附著於鑽頭 而使物性降低’甚至會降低效率性而可能造成使用困難。 此係為了調節在相異特性之樹脂層的界面樹脂層對溶劑之 相溶度，藉由添加有乳化劑時可獲得較小之微細相，而表 面均勻度提升而可防止黏著，再者’藉由調節機械強度，(Example 1) First, a two-pack type polyurethane resin rod was applied to a 12 μm aluminum sheet to introduce a 5 μm thick subsequent layer. Next, 50 g of linear polyethylene glycol (MEISEI company ALKOX R-400, molecular weight 180,000 to 250,000) and 50 g of linear polyethylene glycol (GREEN s〇FT CEM company KONION PEG-20000F, molecular weight 20,000) were dissolved in water 7 After 〇〇g and 300 g of alcohol, 5 g of a nonionic surfactant peg (4 Å) was added to produce a coating liquid. The coating liquid was applied to a 120 μm aluminum sheet (purity of 99% or more) on which the subsequent enlarged layer was formed by using a doctor blade having a thickness adjustable to form a resin layer. After coating, the coated test piece was placed in a heat cycle drying oven at 90 ° C to volatilize the solvent, whereby a lubricative sheet having a dried coating film thickness of 40 μm was produced. (Example 2) 50 g of linear polyethylene glycol (MEISEI company ALKOX R-150, molecular weight 100,000 to 170,000) and denatured polyethylene glycol having a molecular weight of 1,000,000 (a polyethylene glycol having a molecular weight of 6000) Polybasic carboxylic acid and acid catalyst are condensed 15 201026780 Polymerization to synthesize a resin having a functional group substituted with an ester in a molecular chain. The solubility of the synthesized resin is 60% or more in water at room temperature) 50 g dissolved in water After 700 g of alcohol and 300 g of alcohol, 7 g of a nonionic surfactant PEG (400) denatured ester was added to prepare a coating liquid. A lubricating sheet was produced in the same manner as in Example 1 using the resulting coating liquid. (Example 3) The content of the nonionic surfactant PEG (400) denatured ester in the above Example 2 was changed to 20 g (20% by weight based on the solid powder) to prepare a coating liquid, in the same manner as the foregoing examples. 2 The same method is used to manufacture the lubricating sheet. (Example 4) The content of the nonionic surfactant PEG (400) denatured ester in the above Example 2 was changed to 25 g (25% by weight based on the solid powder) to prepare a coating liquid, in the same manner as the foregoing examples. 2 The same method is used to manufacture the lubricating sheet. (Example 5) The content of the nonionic surfactant PEG (400) denatured ester in the above Example 2 was changed to lg (1% by weight based on the solid powder) to prepare a coating liquid, in the same manner as the foregoing examples. 2 The same method is used to manufacture the lubricating sheet. (Comparative Example 1) 50 g of linear polyethylene glycol (MEISEI company ALKOX R-400, molecular weight 180,000 to 250,000) and 50 g of linear polyethylene glycol (GREEN SOFT CEM KONION PEG-20000F, molecular weight 20,000) were dissolved in 700 g of water and 300 g of alcohol were used to produce a coating liquid. A lubricant sheet was produced in the same manner as in Example 1 using the resulting coating liquid. (Comparative Example 2) 201026780 A copolymer of vinylpyrrolidone and vinyl acetate, that is, Luviskol of BASF Corporation (content of vinylpyrrolidone/vinyl acetate = 6/4) VA64 powder 40g and GREEN SOFT CEM The linear polyethylene glycol KONION PEG-6000 60 g was added to a mixed solvent of 700 g of water and 300 g of ethanol to dissolve completely, thereby performing the same procedure as in the above Example 1 except that a uniform coating liquid having a viscosity was used. The process was carried out to produce a full-slip sheet having a dry coating film thickness of 40 μm. (Comparative Example 3) ®.. Copolymer of vinylpyrrolidone and vinyl acetate, which is the content of Luviskol (Ethyl) Biro/Ethyl acetate vinegar of BASF Co., Ltd. = 6/4) VA64 powder 40g The linear polyethylene glycol KONION PEG-6000 60g of GREEN SOFT CEM Co., Ltd. is added to a mixed solvent of 700 g of water and 300 g of ethanol to dissolve completely, thereby using a uniform coating liquid having a viscosity. The same procedure as in the above Example 1 was carried out to prepare a lubricative sheet having a dry coating film thickness of 40 μm. (Comparative Example 4) w 50 g of linear polyethylene glycol (MEISEI company ALKOX R-400, molecular weight: 180,000 to 250,000) was dissolved in 500 g of water to prepare a coating liquid, and lubrication was produced in the same manner as in Example 1. sheet. (Experimental Example 1) The test pieces manufactured in the above Comparative Examples 1, 2, 3 and 4 were attached to a CNC perforating machine having a speed of 120,000 rpm, and perforated using a drill having a diameter of 0.25 mm. When perforating, the PCB substrate is laminated with a layer of FR-4 material and a substrate having a thickness of 0.2T, and the number of perforations is 1 time. After piercing, observe the phenomenon that the drill 17 201026780 head breakage and the chip reel attached to the periphery of the drill bit'. The results are shown in Table 1 below. Table 1 Distinction Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Drill cuttings of the drill bit Some occurrences occurred some of the occurrence of some large-scale occurrence of the distortion of the drill bit, some occurred and some occurred in large quantities (Experimental Example 2) The test pieces manufactured in the aforementioned Comparative Examples 1, 4 and Examples 1, 2 were installed at a speed of 120,000 rpm. CNC perforating machine, perforated with a 25.25mm drill. In the case of perforation, the PCB substrate is laminated with a layer of FR-4 material and a thickness of 〇·2T, and the number of perforations is 1 〇〇〇. The state of the drill bit and the degree of damage are determined after piercing. The hole position accuracy of the perforation is expressed as a step variable (Cpk) at the error range of ±50 μηι. The position accuracy of the PCB substrate of the lowermost board of the quality reference plane is set to Cpk=1.33 or more. Further, the perforated test piece was washed, and then subjected to copper plating, and the hole portion was micro-sectioned (MiCrosection), and the inner surface flatness of the hole section was observed (if it is 2 〇μΐη or less), the resin layer was infiltrated. (Wicking, if it is 5〇μηη or less, κ), the defect caused by peeling of the resin layer (Nail Head, if it is 200% or less, OK) and the smear phenomenon caused by melting of the PCB resin layer, The results are shown in Table 2 below. 'Evaluate the accuracy of the hole position in the perforation processing step. The microscopic section of the hole after the money is applied, and the quality of the inner wall of the hole is shown in Fig. 1 and Fig. h 18 201026780 Table 2 The resin of the project is attached to the drill bit. The flatness of the hole is infiltrated and stripped. Comparative example 1 occurs some 0.89 0K QK 0K 4fff Comparative Example 4 Large amount of occurrence 0.7 NG 0K 0K m /iw 霣Example 1 No 1.35 0K 0K 0K 4Tff /s\\ Implementation Example 2 No 1.55 0K 0K 0K Bu (Experimental Example 3) φ For the test pieces obtained in Comparative Examples 4 and 2, the surface characteristics and the roughness of the resin layer during drying were observed by an optical microscope and are shown in the figure. 3 and FIG. 5, the surface of the resin layer of the above-mentioned Example 5 was observed by an optical microscope for comparison of the fine phase separation system, and is shown in FIG. As shown in Fig. 3, in the case of Comparative Example 4 in which the nonionic surfactant pEG (4〇〇) denatured ester was not added, the solubility of the resin in the solvent was low, so that a large number of mud cracks were generated. The problem of the hole position accuracy (Cpk) is deteriorated due to the winding of the drill cuttings during drilling. ® Figure 4 shows that when the content of the emulsifier for forming a fine phase is low, good phase separation is not caused, and the fracture of the drill bit and the position of the perforation hole are accurate. The degree of improvement is improved, but the resinous phase of the coating layer is obtained. The separated portion is uneven. In order to obtain a fine phase separation of a uniform micro-size of the resin layer, Example 2 obtained by adding an emulsifier for forming a fine phase of 7 parts by weight with respect to 100 parts by weight of the solid powder is as shown in Fig. 5, and it is found that uniformity can be obtained. The fine phase separation is excellent, so the hole position accuracy is excellent. Knife (Experimental Example 4) Further, the viscosity of the coating liquid prepared in Example 1, 201026780, Example 1, Examples 2, 3 and 4 was measured by a rotational rheometer (RMS) under low shear conditions and is shown in Fig. 6 From Fig. 6, it can be confirmed that when the nonionic surfactant PEG (400) denatured ester is not added and when it is added, it is confirmed that the added content causes a decrease in viscosity. Therefore, it has been found that when a pEG(400)-modified ester is added to a polymer resin, the bonding strength between the resin molecules is weakened, the viscosity is lowered, and a function of lubricating oil is present between the resin molecules to impart flexibility. On the other hand, it is understood that the content of the nonionic surfactant pEG (4〇〇) denatured S exceeds 25 g (25 parts by weight relative to 1 part by weight of the solid powder) Θ, as shown in Fig. 6, lubrication The composition has become unstable, and the surface is sticky when exposed to moisture and gas. Further, it has been known that the resin layer becomes brittle and the mechanical strength of the coated resin layer is lowered, and the swarf adheres to the drill bit when the drill bit is perforated to lower the physical properties, which may even reduce the efficiency and may cause difficulty in use. In order to adjust the compatibility of the resin layer of the resin layer in the resin layer having different characteristics to the solvent, a small fine phase can be obtained by adding an emulsifier, and the surface uniformity is improved to prevent adhesion, and By adjusting the mechanical strength,
可提升物性並增加錢頭加工的效率性。 G (實驗例5) 將前述比較例4與實施例2所製造之試驗片以具有 15,000rPm速度之桌上型穿孔鑽頭使用〇 2mm徑之鑽頭進 行1000次穿孔。對於穿孔後之鑽頭的狀態，使用光學顯微 鏡確認鐵頭表面之樹脂卷附程度，並將其結果表示於圖7 及8 〇 由圖7可了解到：僅使用機械特性優異之高分子量樹 20 201026780 脂的情況時’因韌性增加而塗佈層不會因外部衝擊而破裂 或剝離，故發生了切削屑卷附至鑽頭周邊之現象。相反地， 圖8中，藉由以適當配合比調製製造相對較低分子量之樹 脂，因韌性減少而易於破裂，再者未添加有非離子性界面 活性劑PEG(400)變性酯的情況時，確認到藉由調節微細相 - 分離’切削屑卷附至鑽頭周邊之現象獲得改善。 (實驗例6) 對於前述實施例1及2所得之潤滑片，在塗佈層（樹脂 Φ 層）於150°c熔融之狀態下及低剪切條件下測定其黏度，使 用光學顯微鏡確認穿孔後之鑽頭狀態，並癌認鑽頭表面之 樹脂之卷附程度’將其結果表示於圖9、圖及圖η。 由上述結果可明瞭：使用對水之溶解度為4〇%以下之 較低溶解度且韌性與機械特性優異之高分子量樹脂與、溶 解度為40%以上且相對較低分子量之樹脂係相同但實施 例1的情況時，l〇〇mm/sec以下之剪切條件下可見到黏度的 變化差。此乃潤滑片形成用組成物所含之溶解度相異之2 Φ 禮樹脂之分子量差所造成。相反地，實施例2的情況時， •使用有計算分子量為1〇萬之變性聚乙二醇（將分子量6000 ^ 之聚乙二醇在多元烷基羧酸與酸觸媒下加以縮合，合成分 子鍵中具有取代有S旨之官能基之樹脂）之結果，在同一條件 下之黏度係顯示一般之熱可塑性樹脂所具有之非牛頓流 雜，且呈現黏度無變化之安定狀態。藉由此種結果，提供 了雉持樹脂層之機械強度，改善樹脂質感所致之卷附至鑽 頦阉邊之現象之效果，並提供了鑽頭加工令潤滑片形成用 21 201026780 組成物所具有之較佳黏度。 (實驗例7) 為了理解對前述實施例2所得之潤滑片之鑽頭加工的 效率性提升可能性，與市售製品相比較並記載於下述表3， 將實施例2所得之潤滑片樹脂層（1)與市售製品Ο樹脂層（2) 在150°C熔融之狀態下比較其之黏度，將其結果表示於圖 12 ° <加工條件> 鑽頭：直徑〇.3mm、旋轉數：120,000rpm 移動速度：36mm/sec、鑽頭數：2,000hit Hole ： 14,000、PCB : 0.7Tx4stacks 表3 LE 400 (1) LX025 (2) 製造公司 MGC 實施例2 潤滑劑 水溶性樹脂 水溶性樹脂 鑾曲之鑽頭 0 0 〇.3咖洞之位置準確度（Cpk) 1.65 1.76 洞之粗度(um) Max· 12.8 8.7 Avg, 8.0 6.3 Nai1-HeadC%) Max. 184 151 Avg. 149 123 (實驗例8) 為了理解前述實施例2所得之潤滑片（1)以鑽頭加工之 效率性提升可能性，比較市售製品（2)與鑽頭表面狀態，將 其結果表示於圖13。 201026780 <加工條件> 鑽頭：直徑0.2mm、旋轉數：160,000rpm 移動速度：3.2m/min、鑽頭數：3,000hit Hole ·· 14,〇〇〇、pcb : 0.8Tx3stacks 以下列評估基準比較前述實驗例7及8。所穿孔之洞位 置準確度以在誤差範圍±50μιη基準時之步驟變數（Cpk)來表 示。品質基準方面，最下方之板的PCB基板的位置準確度 定為Cpk= 1.33以上。又，將所穿孔之試驗片洗淨後進行銅 鍍敷，並將洞部位顯微切片（Microsection)，觀察洞截面的 内面平坦度（若為20μπι以下則〇K)、樹脂層之剝離所致之 不良（Nail Head，若為200%以下則〇κ)。由表3可明瞭： 步驟變數、截面之内面平坦度及樹脂之剝離所致之不良方 面，本發明之實施例較佳，又，如圖丨2所示，使塗佈樹脂 層熔融，之狀態下所測得之黏度在1〇〇mm/sec以下之條件下 有類似於5.0x104〜1.〇xi〇5CP之水準。即使如此，以實驗例 8之加工條件來看鑽頭表面屑的卷附狀態則如圖13所示， 與實驗例7的情況相同，還是本發明之實施例較優異。此 含有使溶解度相異之2種的樹脂及相分離均勻化之乳化劑 之本發明之奶合物提供了適合印刷電路基板穿孔用潤滑片 製&之黏度’且抑制了屑卷附至鐵頭周邊同時可以 提供鑽頭發熱抑制效果優異之水溶性㈣片，因此大幅增 加了穿孔加工步驟之效率性。 (實驗例9) 測疋别述實施例2所得之湖滑片樹脂層嫁融於7〇〜15〇 23 201026780 °c之狀態下的熔融黏度，並將其結果表示於圖14。 如實施例2那樣’於韌性優異之高分子水溶性樹脂混 合易破裂之水溶性樹脂的情況時，無屑卷附至鑽頭周邊之 現象及鑽頭的破損。相反地，單獨使用有韌性優異之高分 子量樹脂之比較例4的情況時，樹脂卷附至鑽頭周邊之現 象會發生而鑽頭大多發生折損，因此無法進行順利之穿孔 加工步驟。 由前述實施例與比較例可了解到：藉由具有相異特性 之樹脂之組合可構成無屑卷附至鑽頭周邊與破裂之潤滑性 ❿ 樹脂層。 (實驗例10) 將前述實施例2之潤滑性片置入恆溫恆濕試驗器，於 25°C /90%濕度水準放置24小時，並評估表面黏著與表面白 化。確認到顯示良好之表面特性且具有優異之对濕特性。 由前述比較例與實施例可了解到：本發明之潤滑片形 成用組成物係包含：含有對水之溶解度相異之第1水溶性 樹脂與第2水溶性樹脂及使樹脂層之微細相分離均勻化之 〇 乳化劑而成之混合物、與溶劑，其特徵在於：常溫下因樹 脂層微細相分離之液狀黏度在剪切速度條件1 〇 〇mm/s e c下 為5xl03〜lxl04cp之範圍内，潤滑片樹脂層在熔融於i50°c 之狀態時黏度在剪切速度條件lOOmm/sec下為5xl04〜lx l〇5cp之範圍内。了解到因此可提升屑卷附至鑽頭周邊及此 所造成之穿孔洞的特性，進一步確認到因樹脂層的微細相 分離而可製造具有鑽頭穿孔特性更佳改善之潤滑片。 24 201026780 【圖式簡單說明】 圖1’係在實施例2中之穿孔加工步驟所測定之穿孔洞 位置準確度之資料。 圖2 ’係鑽孔鍍敷後，探討洞的顯微切片、洞内壁的品 質之圖。 圖3,係以光學顯微鏡觀察比較例4中之微細相分離前 之樹脂層表面之圖像。It can improve physical properties and increase the efficiency of money processing. G (Experimental Example 5) The test pieces manufactured in the above Comparative Example 4 and Example 2 were perforated 1000 times using a drill having a diameter of 15,000 rPm using a drill having a diameter of 2 mm. For the state of the drilled bit, the degree of resin wrap on the surface of the iron head was confirmed using an optical microscope, and the results are shown in Figs. 7 and 8. From Fig. 7, it can be understood that only the high molecular weight tree 20 having excellent mechanical properties is used. In the case of fat, the coating layer is not broken or peeled off due to an external impact due to an increase in toughness, so that a phenomenon in which the chips are attached to the periphery of the drill bit occurs. Conversely, in Fig. 8, when a resin having a relatively low molecular weight is produced by an appropriate compounding ratio, it is easily broken due to a decrease in toughness, and when a nonionic surfactant PEG (400) modified ester is not added, It was confirmed that the improvement was obtained by adjusting the phenomenon of the fine phase-separation of the cutting chip attached to the periphery of the drill bit. (Experimental Example 6) The lubricating sheets obtained in the above Examples 1 and 2 were measured for their viscosity in a state where the coating layer (resin Φ layer) was melted at 150 ° C and under low shear conditions, and confirmed by optical microscopy. The state of the drill bit and the degree of adhesion of the resin to the surface of the drill bit are shown in Fig. 9, Fig. 9, and Fig. η. From the above results, it is understood that a high molecular weight resin having a low solubility of water of 4% by weight or less and excellent toughness and mechanical properties is used, and a resin having a solubility of 40% or more and a relatively low molecular weight is the same but Example 1 In the case of the shearing condition of l〇〇mm/sec or less, the difference in viscosity is observed. This is caused by the difference in molecular weight between the Φ resin and the solubility of the composition for forming a lubricating sheet. On the contrary, in the case of Example 2, • a denatured polyethylene glycol having a calculated molecular weight of 100,000 was used (the polyethylene glycol having a molecular weight of 6000 μ was condensed under a polybasic alkylcarboxylic acid and an acid catalyst to synthesize As a result of the resin having a functional group substituted with S in the molecular bond, the viscosity under the same conditions shows a non-Newtonian flow which is common to the thermoplastic resin, and exhibits a stable state in which the viscosity does not change. With such a result, the effect of the mechanical strength of the resin layer is improved, the effect of the resin texture on the edge of the drill collar is improved, and the processing of the drill bit is provided to form the lubricant sheet 21 201026780. The preferred viscosity. (Experimental Example 7) In order to understand the possibility of improving the efficiency of the bit processing of the lubricating sheet obtained in the above-mentioned Example 2, it is described in Table 3 below in comparison with a commercially available product, and the lubricating sheet resin layer obtained in Example 2 was used. (1) The viscosity of the commercially available resin layer (2) was compared at 150 ° C, and the results are shown in Fig. 12 ° <Processing conditions> Drill: diameter 〇.3 mm, number of revolutions: 120,000 rpm moving speed: 36 mm/sec, number of drills: 2,000 hit Hole: 14,000, PCB: 0.7Tx4stacks Table 3 LE 400 (1) LX025 (2) Manufacturing company MGC Example 2 Lubricating water-soluble resin Water-soluble resin distort Bit 0 0 〇.3 Position accuracy of the cacao (Cpk) 1.65 1.76 Thickness of the hole (um) Max· 12.8 8.7 Avg, 8.0 6.3 Nai1-HeadC%) Max. 184 151 Avg. 149 123 (Experimental Example 8) In order to understand the possibility that the lubricating sheet (1) obtained in the foregoing Example 2 is improved in the efficiency of the drill processing, the commercially available product (2) and the surface condition of the drill are compared, and the results are shown in Fig. 13. 201026780 <Processing conditions> Drill: 0.2 mm in diameter, number of revolutions: 160,000 rpm Movement speed: 3.2 m/min, number of drills: 3,000 hit Hole ·· 14, 〇〇〇, pcb: 0.8Tx3stacks The above evaluation criteria were compared. Experimental Examples 7 and 8. The positional accuracy of the perforated hole is expressed as a step variable (Cpk) at the error range of ±50 μm. In terms of the quality standard, the positional accuracy of the PCB substrate at the bottom of the board is set to Cpk = 1.33 or more. Further, the perforated test piece was washed, and then subjected to copper plating, and the hole portion was microsectioned, and the inner surface flatness of the hole cross section was observed (if it was 20 μm or less, 〇K), and the resin layer was peeled off. Bad (Nail Head, if it is 200% or less, 〇κ). As is clear from Table 3, the embodiment of the present invention is preferable in that the step variable, the flatness of the inner surface of the cross section, and the peeling of the resin are poor, and the state of the coating resin layer is melted as shown in Fig. 2 The viscosity measured under the condition of 1 〇〇mm/sec or less has a level similar to 5.0x104~1.〇xi〇5CP. Even in this case, the state of the wound surface of the drill bit was observed as shown in Fig. 13 under the processing conditions of Experimental Example 8, as in the case of Experimental Example 7, and the embodiment of the present invention was superior. The present invention contains a resin which is obtained by dissolving two kinds of resins having different solubility and an emulsifier which is uniform in phase separation, and provides a viscosity suitable for a lubricated sheet for printed circuit board perforation and suppresses the sticking of iron to the iron. At the same time, the water-soluble (four) sheet excellent in the heat suppression effect of the drill can be provided at the periphery of the head, thereby greatly increasing the efficiency of the piercing processing step. (Experimental Example 9) The melt viscosity of the lake slip resin layer obtained in Example 2 was measured in the state of 7〇15〇23 201026780 °c, and the result is shown in Fig. 14. When the polymer water-soluble resin excellent in toughness is mixed with a water-soluble resin which is easily broken as in the case of the second embodiment, the phenomenon of sticking to the periphery of the drill and the breakage of the drill are eliminated. On the other hand, in the case of Comparative Example 4 in which a high molecular weight resin having excellent toughness was used alone, the phenomenon that the resin was attached to the periphery of the drill bit occurred and the drill bit was often broken, so that the smooth piercing processing step could not be performed. As is apparent from the foregoing examples and comparative examples, a combination of resins having different characteristics can constitute a lubricious ruthenium resin layer which is attached to the periphery of the drill bit and which is ruptured by the chipless winding. (Experimental Example 10) The lubricative sheet of the above Example 2 was placed in a constant temperature and humidity tester, and allowed to stand at 25 ° C / 90% humidity level for 24 hours, and surface adhesion and surface whitening were evaluated. It was confirmed that it exhibited good surface characteristics and had excellent wet properties. It is understood from the above-mentioned comparative examples and examples that the composition for forming a lubricating sheet of the present invention comprises: a first water-soluble resin having a solubility in water different from that of the second water-soluble resin and a fine phase of the resin layer a mixture of a homogenized emulsifier and a solvent, wherein the liquid viscosity due to the fine phase separation of the resin layer at a normal temperature is in the range of 5 x 10 3 to 1 x 10 cp at a shear rate condition of 1 〇〇 mm/sec. The lubricating sheet resin layer was in a range of 5 x 10 4 to 1 x 10 cp 5 cp at a shear rate condition of 100 mm/sec when it was melted at i50 ° C. It is understood that the characteristics of the perforation hole attached to the periphery of the drill bit and the resulting hole can be improved, and it is further confirmed that the lubricating sheet having better perforation characteristics of the drill can be manufactured due to the fine phase separation of the resin layer. 24 201026780 [Simple description of the drawings] Fig. 1' is information on the positional accuracy of the perforation holes measured in the piercing processing step in the second embodiment. Figure 2 ” After the drilling of the hole, the microscopic section of the hole and the quality of the inner wall of the hole are discussed. Fig. 3 is an image of the surface of the resin layer before the fine phase separation in Comparative Example 4 was observed with an optical microscope.
圖4 ’係以光學顯微鏡觀察實施例5所得之塗佈樹脂層 表面之圖像。 圖5 ’係以光學顯微鏡觀察實施例2所得之塗佈樹脂層 表面之圖像。 圖6,係對於比較例丨、實施例2、3及4所得之塗佈 液在常溫及低剪切條件下以旋轉流變計（RMS)測定非離子 性界面活性劑PEG(400)變性酯的含量之黏度。 圖7’係將比較例4所得之試驗片使用具有15〇〇〇㈣ 速度之桌上型穿孔鑽頭以〇 2mm徑之鑽頭進行㈧次穿 孔，對穿孔後之鑽頭狀態，使用光學顯微鏡，表示鑽頭表 面之樹脂之卷附程度。 圖8,係將實施例2所得之試驗片使用具有15〇〜m 速度之桌上型穿孔鑽頭以G.2inm經之鑽頭 孔，對穿孔後之鑽頭狀態，使用光學顯微鏡，表示鑽= 面之樹脂之卷附程度。 圖9 係表示實施例！及2之潤滑片樹脂層纟15代炼 25 201026780 融時之狀態且低剪切條件下使用旋轉流變計所測得之箱1融 黏度之圖。 圖10’係將實施例1所得之試驗片使用具有15,000rPm 速度之桌上型穿孔鑽頭以0.2mm徑之鑽頭進行1000次穿 孔，對穿孔後之鑽頭狀態，使用光學顯微鏡，表示鑽頭表 面之樹脂之卷附程度。 . 圖11，係將實施例2所得之試驗片使用具有15,000rpm 速度之桌上型穿孔鑽頭以0.2mm徑之鑽頭進行1000次穿 孔’對穿孔後之鑽頭狀態，使用光學顯微鏡，表示鑽頭表 © 面之樹脂之卷附程度。 圖12，係表示使實施例2所得之潤滑片樹脂層與市售 製品之樹脂層在15CTC熔融狀態下之黏度。 圖13，係表示用以理解實施例2所得之潤滑片與鑽頭 加工之效率性的提升可能性’將市售製品與鑽頭表面狀態 加以比較之圖。 圖14，係表示實施例2所得之塗佈樹脂層在溫度變化 之低剪切條件下之熔融黏度。 〇 【主要元件符號說明】 - 無 26Fig. 4' is an image of the surface of the coating resin layer obtained in Example 5 observed by an optical microscope. Fig. 5' is an image of the surface of the coating resin layer obtained in Example 2 observed by an optical microscope. Figure 6. Determination of nonionic surfactant PEG (400) denatured ester by rotational rheometer (RMS) under normal temperature and low shear conditions for coating solutions obtained in Comparative Examples, Examples 2, 3 and 4. The viscosity of the content. Fig. 7' is a test piece obtained in Comparative Example 4, using a table-type perforated drill having a speed of 15 〇〇〇 (4) for (eight) times of perforation with a drill having a diameter of 2 mm, and using a light microscope to indicate the position of the drill after perforation. The degree of adhesion of the resin on the surface. Figure 8 is a test piece obtained in Example 2 using a table-type perforated drill having a speed of 15 〇 to m at a G.2 inm bit hole, and the state of the drilled bit is determined by using an optical microscope to indicate the diameter of the drill. The degree of resin attachment. Figure 9 shows the embodiment! And 2 of the lubricating sheet resin layer 代 15 generation 25 201026780 The state of the melt of the box 1 measured by the rotational rheometer in the state of melting time and under low shear conditions. Fig. 10' is a test piece obtained in Example 1 using a table-type perforated drill having a speed of 15,000 rPm for 1000 times of perforation with a drill having a diameter of 0.2 mm. For the state of the drill after perforation, an optical microscope is used to indicate the resin on the surface of the drill. The degree of attachment. Figure 11, the test piece obtained in Example 2 was subjected to 1000 perforation using a table-type perforated drill having a speed of 15,000 rpm with a drill having a diameter of 0.2 mm. The degree of resin attached to the surface. Fig. 12 is a view showing the viscosity of the resin sheet layer obtained in Example 2 and the resin layer of the commercially available product in a molten state of 15 CTC. Fig. 13 is a view for explaining the possibility of improving the efficiency of the processing of the lubricating sheet and the drill obtained in the second embodiment, comparing the commercially available product with the surface state of the drill. Fig. 14 is a view showing the melt viscosity of the coating resin layer obtained in Example 2 under low shear conditions of temperature change. 〇 [Main component symbol description] - None 26