TW201043362A - Entry sheet for drilling - Google Patents
Entry sheet for drilling Download PDFInfo
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- TW201043362A TW201043362A TW099117578A TW99117578A TW201043362A TW 201043362 A TW201043362 A TW 201043362A TW 099117578 A TW099117578 A TW 099117578A TW 99117578 A TW99117578 A TW 99117578A TW 201043362 A TW201043362 A TW 201043362A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26F—PERFORATING; PUNCHING; CUTTING-OUT; STAMPING-OUT; SEVERING BY MEANS OTHER THAN CUTTING
- B26F1/00—Perforating; Punching; Cutting-out; Stamping-out; Apparatus therefor
- B26F1/16—Perforating by tool or tools of the drill type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B35/00—Methods for boring or drilling, or for working essentially requiring the use of boring or drilling machines; Use of auxiliary equipment in connection with such methods
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B26—HAND CUTTING TOOLS; CUTTING; SEVERING
- B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
- B26D7/00—Details of apparatus for cutting, cutting-out, stamping-out, punching, perforating, or severing by means other than cutting
- B26D7/08—Means for treating work or cutting member to facilitate cutting
- B26D7/088—Means for treating work or cutting member to facilitate cutting by cleaning or lubricating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0044—Mechanical working of the substrate, e.g. drilling or punching
- H05K3/0047—Drilling of holes
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/02—Details related to mechanical or acoustic processing, e.g. drilling, punching, cutting, using ultrasound
- H05K2203/0214—Back-up or entry material, e.g. for mechanical drilling
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/12—Using specific substances
- H05K2203/127—Lubricants, e.g. during drilling of holes
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Forests & Forestry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Perforating, Stamping-Out Or Severing By Means Other Than Cutting (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Lubricants (AREA)
- Laminated Bodies (AREA)
- Drilling And Boring (AREA)
Abstract
Description
201043362 六、發明說明： 【發明所屬之技術領域】 加層板或多層板的鑽頭鑽孔 【先前技術】 的鋼_層板或多層板的最上部片重叠 =有樹脂組成物層的板(以下，於本說明;中Ϊΐ 的減小等的高品質的鑽孔加工，為二 (P*e: 並實際應用：使用由聚乙烯乙二醇 法（你丨伽〇1)等的水溶性樹脂形成的板的鑽孔加工 芦^科散獻〜於金屬訂形成有水溶性樹脂 ^鑽孔用潤滑劑板（例如參照專利文獻2)、於形成有妖 性樹脂薄膜的銘訂形成有水溶性樹脂層的鑽孔用^ ，如參照專利文獻3) #。近年來，於印刷電路板的 问，^化方面，需求銅箔積層板或多層板的加工孔間的 兩通可罪性。因此，為了確保孔間彼此的絕緣可靠性，必 而維持優異的孔位置精度，並且進―步減小孔壁粗糖度。 又，亦必需減少鑽頭上的樹脂捲附，藉此使鑽頭折損率下 降或鑽頭的再研磨效率提高等，由此使生產性提高。因此， 201043362 迫切期望發揮出如下性能的由水溶性樹脂層所形成的鑽孔 用蓋板，即，孔位置精度優異、孔壁粗糙度減小、及鑽頭 上的樹脂捲附減少。 專利文獻1 ··曰本專利特開平4-92494號公報 專利文獻2:曰本專利特開平5_1694〇〇號公報 專利文獻3 :日本專利特開2〇〇3_136485號公報 【發明内容】 Q 已知悉，若使水溶性樹脂組成物層變薄，則可減少樹 脂捲附，但孔壁粗糙度變粗糙，為兩相矛盾的關係。本發 明的課題在於提供一種使水溶性樹脂組成物層的厚度變薄 而減少鑽頭上的樹脂捲附、同時不使孔位置精度下降而實 現孔壁粗縫度減小的鑽孔用蓋板。 本發明人等為解決上述課題而進行了各種研究，結果 發現，即使將水溶性樹脂組成物層變得比習知的鑽孔用蓋 板的要薄，將由特定的水溶性樹脂、特定的聚乙烯乙二醇、 特定的水溶性潤滑劑樹脂及特定的水溶性物質構成的水溶 〇 性樹脂組成物的層形成於金屬箱表面而得到的鑽孔用蓋板 亦月b解決上述課題。即，本發明如下述。 匕]一種鑽孔用蓋板，包括金屬箔、及於該金屬箔的 至少單面上積層-體化的水溶性細旨纟讀物的層， 上述鑽孔用蓋板的特徵在於上述水溶性樹脂組成物包 含： 3〇重I份〜85重量份的數量平均>子量$ 8〇〇〇〇〜 400,000的水溶性樹脂（A); 5 201043362 10重量份〜60重量份的查 25，_㈣乙烯乙二醇⑻h平均分子量為15,000〜 ⑽綱m (c);以及 t於由上述水溶性_(朴上述聚乙烯乙 滑劑樹脂（c)構成的水溶性樹脂混合物 x) i〇 物質⑺’其疋選自由多it醇類、胺基酸衍生物醇類、有 機酸類及有機酸鹽類所組成族群中的—種或兩種以上。 [2]如上述第[1]項所記載之鑽孔用蓋板其中上述水 溶性樹脂（A)為選自由聚環氧乙烷、聚環氧丙烷、聚丙 烯酸鈉、聚丙烯醯胺、聚乙烯吡咯啶酮（p〇ly vinyl pyirolidone)、羧曱基纖維素、聚伸丁二醇（p〇ly tetramethylene glycol)及聚烯烴乙二醇的聚酯所組成族群中 的一種或兩種以上。 [3]如上述第[1]項所記載之鑽孔用蓋板，其中上述水 溶性潤滑劑樹脂（C)是由下述詰構式（1)所示： R1^CnH2n-〇^rR2 ⑴ (式中，R2為氫或碳數1^3的烷基，艮為選自烷氧 基、烯氧基、芳氧基、胺基、下述式（2)所示的醯胺基及 下述式（3)所示的酯基中的基，111為10〜450的整數，η 為1〜5的整數）， ^3—C—NH-0 (2) 201043362 R3~C—Ο— s ⑴ h β (式中，R3表示氫、碳數1〜20的烷基或碳數2〜20 的烯基）。 [4]如上述第[1]項所記載之鑽孔用蓋板其中上述水 〜續脂組成物於1GG°C下⑽融減為5GPa.s以上。 ❹ [5] *上述第⑴項至第[4]項中任-項所記載之鑽孔 盍板，其中上述金屬箔的厚度為〇 〇5 mm〜〇 5 mm，上 述水溶性樹脂組成物的層的厚度為〇 〇1 mm〜〇 3 mm。 [發明之效果] 藉由使用本發明的鑽孔用蓋板，即便將水溶性樹脂組 成物層變得比習知的厚度要薄，也能不使孔位置精度下 降，進而讓孔壁的粗糙度變小，可減少鑽頭上的樹脂捲附。 藉此’可實現高品質且生產性優異的鑽孔加工。 Q 為讓本發明之上述和其他目的、特徵和優點能更明顯 易懂，下文特舉較佳實施例，並配合所附圖式，作詳細說 明如下。 【實施方式】 本發明是一種鑽孔用蓋板’包括金屬箔、及於該金屬 、冶的至少單面上積層一體化的水溶性樹脂組成物的層，上 述鑽孔用蓋板的特徵在於上述水溶性樹脂組成物包含：30 重量份〜85重量份的數量平均分子量為8〇,〇〇〇〜400,〇〇〇 的水溶性樹脂（A); 10重量份〜60重量份的數量平均分 201043362 子量為15,〇00〜25〇〇〇的聚乙烯乙二醇（B) ; $重量份〜 50重量份的水溶性潤滑劑樹脂（C);以及相對於由上述水 洛性樹脂（A)、上述聚乙烯乙二醇（B)及上述水溶性潤 滑劑樹脂（C)構成的水溶性樹脂混合物（X) 100重量份 而為0.1重量份〜5重量份的水溶性物質（Y)，其是選自 由多兀醇類、胺基酸衍生物醇類、有機酸類及有機酸鹽類 所組成族群中的一種或兩種以上的物質。上述鑽孔用蓋板 可利用以下所示的方法來製造，但不限定於此。 於本發明的鑽孔用蓋板中，水溶性樹脂混合物（X) 可使用數量平均分子量為80,000〜400,000、較佳是80,〇〇〇 〜150,〇〇〇的水溶性樹脂（A)及數量平均分子量為15〇〇〇 〜25,000的聚乙烯乙二醇（b)以及較佳是數量平均分子 量為15,00〇以下、更佳是1，〇〇〇〜1〇,〇〇〇的水溶性潤滑劑 樹脂（C)的混合物。關於其調配量，於水溶性樹脂（A)、 聚乙烯乙二醇（B)及水溶性潤滑劑樹脂（C)合計為100 重量份中，水溶性樹脂（A)為30重量份〜85重量份、較 佳是40重量份〜70重量份；聚乙烯乙二醇（B)為1〇重 量份〜60重量份，較佳是15重量份〜50重量份；水溶性 潤滑劑樹脂（C)為5重量份〜5〇重量份，較佳是15重量 份〜40重量份。 當水溶性樹脂（A)的數量平均分子量小於80,000時， 水溶性樹脂組成物層會變脆，因此使孔位置精度下降，另 外水溶性樹脂組成物的熔融黏度也會下降，因此可能發生 孔壁粗糙度的惡化。另一方面，若水溶性樹脂（A)的數 201043362 量平均分子量超過400,000，則鑽頭上的樹脂捲附量會增 加，可能發生孔位置精度的下降。另外，當聚乙烯乙二醇 (B)的數量平均分子量小於15 〇〇〇時，水溶性樹脂組成 物層會變脆。另一方面，若聚乙稀乙二醇（B)的數量平 均分子量超過25,000，則鑽頭上的樹脂捲附量會增加，可 能發生孔位置精度的下降。此外’若水溶性潤滑劑樹脂（C ) 的數量平均分子量超過15,000，則鑽頭上的樹脂捲附量會 0 增加，可能發生孔位置精度的下降，因此欠佳。 另外’當水溶性樹脂（A)的調配量小於3〇重量份時， 由於水溶性樹脂組成物的溶融黏度的下降，而發生孔壁粗 糙度的惡化；另一方面，若水溶性樹脂（A)的調配量超 過85重量份，則鑽頭上的樹脂捲附量會增加，可能發生孔 位置精度的下降。另外，當聚乙稀乙二醇（B)的調配量 小於10重量份時’板表面會變柔軟而發生孔位置精度的惡 化；另一方面，若聚乙烯乙二醇（B)的調配量超過6〇重 量份，則由於水溶性樹脂組成物的熔融黏度的下降而發生 Ο 孔壁粗糙度的惡化。另外，當水溶性潤滑劑樹脂（c)的 調配量小於5重量份時，切割屑屑的排出性會惡化，而發 生孔壁粗糙度的惡化及鑽頭折損；另一方面，若水溶性潤 滑劑樹脂（C)超過50重量份，則板表面會變柔軟而可能 發生孔位置精度的惡化。 本發明中適用的水溶性樹脂（A)較佳是選自由聚環 氧乙烷（poly ethylene oxide )、聚環氧丙烷（p〇iy propylene oxide)、聚丙稀酸納（poly sodium acrylate)、聚丙烯醢胺 9 201043362 (poly acrylamide )、聚乙烯吼咯咬酮（poly vinyl pyrrolidone)、羧曱基纖維素（carboxymethyl cellulose)、 聚伸 丁二醇（poly tetramethylene glycol)及聚烯烴乙二醇 (poly alkylene glycol)的聚酯所組成族群中的一種或兩種 以上。此處，所謂聚烯烴乙二醇的聚酯，是指使聚烯烴乙 二醇與二元酸反應所得的縮合物。聚烯烴乙二醇之例可列 舉聚乙烯乙二醇（poly ethylene glycol)、聚丙二醇、聚伸 丁二醇或該些二醇的共聚物所例示的二醇類。另外，二元 酸較佳的是選自鄰苯二甲酸（phthalic acid)、間苯二甲酸 (isophthalic acid)、對苯二曱酸（terephthalic acid)、癸二 酸（sebacic acid)及均苯四甲酸（pyromellitic acid)等的 多元羧酸的部分酯、與該些酸的酸酐等。 本發明中使用的水溶性潤滑劑樹脂（C )較佳是具有 下述結構式（1 )所示的結構。式（1)中，m表示10〜45〇、 較佳的是10〜200的整數，η表示1〜5、較佳的是1^3 的整數。當m小於10時，板會變脆，可能發生孔位裏精 度的下降、内壁狀態的惡化等。另外，R2為氫或碳數I〆3 的蝝基；心為選自烷氧基、烯氧基、芳氧基、胺基、卞述 式（2)所示的醯胺基及下述式（3)所示的酯基中的基。 再者’式（2)及式（3)中，R3表示氫、碳數1〜2〇的姨 基、或碳數2〜20的烯基。201043362 VI. Description of the Invention: [Technical Field of the Invention] Drilling of a drilled layer or a multi-layered plate [Prior Art] The uppermost sheet of the steel-layered or multi-layered board is overlapped = the board having the resin composition layer (below In this description; the high-quality drilling process such as the reduction of the middle cymbal is two (P*e: and practical application: using a water-soluble resin such as polyethylene glycol method (your sangha 1) The hole forming of the formed plate is made of a water-soluble resin, a lubricant plate for drilling (for example, refer to Patent Document 2), and a water-soluble resin film is formed to form a water-soluble material. For the drilling of the resin layer, as described in Patent Document 3) #. In recent years, in terms of the printed circuit board, the two-way sin between the processing holes of the copper foil laminate or the multilayer board is required. In order to ensure the insulation reliability between the holes, it is necessary to maintain excellent hole position accuracy, and further reduce the brown sugar content of the hole wall. Also, it is necessary to reduce the resin wrap on the drill bit, thereby reducing the bit breakage rate. Or the regrind efficiency of the drill bit is improved, etc. Therefore, 201043362 is expected to have a drilling cover plate formed of a water-soluble resin layer that exhibits the following properties, that is, excellent hole position accuracy, reduced hole wall roughness, and reduced resin wrap on the drill bit. [Patent Document 1] 曰 专利 专利 4- 4- 4- 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 92 Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q Q It is understood that when the water-soluble resin composition layer is made thinner, the resin wrap is reduced, but the hole wall roughness is roughened, which is a contradiction between the two phases. It is an object of the present invention to provide a water-soluble resin composition layer. The inventors of the present invention have conducted various studies to solve the above problems, and have reduced the thickness of the resin to reduce the resin wrap on the drill and to reduce the accuracy of the hole position. It has been found that even if the water-soluble resin composition layer is made thinner than the conventional drilling cover sheet, it will be composed of a specific water-soluble resin, a specific polyethylene glycol, and a specific water solubility. The above-mentioned problem is solved by the fact that the layer of the water-soluble resin composition composed of the slip resin and the specific water-soluble substance is formed on the surface of the metal case, and the present invention is as follows. 匕] A drill The hole cover plate includes a metal foil and a layer of a water-soluble fine-grained material laminated on at least one side of the metal foil, and the hole-covering cover plate is characterized in that the water-soluble resin composition comprises: 3 〇 weighs 1 part to 85 parts by weight of the average amount > sub-quantity of $ 8 〇〇〇〇 ~ 400,000 of water-soluble resin (A); 5 201043362 10 parts by weight to 60 parts by weight of 25, _ (tetra) ethylene glycol (8) h has an average molecular weight of 15,000 Å to 10 (m); and t is a water-soluble resin mixture x composed of the above-mentioned water-soluble _ (the above-mentioned polyethylene ethyl slip resin (c)) i 〇 substance (7)' One or more of the group consisting of a poly-alcohol, an amino acid derivative alcohol, an organic acid, and an organic acid salt. [2] The cover sheet for drilling according to the above [1], wherein the water-soluble resin (A) is selected from the group consisting of polyethylene oxide, polypropylene oxide, sodium polyacrylate, polypropylene decylamine, and poly One or more of the group consisting of p〇ly vinyl pyirolidone, carboxymethyl cellulose, p〇ly tetramethylene glycol, and polyester of polyolefin glycol. [3] The cover sheet for drilling according to the above [1], wherein the water-soluble lubricant resin (C) is represented by the following formula (1): R1^CnH2n-〇^rR2 (1) (wherein R 2 is hydrogen or an alkyl group having 1 3 carbon atoms; and hydrazine is an alkoxy group selected from the group consisting of an alkoxy group, an alkenyloxy group, an aryloxy group, an amine group, and the following formula (2) The group in the ester group represented by the formula (3), 111 is an integer of 10 to 450, and η is an integer of 1 to 5), ^3—C—NH-0 (2) 201043362 R3~C—Ο—s (1) h β (wherein R3 represents hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms). [4] The perforated cover sheet according to the above [1], wherein the water-renewing fat composition is reduced to 5 GPa.s or more at 1 GG ° C (10). The boring board according to any one of the items (1) to (4), wherein the thickness of the metal foil is 〇〇5 mm to 〇5 mm, and the water-soluble resin composition is The thickness of the layer is 〇〇1 mm~〇3 mm. [Effects of the Invention] By using the drilling cover plate of the present invention, even if the water-soluble resin composition layer is made thinner than the conventional thickness, the hole position accuracy can be prevented from being lowered, and the hole wall roughness can be made. The smaller the degree, the less the resin wrap on the drill bit. This enables high-quality and highly productive drilling. The above and other objects, features, and advantages of the present invention will become more apparent from the understanding of the appended claims appended claims [Embodiment] The present invention relates to a drilling cover plate which comprises a metal foil and a layer of a water-soluble resin composition which is integrated on at least one side of the metal and metallurgy. The above water-soluble resin composition comprises: 30 parts by weight to 85 parts by weight of a water-soluble resin (A) having a number average molecular weight of 8 Å, 〇〇〇 400, 〇〇〇; 10 parts by weight to 60 parts by weight a sub-201043362 sub-amount of 15, 00~25 〇〇〇 polyethylene glycol (B); a part by weight to 50 parts by weight of a water-soluble lubricant resin (C); and relative to the above water-based resin (A), the water-soluble resin mixture (X) composed of the polyethylene glycol (B) and the water-soluble lubricant resin (C), and a water-soluble substance (Y) in an amount of 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the water-soluble resin mixture (X) It is one or two or more selected from the group consisting of polyhydric alcohols, amino acid derivative alcohols, organic acids, and organic acid salts. The above-mentioned drilling cover can be manufactured by the method described below, but is not limited thereto. In the drilling cover plate of the present invention, the water-soluble resin mixture (X) may be a water-soluble resin (A) having a number average molecular weight of 80,000 to 400,000, preferably 80, 〇〇〇 150, 〇〇〇, and The polyethylene glycol (b) having a number average molecular weight of 15 Å to 25,000 and preferably having a number average molecular weight of 1,500 Å or less, more preferably 1, 〇〇〇 1 〇, water soluble in hydrazine A mixture of lubricant resins (C). The water-soluble resin (A) is 30 parts by weight to 85 parts by weight of the water-soluble resin (A), the polyethylene glycol (B), and the water-soluble lubricant resin (C) in a total amount of 100 parts by weight. And preferably 40 parts by weight to 70 parts by weight; polyethylene glycol (B) is 1 part by weight to 60 parts by weight, preferably 15 parts by weight to 50 parts by weight; water-soluble lubricant resin (C) It is 5 parts by weight to 5 parts by weight, preferably 15 parts by weight to 40 parts by weight. When the number average molecular weight of the water-soluble resin (A) is less than 80,000, the water-soluble resin composition layer becomes brittle, so that the hole positional accuracy is lowered, and the melt viscosity of the water-soluble resin composition is also lowered, so that pore walls may occur. Deterioration of roughness. On the other hand, if the number average of the water-soluble resin (A) 201043362 exceeds 400,000, the amount of resin wound on the drill bit increases, and the accuracy of the hole position may decrease. Further, when the number average molecular weight of the polyethylene glycol (B) is less than 15 Å, the water-soluble resin composition layer becomes brittle. On the other hand, if the average molecular weight of the polyethylene glycol (B) exceeds 25,000, the amount of resin wound on the drill bit increases, and the accuracy of the hole position may decrease. Further, if the number average molecular weight of the water-soluble lubricant resin (C) exceeds 15,000, the amount of resin wound on the drill bit increases by 0, and the accuracy of the hole position accuracy may be lowered, which is not preferable. In addition, when the amount of the water-soluble resin (A) is less than 3 parts by weight, the roughness of the pore wall is deteriorated due to a decrease in the melt viscosity of the water-soluble resin composition; on the other hand, if the water-soluble resin (A) When the blending amount exceeds 85 parts by weight, the amount of resin wound on the drill bit increases, and the accuracy of the hole position accuracy may decrease. In addition, when the blending amount of the polyethylene glycol (B) is less than 10 parts by weight, the surface of the sheet becomes soft and the accuracy of the hole position is deteriorated; on the other hand, if the amount of polyethylene glycol (B) is adjusted, When the amount is more than 6 parts by weight, the surface roughness of the boring wall is deteriorated due to a decrease in the melt viscosity of the water-soluble resin composition. In addition, when the compounding amount of the water-soluble lubricant resin (c) is less than 5 parts by weight, the discharge property of the cutting chips is deteriorated, and the roughness of the hole wall and the bit breakage occur; on the other hand, if the water-soluble lubricant resin When the amount of (C) exceeds 50 parts by weight, the surface of the sheet may become soft and the accuracy of the positional accuracy of the pores may occur. The water-soluble resin (A) suitable for use in the present invention is preferably selected from the group consisting of poly ethylene oxide, p-propylene oxide, poly sodium acrylate, and poly Acrylamide 9 201043362 (poly acrylamide ), poly vinyl pyrrolidone, carboxymethyl cellulose, polytetramethylene glycol and polyolefin glycol (poly One or more of the group consisting of polyesters of alkylene glycol). Here, the polyester of polyolefin ethylene glycol means a condensate obtained by reacting polyolefin ethylene glycol with a dibasic acid. Examples of the polyolefin ethylene glycol include polyethylene glycols, polypropylene glycols, polybutadiene diols, or diols exemplified as copolymers of the diols. Further, the dibasic acid is preferably selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, sebacic acid, and pyromelli. a partial ester of a polyvalent carboxylic acid such as pyromellitic acid, an acid anhydride of these acids, or the like. The water-soluble lubricant resin (C) used in the present invention preferably has a structure represented by the following structural formula (1). In the formula (1), m represents an integer of 10 to 45 Å, preferably 10 to 200, and η represents an integer of 1 to 5, preferably 1^3. When m is less than 10, the plate becomes brittle, and the accuracy in the hole position may be deteriorated, and the state of the inner wall may be deteriorated. Further, R 2 is hydrogen or a fluorenyl group having a carbon number of I 〆 3 ; the core is an alkoxy group selected from the group consisting of an alkoxy group, an alkenyloxy group, an aryloxy group, an amine group, and the following formula (2); (3) A group in the ester group shown. Further, in the formulae (2) and (3), R3 represents hydrogen, a fluorenyl group having 1 to 2 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms.
Rl-{〇nH2n-〇^rR2 ⑴ 10 201043362 (2) Ο R3~c—o— 〇 ⑴ 被士更f體而言，R1例如較佳是選自由下述基所組成的族 群中.相t騎脂細(steaTyl ethef)或異魏_等的烧 〇 基醚、，油基_(〇1刮ether)或烯丙基醚等的烯基醚、芳基醚 或取代芳基咐_鍵的硬脂基氧基或異硬脂基氧基^ 烷氧基、油基氧基或烯丙基氧基等的烯氧基、苯氧基、取 ，苯氧基等的芳氧基等；烷基胺基等的胺基；烷基醯胺基 等的醯胺基；以及油酸酯、硬脂酸酯等的酯基。另外，水 溶性滑材樹脂（C)可使用一種或併用兩種以上。 通常，高分子之分子量是指具有各種分子量的高分子 的平均值。平均分子量的計算方法中，有以每丨個分子的 ◎ 平均分子量的形式而計算出的數量平均分子量Mn、或對 重里進行加權而计舁出的重量平均分子量Mw等。本發明 中的刀子里疋指利用凝膠滲透層析儀（gel permeati〇n chromatography，GPC)測定的數值。 本發明中的數量平均分子量是指在水系GPC分析條 件下進行’將 Shodex SB-G、Shodex SB-803HQ 及 Shodex SB-806MHQ (昭和電工股份有限公司製造）的管柱串聯而 測定的值。於本發明中’將分析試樣的載體（carrier)設 定為50 mM—NaCl水溶液，於注入量為20 μ卜流速為0.7 11 201043362 ml/min、烘箱溫度為35°C的條件下，利用示差折射計 (RID-6A，島津製作所股份有限公司製造）進行測定，使 用聚乙細乙二醇試劑盒（POLYMER LABORATORIES Ltd. 製造）作為標準物質’計算出高分子化合物的數量平均分 子量及重量平均分子量。進而，根據所得的GPC資料來分 取各波峰成分，使用FT-IR(日本分光股份有限公司製造 FT/IR-6100)來進行成分鑑定。 本發明的鑽孔用蓋板中所用的水溶性樹脂組成物於 100 C下的炼融黏度較佳的是50 Pa*s以上，更佳的是50 Pa«s〜600 Pa*s。若水溶性樹脂組成物的熔融黏度為5〇 Pa，s 以上，則有利於孔壁粗糖度的減小，進而若水溶性樹脂組 成物的熔融黏度為600 Pa*s以下’則鑽頭上的樹脂捲附量 亦可減少。 本發明中’於水溶性樹脂組成物的熔融黏度的測定方 法’是使用由在内孔底部設置有可更換的毛細管 (capillary)的附有加熱器的圓筒（cylinder)所構成的熔 融黏度測定裝置（CFT-500D : SHIMADZU (股）製造）。 對圓筒中所填充的熔融試樣於空氣壓下施加試驗壓力。毛 細管疋使用口徑為0.5 mm、長度為1 〇.〇 mm的毛細管。此 時的測定條件是設定為試驗溫度為l〇〇°c、試驗壓力為 980,000Pa ’來實施熔融黏度測定。 本發明中使用的水溶性物質（γ)只要是選自由多元 醇類、胺基酸衍生物醇類、有機酸類及有機酸鹽類所組成 族群中的水溶性物質，則並無特別限定，可使用一種或適 12 201043362 Ο ❹ 當混合而使用兩種或兩種以上。關於較佳的水溶性物質 (Υ)，多元醇類可列舉三經甲基丙烧（trimethylol propane )、季戊四醇（pentaerythritol )、新戊二醇（neopentyl glycol )、三經甲基乙烧、山梨糖醇（sorbit〇l )、木糖醇 (xylitol)、肌醇（inosit〇i)等；胺基酸衍生物醇類可列舉 酿胺酸（tyrosine)、糖基胺（glycosyl amine)等；有機酸 類可列舉蘋果酸（malic acid)、丙二酸（malonic acid)、琥 珀酸、反丁 烯二酸（fumaric acid )、順丁 稀二酸（maleic acid)、曱酸、乙酸、丙酸、硬脂酸等；有機酸鹽類可列舉 上文所列舉的有機酸類的金屬鹽類。此處，金屬鹽類可列 舉鈉鹽等。水溶性物質（γ)的調配量相對於水溶性樹脂 混合物（X) 1〇〇重量份而為〇丨重量份〜5重量份，較佳 疋0.3重置份〜4重量份。當水溶性物質（γ)的調配量在 上述範圍外時，於鑽頭鑽孔加工時會發生孔位置精度的下 降或鑽頭上的樹脂捲附的增加，進而發生鑽頭折損而欠佳。 水溶性樹脂組成物的製備方法可例示如下方法等：將 =溶性樹脂（A)、聚乙烯乙二醇（B)及水溶性潤滑劑 樹脂（C)構成的水溶性樹脂混合物（X)溶解於溶劑中之 後，、於該溶液巾添加水紐㈣（γ)㈣成水溶性樹脂 組成物的溶液；或使由水紐旨（Α)、聚乙私二醇⑻ 及水f性潤滑劑樹脂（C)構成的水溶性樹脂混合物（X) =的熱=加水溶性物f⑺而形成水溶性樹脂組 本發明的鑽孔用蓋板中使用的金屬箱的金屬麵較佳 13 201043362 疋鋁，金屬箔的厚度通常為0.05 mm〜0.5 mm，較佳的是 0·05 mm〜〇·3 mm。若金屬箔的厚度小於〇 〇5 ，則鑽頭 鑽=加工時容易產生積層板的毛邊，另一方面，若金屬猪 的，度超過G.5mm’卿以將綱鑽孔加王時所產生的切 割粉末排出。另外，鋁箔的材質較佳是純度為95%以上的 鋁，具體可例示JIS-H4160所規定的5052、3004、3003、 1 二30、丄N99、1〇5〇、1070、1〇85、8〇21 等。藉由對金屬 /6使用尚純度的|呂箔，能提高鑽針（driH bit)的衝擊的缓 和鑽入性提高，赫水雜触城麟帶來的鑽針的潤 /月放果相互作用’能提高加工孔的孔位置精度。另外，若 5 =在這些銘上預先形成厚度為〇 〇〇1 mm〜0.01 mm 的 ^月曰皮膜’則就與水溶性_組成物的密著性的方面而言 ^•樣的銘紐佳。_細所使㈣麵並無翻限定， 熱塑性樹脂、熱硬化性樹脂均可。例如，熱塑性樹脂可例 胺基曱_旨系、乙酸乙_旨系、氯乙烯系、聚醋系及 1些樹脂的共聚物。熱硬化性樹脂可例示：環氧系、氮酸 酉曰（cyanurate)系等的樹脂。另外，本發明的金屬箔亦可 使用在市f的金屬訂縣利用公知方法塗佈樹脂而成的 金屬箔。 、於金屬4的至少單面上形成水溶性樹脂㈣物的層的 方法可例不：預先製作水溶性樹脂組成物的板(sheet)並與 金屬箱貼合的熱熔層疊法（h〇t_mdt lami她meth〇d)、或 將水浴性樹脂組成物的熱料物或溶液錢塗佈於金屬箱 上並進仃錢的塗佈法等。再者，_塗佈法所製作的蓋 201043362 板與利用先前的熱溶層疊法所製作的板相比，可使水溶性 樹脂組成物層的厚變薄，但藉由使用本發明的水溶性樹脂 組成物而保持如下優異特徵：不使鑽孔加工時的孔位置精 度下降’進而於孔壁粗糙度的減小方面優異，鑽頭上的^ 脂捲附少。另外，於使金屬箱與水溶性樹脂組成物層積層 一體化的方面而言，熱熔層疊法、塗佈法均較佳的是於^ 屬箔上預先形成有樹脂皮膜。 、、 〇 f發明的鑽孔用蓋板中的水溶性樹脂組成物的層的厚 度，是根據鑽頭鑽孔加工時所使用的鑽頭徑或所加工的銅 箔積層板或多層板的構成等而不同，通常為〇〇1 mm〜〇3 mm的範圍，較佳的是0.02mm〜〇 2mm的範圍，更佳的 是0.03 mm〜0.12 mm的範圍。若水溶性樹脂組成物的層 的厚度小於0.01 mm，則無法獲得充分的潤滑效果，孔壁 粗糙度會惡化，另外鑽頭所受的負荷變大而會發生鑽頭折 才貝。另一方面，右水 >谷性樹脂組成物的層的厚度超過〇 3 mm，則有時鑽頭上的樹脂的捲附會增加。 〇 構成鑽孔用蓋板的各層的厚度是以如下方式而測定。 自蓋板的水溶性樹脂組成物層的表面，利用橫戴面研磨機 (CROSS-SECTION POLISHER SM-09010，日本電子 DATUM (股）製造）、或超薄切片機（ultramicr〇t〇me，Rl-{〇nH2n-〇^rR2 (1) 10 201043362 (2) Ο R3~c-o- 〇(1) For the terminus, R1 is preferably selected, for example, from the group consisting of the following groups. An alkenyl ether, an aryl ether or a substituted aryl 咐 bond, such as steaTyl ethef or isobutyl ketone, oleyl ether or allylic ether An alkenyloxy group such as a stearyloxy group or an isostearyloxy alkoxy group, an oleyloxy group or an allyloxy group; an aryloxy group; or an aryloxy group such as a phenoxy group; An amine group such as an amino group; a guanamine group such as an alkylguanamine group; and an ester group such as an oleate or a stearate. Further, the water-soluble sliding material resin (C) may be used alone or in combination of two or more. Generally, the molecular weight of a polymer means an average value of a polymer having various molecular weights. In the calculation method of the average molecular weight, there are a number average molecular weight Mn calculated as the average molecular weight of each molecule, or a weight average molecular weight Mw calculated by weighting the weight. The knife in the present invention refers to a value measured by gel permeatisic chromatography (GPC). The number-average molecular weight in the present invention is a value measured by connecting a column of Shodex SB-G, Shodex SB-803HQ, and Shodex SB-806MHQ (manufactured by Showa Denko KK) in series under an aqueous GPC analysis condition. In the present invention, the carrier of the analysis sample is set to a 50 mM-NaCl aqueous solution, and the amount of the injection is 20 μb, the flow rate is 0.7 11 201043362 ml/min, and the oven temperature is 35 ° C. The refractometer (RID-6A, manufactured by Shimadzu Corporation) was measured, and the number average molecular weight and the weight average molecular weight of the polymer compound were calculated using a polyethylene glycol kit (manufactured by POLYMER LABORATORIES Ltd.) as a standard material. . Further, each peak component was fractionated based on the obtained GPC data, and component identification was performed using FT-IR (FT/IR-6100 manufactured by JASCO Corporation). The water-soluble resin composition used in the drilling cover sheet of the present invention preferably has a smelting viscosity at 100 C of 50 Pa*s or more, more preferably 50 Pa«s to 600 Pa*s. If the melt viscosity of the water-soluble resin composition is 5 〇 Pa or more, the thickness of the pore wall is reduced, and if the melt viscosity of the water-soluble resin composition is 600 Pa*s or less, the resin is attached to the drill. The amount can also be reduced. In the present invention, the 'method for measuring the melt viscosity of the water-soluble resin composition' is a melt viscosity measurement using a heater-equipped cylinder provided with a replaceable capillary at the bottom of the inner hole. Device (CFT-500D: manufactured by SHIMADZU (share)). The molten sample filled in the cylinder was subjected to a test pressure under air pressure. The capillary tube is a capillary having a diameter of 0.5 mm and a length of 1 〇.〇 mm. The measurement conditions at this time were set to a test temperature of 10 ° C and a test pressure of 980,000 Pa ' to carry out melt viscosity measurement. The water-soluble substance (γ) used in the present invention is not particularly limited as long as it is a water-soluble substance selected from the group consisting of a polyol, an amino acid derivative alcohol, an organic acid, and an organic acid salt. Use one or more suitable for 201043362 Ο 使用 Use two or more when mixing. As a preferred water-soluble substance (polyhydric alcohol), examples of the polyhydric alcohol include trimethylol propane, pentaerythritol, neopentyl glycol, trimethyl ketone, and sorbose. Alcohol (sorbit〇l), xylitol (xylitol), inositol (inosit〇i), etc.; amino acid derivative alcohols may include tyrosine, glycosyl amine, etc.; organic acids Examples thereof include malic acid, malonic acid, succinic acid, fumaric acid, maleic acid, citric acid, acetic acid, propionic acid, and stearic acid. The acid or the like; the organic acid salts include metal salts of the above-exemplified organic acids. Here, the metal salt may, for example, be a sodium salt or the like. The amount of the water-soluble substance (γ) to be added is from 5% by weight to 5% by weight, preferably from 重置0.3 to 4 parts by weight, based on 1 part by weight of the water-soluble resin mixture (X). When the blending amount of the water-soluble substance (γ) is outside the above range, the accuracy of the hole position accuracy or the increase in the resin wrap on the drill bit may occur during the drilling of the drill bit, and the drill bit may be broken and may be unsatisfactory. The method for producing the water-soluble resin composition can be exemplified by a method in which a water-soluble resin mixture (X) composed of a soluble resin (A), a polyethylene glycol (B), and a water-soluble lubricant resin (C) is dissolved in After the solvent, a solution of the water-soluble resin composition is added to the solution towel, or a solution of the water-soluble resin composition; or a water-based lubricant resin ((), polyethylene glycol (8), and water-based lubricant resin ( C) Water-soluble resin mixture (X) = heat = water-soluble substance f (7) to form a water-soluble resin group The metal surface of the metal case used in the drilling cover plate of the present invention is preferably 13 201043362 疋 aluminum, metal foil The thickness is usually from 0.05 mm to 0.5 mm, preferably from 0.05 mm to 〇·3 mm. If the thickness of the metal foil is less than 〇〇5, then the drill bit = the burr of the laminate is easy to be produced during processing. On the other hand, if the metal pig is more than G.5mm, the result is that the diamond is added to the king. The cutting powder is discharged. Further, the material of the aluminum foil is preferably aluminum having a purity of 95% or more, and specific examples thereof are 5052, 3004, 3003, 1 2 30, 丄N99, 1〇5〇, 1070, 1〇85, 8 as defined by JIS-H4160. 〇21 and so on. By using the purity of the metal / 6 | Lu foil, the impact of the driH bit can be improved, and the penetration of the drill needle can be improved. 'It can improve the hole position accuracy of the machined hole. In addition, if 5 = pre-formed a film of thickness 〇〇〇1 mm to 0.01 mm on these marks, it is in terms of the adhesion of the water-soluble _ composition. . _There is no limitation on the (4) surface, and both thermoplastic resin and thermosetting resin can be used. For example, the thermoplastic resin may, for example, be a copolymer of an amine group, a cellulose acetate system, a vinyl chloride resin, a polyester resin or a resin. The thermosetting resin may, for example, be a resin such as an epoxy-based or a cyanurate-based resin. Further, the metal foil of the present invention can also be used as a metal foil obtained by coating a resin by a known method in a metal book of the city of F. A method of forming a layer of a water-soluble resin (four) on at least one surface of the metal 4 may be, for example, a hot-melt lamination method in which a sheet of a water-soluble resin composition is prepared in advance and bonded to a metal case (h〇t_mdt) Lami meth〇d), or a hot material or solution of a water-based resin composition, is applied to a metal box, and a coating method such as a money is applied. Further, the cover 201043362 plate produced by the _ coating method can make the thickness of the water-soluble resin composition layer thinner than the plate produced by the previous hot-melt lamination method, but by using the water-soluble water of the present invention. The resin composition maintains the excellent characteristics of not lowering the hole position accuracy during the drilling process, and further excellent in the reduction of the hole wall roughness, and the attachment of the grease on the drill bit is small. Further, in the aspect of integrating the metal case and the water-soluble resin composition, it is preferable that the hot-melt lamination method and the coating method have a resin film formed on the metal foil in advance. The thickness of the layer of the water-soluble resin composition in the drilling cover plate of the invention is based on the drill diameter used in the drilling of the drill or the composition of the copper foil laminate or the multilayer plate to be processed. The difference is usually in the range of 〇〇1 mm to 〇3 mm, preferably in the range of 0.02 mm to 〇2 mm, and more preferably in the range of 0.03 mm to 0.12 mm. When the thickness of the layer of the water-soluble resin composition is less than 0.01 mm, a sufficient lubricating effect cannot be obtained, the roughness of the hole wall is deteriorated, and the load on the drill bit becomes large, and the drill bit is broken. On the other hand, when the thickness of the layer of the right water > cereal resin composition exceeds 〇 3 mm, the resin on the drill may increase in the amount of the wound.厚度 The thickness of each layer constituting the drilling cover is measured as follows. The surface of the water-soluble resin composition layer of the cover plate is a cross-surface grinder (CROSS-SECTION POLISHER SM-09010, manufactured by JEOL DATUM Co., Ltd.) or an ultra-thin slicer (ultramicr〇t〇me,
Leica公司製造）將蓋板切斷後，利用掃描電子顯微鏡 (Scanning Electron Microscope，SEM ) ( VE-7800， KEYENCE製造）對剖面自垂直方向觀察剖面，於％〇倍 的視場下測定銘層及水溶性樹脂組成物層的厚度。對1视 15 201043362 場測定5處的厚度，將其平均值作為厚度。 使用本發明的鑽孔用蓋板的鑽頭鑽孔加工為：於對印 刷電路材料、例如銅箱積層板或多層板進行鑽頭鑽孔加工 時，於一片或多片重疊的銅箔積層板或多層板的至少最上 面，以該蓋板的金屬镇側與印刷電路材料接觸的方式而配 置，自鑽孔用蓋板的水溶性樹脂組成物層的面進行鐵頭鑽 孔加工。 再者’本發明的鑽孔用蓋板不限定於銅箱積層板或多 層板的鑽孔加工’亦可應用於樹脂形成物、金屬框體、太 陽電池等的加工。 實例 以下示出實例、比較例來對本發明進行具體說明，但 本發明不限定於該些示例。 對實例及比較例中使用的水溶性樹脂（A)、聚乙稀乙 二醇（B)及水溶性潤滑劑樹脂（C)進行GPC測定，將 其數量平均分子量示於表1中。另外，關於水溶性樹脂組 成物的層所含的各樹脂成分的數量平均分子量，是記載於 各實例、比較例的項目内。 (實例1) 使數量平均分子量為110,000的聚環氧乙烷（Alkox L-11，明成化學工業股份有限公司製造）6〇重量份、數量 平均分子量為20,000的聚乙烯乙二醇（PEG20000，三洋 化成工業股份有限公司製造）20重量份及聚氧乙烯硬脂醚 (polyoxyethylene stearyl ether) (S-220 ’ 青木油脂工業股份 16 201043362 有限公司製造）20重量份，以水溶性樹脂混合物100重量 份達到固體成分30 wt% (重量百分比）的方式而溶解於水 =C進而，相對於該水溶性樹脂混合物的固體成分1〇〇重 里份而添加1.0重量份的曱酸鈉（三菱瓦斯化學股份有限 公1製造）’使其完全溶解而獲得水溶性樹脂組成物。對該 水洛性樹脂組成物的一部分利用乾燥機將溶劑充分去除 後’使用溶融黏度測定裝置（CFT-500D，SHIMADZU (股） 〇 衣^ )於毛細管口徑為mm、長度為1.〇 mm、溫度為 i〇〇°c、試驗壓力為980,000 Pa的條件下，測定水溶性樹脂 組成物的熔融黏度。進而，使用棒塗機，將該水溶性樹脂 組成物的水溶液以乾燥後的水溶性樹脂組成物層的厚度達 = ^〇5lnm的方式塗佈於單面上形成有厚度為〇.〇1 mm的 環，樹脂皮膜的銘箱（使用銘箱：肋0，（厚度為ο] mm) ^菱鋁股份有限公司製造）上，利用乾燥機於12〇ΐ下乾 燥3分鐘，而獲得鑽孔用蓋板。將該鑽孔用蓋板以水溶性 樹脂組成物的層朝上的方式，配置於重疊了三片厚度為〇8 随_的銅_層板（CCL-HI^HSUT，銅_兩面12μηι， 士菱瓦斯化學股份有限公司製造）的板上，於所重疊的銅 箔積層板的下側配置接合板（烘烤板）。於鑽針為〇25 叫)、轉速為120，_啊、進給速度為2 4她匕的條件 下’以每1根鑽針3,000 hits而進行20根的鑽頭鑽孔加工， 對孔壁粗糙度、孔位置精度、鑽針上的樹脂捲附量進行 價，獲得了表2所示的結果。再者，藉自Gpc及紅外 Infrared，IR)光譜測定來對水溶性樹脂組成物進行分 17 201043362 析’結果數量平均分子量為94,600的聚環氧乙烷為61.9 重量份’數量平均分子量為20,600的聚乙烯乙二醇為2U 重量份，數量平均分子量為2,800的聚氧乙烯硬脂醚為17 〇 重量份，且曱酸鈉為1.0重量份。對於孔壁粗糙度、孔位 置精度、樹脂捲附’獲得了良好的數值。 (實例2) 使數量平均分子量為110,000的聚環氧乙烷（Alk〇x L-11，明成化學工業股份有限公司製造）重量份、數量After the cover plate was cut, the cross section was observed from the vertical direction by a Scanning Electron Microscope (SEM) (VE-7800, manufactured by KEYENCE), and the layer and the water-soluble layer were measured under a field of view of %〇 times. The thickness of the resin composition layer. The thickness at 5 points was measured for 1 field 15 201043362 field, and the average value was taken as the thickness. Drilling of a drill using the drilling cover of the present invention is performed on one or more overlapping copper foil laminates or layers when drilling a printed circuit material, such as a copper box laminate or a multilayer board. At least the uppermost portion of the plate is disposed such that the metal side of the cover plate is in contact with the printed circuit material, and the surface of the water-soluble resin composition layer of the cover plate for drilling is subjected to iron head drilling. Further, the drilling cover plate of the present invention is not limited to the drilling process of the copper box laminate or the multi-layer board. It can also be applied to the processing of a resin formed product, a metal frame, a solar battery or the like. EXAMPLES Hereinafter, the invention will be specifically described by way of examples and comparative examples, but the invention is not limited to the examples. The water-soluble resin (A), the polyethylene glycol (B) and the water-soluble lubricant resin (C) used in the examples and the comparative examples were subjected to GPC measurement, and the number average molecular weight thereof is shown in Table 1. In addition, the number average molecular weight of each resin component contained in the layer of the water-soluble resin composition is described in the items of the respective examples and comparative examples. (Example 1) A polyethylene oxide (PEG 20000, Sanyo) having a number average molecular weight of 110,000 and a polyethylene oxide (available from Alkox L-11, manufactured by Mingcheng Chemical Industry Co., Ltd.) of 6 parts by weight and having a number average molecular weight of 20,000. 20 parts by weight of polyoxyethylene stearyl ether (S-220 'made by Aoki Oil & Fats Industry Co., Ltd. 16 201043362), 20 parts by weight of water-soluble resin mixture The solid content is 30 wt% (% by weight) dissolved in water = C. Further, 1.0 part by weight of sodium citrate is added to the solid content of the water-soluble resin mixture, and the amount of sodium citrate is added (Mitsubishi Gas Chemical Co., Ltd. (manufacturing) 'It is completely dissolved to obtain a water-soluble resin composition. After a part of the water-repellent resin composition is sufficiently removed by a dryer, 'the melt viscosity measuring device (CFT-500D, SHIMADZU) is used for a capillary diameter of mm and a length of 1. 〇mm. The melt viscosity of the water-soluble resin composition was measured under the conditions of a temperature of i〇〇°c and a test pressure of 980,000 Pa. Further, an aqueous solution of the water-soluble resin composition is applied to one surface by a thickness of 〇.〇1 mm by using a bar coater so that the thickness of the dried water-soluble resin composition layer is up to 〇5 lnm. Ring, resin film case (using the name box: rib 0, (thickness ο) mm) ^ manufactured by Ryo Aluminum Co., Ltd.), dried by a dryer at 12 3 for 3 minutes to obtain a hole for drilling Cover plate. The hole for the drilling is disposed with the layer of the water-soluble resin composition facing upward, and three copper sheets (CCL-HI^HSUT, copper_two sides, 12μηι, with a thickness of 〇8 and _) are overlapped. A plate (bake plate) is placed on the lower side of the copper foil laminate which is laminated on the plate of the Rhombus Chemicals Co., Ltd.). Under the condition that the drilling needle is 〇25, the rotation speed is 120, _ah, and the feed speed is 2 4, the boring is performed with 20 drill bits per 3,000 hits, and the hole wall is rough. The degree, the hole positional accuracy, and the amount of the resin wound on the drill needle were used to obtain the results shown in Table 2. Furthermore, by means of Gpc and infrared Infrared, IR) spectrometry, the water-soluble resin composition was subjected to 17 201043362. The results showed that the number of polyethylene oxides having a number average molecular weight of 94,600 was 61.9 parts by weight, and the number average molecular weight was 20,600. The polyethylene glycol was 2 U parts by weight, the polyoxyethylene stearyl ether having a number average molecular weight of 2,800 was 17 parts by weight, and the sodium citrate was 1.0 part by weight. Good values were obtained for the hole wall roughness, the hole position accuracy, and the resin wrap. (Example 2) A polyethylene oxide (Alk〇x L-11, manufactured by Mingcheng Chemical Industry Co., Ltd.) having a number average molecular weight of 110,000 was used in parts by weight.
平均分子量為20,000的聚乙烯乙二醇（PEG2〇〇〇〇 ’三洋 化成工業股份有限公司製造）60重量份及數量平均分子量 為1,000的聚氧乙烯硬脂基醚（NonionS_22〇，日油股份有 限公司製造）10重量份以水溶性樹脂混合物1〇〇重量份達 到固體成分30 Wt%的方式而溶解於水中。進而，相對於該 水溶性樹脂混合物的固體成分1〇〇重量份而添加1〇重量 份的甲酸鈉（三菱瓦斯化學股份有限公司製造），使其完全 洛解而獲侍水溶性樹脂組成物。與實例i同樣地測定該水60 parts by weight of polyethylene glycol (PEG2〇〇〇〇' Sanyo Chemical Industry Co., Ltd.) having an average molecular weight of 20,000 and polyoxyethylene stearyl ether having a number average molecular weight of 1,000 (Nonion S_22〇, Nippon Oil Co., Ltd.) 10 parts by weight of the water-soluble resin mixture was dissolved in water in such a manner that 1 part by weight of the water-soluble resin mixture reached 30 Wt% of the solid content. Furthermore, 1 part by weight of sodium formate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added in an amount of 1 part by weight based on the solid content of the water-soluble resin mixture, and the mixture was completely dissolved to obtain a water-soluble resin composition. The water was measured in the same manner as in Example i.
溶性樹脂組成物的熔融黏度，將其結果示於表2中。再者， 藉由GPC A IR光譜败㈣核輯驗成物進行分 析，結果數量平均分子量為117，_的聚環氧乙烧為30.2 量日平均分子量為21,_的聚乙烯乙二醇為59·6 平均分子量為980的聚氧乙稀硬脂基醚為 H).2重量份，且甲酸納為1〇重量份。進而 樣地製作鑽孔用蓋板，雄仵構 里一 &主1 + 進仃鑽孔加工性評價，將各評價結 果不於表2中。對於孔壁粗私 祖槌度孔位置精度、樹脂捲附， 18 201043362 獲得了良好的數值。 (實例3 ) 使數量平均分子量為100,000的聚乙烯乙二醇-對苯二 甲酸二甲酯(dimethyl terephthalate)縮聚物（Paogen PP-15， 第一工業製藥股份有限公司製造）40重量份、數量平均分 子量為20,000的聚乙烯乙二醇（PEG2〇〇〇〇，三洋化成工 業股份有限公司製造）55重量份及數量平均分子量為 0 7,000的聚氧乙烯硬脂基醚（SR-7200，青木油脂工業股份 有限公司製造）5重量份以水溶性樹脂混合物1〇〇重量份 達到固體成分30 wt°/〇的方式而溶解於水中。進而，相對於 s玄水溶性樹脂混合物的固體成分100重量份而添加1.0重 量份的甲酸鈉（三菱瓦斯化學股份有限公司製造），使其完 全溶解而獲得水溶性樹脂組成物。與實例1同樣地測定該 水溶性樹脂組成物的熔融黏度，將其結果示於表2中。再 者，藉由GPC及IR光譜測定來對水溶性樹脂組成物進行 分析，結果數量平均分子量為1〇1，〇〇〇的聚乙烯乙二醇對 〇 本甲酸一甲醋縮聚物為38.5重量份，數量平均分子量為 21,200的聚乙烯乙二醇為55.9重量份，數量平均分子量為 6’800的聚氧乙烯硬脂基鱗為5.6重量份，且甲酸鈉為 重量份。進而，與實例1同樣地製作鑽孔用蓋板，進行鑽 孔加工性评價’將各評價結果示於表2中。對於孔壁粗链 度、孔位置精度、樹脂捲附，獲得了良好的數值。 (實例4) 使數量平均分子量為ιιο,οοο的聚環氧乙烷（Alk〇x 19 201043362 L-ll ’明成化學工業股份有限公司製造）85重量份、數量 平均分子量為20,000的聚乙烯乙二醇（PEG20000，三洋 化成工業股份有限公司製造）1〇重量份及數量平均分子量 為1，〇〇〇的聚氧乙烯硬脂基醚（NonionS-220,日油股份有 限公司製造）5重量份以水溶性樹脂混合物100重量份達 到固體成分30 wt%的方式而溶解於水中。進而，相對於該 水溶性樹脂混合物的固體成分1〇〇重量份而添加1 〇重量 ，的甲酸鈉（三菱瓦斯化學股份有限公司製造），使其完全 溶解而獲得水溶性樹脂組成物。與實例丨同樣地測定該水 溶性樹脂組成物的溶融黏度，將其結果示於表2中。再者， 藉由GPC及IR《譜測定來對水溶性樹脂組成物進行分 ^結果數量平均分子量為⑽議㈣環氧乙料82 4 舌Ϊί平均分子量為18,300的聚乙烯乙二醇為11.3 6·4二气量曰平均ί子量為1,560的聚氧乙烯硬脂基醚為 地製作^用納為L〇重量份。進而，與實例1同樣 示絲2中。=孔孔加卫性評價，將各評價結果 獲得了良好的數值。赶。度、孔位置精度、樹脂捲附’ (實例5) 使數量平均分+ & L-8，明成化學工業股份有限乙二(A:x 平均分子量為20，_6〇重心、數重 仆赤工鳘日η·八士 的t乙烯乙二醇（PEG20000，三洋 化成工業股份有限公司製 千 (S-220，青木1G重量份及聚氧乙稀硬脂謎 曰業股份有限公司製造）30重量份以 20 201043362 水溶性樹脂混合物100重量份達到固體成分30 wt%的方式 而溶解於水中。進而，相對於該水溶性樹脂混合物的固體 成分100重量份而添加1.0重量份的曱酸鈉（三菱瓦斯化 學股份有限公司製造）’使其完全溶解而獲得水溶性樹脂組 成物。與實例1同樣地測定該水溶性樹脂組成物的熔融黏 度，將其結果示於表2中。再者，藉由GPC及IR光譜測 定來對水溶性樹脂組成物進行分析，結果數量平均分子量 為80,200的聚環氧乙烷為59.0重量份，數量平均分子量 為18,900的聚乙烯乙二醇為13·4重量份，數量平均分子量 為2,300的聚氧乙烯硬脂醚為27 6重量份，且曱酸鈉為1〇 重量份。進而，與實例1同樣地製作鑽孔用蓋板，進行鑽 孔加工性评價’將各§平價結果示於表2中。對於孔壁粗才造 度、孔位置精度、樹脂捲附，獲得了良好的數值。 (實例6) 使數量平均分子量為100,000的聚乙烯乙二醇_對笨二 甲酸二曱酯縮聚物（Paogen PP-15，第一工業製藥股份有 Ο 限公司製造）40重量份、數量平均分子量為20,000的聚乙 稀乙二醇（PEG20000 ’二洋化成工業股份有限公司製造） 55重量份及數量平均分子量3,500的聚氧乙稀單硬脂酸醋 (Nonion S-40，日油股份有限公司製造）5重量份以水溶 性樹脂混合物1〇〇重量份達到固體成分30 wt%的方式而溶 解於水中。進而’相對於該水溶性樹脂混合物的固體成分 100重量份而添加1.0重量份的甲酸鈉（三菱瓦斯化學股 份有限公司製造）’使其完全溶解而獲得水溶性樹脂組成 21 201043362 與^例1同樣地測定該水溶性樹脂 度，將其結果示於表2中。再者，藉由Gpc及 = 定來對水溶性職組成物進行分析，結果數量平均分子量】 為1〇3,300的聚乙烯乙二醇_對苯二甲酸二甲醋縮聚物為 39.4重量份，數量平均分子量為219⑻的聚乙烯乙二醇= 54.3重量份，數量平均分子量為3,5⑻㈣氧乙烯單硬脂 酸醋為6.3重量份，且f酸鈉為1()重量份。進而，The melt viscosity of the soluble resin composition is shown in Table 2. Furthermore, by GPC A IR spectroscopy (four) nuclear assay, the number average molecular weight was 117, the poly Ethylene bromide was 30.2, and the average molecular weight was 21, and the polyethylene glycol was 59·6 The polyoxyethylene stearyl ether having an average molecular weight of 980 is H). 2 parts by weight, and the sodium formate is 1 part by weight. Further, a drilling cover plate was prepared in the same manner, and the main 1 + inlet drilling processability evaluation of the male structure was carried out, and the evaluation results were not shown in Table 2. For the hole wall rough private ancestors hole position accuracy, resin coil attachment, 18 201043362 obtained good values. (Example 3) 40 parts by weight of polyethylene glycol-dimethyl terephthalate polycondensate (Paogen PP-15, manufactured by Dai-Il Pharmaceutical Co., Ltd.) having a number average molecular weight of 100,000 55 parts by weight of polyethylene glycol (PEG 2 〇〇〇〇, manufactured by Sanyo Chemical Industry Co., Ltd.) having an average molecular weight of 20,000 and polyoxyethylene stearyl ether (SR-7200, Aoki Oil) having a number average molecular weight of 0 7,000 Industrial Co., Ltd.) 5 parts by weight of the water-soluble resin mixture was dissolved in water so as to have a solid content of 30 wt%/〇. Furthermore, 1.0 part by weight of sodium formate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to 100 parts by weight of the solid content of the sigma-soluble resin mixture, and completely dissolved to obtain a water-soluble resin composition. The melt viscosity of the water-soluble resin composition was measured in the same manner as in Example 1. The results are shown in Table 2. Further, the water-soluble resin composition was analyzed by GPC and IR spectrometry, and the number average molecular weight was 1〇1, and the polyethylene glycol of hydrazine was 38.5 by weight of the guanidinecarboxylic acid monomethyl condensate. The polyethylene oxide glycol having a number average molecular weight of 21,200 was 55.9 parts by weight, the polyoxyethylene stearin scale having a number average molecular weight of 6'800 was 5.6 parts by weight, and sodium formate was part by weight. Further, a drilling cover plate was produced in the same manner as in Example 1 to carry out a drilling processability evaluation. The results of the respective evaluations are shown in Table 2. Good values were obtained for the thick wall of the hole wall, the accuracy of the hole position, and the resin wrap. (Example 4) 85 parts by weight of polyethylene oxide having a number average molecular weight of ιιο, οοο (Alk〇x 19 201043362 L-ll 'Mingcheng Chemical Industry Co., Ltd.), and a polyethylene glycol having a number average molecular weight of 20,000 Alcohol (PEG 20000, manufactured by Sanyo Chemical Industries Co., Ltd.) 1 part by weight and a number average molecular weight of 1, fluorene polyoxyethylene stearyl ether (Nonion S-220, manufactured by Nippon Oil Co., Ltd.) 5 parts by weight The water-soluble resin mixture was dissolved in water in such a manner that 100 parts by weight of the solid content reached 30% by weight of the solid content. Furthermore, 1 part by weight of sodium formate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to the solid content of the water-soluble resin mixture, and the mixture was completely dissolved to obtain a water-soluble resin composition. The melt viscosity of the water-soluble resin composition was measured in the same manner as in Example ,, and the results are shown in Table 2. Furthermore, the number average molecular weight of the water-soluble resin composition is determined by GPC and IR "spectroscopy". The number average molecular weight is (10) (4) Ethylene glycol 82 4 tongue Ϊ The average molecular weight of 18,300 polyethylene glycol is 11.3 6 · 4 vol. 曰 曰 ί ί 1 1 1 1 1 1 1 1 1 1 1 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Further, in the same manner as in Example 1, the yarn 2 was shown. = Hole hole evaluation, and the evaluation results obtained good values. Hurry. Degree, hole position accuracy, resin coil attachment '(Example 5) The average number of points + & L-8, Mingcheng Chemical Industry Co., Ltd. limited A2 (A: x average molecular weight is 20, _6 〇 center of gravity, number of heavy servants Η200·T-ethylene glycol (PEG20000, manufactured by Sanyo Chemical Industry Co., Ltd., 30 parts by weight (S-220, Aoki 1G by weight and polyoxyethylene hard fat mystery Co., Ltd.) 30 parts by weight It is dissolved in water so that 100 parts by weight of the water-soluble resin mixture is 30 wt% of 20 201043362. Further, 1.0 part by weight of sodium citrate (Mitsubishi Gas) is added to 100 parts by weight of the solid content of the water-soluble resin mixture. (manufactured by Chemicals Co., Ltd.) 'They were completely dissolved to obtain a water-soluble resin composition. The melt viscosity of the water-soluble resin composition was measured in the same manner as in Example 1. The results are shown in Table 2. Further, by GPC And IR spectrum measurement to analyze the water-soluble resin composition, the result is that the number average molecular weight is 80,200, the polyethylene oxide is 59.0 parts by weight, and the number average molecular weight is 18,900. 4 parts by weight, a polyoxyethylene stearyl ether having a number average molecular weight of 2,300 was 27 6 parts by weight, and sodium citrate was 1 part by weight. Further, a drilling cover plate was produced in the same manner as in Example 1 to perform drilling processing. The evaluation of each of the § parity results is shown in Table 2. For the wall thickness, hole position accuracy, resin coiling, good values were obtained. (Example 6) Polyethylene having a number average molecular weight of 100,000 Ethylene glycol_diisopropyl phthalate polycondensate (Paogen PP-15, manufactured by Daiichi Kogyo Co., Ltd.) 40 parts by weight of polyethylene glycol having a number average molecular weight of 20,000 (PEG 20000 '2 (available from Ocean Chemical Industry Co., Ltd.) 5 parts by weight of a polyoxyethylene monostearic acid vinegar (Nonion S-40, manufactured by Nippon Oil Co., Ltd.) of 5 parts by weight and a molecular weight of 3,500. The weight fraction is dissolved in water so as to be 30 wt% of the solid content. Further, 1.0 part by weight of sodium formate is added to 100 parts by weight of the solid content of the water-soluble resin mixture (Mitsubishi Gas Chemical Co., Ltd.) "They are completely dissolved to obtain a water-soluble resin composition. 21 201043362 The water-soluble resin degree was measured in the same manner as in Example 1, and the results are shown in Table 2. Further, the water-soluble service was carried out by Gpc and =. The composition was analyzed and found to have a number average molecular weight of 3,3,300 of polyethylene glycol _terephthalic acid dimethylacetate polycondensate of 39.4 parts by weight, and a number average molecular weight of 219 (8) of polyethylene glycol = 54.3 parts by weight. The number average molecular weight is 3,5 (8) (tetra) oxyethylene monostearic acid vinegar is 6.3 parts by weight, and sodium f is 1 part by weight. and then,
例1同樣地製作鑽孔用蓋板’進行鑽孔加工性評價，將各 評價結果示於表2中。對於孔壁_度、孔位置精度、樹 脂捲附’獲得了良好的數值。 (實例7)In Example 1, a drilling cover plate was produced in the same manner, and the drilling processability evaluation was performed. The evaluation results are shown in Table 2. Good values were obtained for the hole wall _ degree, hole position accuracy, and resin roll attachment. (Example 7)
使數量平均分子量為1〇〇,〇〇〇的聚乙烯乙二醇-對苯二 曱酸一曱醋縮聚物（Pa〇gen PP-15，第一工業製藥股份有 限公司製造）40重量份 '數量平均分子量為2〇 〇〇〇的聚乙 烯乙二醇（PEG20000,三洋化成工業股份有限公司製造） 55重量份及數量平均分子量為3,5〇〇的聚氧乙烯單硬脂酸 酯（Nonion S-40 ’日油股份有限公司製造）5重量份以水 溶性樹脂混合物100重量份達到固體成分3〇 wt%的方式而 溶解於水中。進而，相對於該水溶性樹脂混合物的固體成 分100重量份而添加1.0重量份的季戊四醇（三菱瓦斯化 學股份有限公司製造）’使其完全溶解而獲得水溶性樹脂組 成物。與實例1同樣地測定該水溶性樹脂組成物的溶融黏 度，將其結果示於表2中。再者，藉由GPC及IR光譜測 定來對水溶性樹脂組成物進行分析，結果數量平均分子量 22 201043362 為？曰οο的聚乙烯乙二醇·對苯二甲酸二甲酯縮聚物為 39.0重=份，數量平均分子量為2()，彻的聚乙稀乙二醇為 55.0重1份，數量平的公1 4曰 勺刀子里為3,5〇〇的聚氧乙烯單硬脂 W曰為6.G重心’且季戊四醇為1()重量份。進而，盘 實例1同樣地製作鑽孔用蓋板，進行鑽孔加工性評價，將 各評價結果讀表2巾。躲孔壁粗财、隸置精度、 樹脂捲附，獲得了良好的數值。 ΟA polyethylene glycol-terephthalic acid monoacetate polycondensate (Pa〇gen PP-15, manufactured by Daiichi Kogyo Co., Ltd.) of 40 parts by weight of the average molecular weight of the crucible Polyethylene glycol (manufactured by Sanyo Chemical Industry Co., Ltd.) having a number average molecular weight of 2 55 55 parts by weight and a polyoxyethylene monostearate having a number average molecular weight of 3,5 Å (Nonion) 5 parts by weight of S-40 'Nippon Oil Co., Ltd.) was dissolved in water so that 100 parts by weight of the water-soluble resin mixture reached 3 wt% of the solid content. Furthermore, 1.0 part by weight of pentaerythritol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to 100 parts by weight of the solid content of the water-soluble resin mixture to completely dissolve it, thereby obtaining a water-soluble resin composition. The melt viscosity of the water-soluble resin composition was measured in the same manner as in Example 1. The results are shown in Table 2. Further, by analyzing the water-soluble resin composition by GPC and IR spectroscopy, the number average molecular weight 22 201043362 is ? The polyethylene glycol ethylene terephthalate polycondensate of 曰οο is 39.0 parts by weight, the number average molecular weight is 2 (), and the polyethylene glycol is 55.0 parts by weight, and the quantity is flat. In the 4 曰 knife, 3,5 〇〇 of polyoxyethylene monostearyl W 曰 is 6.G center of gravity 'and pentaerythritol is 1 () parts by weight. Further, in the disk example 1, a drilling cover plate was produced in the same manner, and the drilling processability evaluation was performed, and each evaluation result was read into a table towel. Obtaining a good value by hiding the wall of the hole, the accuracy of the placement, and the resin coil. Ο
(比較例1) 使數量平均分子量為110,_的聚環氧乙烧（尬似 L_1卜曰月成化學工業股份有限公司製造）1〇重量份、數量 平均分子置為20,000的聚乙烯乙二醇（pEG2〇〇〇〇，三洋 化成工業股份有限公司製造）6Gf量份及聚氧乙稀硬脂趟 (S-220，月木油脂工業股份有限公司製造）3〇重量份以 水溶性樹脂混合物100¾量份達到固體成分3〇wt%的方式 而溶解於水巾。進而，相對於該水溶性樹脂混合物的固體 成分10G重量份而添加i 〇重量份的甲酸納（三菱瓦斯化 學股份有限公㈣造）’使其完全轉喊得水雜樹脂組 成物。與實m同樣地測定該水溶賴餘成物的溶融黏 度其結果示於表2中。進而，與實例丨同樣地製作鑽 孔用蓋板，進行鑽孔加工性評價，將各評價結果示於表2 中。该比較例1獲得了孔壁粗链度惡化的結果。 (比較例2) 使數量平均分子量為11〇,_的聚環氧乙烧（Alk〇x L-11，明成化學工業股份有限公司製造）9〇重量份、數量 23 201043362 ~----r-- 平均分子量為20,000的聚乙烯乙二醇（PEG2〇〇〇〇,三洋 化成工業股份有限公司製造）8重量份及聚氧乙烯硬脂醚 (S-220，青木油脂工業股份有限公司製造）2重量份以水 溶性樹脂混合物的固體成分達到3〇 wt%的方式而溶解於 水中。進而，相對於該水溶性樹脂混合物的固體成分1〇〇 重量份而添加1.0重量份的曱酸鈉（三菱瓦斯化學股份有 限公司製造），使其完全溶解而獲得水溶性樹脂組成物。與 實例1同樣地測定該水溶性樹脂組成物的熔融黏度，將其 結果不於表2中。進而，與實例丨同樣地製作鑽孔用蓋板， 進行鑽孔加工性評價，將各評價結果示於表2中。該比較 例2獲得了鑽頭上的樹脂捲附量增加的結果。 (比較例3 ) 使數量平均分子量為6〇，_的聚環氧乙烧（Alk〇x L-6,明成化學工業股份有限公司製造）4〇重量份、數量 平均分子量為2〇，_的聚乙燁乙二醇（PEG20000，三洋 化成工業麟有限公司製造W重量份絲氧乙烯硬脂鍵 (S-220 ’肖木輕卫業股份有限公司製造）$重量份以水 溶性樹脂混合物的固體成分達到30 wt%的方式而溶解於 t ^於^二，對於該水溶性樹脂混合物的固體成分10 0 限公司製造），使装!甲酸納（二愛瓦斯化學股份有 ϋαμ η#01」疋王，谷解而獲得水溶性樹脂組成物。與 該水溶性樹脂組成物的熔融黏度，將其 溶性樹脂組成物進行分IR光譜収來對水 遣仃刀析，結果數量平均分子量為65,200 24 201043362 的聚環氧乙烷為37.2重量份，數量平均分子量為21，9〇〇 的聚乙烯乙二醇為58.0重量份，數量平均分子量為3,7〇〇 的聚氧乙烯硬脂醚為4.8重量份，且曱酸鈉為ι·〇重量份。 進而，與實例1同樣地製作鑽孔用蓋板，進行鑽孔加工性 評價，將各評價結果示於表2中。該比較例3獲得了孔壁 粗糙度惡化的結果。 (比較例4) 0 使數量平均分子量為100,000的聚乙烯乙二醇-對苯二 甲酸二甲酯縮聚物（paogen ρρ_15，第一工業製藥股份有 限公司製造）40重量份、數量平均分子量為1〇,〇〇〇的聚乙 烯乙二醇（PEG10000，青木油脂工業股份有限公司製造） 55重量份及數量平均分子量為3,5〇〇的聚氧乙烯單硬脂酸 酯（Nonion S-40，日油股份有限公司製造）5重量份以水 溶性樹脂混合物100重量份達到固體成分3〇 wt%的方式而 溶解於水中。進而，相對於該水溶性樹脂混合物的固體成 分100重量份而添加1.0重量份的曱酸鈉（三菱瓦斯化學 〇 股份有限公司製造），使其完全溶解而獲得水溶性樹脂組成 物。與實例1同樣地測定該水溶性樹脂組成物的熔融黏 度，將其結果示於表2中。再者，藉由及IR光譜測 定來對水溶性樹脂組成物進行分析，結果數量平均分子量 為91，1〇〇的聚乙烯乙二醇_對苯二曱酸二曱酯縮聚物為 40.6重量份，數量平均分子量為1〇,〇⑻的聚乙烯乙二醇為 54.9重量份，數量平均分子量為2,6〇〇的聚氧乙烯單硬脂 酸酯為4.5重量份，且甲酸鈉為1〇重量份。進而，與實 25 201043362 例1同樣地製作鑽孔用蓋板，進行鑽孔加工性評價，將各 評價結果示於表2中。該比較例4獲得了孔壁粗繞产 位置精度惡化的結果。 & (比較例5) 使數量平均分子量為100,000的聚乙烯乙二醇對苯二 曱酸二曱S旨縮聚物（Pa〇gen PP_15 ’第—工業製藥 ^ 限，，製造；)4。重量份及數量平均分子量為S’·的聚 乙烯單硬脂酸S旨（Nonion S-4G’日油股份有限公司製造） 6〇重量份以水溶性樹脂混合物10〇重量份達到固體成<分刈 職的方式而溶解於水巾。進而，相對於 ^ 合物的固體成分⑽重量份而添加U重量份的 公31製造）’使其完全溶解而獲得轉 且f 實例1同樣地測定該水溶性樹脂組成物 井级黏度，將其結果示於表2巾。再者，藉由咖及瓜 ^曰測定㈣水溶性龍組錢進行分析，結果數量平均 =1為7二:、°?乙稀乙蹲對笨二甲酸二甲酷縮聚 硬H f 4平^子^為3_的聚氧乙稀單 2从為59.3重量份，且甲酸納為1()重量份。進而， 二實例1同樣地製作鑽孔用蓋板，進行鑽孔加I性 價結果示於表2中。該比較例5獲得了孔壁粗糖度、 孔位置精度惡化的結果。 (比較例6) 使數量平均分子量為1〇〇,〇〇〇的聚乙烯乙二醇_對笨二 甲酸二曱醋縮聚物（Pac)gen pp_15 ’第一工業製藥股份有 26 201043362 限公司製造）50重量份及數量平均分子量為3 5〇〇的聚氧 乙烯單硬脂酸酯（Nonion S-40’日油股份有限公司製造） 5〇重里份以水溶性樹脂混合物1〇〇重量份達到固體成分3〇 wt%的方式而溶解於水中。進而，相對於該水溶性樹脂混 ^物的固體成分100重量份而添加1G重量份的甲酸納（三 f =化學股份有限公司製造）’使其完全溶解而獲得水溶(Comparative Example 1) A polyethylene oxide having a number average molecular weight of 110, _, and a weight average molecular weight of 20,000, which is a polyethylene oxide (manufactured by L_1 Divine Chemical Co., Ltd.) Alcohol (pEG2〇〇〇〇, manufactured by Sanyo Chemical Industry Co., Ltd.) 6Gf parts and polyoxyethylene stearin (S-220, manufactured by Yuemu Oil & Fats Co., Ltd.) 3 parts by weight of water-soluble resin mixture The 1003⁄4 parts were dissolved in a water towel in such a manner that the solid content was 3 〇wt%. Further, i.e. parts by weight of sodium formate (Mitsubishi Gas Chemical Co., Ltd.) was added to 10 parts by weight of the solid content of the water-soluble resin mixture, and the water-hybrid resin composition was completely shouted. The molten viscosity of the water-soluble residue was measured in the same manner as in the case of the real m. The results are shown in Table 2. Further, a drill plate cover was produced in the same manner as in Example ,, and the drilling processability evaluation was performed, and the results of the respective evaluations are shown in Table 2. In Comparative Example 1, the result of deterioration of the pore wall thick chain degree was obtained. (Comparative Example 2) A polyethylene oxide (Alk〇x L-11, manufactured by Mingcheng Chemical Industry Co., Ltd.) having a number average molecular weight of 11 Å, _ 9 parts by weight, quantity 23 201043362 ~----r - 8 parts by weight of polyethylene glycol (PEG 2 〇〇〇〇, manufactured by Sanyo Chemical Industries Co., Ltd.) having an average molecular weight of 20,000 and polyoxyethylene stearyl ether (S-220, manufactured by Aoki Oil & Fats Co., Ltd.) 2 parts by weight was dissolved in water in such a manner that the solid content of the water-soluble resin mixture reached 3 Å by weight. Furthermore, 1.0 part by weight of sodium decanoate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to 1 part by weight of the solid content of the water-soluble resin mixture, and completely dissolved to obtain a water-soluble resin composition. The melt viscosity of the water-soluble resin composition was measured in the same manner as in Example 1, and the results were not shown in Table 2. Further, a drilling cover plate was produced in the same manner as in the example, and the drilling processability evaluation was performed, and the results of the respective evaluations are shown in Table 2. This Comparative Example 2 obtained the result of an increase in the amount of resin wound on the drill. (Comparative Example 3) 4 parts by weight of a polyethylene oxide (Alk〇x L-6, manufactured by Mingcheng Chemical Industry Co., Ltd.) having a number average molecular weight of 6 Å, and a number average molecular weight of 2 Å, _ Polyethylene glycol (PEG20000, manufactured by Sanyo Chemical Industry Co., Ltd.) W parts by weight of methyloxyethylene hard fat bond (S-220 'Shaomu Light Industry Co., Ltd.) $ parts by weight of solids of water-soluble resin mixture The composition is 30 wt% and dissolved in t ^ 2 , for the solid content of the water-soluble resin mixture, which is manufactured by the company, and is made up of sodium formate (two Avas Chemicals Co., Ltd. has ϋαμ η#01)疋Wang, glutinous solution to obtain a water-soluble resin composition. The melt viscosity of the water-soluble resin composition, the soluble resin composition was subjected to IR spectrum analysis, and the average molecular weight was 65,200 24 201043362. The polyethylene oxide is 37.2 parts by weight, the number average molecular weight is 21,9 Å, the polyethylene glycol is 58.0 parts by weight, and the polyoxyethylene stearyl ether having a number average molecular weight of 3,7 为 is 4.8 parts by weight. And sodium citrate is Further, in the same manner as in Example 1, a drilling cover plate was produced, and the drilling processability evaluation was performed, and the results of the respective evaluations are shown in Table 2. In Comparative Example 3, the results of the deterioration of the hole wall roughness were obtained. (Comparative Example 4) 0 A polyethylene glycol-terephthalate condensate (paogen ρρ_15, manufactured by Dai-Il Pharmaceutical Co., Ltd.) having a number average molecular weight of 100,000 was 40 parts by weight, and the number average molecular weight was 1 〇, 聚乙烯 polyethylene glycol (PEG 10000, manufactured by Aoki Oil & Fats Co., Ltd.) 55 parts by weight and a polyoxyethylene monostearate having a number average molecular weight of 3,5 Å (Nonion S-40, 5 parts by weight of the water-soluble resin mixture is dissolved in water so as to be 100% by weight of the solid content of the water-soluble resin mixture. Further, 1.0 part by weight is added to 100 parts by weight of the solid content of the water-soluble resin mixture. The sodium carbonate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was dissolved in a total amount to obtain a water-soluble resin composition. The composition of the water-soluble resin was measured in the same manner as in Example 1. The melt viscosity was measured in Table 2. Further, the water-soluble resin composition was analyzed by IR spectrometry, and the number average molecular weight was 91, 1 Å of polyethylene glycol _ The dinonyl phthalate polycondensate was 40.6 parts by weight, the number average molecular weight was 1 〇, the polyethylene glycol of ruthenium (8) was 54.9 parts by weight, and the polyoxyethylene monostearyl having a number average molecular weight of 2,6 Å. The amount of the acid ester was 4.5 parts by weight, and the amount of sodium formate was 1 part by weight. Further, a cover plate for drilling was prepared in the same manner as in Example 1 of 201025,362, and the drilling processability evaluation was performed, and the evaluation results are shown in Table 2. In Comparative Example 4, the result of deterioration in the accuracy of the rough winding position of the pore walls was obtained. & (Comparative Example 5) A polyethylene glycol terephthalic acid diterpene S polycondensate having a number average molecular weight of 100,000 (Pa gen PP _ 15 '--Industrial Pharmaceutical Co., Ltd., manufactured;) 4. The weight fraction and the number average molecular weight of S'·polyethylene monostearate S (manufactured by Nonion S-4G's Nippon Oil Co., Ltd.) 6 parts by weight of the water-soluble resin mixture is 10 parts by weight to reach a solid content < Dissolved in water towels by way of dereliction of duty. Further, with respect to the solid content (10) by weight of the compound, U weight part of the public 31 was added to make it completely dissolved, and the result was obtained. In the same manner, the water-soluble resin composition was measured in the same manner, and the result was measured. Shown in Table 2 towel. Furthermore, by means of coffee and melon, the amount of water-soluble dragon group is analyzed. The average number of results is 7: 2: °? The polyoxyethylene single 2 having a 3 of 3_ was from 59.3 parts by weight, and the sodium formate was 1 part by weight. Further, in the same manner as in the second example 1, a cover plate for drilling was produced, and the result of drilling and adding I was shown in Table 2. In Comparative Example 5, the results of the deterioration of the pore wall roughness and the hole position accuracy were obtained. (Comparative Example 6) The number average molecular weight was 1 〇〇, and the polyethylene glycol of hydrazine _ 笨 笨 笨 笨 gen 笨 笨 ' ' ' 第一 第一 第一 第一 第一 第一 第一 第一 第一 第一 第一 第一 第一 第一 第一 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 50 parts by weight and polyoxyethylene monostearate having a number average molecular weight of 35 ( (manufactured by Nonion S-40' Nippon Oil Co., Ltd.) 5 〇 by weight of the water-soluble resin mixture 1 〇〇 by weight The solid component was dissolved in water in a manner of 3 wt%. Further, 1 G by weight of sodium formate (manufactured by Chemical Co., Ltd.) was added in an amount of 100 parts by weight of the solid content of the water-soluble resin mixture to completely dissolve it to obtain a water-soluble solution.
G Ο 沾#二Ϊ物。與實例1同樣地測定該水溶性樹脂組成物 、，將其結果示於表2中。再者，由GPc及IR 3 =來對水溶性樹脂組成物進行分析，日結果數量平均 λ I0,800的聚乙烯乙二醇-對苯二曱酸二曱酯縮聚 Α蕙份，數量平均分子量為3,7〇〇的聚氧乙烯單 夂-日，'、' 49.6重量份，且曱酸鈉為1 〇重量 盘眚你Μ ΡΠ说 ^ 17 a "，j 將久w^地製作鑽孔用蓋板，進行鑽孔加工性評價， iwu Ια 果不於表2中。該比較例6獲得了孔壁粗链度 惡化的結果。 [表1] 樹脂成分名 丨產品名 數量平均分子量 定結果） 聚環氧乙烷 聚乙烯乙二醇 iAlkox L-11 I明成化學工業股份有限公司製造 109,600 (PEG20000 |三洋化成工業股份有限公司製 20,300G Ο 沾# 二Ϊ物. The water-soluble resin composition was measured in the same manner as in Example 1, and the results are shown in Table 2. Furthermore, the water-soluble resin composition was analyzed by GPc and IR 3 =, and the average number of molecular weights of the polyethylene glycol-terephthalate diterpene ester of the average number of λ I0,800 was obtained. It is 3,7 〇〇 polyoxyethylene monoterpene-day, ', '49.6 parts by weight, and sodium citrate is 1 〇 weight 眚 Μ ΡΠ ^ 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 The hole was covered with a cover plate for evaluation of drilling processability, and iwu Ια was not shown in Table 2. This Comparative Example 6 obtained the result of deterioration of the pore wall thick chain. [Table 1] Resin component name 丨 Product name Quantitative average molecular weight Determination result) Polyethylene oxide Polyethylene glycol iAlkox L-11 I manufactured by Mingcheng Chemical Industry Co., Ltd. 109,600 (PEG20000 | Sanyo Chemical Industry Co., Ltd. 20,300
聚乙烯乙二醇-爾 二曱酯縮聚物 ^ogenPP-lS 丨第一工業股份有限公司製造 96,900 27 201043362 聚氧乙烯硬脂基醚 SR-7200 青木油脂工業股份有限公司製造 7,900 聚環氧乙烷 Alkox L-8 明成化學工業股份有限公司製造 80,900 聚氧乙烯單硬脂酸酯 Nonion S-40 日油股份有限公司製造 3,600 聚環氧乙烧 Alkox L-6 明成化學工業股份有限公司製造 68,400 聚乙烯乙二醇 PEG10000 青木油脂工業股份有限公司製造 9,860 28 201043362 [表2] 實例2 實例3 實例4 實例5 實例6 實例7 水溶性樹脂組成物的熔融黏庶（pa·；^ 150 55 75 300 155 110 110 孔壁粗糙度 最大值的平均值（μπι) 2.8 3.6 3.7 2.7 3.5 4.1 4.0 孔位置精度 Ave_ + 3o的平均值（gm) 38.9 40.5 38.5 39.8 40.3 42.3 41.9 敢大值的平均值（um) 50 51 49 H 51 51 54 53 樹脂捲附量 20根鑽頭的平均值（胃3) 0 0 0 0 0 0 0 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 水溶性樹脂組成物的熔融黏度（Pa*s) 15 340 45 64 52 88 孔壁粗糙度 最大值的平均值（um) 5.8 3.1 4.9 4.8 4.9 4.9 孔位置精度 Ave. + 3a的平均值（um) 42.0 44.2 41.6 47.6 45.8 37.3 最大值的平均值（ιαπΟ 55 54 51 63 78 60 樹脂捲附量 20根鑽頭的平均值（mm3) 0 0.08 1 0 0 0 0Polyethylene glycol-dioxalate polycondensate ^ogenPP-lS 丨First Industrial Co., Ltd. manufacture 96,900 27 201043362 Polyoxyethylene stearyl ether SR-7200 Aoki Oil & Fat Industry Co., Ltd. manufactures 7,900 polyethylene oxide Alkox L-8 Mingcheng Chemical Industry Co., Ltd. manufactures 80,900 polyoxyethylene monostearate Nonion S-40 Nippon Oil Co., Ltd. manufactures 3,600 polyethylene oxide Alkox L-6 Mingcheng Chemical Industry Co., Ltd. manufactures 68,400 polyethylene Ethylene glycol PEG10000 manufactured by Aoki Oil & Fats Co., Ltd. 9,860 28 201043362 [Table 2] Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Melt adhesion of a water-soluble resin composition (pa·; ^ 150 55 75 300 155 110 Average value of the maximum value of the wall roughness of the hole (μπι) 2.8 3.6 3.7 2.7 3.5 4.1 4.0 The average position of the hole position accuracy Ave_ + 3o (gm) 38.9 40.5 38.5 39.8 40.3 42.3 41.9 The average value of the dare value (um) 50 51 49 H 51 51 54 53 Resin roll amount Average value of 20 drill bits (stomach 3) 0 0 0 0 0 0 0 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Water-soluble Melt viscosity of the fat composition (Pa*s) 15 340 45 64 52 88 Average value of the maximum roughness of the hole wall (um) 5.8 3.1 4.9 4.8 4.9 4.9 Hole position accuracy Ave. + 3a average value (um) 42.0 44.2 41.6 47.6 45.8 37.3 Average value of the maximum value (ιαπΟ 55 54 51 63 78 60 Resin volume approximation of 20 drill bits (mm3) 0 0.08 1 0 0 0 0
<評價方法> 1) 熔融黏度： 利用乾燥機將水溶性樹脂組成物的一部分之溶劑充分 去除後’使用熔融黏度測定裝置（CFT-500D，SHIMADZU (股）製造），於毛細管口徑為〇.5 mm、長度為10.0 mm、 溫度為100°C、試驗壓力為980,000 Pa的條件下，測定水 溶性樹脂組成物的溶融黏度。 2) 内壁粗縫度： 於鑽頭鑽孔加工後，對所重疊的銅箔積層板中最上方 的銅箔積層板以通過加工孔的中心的剖面切斷並進行研 磨’對孔壁的-個侧面内的最大凸部至最深凹部為止的距 離進行測定。測定部位為每丨根鑽頭的第2996個孔至第 3000個孔的加工孔側面10處，將5根鑽頭的共計5〇處的 29 201043362<Evaluation method> 1) Melt viscosity: After the solvent of a part of the water-soluble resin composition is sufficiently removed by a dryer, 'the melt viscosity measuring device (CFT-500D, manufactured by SHIMADZU Co., Ltd.) is used, and the capillary diameter is 〇 The molten viscosity of the water-soluble resin composition was measured under the conditions of .5 mm, length of 10.0 mm, temperature of 100 ° C, and test pressure of 980,000 Pa. 2) Thickness of the inner wall: After drilling the drill bit, the uppermost copper foil laminate in the overlapped copper foil laminate is cut and ground by the cross section of the center of the machined hole. The distance from the largest convex portion to the deepest concave portion in the side surface was measured. The measurement position is from the 2996th hole to the 3000th hole of the machining hole side 10 of each root drill bit, and the total of 5 drill bits is 5〇 29 201043362
W « W A 平均值作為内壁粗糙度的平均值。另外，所謂最大值的平 均值’是指對5根鑽頭取每1根鑽頭的最大值並加以平均 所得的值。 3) 孔位置精度·· 利用孔分析儀（Hitachi Via Mechanics製造）對所重叠 的銅箔積層板的最下板的背面中的3,000hit的孔位置與指 定座標的偏移進行測定，對每1根鑽頭計算平均值及標準 偏差（σ) ’計算出平均值+ 3(7及最大值，記載2〇次鑽頭 鑽孔加工的平均值。 4) 樹脂捲附量： 利用倍率為25倍的顯微鏡（microscope)對3,000 hit 加工後的20根鑽針分別進行觀察，測定相對於鑽針徑的樹 脂捲附的最大徑及鑽頭軸方向的長度，求出捲附樹脂的體 積’計算出20根的平均值。 5) 數量平均分子量及成分鑑定： 於將 Shodex SB-G、Shodex SB-803HQ 及 Shodex SB-806MHQ (昭和電工股份有限公司製造）的管柱串聯的 水系GPC分析條件下進行。將分析試樣的載體設定為5〇 mM-NaCl水溶液’於注入量為20 4、流速為〇 7 ml/min、 供箱溫度為35°C的條件下，利用示差折射計（rid_6a，島 津製作所股份有限公司製造）進行測定，使用聚乙浠乙二 醇試劑盒（POLYMER LABORATORIES Ltd.製造）作為標 準物質，計异出高分子化合物的數量平均分子量及重量平 均分子量。進而，根據所得的GPC資料來分取各波峰成 30 201043362 分，使用FT-IR(日本分光股份有限公司製造 來進行成分鑑定。 雖然本發明已以較佳實施例揭露如上，然其並 限定本發任何所屬麟領域巾具麵常 脫離本發明之精神和範圍内，當可作些許之^ 不 因此本發明之倾範圍#減社ψ =飾’ 為準。 〜祀固所界定者 【圖式簡單說明】 益 【主要元件符號說明】 #»»> 31The W « W A average is taken as the average of the inner wall roughness. Further, the average value of the maximum value is a value obtained by averaging the maximum value of each of the five drill bits and averaging them. 3) Hole position accuracy. · Using a hole analyzer (manufactured by Hitachi Via Mechanics), measure the offset of the 3,000hit hole position and the specified coordinate in the back surface of the lowermost plate of the overlapped copper foil laminate. Calculate the mean value and standard deviation (σ) of the root drill bit. Calculate the average value + 3 (7 and the maximum value, and record the average value of the drilling process for the 2 times drill bit. 4) Resin coil amount: Use a microscope with a magnification of 25 times (microscope) 20 rigs after 3,000 hits were observed, and the maximum diameter of the resin coil and the length in the direction of the drill axis with respect to the drill diameter were measured, and the volume of the wound resin was determined. average value. 5) Quantitative average molecular weight and component identification: It was carried out under the conditions of aqueous GPC analysis in which the columns of Shodex SB-G, Shodex SB-803HQ and Shodex SB-806MHQ (manufactured by Showa Denko KK) were connected in series. The carrier of the analysis sample was set to a 5 mM NaOH-NaCl aqueous solution at a flow rate of ml7 ml/min, a supply tank temperature of 35 ° C, and a differential refractometer (rid_6a, Shimadzu Corporation). The measurement was carried out by using a polyethylene glycol kit (manufactured by POLYMER LABORATORIES Ltd.) as a standard material, and the number average molecular weight and the weight average molecular weight of the polymer compound were determined. Further, each peak is divided into 30 201043362 points according to the obtained GPC data, and component identification is performed using FT-IR (manufactured by JASCO Corporation). Although the present invention has been disclosed in the preferred embodiment as above, It is often within the spirit and scope of the present invention to make any of the lining of the lining of the lining of the present invention, and it is possible to make some of it. Therefore, the scope of the invention is not limited to 减 ψ 饰 饰 饰 饰 饰 。 。 。 。 。 。 。 祀 祀 祀 祀 祀 图 图 图 图Brief description] Benefit [main component symbol description] #»»> 31
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| CN103282168A (en) * | 2010-12-28 | 2013-09-04 | 三菱瓦斯化学株式会社 | Drill entry sheet |
| TWI601461B (en) * | 2012-03-21 | 2017-10-01 | 三菱瓦斯化學股份有限公司 | Auxiliary plate for drilling and drilling method |
| US10159153B2 (en) | 2012-03-27 | 2018-12-18 | Mitsubishi Gas Chemical Company, Inc. | Entry sheet for drilling |
| US10674609B2 (en) | 2014-03-31 | 2020-06-02 | Mitsubishi Gas Chemical Company, Inc. | Entry sheet for drilling |
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| KR101859699B1 (en) | 2011-01-07 | 2018-05-18 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Drill entry sheet |
| CN103937387B (en) * | 2014-04-22 | 2016-06-29 | 深圳市柳鑫实业股份有限公司 | A kind of boring overlay film aluminum-based cover plate of PCB and preparation method thereof |
| CN105583889A (en) * | 2014-10-22 | 2016-05-18 | 合正科技股份有限公司 | Cover plate for hole drilling |
| MY185904A (en) * | 2015-03-19 | 2021-06-14 | Mitsubishi Gas Chemical Co | Entry sheet for drilling and method for drilling processing using same |
| WO2016147818A1 (en) * | 2015-03-19 | 2016-09-22 | 三菱瓦斯化学株式会社 | Entry sheet for drilling holes, and hole drilling method using same |
| KR101918438B1 (en) | 2016-03-11 | 2018-11-13 | 미츠비시 가스 가가쿠 가부시키가이샤 | Entry sheet for drilling holes, and hole drilling method in which said sheet is used |
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| WO1988003743A1 (en) * | 1986-11-13 | 1988-05-19 | Johnston James A | Method and apparatus for manufacturing printed circuit boards |
| JP2855824B2 (en) * | 1990-08-08 | 1999-02-10 | 三菱瓦斯化学株式会社 | Drilling method for printed wiring boards |
| JP4543243B2 (en) * | 1999-06-01 | 2010-09-15 | 昭和電工パッケージング株式会社 | Small diameter drilling plate and small diameter drilling method |
| JP4201462B2 (en) * | 2000-06-05 | 2008-12-24 | 利昌工業株式会社 | Entry board for drilling |
| JP4968652B2 (en) * | 2001-07-17 | 2012-07-04 | 日本合成化学工業株式会社 | Water-dispersible resin composition for perforating printed wiring board, sheet made of the composition, and method for perforating printed wiring board using such sheet |
| JP2003225892A (en) * | 2002-02-05 | 2003-08-12 | Mitsubishi Gas Chem Co Inc | Method for drilling |
| JP2004017190A (en) * | 2002-06-13 | 2004-01-22 | Kobe Steel Ltd | Resin coated metal sheet used for drilling printed wiring board |
| US20050003169A1 (en) * | 2003-01-28 | 2005-01-06 | Nobuyuki Ikeguchi | Lubricant sheet for drilling and method of drilling |
| TWI306369B (en) * | 2003-01-28 | 2009-02-11 | Mitsubishi Gas Chemical Co | Lubricant sheet for drilling and method of drilling |
| JP4541132B2 (en) * | 2004-12-27 | 2010-09-08 | 昭和電工パッケージング株式会社 | Entry board for small-diameter drilling and small-diameter drilling method |
| CN100531517C (en) * | 2005-07-25 | 2009-08-19 | 合正科技股份有限公司 | High-heat radiation lubricating aluminium cover plate for drilling |
| JP5011823B2 (en) * | 2006-05-30 | 2012-08-29 | 三菱瓦斯化学株式会社 | Method of manufacturing entry sheet for drilling |
| KR20080055264A (en) * | 2006-12-15 | 2008-06-19 | 홍부진 | Sheets for drilling |
| JP5198809B2 (en) * | 2007-07-12 | 2013-05-15 | 三菱瓦斯化学株式会社 | Entry sheet for drilling |
| KR100879284B1 (en) * | 2008-02-12 | 2009-01-16 | (주)상아프론테크 | Lublicant sheet for pcb drilling and composition for forming the same |
| MY152828A (en) * | 2008-06-10 | 2014-11-28 | Mitsubishi Gas Chemical Co | Entry sheet for drilling |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103282168A (en) * | 2010-12-28 | 2013-09-04 | 三菱瓦斯化学株式会社 | Drill entry sheet |
| CN103282168B (en) * | 2010-12-28 | 2015-09-30 | 三菱瓦斯化学株式会社 | Cover plate for drilling hole |
| TWI547358B (en) * | 2010-12-28 | 2016-09-01 | Mitsubishi Gas Chemical Co | Drilling cover |
| TWI601461B (en) * | 2012-03-21 | 2017-10-01 | 三菱瓦斯化學股份有限公司 | Auxiliary plate for drilling and drilling method |
| US9826643B2 (en) | 2012-03-21 | 2017-11-21 | Mitsubishi Gas Chemical Company, Inc. | Entry sheet for drilling and drilling method |
| US10159153B2 (en) | 2012-03-27 | 2018-12-18 | Mitsubishi Gas Chemical Company, Inc. | Entry sheet for drilling |
| US10674609B2 (en) | 2014-03-31 | 2020-06-02 | Mitsubishi Gas Chemical Company, Inc. | Entry sheet for drilling |
Also Published As
| Publication number | Publication date |
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| KR101153259B1 (en) | 2012-06-07 |
| KR20120008533A (en) | 2012-01-30 |
| RU2011148789A (en) | 2013-07-20 |
| CN102458783A (en) | 2012-05-16 |
| MY153546A (en) | 2015-02-27 |
| TWI503191B (en) | 2015-10-11 |
| WO2010140333A1 (en) | 2010-12-09 |
| JP4798308B2 (en) | 2011-10-19 |
| JPWO2010140333A1 (en) | 2012-11-15 |
| RU2534178C2 (en) | 2014-11-27 |
| BRPI1011865A2 (en) | 2019-05-14 |
| CN102458783B (en) | 2013-07-24 |
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