TW201247761A

TW201247761A - Entry sheet for drilling

Info

Publication number: TW201247761A
Application number: TW100133460A
Authority: TW
Inventors: Yousuke Matsuyama; Shigeru Horie; Takuya Hasaki; Kenichi Shimizu
Original assignee: Mitsubishi Gas Chemical Co
Priority date: 2010-09-17
Filing date: 2011-09-16
Publication date: 2012-12-01
Also published as: CN103108730B; CN103108730A; WO2012035771A1; TWI470017B; RU2526106C1; BR112013006112A2; KR101705064B1; KR20140012612A; MY165940A; JPWO2012035771A1; JP5845901B2

Abstract

The present invention pertains to an entry sheet for drilling, said sheet having excellent hole positioning accuracy, even in high temperature conveyance and/or storage environments. The present invention particularly pertains to an entry sheet for drilling which is characterised by being formed by the formation of a water-soluble resin composition layer on at least one surface of a metal support foil, said composition containing a water-soluble resin, a water-soluble lubricant, and 2, 7-naphthalenedisulfonic acid, 3-hydroxy-4-[(4-sulfo-1-naphthalene) azo]-, and trisodium salt (Red No. 2). Said water-soluble resin composition layer is formed by being cooled from a cooling initiation temperature of 120-160 DEG C to a cooling completion temperature of 25-40 DEG C in no more than 60 seconds and at a cooling speed of at least 1.5 DEG C/second, with the degree of crystallisation of the water-soluble resin composition being at least 1.2, and the standard deviation(s) of the surface hardness of the water-soluble resin composition layer being no more than 2, and the surface hardness being 8.5N/mm2-20N/mm2.

Description

201247761 六、發明說明：【發明所屬之技術領域】本發明係關於-種S對銅箱堆疊板或多I才反進行鑽孔加工時所使用的鑽孔用蓋板。【先前技術】、、關於印刷基板所使用之銅箔堆疊板或多層板的鑽孔加工方法，一般係採用.取1片銅箔堆疊板或多層板，或取複數片堆疊 ^，在其最上部配置域單體或是㈣表社形成了樹脂組成物巧片材（以下，本制書職「片材」稱為「鑽賴蓋板」）作為盍板並進行鑽孔加工的方法。近年來’隨著吾人對提高印刷基板可靠度的需求或高密度化 =展，遂要求能夠做到提高銅齡·或多層板關孔位置精度或降低孔壁粗糙度等高品質的開孔加工，為了應付該等需求， «人，出了制由聚乙二㈣水雜樹賴構成的#材的開孔加 ϋ ΐ照例如專利文獻0、在金屬支持紅形成水溶性樹脂層月材（麥照例如專利文獻2)、在形成了熱硬化性樹 1曰f膜的泊上形成水溶性樹脂層的開孔用蓋板（參照例如專利潤滑Γ旨組成物中調合了非_素著色劑的開孔用滑劑片材（麥照例如專利文獻4)等技術内容，並將其實用化。另外，關於最近的發展趨勢，可列舉出以下特徵。雄田Γ印刷基板的高密度，其持續地進展i仰賴於銅箱芦M於印刷基板的生産國，基於降低成本以及與半導體生業…&的動機’從日本移到台灣、韓國.、中國、 ^ 的全球化趨勢翻發展。他亞W各國第三，在台灣、韓國，鑽孔用蓋板生產商蓬勃座成，盥在地生產商競爭的市場環境持續發展。 /、息第四，由於係半導體_産#，故其f要_較大，在需求 201247761 ，減時期供應鏈會產生鑽刻蓋求回暖時期之後才會再次使用。另外，由子存官理直到需 :^吏在經辨理之後仍要求其必槪触運送=;的勢=運住例如船舶常溫貨櫃運送等長時間的其f頁能夠承党得运或保謂溫度難，也健卿成做、專運吾人殷切期望能夠開發出一種即使經過比^二，亦即，程’也仍能夠形成優良的開孔位置精度 =的，皿度歷 [習知技術文獻] X谓孔用盍板。 [專利文獻] [專利文獻1]日本特開平4 —92494號公報 [專利文獻2]日本特開平5 —1694〇〇號巧利文獻3]日本特開細―⑽85號公報 [專利文獻4]日本特開2〇〇4一23〇47〇號公報【發明内容】 [發明所欲解決的問題] 長時間的常溫輸送及人更:其即使經過理’也能夠形成優㈣開孔位置精度。^純下保存管 [解决問題之技術手段] j了解決上述問題，本發明人進行各種研究，成於鑽孔用蓋板表面上的水溶性樹脂組成物現在形以下所 ί異的開孔位置精度’進而解決上述問題。亦即本發屬支持 ⑴-種堆疊板或多層板用的鑽孔用蓋板，其具備金 4 201247761 =’ 於該金屬支持箱的至少單面上的水溶性樹脂組成物二^、’仏為.该水溶性樹脂組成物包含水溶性樹脂、水溶性潤 =萘二视3铺_4·[(“键基]萘基）偶氮基]、i 今唬）’该水溶性樹脂組成物層，係在該金屬支持鶴上 ::、且成物的:谷液並使其乾燥之後，從冷卻開始溫度。。。。叫了 ΐ了溫度25°c〜4(rc ’在6°秒以内’以L5t：/秒以上的 :部速度冷卻所形成者，該水溶性樹脂組成物的結晶度在12以〕，叆水溶性樹脂組成物層的表面硬度的標準偏差口在2以表面硬度在8.5N/mm2以上20N/mm2以下。從由ϋ如人 1〕所記載之鑽孔用蓋板’其中’該水溶性樹脂係乙烧以及聚烯烴乙二醇的聚g旨所構成的群組中種以上者，該水溶性潤滑劑係聚乙二醇。加量/目3對〕於如載之鑽孔用蓋板，其中’該紅色2號的添 _重量份溶性潤滑劑合計勘重量份在成物Γ包〕含如甲ϋ所記載之鎖孔用蓋板’其中’該水溶性樹脂組旦〔5〕如〔4〕所記載之鑽孔用蓋板，其中，該曱酸鈉天二^對於該水溶性樹脂與該水溶性潤滑劑合重量份以上1.5重量份以下。里里切在0.01 占& 如〔丨〕所記載之鑽孔用蓋板，其中，該水溶性樹月匕相成物的固化溫度在3〇〇C以上7〇°C以下。 3、、且 ^如〔1〕所記載之鑽孔用蓋板，其使用於鑽頭徑在〇以上〇.3mm(p以下的堆疊板或多層板的鑽孔加工中。瓜9 ^〕如⑴所記載之鑽孔用蓋板，其中，該金屬支；^ζ5：：：.3^5Γτατ' [對照先前技術之功效] 本發明的鑽制蓋板，在條件為例如5Gt、1小時的熱劣化 201247761 加速實驗翻隸置精度的變化率在+戰叫間的常溫輸送及/或在比曰本更高溫的溫：竟: 官，也能夠防止開孔位置精度因熱劣化，甚保藉此，便可目齡槪與絲魏，並軸^度力=；^工^ 【實施方式】本發明係-種堆疊板或多層板用賴孔用蓋板，1 ίΓΙ及形成於該金屬支持躺至少—面上的水溶性^旨组ΐ 層笑if峨脂組成物包含水溶性樹脂、水溶性潤滑劑以及 “工石'，，經基冰[(4_磺酸基_1_萘基）偶氮基]-，三納鹽（紅唬），该水溶性樹脂組成物層係在該金屬 =脂^物的齡融物之後或塗布含有該水溶性樹月日^成；^ 之後，從冷卻開始溫度12叱〜16叱到冷卻終了 :皿=5C〜40C ’在60秒以内’以ec/秒以上的冷卻速度冷 =P形成者，该水溶性樹脂組成物的結晶度在12以上，該水溶性 3組成，的表面硬度的標準偏差。在2以下，且絲硬 8.5N/mm2 以上 20N/mm2 以下。士發明的水溶性樹脂係&子量較高者。為了將該水溶性樹脂 ^ 形成片狀，必須具備成膜性，水溶性樹脂摻合於水溶性樹成物中以賦予成膜性，其分子構造在所不問，重量平均分子 ίΎ在6〇，_以上4〇0,000以下。例如，該水溶性樹脂宜 ^ t辰氧乙烧、聚環氧丙燒、聚丙稀酸納、聚丙稀醯胺、聚乙、广客领、羧曱基纖維素、聚四亞曱基二_及輯烴乙二醇旨所組成的群組之中選出丨種以上。在此，聚稀烴乙二醇的 =醋係指料烴乙二醇與二元酸反應所得義合物。關於聚稀煙例如：聚乙二醇、聚丙二醇、聚四亞曱基三醇或該等物聚合物所例示的二醇類。另外，關於二磁，例如：苯二 ^異苯二甲酸、對苯二曱酸、癸二酸等。另外，將苯均四酸 ϋ價細变部分酷化而形成具有2個緩基的形態者亦可。該等貝亦可為酸酐。亦可使用該等物質其中丨種，或將2種以上適 201247761 當混合使用’惟更宜使用聚環氧乙烷（PEO)。，如明的水溶性潤滑劑係分子量較低者。該水溶性潤滑劑換 &於該水溶性樹脂組成物中以賦予潤滑性，其分子構造在所不夕 (Mw) 巧潤,月劑，具體而言，例如：聚乙二醇、聚丙二醇乙乙烤十六烧基趟、聚氧乙稀硬脂峻、聚氣乙烯月 ^ -、0水虱乙烯壬酚醚.、聚氧乙烯辛基苯基醚等所例示之 ;聚氧乙烯單硬脂酸@旨、聚氧乙婦山梨醇單硬脂酸脂；二聚甘油早硬脂酸醋、十(六聚甘油單硬脂酸軺等所例示之 5硬脂酸_;聚氧乙稀丙烯共聚合物等，亦可使用其中ρ種，將2種以上適當摻合制，惟更宜使用聚乙二醇& 1 *5 ° 31 則鑽頭會沾上太錯脂水溶性樹脂超過80重量份在本發明中’水溶性樹脂組成物的結晶樹脂組成物的結晶度更進—牛^古 '、\ ”牛之後，水溶性使水溶性樹脂組成實驗條件之ί麦由該作用效果，本發明的鑽孔用苔、、特彳放性作用。藉送及/或在比日本更高溫的溫度環境下二=長，間的常溫輸孔位精度的熱劣化或有助於開 ::也成夠防止開另外，該熱劣化加速實驗條件触在比常^高的溫度下放 201247761 置既定時間的條件。該溫度化溫度更高，比熔點更低的適“溢度。〜水溶性樹脂組成物的固計100重量份"宜在生樹脂與該水溶性潤滑劑合 =量未達讀«料，號的就的添加量超過1〇 «份時，“ 面’當紅色2 樹脂組成物t變得味ϋ難，&、自》散於該水溶性表面析出。若紅色2梦析中合女虮θ從水溶性樹脂組成物層頭折損、紅色2 有鑽頭鑽孔的位置精度惡化、ί 紅色2號的添加量宜在⑽力^能性。因此，當調整以最佳化。例如，红色ϋΐ(ΐ下’並經過適 ^ S t5〇 f^：± ff f；·05 樹脂組i物的結晶4的作組f物中’有提高該水溶性劑。甲酸納的添加量，相對孔位置精度的成核計⑽重量份宜在潤滑劑合甲‘ϋ曰ί時’便不易發現提高結晶度的作用。因此， i重讀以上，最好是在G.25，量份以上1.0重量份ΐ 另一方面，當曱酸鈉的添加量超，. :議組成物層的表面析出，會產生不良的本發明中的紅色2號與曱酸鈉，如前所述，目的作因此’比起單獨使用紅色2號，更宜一併使用紅色2號酉欠鈉。例如，如後述之比較例所示的，未添加紅色2號以及甲二二其在贼、1小時的熱劣化加速實驗後的開孔^ 声在5〇C、1小時的熱劣化加速實驗前的開孔位置精又而5更加心化。相反的，如後述之實施例所示的，包含树脂、水溶性潤滑劑、紅色2號以及曱酸納的樹脂組成，在、 8 201247761 1小時的熱劣化加速實驗後，開孔位置精度的惡化程度較小有所提高。這個事實是以往所不知道的。本發明人認為這是至在該水溶性樹脂組成物中，該結晶構造為3維構造，球面方向（XY方向）上推撥聚合，且在深度方向（z方向）上形成層的=晶層構造，然後’高分子並未全部球晶化而存在非結晶部I， ίϊΐι紅色2號會分散到3維構造的細部，有助於使非結晶部二形成球晶，故具有形成緻密球晶與更進—步提高其結晶度的作另外’由於紅色2號係不含_素的著色劑，故比較環保。且’由於紅色2號係水溶性的，故即使在鑽孔加工後殘存於孔上，也能夠用水洗淨，故係較佳的選擇。、主紅色2號的添加方法可選擇任意方法。可預先將紅色2號溶解於水等溶劑中再添加到該水溶性樹脂組成物中，亦可直到水溶性樹脂組成物中。將紅色2號預先溶解於水或溶劑中再加到水溶性樹脂組成物中的方法，比較容易使其均勻分散。、、另外，當在該水溶性樹脂組成物的調製步驟使溶媒中添加曱醇、異丙醇等的醇類，可防止氣泡月曰組成物中，提高水溶性樹脂組成物的結晶度，是較佳的態樣。 X > DSC (Differential Scanning falor^netry，示歸鋪分析）#方法，本發明使肖置的相値定義結晶度。第一，使用 DSC (SIINanotechnology inc.製 DSC622〇)，從 3(TC升溫到赃，之後在·c保持3分鐘，接著，從1〇)〇。= 卻到3(TC，之後在3(TC保持3分鐘，此時升溫速度為+3以分' 二部速^為-3 C/分。將該循環實施2次，算出第2次降溫時的，化熱量。第2次固化時的峰值，比起第i次而言，固化溫度並未產生差異，可麟雜成本身_化溫度，故使用該數值。使用10mg的水溶性樹脂組成物試料進行測量， ^料每_的固化熱量，將其當作水溶性樹脂試熱量。 201247761 第^，在本發明中，所謂標準樹脂組成物（A)，係指相對於 100重量份的重量平均分子量（Mw)為110,000的聚環氧乙烷（，工業化學股份有限公司製ALK0XL11)添加5重量份的紅色2 號者。然後’標準樹脂組成物（A)的結晶度，使用dsc，算出第2次降溫時的固化熱量，將該固化熱量當作標準樹脂組成物（八的固化熱量，定義出結晶度丨.〇。第—，在本發明中，各试料的結晶度，按照接下來的步驟算土。例如，在實施例以及比較例的情況下，進行前述的Dsc分析，异出第2次降溫時的固化熱量。然後，根據以下算式算出試料的結晶度。試料的結晶度=試料的固化熱量+標準樹脂組成物（A)的固化熱量在本發明中，水溶性樹脂組成物的固化溫度，與前述相同，利用DSC的測量求出。測量條件與該結晶度測量條件相同，用第 2次降溫固化時的發熱尖峰的峰頂溫度當作固化溫度。201247761 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a cover plate for drilling used in the case where S is used for the reverse drilling of a copper box stacking plate or a multi-I. [Prior Art] The method of drilling a copper foil stacking board or a multilayer board used for a printed circuit board is generally adopted. Take a copper foil stacked board or a multi-layer board, or take a plurality of stacks ^, at its most The upper configuration domain unit or (4) watch company forms a resin composition material sheet (hereinafter, the "sheet material" is referred to as "drilling cover plate") as a seesaw and is drilled. In recent years, with the increasing demand for high reliability of printed substrates, or the need for high-density drilling, it is required to improve the copper age, or the positional accuracy of the multi-layer board or reduce the roughness of the hole wall. In order to cope with these demands, «People, out of the hole made up of polyethylene (4) water mixed tree lais, for example, the patent document 0, in the metal support red to form a water-soluble resin layer moon ( For example, Patent Document 2) discloses a perforated cover plate in which a water-soluble resin layer is formed on a poise in which a thermosetting tree 1曰f film is formed (see, for example, a patented lubricating composition). The technical content of the lubricant sheet for the opening (Mu Zhao, for example, Patent Document 4) is put into practical use. The recent development trend includes the following features. Continued progress i relies on the development of copper box reed M in printed circuit boards, based on the trend of lowering costs and moving with the semiconductor industry...&'s move from Japan to Taiwan, Korea, China, ^. Asian W countries third, In Taiwan and South Korea, manufacturers of drilling cover plates are flourishing, and the market environment in which competitors compete in the market continues to develop. /, Fourth, due to the semiconductor_production#, its f is larger, Demand 201247761, the supply chain will reduce the supply period and will be used again after the recovery period. In addition, from the sub-existing authority until the need: ^ 吏 after the clarification still requires that it must touch the transport =; For a long time, such as the ship's normal temperature container transportation, the f page can be accepted by the party or it is difficult to maintain the temperature. It is also the case that Jianqing Chengcheng and the special transporter are eager to develop a kind of even if the ratio is two, that is, In addition, it is also possible to form an excellent opening position accuracy=, and the degree of the dish is known in the prior art. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei-4-92494 (Patent Document 2) Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. 5, No. 5, No. 5, No. 5, No. 5, No. 5, No. Solved problem] Long-term normal temperature transport and people more: even after it passes 'It is also possible to form an excellent (4) hole position accuracy. ^ Pure lower storage tube [Technical means for solving the problem] j. To solve the above problems, the inventors conducted various studies to form a water-soluble resin on the surface of the drilling cover plate. The object now has the following hole position accuracy, which further solves the above problem. That is, the present invention supports the drilling cover for (1)-stacked or multi-layer board, which has gold 4 201247761 =' The water-soluble resin composition on at least one side of the support box is two, '仏. The water-soluble resin composition comprises a water-soluble resin, a water-soluble run, a naphthalene, a wrapper, and a naphthene. The azo group], i 唬唬) 'The water-soluble resin composition layer is on the metal support crane::, and the product: the valley liquid and dried, from the cooling start temperature. . . . It is called a temperature of 25 ° c ~ 4 (rc ' within 6 ° seconds 'with L5t: / sec or more: part of the speed formed by the formation, the water-soluble resin composition crystallinity of 12], water-soluble The standard deviation of the surface hardness of the resin composition layer is 2, and the surface hardness is 8.5 N/mm 2 or more and 20 N/mm 2 or less. The drilling cover sheet 'from the '1' is a water-soluble resin. The above-mentioned type of the group consisting of the group consisting of the group consisting of the group consisting of the group consisting of the group consisting of the group consisting of the group consisting of the group consisting of the group consisting of the group , wherein 'the red 2nd addition _ part by weight of the soluble lubricant total weight of the weight of the package in the product package> contains the cover plate for the keyhole as described in the scorpion 'where' the water-soluble resin group [5] [4] The perforated cover sheet according to [4], wherein the sodium citrate is 1.5 parts by weight or less based on the water-soluble resin and the water-soluble lubricant, and the lining is in 0.01% & [丨] The drilling cover plate according to [,], wherein the water-soluble tree ruthenium phase solidification temperature is 3 〇〇 C or more and 7 〇 ° C 3. The drilling cover plate according to [1], which is used in the drilling process of a stacking plate or a multi-layer plate having a drill diameter of 〇.3 mm or more. The melon 9 ^] The cover for drilling according to (1), wherein the metal branch; 5ζ:::3^5Γτατ' [control against the prior art] The drill cover of the present invention, under conditions of, for example, 5 Gt, 1 hour The thermal degradation of 201247761 accelerates the rate of change of the accuracy of the turret to the normal temperature of the + warfare and / or the temperature of the higher temperature than the sputum: actually: can also prevent the accuracy of the hole position due to thermal degradation, even In this way, the 目槪丝 , , , , , , , 【【【【【【【【【【【【【【【【【【【【【【【【【【【【【【【【【【【【【 Supporting at least the water-soluble surface of the ^ 旨 layer 笑峨 if 峨 composition contains water-soluble resin, water-soluble lubricant and "Wenshi", via base ice [(4_sulfonyl-1_naphthalene) (A) azo]-, a tri-nano salt (red cerium), the water-soluble resin composition layer is after the metal melt of the metal = fat or coated The soluble tree is formed on the day of the month; ^, after the cooling start temperature is 12叱~16叱 to the end of the cooling: the dish = 5C~40C 'within 60 seconds' at a cooling rate of ec/sec or more = P is formed, the water is soluble The crystallinity of the resin composition is 12 or more, and the standard deviation of the surface hardness of the water-soluble 3 composition is 2 or less, and the wire hardness is 8.5 N/mm 2 or more and 20 N/mm 2 or less. The water-soluble resin system of the invention is & In order to form the water-soluble resin into a sheet form, it is necessary to have film formability, and the water-soluble resin is blended in the water-soluble resin to impart film formability, and its molecular structure is not required, and the weight average The numerator Ύ is at 6〇, _ is above 4〇0,000. For example, the water-soluble resin is preferably oxy-ethene, poly-glycid, sodium polyacrylate, polyacrylamide, polyethylidene, guangke collar, carboxymethyl cellulose, polytetradecyl ruthenium _ Among the groups consisting of hydrocarbon glycols, more than one species are selected. Here, the polyglycol glycol = vinegar is a compound obtained by reacting a hydrocarbon glycol with a dibasic acid. Regarding the polydue smoke, for example, polyethylene glycol, polypropylene glycol, polytetradecyltriol or the diols exemplified as the polymers. Further, regarding the two magnetisms, for example, benzene diphthalic acid, terephthalic acid, sebacic acid, and the like. Further, it is also possible to form a form having two slow bases by cooling the fineness of the pyromellitic acid quinone. The shells may also be anhydrides. It is also possible to use these substances, or to use two or more kinds of 201247761 in combination, but it is more preferable to use polyethylene oxide (PEO). The water-soluble lubricants such as Ming are the lower molecular weight. The water-soluble lubricant is exchanged and applied to the water-soluble resin composition to impart lubricity, and the molecular structure thereof is in the form of a mist (Mw), a monthly agent, specifically, for example, polyethylene glycol or polypropylene glycol. Ethylene-baked hexadeced sulphur, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur, sulphur Stearic acid @, polyoxyethylene sorbitan monostearate; diglycerin early stearate, ten (hexaglycerol monostearate, etc. 5 stearic acid exemplified _; polyoxyethylene For dilute propylene copolymers, etc., it is also possible to use two or more of them in combination with ρ, but it is more preferable to use polyethylene glycol & 1 * 5 ° 31, the drill bit will be stained with too damper water-soluble resin. 80 parts by weight of the liquid crystal resin composition of the water-soluble resin composition in the present invention is more advanced after the crystallinity of the resin composition, and the water-soluble resin composition of the water-soluble resin is composed of the experimental conditions. The purpose of the present invention is to use a coating for the purpose of drilling, and to transfer and/or in a temperature environment higher than that of Japan. The thermal deterioration of the accuracy of the hole position at normal temperature or the opening of the hole is also sufficient to prevent the opening. The thermal deterioration accelerates the experimental condition to the condition that the temperature is lowered at a higher temperature than the constant temperature of 201247761. The temperature is higher. , a lower "melting degree than the melting point. ~ 100 parts by weight of the water-soluble resin composition" " should be in the raw resin and the water-soluble lubricant = the amount is not read «material, the amount of the addition When more than 1 part of « parts, "face" when the red 2 resin composition t becomes miso, &, self is scattered on the water-soluble surface. If the red 2 dreams out in the female 虮 θ from the water-soluble resin The composition layer is damaged, the red 2 has the positional accuracy of the drill hole being deteriorated, and the ί red No. 2 is preferably added at (10) force. Therefore, when the adjustment is optimized, for example, the red ϋΐ (ΐ下' and After the composition of the crystal 4 of the resin group i is improved, the water-soluble agent is increased. The amount of sodium formate added, the nucleation of the relative hole position accuracy (10) It is not easy to find the effect of increasing the crystallinity when the weight of the lubricant is 'A'. Therefore, i rereads the above, preferably in G.25, in an amount of 1.0 part by weight or more. On the other hand, when the amount of sodium citrate added is excessive, the surface of the composition layer is precipitated, which may cause undesirable invention. In the red No. 2 and sodium citrate, as described above, the purpose is therefore 'should be compared to the use of red No. 2 alone, and it is more preferable to use the red No. 2 to owe sodium. For example, as shown in the comparative example described later, The red hole No. 2 and the second two are in the thief, and the opening of the hole after 1 hour of thermal deterioration acceleration test is fine at 5 〇C, 1 hour before the thermal deterioration acceleration experiment. On the contrary, as shown in the examples below, the resin composition including the resin, the water-soluble lubricant, the red No. 2 and the sodium niobate, after the thermal deterioration acceleration test of 1 201247761, the accuracy of the opening position The degree of deterioration has increased less. This fact is not known in the past. The inventors believe that this is a crystal layer having a crystal structure of a three-dimensional structure, a push-up polymerization in a spherical direction (XY direction), and a layer formed in a depth direction (z direction) in the water-soluble resin composition. Structure, then 'polymer does not all spheroidize and there is amorphous part I, ϊΐ 红色 red 2 will be dispersed into the details of the 3D structure, which helps to form spherulites in the amorphous part 2, so it has dense spherulites. In addition, it is more environmentally friendly because it does not contain the coloring agent of the red No. 2 system. Further, since the red No. 2 is water-soluble, it can be washed with water even after remaining in the hole after drilling, so that it is preferably selected. The method of adding the main red number 2 can be selected by any method. Red No. 2 may be dissolved in a solvent such as water in advance and added to the water-soluble resin composition, or may be directly applied to the water-soluble resin composition. The method of dissolving red No. 2 in water or a solvent and adding it to the water-soluble resin composition is relatively easy to uniformly disperse. In addition, when an alcohol such as decyl alcohol or isopropyl alcohol is added to the solvent in the preparation step of the water-soluble resin composition, it is possible to prevent the crystallinity of the water-soluble resin composition from being improved in the bubble composition. The preferred aspect. X > DSC (Differential Scanning falor^netry) method, the present invention defines the crystallinity of the phase. First, DSC (DSC622® manufactured by SIINanotechnology Inc.) was used, and the temperature was raised from 3 (TC to 赃, then held at ·c for 3 minutes, and then from 1 〇). = but it goes to 3 (TC, then 3 (TC keeps for 3 minutes, at this time, the heating rate is +3 in minutes) and the second speed is -3 C/min. This cycle is carried out twice to calculate the second cooling. The calorific value at the second curing is not different from the curing temperature in the second curing, and the temperature is used as the temperature. Therefore, the value is used. 10 mg of the water-soluble resin composition is used. The sample is measured, and the heat of curing per _ is taken as the heat test of the water-soluble resin. 201247761 In the present invention, the standard resin composition (A) means the weight average with respect to 100 parts by weight. Polyethylene oxide having a molecular weight (Mw) of 110,000 (ALK0XL11 manufactured by Industrial Chemical Co., Ltd.) was added with 5 parts by weight of red No. 2. Then, the crystallinity of the standard resin composition (A) was calculated using dsc. The curing heat at the time of two coolings is regarded as the standard resin composition (the curing heat of eight, and the crystallinity is defined as 结晶. 第. In the present invention, the crystallinity of each sample is followed by The steps of calculating soil. For example, in the case of the examples and comparative examples Then, the above-described Dsc analysis was carried out, and the heat of curing at the second cooling was different. Then, the crystallinity of the sample was calculated according to the following formula: Crystallinity of the sample = curing heat of the sample + curing heat of the standard resin composition (A) In the present invention, the curing temperature of the water-soluble resin composition is the same as described above, and is determined by DSC measurement. The measurement conditions are the same as the measurement conditions of the crystallinity, and the peak top temperature of the heat-generating peak when the second cooling is solidified is Curing temperature.

At本發明人認為，影響蓋板特性的水溶性樹脂組成物層的狀悲，係由形成於金屬支持箔表面上的水溶性樹脂組成物層從溶融狀態開始到冷卻固化時的情況所決定的。因此，不必考慮逐漸升溫的溶融溫度或溶融熱量，如前所述的，反而必須注意逐漸降溫的固化f度以及固化熱量。具體而言，水溶性樹脂組成物的固化溫度越高則結晶度也越高，相對於熱趨向穩定。結果，鑽孔用蓋板的水溶性樹脂組成物的結晶狀態，不易受到運搬及/或保管環 ^的熱履歷所影響，開孔位置精度提高。例如，由於在該水溶性，脂組成物中添加紅色2號或紅色2號與甲酸納，比起未添加該等物質的情況而言，更能提高固化溫度，故可提高結晶度，如是，可使開孔位子精度達到優異數値。尤其，在熱劣化加速實驗後，例如，在50。(：、1小時的熱劣化加速實驗後，可使開孔位置精度達到優，數値。。因此，水溶性樹脂組成物的固化溫度宜在3〇它以上，子宜在35C以上，更宜在4〇〇C以上，更宜在42°C以上，更宜在44 C以上，尤其更宜在46。(：以上。另一方面，水溶性樹脂組成 10 201247761 ，的固化溫度越高’越會損失作為鑽孔用蓋板的潤滑特性。因此，水溶性樹脂組成物的固化溫度宜在7〇。在特別宜在6(TC以下。 1且在机以卜到目前為止並未揭示—種在金屬支持箱的成了 i溶===層的堆疊板或多層板用的鑽孔用蓋板，其特徵為·忒水命性树知組成物的結晶度在12以上。 Ϊ的在的數値較高，有助於提高開孔錄精度。例的情況而言’更可提高結晶度，如是，便可盘;到優異的數値。尤其’紅色2號，如前所述的，夂1 I 所不同’具有在熱劣化加速實驗後，例如，在的&因1卜加士速實驗後，使開孔位置精度達到優異數値 '二水/合性树脂組成物的結晶度應在1.2以上，宜在 1.25以上，更宜在丄3以上。私的袅面廊二精度具體而言，水溶性樹脂組成物層 ίί 1 艮重要的因素’有必要控制表面硬度的平均二甲’iff卿隐成物中，添加紅色2號或紅色2 曱敲鈉，比起未添加該等物質的情，^ ^ 時的'、、、劣化加速貫驗後，可縮小表面硬度的差昱。如曰 =使開硫置精度達職異的數値。關喊 t:rijtD^ ；；tf ( ㈣ A J l DUH—211 ) ’ 在壓頭：Triangularll 負荷速度：a7316mN/sec、負荷保持時間：上二t 水溶性樹敝錄制表面硬度（\、ϋ〇點的表面硬度的平均値與標準偏差/从更度）#出此日请得到的 f溶性樹脂組成物層的表面硬度的標準偏差σ必須。虽標準偏差σ超過2時’表面硬度的差異較大，開孔位置精 201247761 ^也會f差不齊’是較差的態樣。因此，水溶性樹脂組成物芦 g硬度的標準偏差σ應在2以下，宜在丨Q以下，最好是在曰〇 5 另外，若水溶性樹脂組成物層的表面硬度比85N/mm2 小，當鑽頭與鑽孔用蓋板接觸時，容易無法固定穿孔位位置精度劣化。因此，水溶性樹脂組成物層的表面硬以上，宜在9N/W以上，更宜在9.5N^m2 好疋在1GN//mm2以上。另—方面’當水溶性樹脂組成物層的表面硬度値比20N/mm2更大時’鐵頭折損的可能性很言。因此，水溶性樹脂組成物層的表面硬度應在20N/mm2以下。冋本發明之觀用蓋板的熱穩定性，可賴魏加速實驗水^匕位置精度變化率（％)以及表面硬度的標準偏差（N/mm2) 來確認。熱劣化加速實驗條件，如前所述的古 SPEC公司製SPHH-202)，在大氣開放（空氣環境）下^將切二:=尺寸的鑽孔用蓋板以水溶性樹脂組成物層為上層 (金屬支持伯為下層）的方式平置，在例如5(rc下放置丨二放置在室溫（25。〇環境下。另外，熱劣化加速實驗溫度 ^又疋在比水溶性樹脂組成物的固化溫度更高且比熔點更低度。在比溶點更高的溫度，水溶性樹脂組成物會溶化，溶化; =具備的性質未必繼續存在’故無法對其作為鑽孔用蓋板的特= 進仃评價。另-方面’若在比固化溫度更低的溫度測驗熱穩定性的加速實驗。 …、在進订鑽孔用蓋板的開孔位置精度會受到加工基材、鑽孔加 $頭控長等因素的影響而有所差異。因此，為了並非單純比= 置精度値而係進行相對比較，可採肢較在熱劣化加速實牛例如50 C、1小時的熱劣化加速實驗前後的開 =%)的方法。在此，開孔位置精度的變化率可= 開孔位黯度的變化率（％)=(熱劣化加速實驗後的開孔 12 201247761 位置精度一熱劣化加速實驗前的開孔位置精度熱劣化加速實驗前的開孔位置精度X100 I在本4明中’在熱劣化加速貫驗條件例如50°C、1小時的熱劣化加速實驗前後的開孔位置精度的變化率（％)宜在+ 10%以内。此意味著：在熱劣化加速實驗前後，若開孔位置精度變小（若置精度提高）數値為負，若開孔位置精度變大（若開孔位 1又惡化）數値為正，負値越大，防止熱劣化的性能越優異。因在熱劣化加速實驗前後的開孔位置精度的變化率，宜在+ 以，：更宜在+ 5%以内’更宜在。％，最好是在—5%以内。 ί異:=該，位置精度變化率(％)的數値-見之下係相當對値的開孔位置精度(_)不甚理想的話，仍 +异付合吾人之目的，自不待古。水溶如：將單，數種 :甲_作為水_齡成物7力^^2 數種水溶性樹脂成分熱溶解將早一或複納作為水溶性樹脂組成物的熱溶解物的=^或紅色2號與甲酸然後塗布在金屬支持“至解=於溶媒中形成液狀，脂組成物層的方法，戋是預弈，使其乾燥以形成水溶性樹 ^屬支獅的至少單層之後，在專加熱或用接合劑等貼合的方柯知、'且成物層，然後用輥子法，只要是工業上使知方、、=溶性樹脂組成物層的製造方言：例如：將水溶性樹脂組成物_PJ:並無特別限定。具體而適當加熱溶顧合，然後 ^軸或其他混練機構成水溶性樹脂組成物層法等方法在脫模片上形或τ-_機等贱形搞續脂組成物用輥子，法。另外’在形成切性樹性樹脂組成物片材上預先形成―‘屬==== 201247761 層堆疊成一體。支持溶性樹脂組成物的溶液直接塗布於金屬乾；=:;=溶At the present inventors, the shape of the water-soluble resin composition layer which affects the characteristics of the cover sheet is determined by the fact that the water-soluble resin composition layer formed on the surface of the metal support foil starts from a molten state to a state of cooling and solidification. . Therefore, it is not necessary to consider the melting temperature or the melting heat of the gradual warming, as described above, but it is necessary to pay attention to the curing degree and the curing heat which are gradually lowered. Specifically, the higher the curing temperature of the water-soluble resin composition, the higher the crystallinity and the tendency to be stable with respect to heat. As a result, the crystal state of the water-soluble resin composition of the drilling cover sheet is less likely to be affected by the heat history of the transport and/or storage ring, and the accuracy of the opening position is improved. For example, by adding red No. 2 or red No. 2 and sodium formate to the water-soluble, fat composition, the curing temperature can be increased more than when the substance is not added, so that the crystallinity can be improved, and, for example, The accuracy of the opening position can be improved to an excellent number. In particular, after the thermal degradation acceleration experiment, for example, at 50. (: After 1 hour of thermal deterioration accelerated test, the accuracy of the opening position can be improved, and the number of defects can be improved. Therefore, the curing temperature of the water-soluble resin composition should be above 3 ,, and the temperature should be above 35C, more preferably Above 4〇〇C, more preferably above 42°C, more preferably above 44 C, especially more preferably 46. (: above. On the other hand, the water-soluble resin composition 10 201247761, the higher the curing temperature, the more It will lose the lubricating properties of the cover plate for drilling. Therefore, the curing temperature of the water-soluble resin composition should be 7 〇. It is particularly suitable to be 6 (TC or less. 1 and has not been revealed so far in the machine) In the metal support box, it is a stacking plate for a layer of i ==== or a cover plate for a multi-layer plate, which is characterized in that the crystallinity of the composition is 12 or more. The higher the number, the better the accuracy of the opening. In the case of the case, 'the crystallinity can be increased, and if so, the disc can be turned; to the excellent number. Especially the red number 2, as mentioned above,夂1 I differs from having a thermal degradation accelerated test, for example, in & After that, the accuracy of the position of the opening is excellent. The crystallinity of the composition of the dihydrate/complex resin should be 1.2 or more, preferably 1.25 or more, and more preferably 丄3 or more. , water-soluble resin composition layer ίί 1 艮 important factor 'It is necessary to control the surface hardness of the average dimethyl 'iff crypt, add red 2 or red 2 曱 knock sodium, compared to the absence of such substances In the case of ^, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , AJ l DUH—211 ) ' In the indenter: Triangularll load speed: a7316mN/sec, load retention time: upper two t water-soluble tree 敝 recorded surface hardness (\, average 値 and standard deviation of surface hardness of ϋ〇 point / from It is necessary to obtain the standard deviation σ of the surface hardness of the composition layer of the soluble resin composition which is obtained on this day. Although the standard deviation σ exceeds 2, the difference in surface hardness is large, and the opening position is fine 201247761 ^ Misalignment' is a poor condition. Therefore, the composition of water-soluble resin The standard deviation σ of the hardness of reed g should be 2 or less, preferably below 丨Q, preferably 曰〇5. In addition, if the surface hardness of the water-soluble resin composition layer is smaller than 85N/mm2, when the drill bit and the drilling cover are used When contacting, it is easy to prevent the positional accuracy of the perforated position from deteriorating. Therefore, the surface of the water-soluble resin composition layer is harder than 9N/W, more preferably 9.5N^m2 or more than 1GN//mm2. Aspect 'When the surface hardness 値 of the water-soluble resin composition layer is larger than 20 N/mm 2 , the possibility of iron head breakage is large. Therefore, the surface hardness of the water-soluble resin composition layer should be 20 N/mm 2 or less.热 The thermal stability of the viewing cover of the present invention can be confirmed by the rate of change (%) of the positional accuracy of the water and the standard deviation (N/mm2) of the surface hardness. Thermal degradation accelerated experimental conditions, as described in the previous SPEC company SPHH-202), in the open atmosphere (air environment) ^ will be cut: = size of the drilling cover plate with water-soluble resin composition layer as the upper layer (Metal support is the lower layer) in a flat manner, for example, placed under 5 (rc) placed at room temperature (25. 〇 environment. In addition, thermal degradation accelerates the experimental temperature ^ and is in the water-soluble resin composition The curing temperature is higher and lower than the melting point. At a temperature higher than the melting point, the water-soluble resin composition dissolves and dissolves; = the properties possessed may not continue to exist, so it cannot be used as a cover for drilling. = Advance evaluation. Another--"If the temperature stability test is accelerated at a temperature lower than the curing temperature. ..., the accuracy of the opening position of the drilling cover plate is subject to the processing of the substrate, drilling There is a difference in the influence of factors such as the length of the head and the length of the control. Therefore, in order to compare the relative accuracy with the accuracy ratio, the available limbs can accelerate faster than the thermal deterioration of the real cattle, for example, 50 C, 1 hour. Method of opening =% before and after the experiment. Here, The rate of change of the hole position accuracy can be changed = the rate of change of the opening position (%) = (opening 12 after the thermal deterioration acceleration test 201247761 Position accuracy - the thermal deterioration before the accelerated position accuracy of the test before the thermal deterioration accelerated test The opening position accuracy X100 I is preferably within +10% of the change rate of the opening position accuracy before and after the thermal deterioration acceleration test condition, for example, 50 ° C for 1 hour. This means that before and after the thermal deterioration acceleration test, if the positional accuracy of the opening becomes small (if the accuracy is increased), the number 値 is negative, and if the position accuracy of the opening becomes large (if the opening position 1 is deteriorated), the number is positive, The greater the negative enthalpy, the better the performance against thermal degradation. The rate of change in the accuracy of the opening position before and after the accelerated thermal degradation test is preferably +, : more preferably within + 5%, more preferably. It is within -5%. ί 异: = The number of positional accuracy change rate (%) - see below is quite accurate for the hole position accuracy (_) is not ideal, still + different The purpose of our people is not to be old. Water soluble as: single, several kinds: A_ as water_aged 7 ^^2 Several kinds of water-soluble resin components are thermally dissolved as early or as a heat-soluble material of the water-soluble resin composition =^ or red No. 2 and formic acid is then coated on the metal support "to solution = formation in a solvent" The method of forming a layer of fat, which is a pre-game, which is dried to form at least a single layer of a water-soluble tree, and is bonded to a concrete layer or a bonding agent. The material layer is then subjected to a roll method, as long as it is industrially known, and the = soluble resin composition layer is manufactured. For example, the water-soluble resin composition _PJ is not particularly limited. Then, the shaft or other kneading machine constitutes a water-soluble resin composition layer method or the like on the release sheet or the τ-_ machine, etc. Further, 'the ‘genus==== 201247761 layer is formed in advance on the sheet on which the incisible dendritic resin composition is formed. The solution supporting the soluble resin composition is directly coated on the metal; =:; = dissolved

120t^l60tTS ； J；^：J 120〇C〜160〇C下保姓r u ν里Α從，、导乙岛，更宜在溫度声120°Γ〜isnv呆持1秒釦〜400秒鐘以使其乾燥，特別宜在溫 : C下保持20秒鐘〜3〇〇秒鐘以使苴齡^。者私乾燥溫度下的保持時間未達^秒“乙樹脂組成物炫或是因為使水溶性均勾。另一方面，當樹脂組成物層不声失蓋=的水溶性樹脂組成物的冷卻條件一般而言冷卻速 ίί欽冷夫關狀該水溶性樹脂組成物的冷卻條 t，轉了溫度25t〜4叱，在6G秒以内，以 1.5 C/私以上的冷卻速度使其冷卻。當然，冷卻終产必定在比水雜樹脂組成物的gj化溫度更低又兮、^ 卻終了溫度低於吹時，該蓋板會產生-，二;^ ίίΐ驟”因’故為較差的態樣。當該冷卻速度未達】.5°C /秒時，冷輕間會變長，可能會超過6()秒，故為較差的態樣。因此，關於冷卻條件，從溫度12(rc〜16〇t^h：^25〇c〜4(rc，宜在5。0秒以内，以2。(：/秒以上的冷卻速度冷卻，從溫度12〇。〇〜160C到溫度25°C〜40°C，更宜在40秒以内，以25t/^、以上的冷卻速度冷卻，從溫度120t〜160t到溫度25t〜4(rc，更宜在3。0秒朗，以3t：/秒以上的冷卻速度冷卻，從溫度12〇。卜 160 C到溫度25t〜4(TC，更宜在20秒以内，以4 5t/秒以上的冷卻速度冷卻，從溫度〗20°(：〜16(TC到溫度25t〜4(rc，最好是 14 201247761 在15秒以内，以6°c/秒以上的冷卻速度冷卻D 本發明之鑽孔用蓋板所使用的金屬支持箱紹，金屬支持箱的厚度通常為0.05〜0.5mmms為 =屬支持朗厚度未達⑽5mm，财觀加面j超i〇.5mm ’則在鑽孔加工 ί 關於峰_，宜域度95%以上的 ' JIS(Jap^ese^^^120t^l60tTS; J;^:J 120〇C~160〇C under the surname ru ν Α from,, the guide island, more suitable for temperature sound 120 ° Γ ~ isnv stay 1 second buckle ~ 400 seconds to To make it dry, it is especially preferable to keep it at a temperature of C for 20 seconds to 3 seconds to make it age. The holding time at the private drying temperature is less than 2 seconds. "The resin composition of the ethyl resin is dazzling or because the water solubility is hooked. On the other hand, when the resin composition layer does not lose the cover, the cooling condition of the water-soluble resin composition = In general, the cooling rate t of the water-soluble resin composition of the water-cooling resin composition is turned to a temperature of 25t to 4 Torr, and is cooled at a cooling rate of 1.5 C/private or less within 6 G seconds. The final production of cooling must be lower than the gj temperature of the composition of the water-containing resin. When the temperature is lower than the blowing temperature, the cover will produce -, 2; ^ ίίΐ "" because it is a poor condition. . When the cooling rate is less than .5 ° C / sec, the cold light will become longer, which may exceed 6 () seconds, so it is a poor condition. Therefore, regarding the cooling conditions, from the temperature 12 (rc ~ 16 〇 t ^ h: ^ 25 〇 c ~ 4 (rc, preferably within 5.0 seconds, with a cooling rate of 2. (: / sec or more, from the temperature 12 〇. 〇 ~ 160C to a temperature of 25 ° C ~ 40 ° C, more preferably within 40 seconds, cooling at a cooling rate of 25t / ^, above, from a temperature of 120t ~ 160t to a temperature of 25t ~ 4 (rc, more preferably 3.0 seconds, cooled at a cooling rate of 3t: / sec or more, from a temperature of 12 〇. Bu 160 C to a temperature of 25t ~ 4 (TC, more preferably within 20 seconds, cooling at a cooling rate of 45t / sec or more From the temperature of 20 ° (: ~ 16 (TC to temperature 25t ~ 4 (rc, preferably 14 201247761 within 15 seconds, cooling at a cooling rate of 6 ° c / sec or more D drilling cover plate of the present invention The metal support box used is usually 0.05~0.5mmms for the thickness of the support box. More than 95% of the 'JIS (Jap^ese^^^)

ToS so "If2'3〇04'3003 ' 1N3°'1N"' 10^〇：^〇 1085、8021專。金屬支持羯使用高純度的紹箱擊或提高咬入性，鱼水溶,j·生、'鑽頭勺衝接古4 丁了丨AA Μ /、 ^組成物對鑽頭的潤滑效果加乘， k冋加工孔_孔位歸度。糾，若在鮮的樹脂皮膜，與水溶性樹脂組成物性，，硬化性樹脂其中任一種。熱可塑性樹脂例如^^ „糸聚合，、醋酸乙湘旨系聚合物、氯乙烯系聚合物、聚“ 聚以及該等物質的共聚合物。熱硬化性樹脂例如系曰; 脂’氰酸醋系樹脂等。另外，本發明所使用的金屬支持；，可^ 用市售之在^屬箱上預先以習知方法塗布樹脂覆膜者。/ 另外，该紅色2號的作用，如前所述的，係添脂組成物巾，使結晶度提高。频果可使絲硬度縣^^树ToS so "If2'3〇04'3003 ' 1N3°'1N"' 10^〇 :^〇 1085, 8021. Metal support 羯 Use high-purity smashing or increase bite, fish water soluble, j·sheng, 'drill spoon rushed to ancient 4 Ding 丨AA Μ /, ^ composition of the lubrication effect of the drill bit, k冋Machining hole _ hole position reduction. Correction, if it is in a fresh resin film, it is composed of a water-soluble resin and a curable resin. The thermoplastic resin is, for example, a polymerization agent, a vinyl acetate polymer, a vinyl chloride polymer, a poly(poly) polymer, and a copolymer of these materials. The thermosetting resin is, for example, a crepe; a sulphuric acid vinegar resin. Further, the metal support used in the present invention can be applied to a commercially available resin coated film in advance by a conventional method. Further, the effect of the red No. 2, as described above, is to add a fat composition towel to improve the crystallinity. Frequency fruit can make silk hardness county ^^ tree

並，開孔位置精度達到優異的數值。因此，即使添加 J 膜中，也未發現所期待之作用效果。〇月曰復本愈明的鑽孔用蓋板，在堆疊板或多層板的鑽孔加工預定使用於鑽頭徑長在〇.〇5mm(p以上0 3mm(p以下的鑽孔加工’、中。特別適用於開孔位置精度相當重要的〇〇5mm(p以上〇.15_ 以下的小徑長用途’其中包含〇.〇5mm(p以上〇1〇5_^以下的極小徑長用途。本發明之鑽孔用蓋板的水溶性樹脂組成物層的厚度的構造相素而會有所差異，㈣常在001〜03mm 201247761 =0.02〜0.2mm的範圍内，更宜在⑽2〜〇 12mm的範圍内。若 ίί生成物層的厚度未達⑽—，則無法獲得充分的潤滑 =折知。另—方面，右水溶性樹脂組成物層的厚度超過〇 3mm，則树脂黏附在鑽頭上的情況會增加。 · 鑽孔用蓋板的各層的厚度，以如下方式測量。從鑽孔用性，組成物層面’用剖面拋光儀（日本電子Datum s_sec™np_hErsm__g)或超薄 1製EMUC7)，相對於水溶性樹脂組成物層朝 ^直方向將鑽細驗靖，之後用SEM (掃描型電子顯微鏡， ^irnmg Electron Microscope，KEYENCE 公司製 VE 78 ，方向觀察，在900倍的視野下測量銘層以及水溶性 ΐΐίΐΪ層的厚度。相對於1個視野測量5處位置的厚度，將其平均當作各層的厚度。以本發明之鑽孔用蓋板的鑽孔加玉，在對印刷基板材料， = ΪΪΐ板ί多層板，進行鑽孔加工時，係將銅綱“ 片堆疊’在其至少最頂面，以該蓋板的金屬支基板材料接綱方式配践蓋板，並㈣孔用蓋板的水浴性樹脂組成物層的那一面進行鑽孔加工。 [實施例] 以下揭示實施例、比較例，以具體説明本發明。另外，下述 =例2係表示本發明之實施形態的—個例子，並非以此為限。在ί貫施例中，將「聚乙二醇」簡稱為「PEG」，將「聚環氧乙烧」賴為「咖」，將「聚議旨」簡稱為「PEE」。 _ 表1實施例以及比較例的鑽孔用蓋板的製造過程中所使用的树脂、著色劑等原料的規格。 [表1] 16 201247761 區分 * — «> -p~--- 1X1 叫 PEO ΡΡΓ； - 商品名製造商備註樹月旨氧乙炫 ALKOXL11 明成化學工業股份有限公司 Mw=l !〇,〇〇〇 PEE~ 聚越酯 PEG20000 PAOGENPP-15 三洋化成股份有限公司 Mw=20,000 著色劑 (a) J^2號 Amaranth 矛丄茶製樂版伤有限公巧關東化學股份有限公司 Mw-1〇〇?〇〇〇 (〇) — — Cc) 號 Orange G p關東化學股份有限公司一核賓青色1號甲酸鈉 Daiwa化成股份有限公司 — 溶媒鑽頭鋁箔、!醇. ~~CFU020S~~ O.lmmt 一烫此斯化學股份有限公司三菱瓦斯化學股份有限公司 Tungaloy股份有限公司三菱鋁業股份有限公司 0.2mnup IS規格1100 〈實施例1 ；> 份有均分子量11G，_的聚環氧淡（明成化學工業股 :t ° I ’ alkoxlu)80重量份與重量平均分子量20〇〇二it二醇（二洋化成工業股份有限公司製PEG20000) 20重量份 & 成分為30%的方式’完全溶解於水與Me〇H的混合2 中時的水與Me〇H的比率為70重量份對％重量份。相對於該水溶性樹脂混合物的固體成分⑽重量份， =σ .重1份的紅色2號（關東化學股份有限公司製布其元全溶解。將該水溶性樹脂組成物的溶液用綱脉til在^面形成有厚度⑽顏的環氧樹脂皮膜的㈣（¾ 的科5度士0.lmm ’三菱減份有限公司製〕上，使乾_ 八户二f'、且成巧層的厚度為’職1，用乾燥機以12叱、5 “使其乾燥，再以31。〇/秒的冷外，、冷卻_溫度為跳，冷卻終Ϊ溫C 了溫产。心的冷°卩速度在30秒内從冷卻開始溫度冷卻到冷卻終 ^ ungaloy股份有限公司製CFU〇2〇s)、轉速：勘，〇⑻興、迷度.Z6m/min的條件，在鑽頭丨支3,〇〇〇hits的情況下， 17 201247761 4支鑽頭的鑽孔加工。 κίί ’/吏用防爆型乾燥機（ESPEC公司製SPHH-202)，在的^孔用境）下’ _出5Gxl°°mm的尺寸，將未使用水溶性樹脂組成物層為上層（金屬支持箱為产二。:平置’在50°C下放置1小時，之後，放置在室溫(25°C) 後，將5片厚度〇.2mm的銅箔堆疊板（CCL—HL832，甘5 vb面12μιη ’三菱瓦斯化學股份有限公司製）堆疊在一起，在水Γ性納旨喊物層在上的方式配置該鑽關蓋板，並在 7隹豐，岛堆疊板的下側配置抵板（背板），以鑽頭：〇2mm(p (ungaloy股份有限公司製CFU〇2〇s )、轉速：2〇〇,〇〇〇啊、進給 5,職的條件，在鑽頭1支3,000hits的情況下，進行 4支鑽頭的鑽孔加工。丁 f 3顯不出開孔位置精度Ave +3(j (脾）、開孔位置精度變化 ! ΔΑνε.+3σ (陴）、開孔位置精度變化率Ave+3 f C )'固化熱量a/mg)、結晶度、表面硬度表面硬，的標準偏差σ (N/mm2)、綜合判定結果。 <實施例2〜5 ’比較例1〜24> 關於貫_ ^〜5以及比較例1〜24，以實施例！為準，調勢 ^1以及表2所示的水溶性樹脂組成物，塗布在鋁箔上，經、紐、冷卻，製作鑽孔用蓋板。制j中，關-於實施例5，塗布、乾燥後的冷卻速度為2.0°C/秒，製。作鑽孔用蓋板。其冷卻開始溫度為12(rc，冷卻終了溫产為 2冷7$終2〇度Μ秒的冷卻速度在46秒内從冷卻開始溫&卻到 1外，關於比較例2、3、5、6、8、1G、11、13，塗布、乾後勺冷部速度為l.(TC/秒，製作鑽孔用蓋板。其、盍秒的冷卻速上^ 接著，使用該鑽孔用蓋板，以實施例丨為準，進行鑽孔加工。另外，以實施例1為準，用使用防爆型乾燥機（挞四/公司 18 201247761 製SPHH一202)，在5(rc下放置1小時，之後放置在室溫（25 Ϊίΐ的方法，製作熱劣化加速實驗後的鑽孔用蓋板，並進行鑽 <標準試料> 將重量平均分子量110,000的聚環氧乙烷（ALK0XL11，成化學工業股份有限公司製）以樹脂固體成分為30%的方 j 溶解於水與Me0H的混合溶液。此時的水與Me〇H的 1王重量份對30重量份。將相對於聚環氧乙烷1〇〇重量份添加了紅 2號5重量份的水雜_域⑽驗，以錢後的水溶性樹，成物層的厚度為a〇5mm的方式’用桿塗布器塗布在單面形J 厚度0.01mm之環氧樹脂皮膜的鋁箔（JIS規格π〇〇,厚度〇，愛銘業股份有限公司製）上，用乾燥機在下進行5 再以3.rC/秒的冷卻速度冷卻，製作鑽孔用蓋板。另外、，如部條件與實施例1相同。以此為結晶度測量用標準試料。 #接著，用防爆型乾燥機（ESPEC公司製SPHH—202)，在大軋開放（空氣環境）下，切割出5〇xl〇〇mm的尺寸，將未使用標準試料，以水溶性樹脂組成物層為上層（金屬 ^持泊為下層）的方式平置，在5(rc下放置1小時，之後，放置量環境下。將其當雜劣化加速實驗後的結晶度測 [表 2-11Moreover, the accuracy of the position of the opening is excellent. Therefore, even if the J film was added, the desired effect was not found. 〇月曰 The replica of the drilling cover plate, the drilling of the stacked plate or the multi-layer plate is scheduled to be used for the diameter of the drill bit at 〇.〇5mm (p above 0 3mm (drilling process below p', It is particularly suitable for 〇〇5mm (a small diameter long use of p or more 〇.15_ or less) which contains 〇.〇5mm (p or more 〇1〇5_^ or less). The structural phase of the thickness of the water-soluble resin composition layer of the drilling cover plate may vary, and (4) is usually in the range of 001 to 03 mm 201247761 = 0.02 to 0.2 mm, more preferably in the range of (10) 2 to 〇 12 mm. If the thickness of the layer of the ίί is less than (10)-, sufficient lubrication = fold is not obtained. On the other hand, if the thickness of the right water-soluble resin composition layer exceeds 〇3 mm, the resin adheres to the drill bit. The thickness of each layer of the drilling cover is measured as follows. From the drilling properties, the composition level 'with a profile polisher (Japanese electronic Datum s_secTMnp_hErsm__g) or ultra-thin 1 EMUC7), relative to The water-soluble resin composition layer will be drilled in the direction of the straight line, After that, the thickness of the inscription layer and the water-soluble layer was measured by a SEM (scanning electron microscope, ^irnmg Electron Microscope, VE 78 by KEYENCE, direction observation, and the position of the water-soluble layer was measured at 900 times. The thickness is averaged as the thickness of each layer. In the drilling of the drilling cover plate of the present invention, jade is added, and in the case of drilling a substrate for a printed substrate material, a slab, a copper plate is used. The sheet stack 'at at least the top surface thereof is provided with a metal plate substrate material of the cover plate to fit the cover plate, and (4) the hole is drilled with the side of the water bath resin composition layer of the cover plate. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples and comparative examples. The following examples 2 are examples of the embodiments of the present invention, and are not limited thereto. Polyethylene glycol is abbreviated as "PEG", "polyethylene oxide" is referred to as "coffee", and "poly" is referred to as "PEE". _ Table 1 Example and Comparative Example Drilling Cover The resin used in the manufacturing process of the board, Specification of raw materials such as toners [Table 1] 16 201247761 Division * — «> -p~--- 1X1 is called PEO ΡΡΓ; - Product Name Manufacturer Remarks Tree Moon Oxygen Ethyl ALKOXL11 Mingcheng Chemical Industry Co., Ltd. Mw =l !〇,〇〇〇PEE~ 聚越酯 PEG20000 PAOGENPP-15 Sanyo Chemical Co., Ltd. Mw=20,000 Colorant (a) J^2 Amaranth Spear Tea 版版版 Limited Gonggong Kanto Chemical Co., Ltd. Mw-1〇〇?〇〇〇(〇)————Cc) No. Orange G p Kanto Chemical Co., Ltd. One-core Bin Cyan No. 1 Sodium Formate Daiwa Chemical Co., Ltd. - Solvent Drill Aluminum Foil, ! Alcohol. ~~CFU020S~~ O.lmmt IHot Chemicals Co., Ltd. Mitsubishi Gas Chemical Co., Ltd. Tungaloy Co., Ltd. Mitsubishi Aluminum Corporation 0.2mnup IS Specification 1100 <Example 1 ;> Polyepoxy having a molecular weight of 11G, _ Light (Mingcheng Chemical Industry Co., Ltd.: t ° I ' alkoxlu) 80 parts by weight and weight average molecular weight 20 〇〇 di diol (PEG 20000 manufactured by Eryang Chemical Industry Co., Ltd.) 20 parts by weight & 'Completely dissolved in the mixing water with the ratio of water to Me〇H Me〇H in time of 2 parts by weight to 70% by weight of the parts. With respect to the solid content (10) parts by weight of the water-soluble resin mixture, = σ. 1 part of red No. 2 (Kuandong Chemical Co., Ltd.) is completely dissolved. The solution of the water-soluble resin composition is used for the solution (4) (3) of the epoxy resin film having a thickness of (10) is formed on the surface of the film (3⁄4 of the 5th grade 0.lmm 'Mitsubishi Subsidiary Co., Ltd.), so that the thickness of the _ 八八 two f', and the thickness of the layer For 'Occupation 1, use a dryer to 12 叱, 5 to make it dry, then 31. 〇 / sec cold outside, cooling _ temperature for jumping, cooling the final temperature C for warmth. Heart cold °卩The speed is cooled from the cooling start temperature to the final cooling in 30 seconds. ^Ungaloy Co., Ltd. CFU〇2〇s), speed: survey, 〇(8) Xing, 迷度.Z6m/min conditions, in the drill bit 3, 〇 In the case of 〇〇hits, 17 201247761 Drilling of 4 drill bits. κίί '/吏 Explosion-proof dryer (SPHH-202 made by ESPEC), under the hole of 'hole' _ out 5Gxl°°mm The size of the unused water-soluble resin composition layer is the upper layer (the metal support box is produced in two.: flat) placed at 50 ° C for 1 hour, After being placed at room temperature (25 ° C), five pieces of copper foil stacking plates (CCL-HL832, Gan 5 vb surface 12 μιη 'Mitsubishi Gas Chemical Co., Ltd.) of thickness 〇2 mm were stacked together in the leeches In the way of the character shouting layer, the drill cover is arranged, and the bottom plate (back plate) is arranged on the lower side of the island stacking board, and the bit is: 〇2mm (p (made by Ungaloy Co., Ltd.) CFU〇2〇s), speed: 2〇〇, 〇〇〇 ah, feed 5, job conditions, in the case of a drill 3,000hits, drilling of 4 drill bits. D3 Outlet position accuracy Ave +3 (j (spleen), opening position accuracy change! ΔΑνε.+3σ (陴), opening position accuracy change rate Ave+3 f C ) 'curing heat a / mg), crystallinity The surface hardness is hard, the standard deviation σ (N/mm2), and the comprehensive judgment result. <Examples 2 to 5 'Comparative Examples 1 to 24> Regarding the _^~5 and the comparative examples 1 to 24, the examples are given. The water-soluble resin composition shown in Table 2 and the water-soluble resin composition shown in Table 2 is coated on an aluminum foil, and the cover plate for drilling is prepared by cooling and cooling. Example 5, the cooling rate after coating and drying was 2.0 ° C / sec. It was used as a cover for drilling. The cooling start temperature was 12 (rc, the end of cooling was 2 cold 7 $ 2 Μ Μ Μ The cooling rate was from the cooling start temperature in the 46 seconds to the outside, and on the comparison examples 2, 3, 5, 6, 8, 1G, 11, and 13, the cold speed of the coated and dried spoon was 1. (TC / Second, a drilling cover plate is produced. The cooling rate of the leap second is then used. Next, the drilling cover is used, and drilling is performed according to the embodiment. In addition, in accordance with the first embodiment, an explosion-proof type dryer (Square/Company 18 201247761 made of SPHH-202) was used, and it was placed at 5 (rc for 1 hour, and then placed at room temperature (25 Ϊίΐ method, making heat). Degradation of the drilling cover plate after the accelerated test, and drilling <standard sample> Polyethylene oxide (ALK0XL11, manufactured by Seiko Chemical Co., Ltd.) having a weight average molecular weight of 110,000 was 30% of the resin solid content. The solution j is dissolved in a mixed solution of water and Me0H. At this time, 30 parts by weight of water and 1 part by weight of Me〇H are added. 5 parts by weight of red No. 2 is added to 1 part by weight of polyethylene oxide. The water miscellaneous _ domain (10) test, the water-soluble tree after the money, the thickness of the layer of the layer is a 〇 5 mm 'coated with a bar coater on a single-sided J-thickness of 0.01 mm thick epoxy film (JIS) The specification π〇〇, thickness 〇, manufactured by Ai Ming Co., Ltd.) is carried out by a dryer at 5 and then cooled at a cooling rate of 3.rC/sec to produce a cover plate for drilling. The same as in Example 1. This is the standard sample for crystallinity measurement. # Next, use explosion-proof Type dryer (SPHH-202 made by ESPEC), cut the size of 5〇xl〇〇mm under large rolling open (air environment), and use the standard sample without water-based resin composition layer (metal) ^Positioned to the lower layer) is placed flat, placed at 5 (rc for 1 hour, then placed under the amount of environment. The crystallinity after accelerated deterioration test) [Table 2-11]

[表 2-2] 19 201247761 區分樹脂著色劑曱酸納添加量 Wt% 溶媒冷卻速度 °C/sec 鑽頭徑 πιιηφ 標準試料組成摻合量 wt% 名稱添加量 wt% H20 ： MeOH 比較例1 A 100 - 0 0 7:3 3.1 0.20 3 比較例2 A 100 - 0 0 6:4 1.0 0.20 1 比較例3 A 100 - 0 0 7:3 1.0 0.20 2 比較例4 A 100 a 0.1 0 7:3 3.1 0.20 3 比較例5 A 100 a 0.1 0 6:4 1.0 0.20 1 比車交歹4 6 A 100 a 0.1 0 7:3 1.0 0.20 2 比車交列7 A 100 a 1 0 7:3 3.1 0.20 3 比較例8 A 100 a 5 0 6:4 1.0 0.20 1 比較例9 A 100 a 10 0 7:3 3.1 0.20 3 比較例10 A 100 b 0.1 0 6:4 1.0 0.20 1 比較例11 A 100 b 5 0 6 4 1.0 0.20 1 比較例12 A 100 c 0.1 0 7:3 3.1 0.20 3 比較例Π A 100 c 0.1 0 7:3 1.0 0.20 2 [表 2_3] 區分樹脂著色劑曱酸納添加量 wt% 溶媒冷卻速度 °C/sec 鑽頭徑 mm(p 標準試料組成摻合量 wt% 名稱添加量 wt% H2〇 : MeOH 比較例14 Β 100 - 0 0.25 7:3 3.1 0.20 3 比較例15 Β 100 - 0 0.5 7:3 3.1 0.20 3 比較例16 Β 100 - 0 0 7:3 3.1 0.20 3 比較例17 Β 100 a 0.5 0 7:3 3.1 0.20 3 比較例18 Β 100 a 10 0 7:3 3.1 0.20 3 比較例19 Β 100 b 0.25 0.25 7:3 3.1 0.20 3 比較例20 Β 100 c 0.25 0.25 7:3 3.1 0.20 3 比較例21 C 100 - 0 0 7:3 3.1 0.20 3 比較例22 C 100 a 0.1 0 7:3 3.1 0.20 3 比較例23 C 100 a 1 0 7:3 3.1 0.20 3 比較例24 C 100 a 10 0 7:3 3.1 0.20 3 [表 2-4] 20 201247761 ϊϊη ***------ -------------- ^著色劑溶媒區分組成摻合量名稱添加量甲酸納添加量 H20 : MeOH 冷卻速度鑽頭徑標準試料標準試料1 Wt% ---— wt% wt% °C/sec mrrup 100 一，—~ a 5 0 6:4 3.1 1 — ί示竿成料2 D 100 -—— a 5 0 7:3 1.0 - 2 标準咸料3 D too a 5 0 7:3 3.1 - 3[Table 2-2] 19 201247761 Distinguishing resin colorant Naphthalate sodium addition amount Wt% Solvent cooling rate °C/sec Bit diameter πιιηφ Standard sample composition Blending amount wt% Name addition amount wt% H20 : MeOH Comparative example 1 A 100 - 0 0 7:3 3.1 0.20 3 Comparative Example 2 A 100 - 0 0 6:4 1.0 0.20 1 Comparative Example 3 A 100 - 0 0 7:3 1.0 0.20 2 Comparative Example 4 A 100 a 0.1 0 7:3 3.1 0.20 3 Comparative Example 5 A 100 a 0.1 0 6:4 1.0 0.20 1 Comparing with the car 4 6 A 100 a 0.1 0 7:3 1.0 0.20 2 Comparing the car 7 A 100 a 1 0 7:3 3.1 0.20 3 Comparative example 8 A 100 a 5 0 6:4 1.0 0.20 1 Comparative Example 9 A 100 a 10 0 7:3 3.1 0.20 3 Comparative Example 10 A 100 b 0.1 0 6:4 1.0 0.20 1 Comparative Example 11 A 100 b 5 0 6 4 1.0 0.20 1 Comparative Example 12 A 100 c 0.1 0 7:3 3.1 0.20 3 Comparative Example Π A 100 c 0.1 0 7:3 1.0 0.20 2 [Table 2_3] Distinguishes the resin colorant sodium phthalate addition amount wt% Solvent cooling rate ° C/sec bit diameter mm (p standard sample composition blending amount wt% name addition amount wt% H2〇: MeOH Comparative Example 14 Β 100 - 0 0.25 7:3 3.1 0.20 3 Comparative Example 15 Β 100 - 0 0.5 7:3 3.1 0.20 3 Comparative Example 16 Β 100 - 0 0 7:3 3.1 0.20 3 Comparative Example 17 Β 100 a 0.5 0 7:3 3.1 0.20 3 Comparative Example 18 Β 100 a 10 0 7:3 3.1 0.20 3 Comparative Example 19 Β 100 b 0.25 0.25 7:3 3.1 0.20 3 Comparison Example 20 Β 100 c 0.25 0.25 7:3 3.1 0.20 3 Comparative Example 21 C 100 - 0 0 7:3 3.1 0.20 3 Comparative Example 22 C 100 a 0.1 0 7:3 3.1 0.20 3 Comparative Example 23 C 100 a 1 0 7 :3 3.1 0.20 3 Comparative Example 24 C 100 a 10 0 7:3 3.1 0.20 3 [Table 2-4] 20 201247761 ϊϊη ***------ ------------- - ^Colorant Solvents Composition Composition Admixture Name Addition Amount of Natrile Addition H20 : MeOH Cooling Rate Bit Diameter Standard Sample Standard Sample 1 Wt% ---- wt% wt% °C/sec mrrup 100 One, —~ a 5 0 6:4 3.1 1 — 竿竿 2 2 D 100 --—— a 5 0 7:3 1.0 - 2 Standard salt 3 D too a 5 0 7:3 3.1 - 3

樹脂組成A 樹脂組成B 樹脂組成C 樹脂組成D PEO : PEG=80重量份：20重量份 PEO : PEG = 20重量份：80重量份 PEE : PEG=20重量份：80重量份 PE0100重量份 <著色劑> a 紅色2號 b 黄色5號 c 青色1號 — 非添加 [表 3-1] 區分開孔位置精度 DSC 表面硬度綜合判定 Ave. + 3o 未處理 50°C、lhr 後 Ave. σ 未處理 μιτι 50°C ' lhr後 μιη Δ μνη 變化率 % 固化溫度 °c 固化 J/mg 結晶度固化 Ά 度 °C 固化熱量 J/mg 結晶度未處理 N/mm2 50°C ' lhr後 N/mm2 未處理 N/mm2 50°C、 lhr後 N/mm2 實施例1 18.7 15.6 -3.1 -16.6% 38.1 -137 1.23 37.1 •143 1.29 13.5 11.3 1.2 1.0 〇 1.2 〇實施例2 17.1 16.1 -1.0 -5.8% 38.9 -138 1.24 37.8 -140 1.26 9.6 11.1 1.2 實施例3 20.6 19.9 -0.7 -3.4% 47.3 -134 1.21 43.9 -144 1.30 9.4 9.4 0.8 0.4 〇實施例4 18.6 18.1 -0.5 -2.7% 39.5 -147 1.32 38.8 -135 L22 9.6 10.9 0.6 0.4 ◎ 實施例5 23.5 23.0 -0.5 -2.0% 42.3 -134 1.21 43.6 -135 1.22 12.3 11.7 1.1 0.9 〇 [表 3-2] 21 201247761Resin composition A Resin composition B Resin composition C Resin composition D PEO : PEG = 80 parts by weight: 20 parts by weight PEO: PEG = 20 parts by weight: 80 parts by weight of PEE: PEG = 20 parts by weight: 80 parts by weight of PE0 100 parts by weight <Colorant> a Red No. 2 b Yellow No. 5 c Cyan No. 1 - Non-addition [Table 3-1] Separation hole position accuracy DSC Surface hardness comprehensive judgment Ave. + 3o Untreated 50°C, 1hr after Ave. σ Untreated μιτι 50°C ' lhr post μιη Δ μνη rate of change % curing temperature °c curing J/mg crystallinity curing degree °C curing heat J/mg crystallinity untreated N/mm2 50°C 'lhr after N/ Mm2 untreated N/mm2 50°C, 1 hour after N/mm2 Example 1 18.7 15.6 -3.1 -16.6% 38.1 -137 1.23 37.1 •143 1.29 13.5 11.3 1.2 1.0 〇1.2 〇Example 2 17.1 16.1 -1.0 -5.8% 38.9 -138 1.24 37.8 -140 1.26 9.6 11.1 1.2 Example 3 20.6 19.9 -0.7 -3.4% 47.3 -134 1.21 43.9 -144 1.30 9.4 9.4 0.8 0.4 〇Example 4 18.6 18.1 -0.5 -2.7% 39.5 -147 1.32 38.8 - 135 L22 9.6 10.9 0.6 0.4 ◎ Example 5 23.5 23.0 -0.5 -2.0% 42.3 -134 1.21 43 .6 -135 1.22 12.3 11.7 1.1 0.9 〇 [Table 3-2] 21 201247761

區分開孔位置精度 DSC 表面硬度綜合 h 定 Ave. + 3a 未處理 50t 、 lhr後 Ave. c τ 未理 μω 50°C ' lhr後 μηι Δ μιη 變化率 % 固化溫度 °c 固化熱量 J/mg 結晶度固化溫度 °C 固化熱量 J/mg 結晶度未處理· N/mm2 50°C ' lhr後 N/mm2 未處理 N/mm2 50°C、 lhr後 N/mm2 比較例1 20.5 24.9 4.4 21.5% 35.8 -108 0.97 36.2 -107 0.96 6.1 6.6 2.1 2.4 X 比較例2 24.9 32.0 7.1 28.5% 45.4 0.60 9.0 11.0 0.4 2.5 XX 比較例3 36.3 36.4 0.1 0.3% 41.5 -134 1.20 40.9 -137 1.22 14.9 15.9 1.3 1.7 X 比較例4 18.5 23.8 5.3 28.6% 41.2 -121 1.09 40.1 -129 1.16 7.2 9.3 1.8 1.9 Δ 比較例5 23.5 24.2 0.7 3.0% 46.3 1.10 8.0 9.0 0.3 0.4 Δ 比較例6 36.4 37.9 1.5 4.1% 40.6 -116 1.04 40.8 -119 1.06 13.6 8.9 0.7 0.5 X 比較例7 18.8 23.1 4.3 22.9% 40.5 -126 1.14 39.9 -131 1.18 4.9 9.6 0.8 2.6 Δ 比較例8 25.3 24.5 -0.8 -3.2% 46.6 1.00 8.0 9.0 0.2 0.3 Δ 比較例9 18.5 23.0 4.5 24.3% 41.5 -128 1.15 40.7 -137 1.23 5.9 6.5 1.4 1.5 Δ 比較例10 26.2 29.5 3.3 12.6% 46.2 1.30 7.0 7.0 0.5 0.4 Δ 比較例11 26.5 29.2 2.7 10.2% 46.7 1.00 6.0 7.0 0.6 0.2 Δ 比較例12 26.2 31.4 5.2 19.8% 39.4 -109 0.98 39.1 -118 1.06 15.0 8.6 1.0 1：6 X 比較例13 43.9 45.3 1.4 3.2% 40.0 •112 1.00 40.6 -115 1.03 15.9 16.1. 0.4 1.4 XXSeparation hole position accuracy DSC Surface hardness comprehensive h Determine Ave. + 3a Untreated 50t, lhr after Ave. c τ Untreated μω 50°C ' lhr post μηι Δ μιη Rate of change % Curing temperature °c Curing heat J/mg Crystallization Degree of curing temperature °C Curing heat J/mg Crystallinity untreated · N/mm2 50°C ' After lhr N/mm2 Untreated N/mm2 50°C, lhr after N/mm2 Comparative Example 1 20.5 24.9 4.4 21.5% 35.8 -108 0.97 36.2 -107 0.96 6.1 6.6 2.1 2.4 X Comparative Example 2 24.9 32.0 7.1 28.5% 45.4 0.60 9.0 11.0 0.4 2.5 XX Comparative Example 3 36.3 36.4 0.1 0.3% 41.5 -134 1.20 40.9 -137 1.22 14.9 15.9 1.3 1.7 X Comparative Example 4 18.5 23.8 5.3 28.6% 41.2 -121 1.09 40.1 -129 1.16 7.2 9.3 1.8 1.9 Δ Comparative Example 5 23.5 24.2 0.7 3.0% 46.3 1.10 8.0 9.0 0.3 0.4 Δ Comparative Example 6 36.4 37.9 1.5 4.1% 40.6 -116 1.04 40.8 -119 1.06 13.6 8.9 0.7 0.5 X Comparative Example 7 18.8 23.1 4.3 22.9% 40.5 -126 1.14 39.9 -131 1.18 4.9 9.6 0.8 2.6 Δ Comparative Example 8 25.3 24.5 -0.8 -3.2% 46.6 1.00 8.0 9.0 0.2 0.3 Δ Comparative Example 9 18.5 23.0 4.5 24.3 % 41.5 -128 1.15 40.7 -137 1 .23 5.9 6.5 1.4 1.5 Δ Comparative Example 10 26.2 29.5 3.3 12.6% 46.2 1.30 7.0 7.0 0.5 0.4 Δ Comparative Example 11 26.5 29.2 2.7 10.2% 46.7 1.00 6.0 7.0 0.6 0.2 Δ Comparative Example 12 26.2 31.4 5.2 19.8% 39.4 -109 0.98 39.1 -118 1.06 15.0 8.6 1.0 1:6 X Comparative Example 13 43.9 45.3 1.4 3.2% 40.0 •112 1.00 40.6 -115 1.03 15.9 16.1. 0.4 1.4 XX

[表 3-3] 區分開孔位置精度 DSC 表面硬度綜合判定 Ave. + 3o 7 t處理 50°C、lhr 後 Ave. σ 未 k 理 μηι 50°C ' lhr後 μηι Δ μηι 變化率 % 固化溫度 °C 固化熱量 J/mg 結晶度固化溫度 °C 固化熱量 J/mg 結晶度未處理 N/mm2 50°C、 lhr後 N/mm2 未處理 N/mm2 50°C ' lhr後 N/mm2 比較例】4 16.3 18.4 2.1 12.9% 47.2 -135 1.22 45.3 -130 1.17 11.4 8.9 4.4 0.7 Δ Δ 比較例15 16.7 17.7 1.0 6.0% 45.8 -134 1.21 45.1 -144 1.30 11.0 7.3 2.4 0.7 比較例16 15.1 19.9 4.8 31.8% 39.1 -119 1.07 37.9 -113 1.02 5.8 7.1 2.2 2.1 X 比較例17 16.8 18.9 2.1 12.5% 38.1 -139 1.25 37.3 -140 1.26 8.4 10.4 0.6 2.0 Δ 比較例18 19.5 23.5 4.0 20.5% 40.1 -141 1.27 40.7 -143 1.29 8.0 7.0 1.8 1.2 比較例19 18.9 17.5 -1.4 -7.4% 41.6 -138 1.24 40.9 -132 1.19 15.7 13.7 6.2 0.8 Δ 比較例20 19.9 21.5 1.6 8.0% 41.6 -145 1.31 41.2 -153 1.38 6.9 8.4 0.3 0.5 △ 比較例21 16.0 19.0 3.0 18.8% 37.0 -104 0.94 36.8 -104 0.94 4.9 7.7 2.4 2.6 X 比較例22 17.5 22.9 5.4 30.9% 32.2 -130 1.17 35.1 -138 1.24 7.2 8.1 0.4 0.4 X 比較例23 18.3 20.7 2.4 13.1% 37.9 -141 1.27 35.3 -122 1.10 7.6 7.8 1.2 0.9 △ 比較例24 19.4 22.6 3.2 16.5% 38.5 -131 1.18 41.4 -117 1.05 6.5 7.9 0.4 0.7 Δ [表 3-4] 22 201247761[Table 3-3] Separation hole position accuracy DSC Surface hardness comprehensive judgment Ave. + 3o 7 t treatment 50 ° C, 1 hr after Ave. σ not k μ μηι 50 ° C ' lhr after μηι Δ μηι change rate % curing temperature °C Curing heat J/mg Crystallinity curing temperature °C Curing heat J/mg Crystallinity untreated N/mm2 50°C, lhr after N/mm2 Untreated N/mm2 50°C 'lhr after N/mm2 Comparative example 】4 16.3 18.4 2.1 12.9% 47.2 -135 1.22 45.3 -130 1.17 11.4 8.9 4.4 0.7 Δ Δ Comparative Example 15 16.7 17.7 1.0 6.0% 45.8 -134 1.21 45.1 -144 1.30 11.0 7.3 2.4 0.7 Comparative Example 16 15.1 19.9 4.8 31.8% 39.1 -119 1.07 37.9 -113 1.02 5.8 7.1 2.2 2.1 X Comparative Example 17 16.8 18.9 2.1 12.5% 38.1 -139 1.25 37.3 -140 1.26 8.4 10.4 0.6 2.0 Δ Comparative Example 18 19.5 23.5 4.0 20.5% 40.1 -141 1.27 40.7 -143 1.29 8.0 7.0 1.8 1.2 Comparative Example 19 18.9 17.5 -1.4 -7.4% 41.6 -138 1.24 40.9 -132 1.19 15.7 13.7 6.2 0.8 Δ Comparative Example 20 19.9 21.5 1.6 8.0% 41.6 -145 1.31 41.2 -153 1.38 6.9 8.4 0.3 0.5 △ Comparative Example 21 16.0 19.0 3.0 18.8% 37.0 -104 0.94 36.8 -104 0.94 4.9 7.7 2.4 2.6 X Comparative Example 22 17.5 22.9 5.4 30.9% 32.2 -130 1.17 35.1 -138 1.24 7.2 8.1 0.4 0.4 X Comparative Example 23 18.3 20.7 2.4 13.1% 37.9 -141 1.27 35.3 -122 1.10 7.6 7.8 1.2 0.9 △ Comparative Example 24 19.4 22.6 3.2 16.5% 38.5 -131 1.18 41.4 -117 1.05 6.5 7.9 0.4 0.7 Δ [Table 3-4] 22 201247761

區分開孔位置精度' Ave. + 3o 未處理 μιη 50°C ' lhr後 μιη Δ μηι 變化率 % 標準試料1 標準試料2 標準試料3 未處理 50°C、lhr後固化熱量 J/mg -110 •112 -111 固化溫度VDistinguish hole position accuracy ' Ave. + 3o Untreated μιη 50°C ' lhr after μιη Δ μηι Change rate % Standard sample 1 Standard sample 2 Standard sample 3 Untreated 50°C, 1hr post-curing heat J/mg -110 • 112 -111 curing temperature V

DSC 表面硬度DSC surface hardness

Ave. σ 固化溫度°c 結晶度 1.00 1.00 1.00 固化熱量 J/mg 結晶度Ave. σ curing temperature °c crystallinity 1.00 1.00 1.00 curing heat J/mg crystallinity

未處理 N/mmJ 50°C、 llii.後 N/mm2 未處理 N/mm2 、後 plr ο Π N/ 綜合判定 -112 -110 -111 1.02 0.98 1.00 [表4] 综合判定基準效果效果 claim要件 claim要件開扎位置精度變化率（％、開孔位置精度（μιη) 結晶度表面硬度（N/mm2) 50 C、lhr 後 50°C、lhr 後未處理未處理 Ανβ. + 3σ Ave. + 3o Ave. σ ◎ 實施例 '**'·*— 0以下 21以下 1.3以上 8.5以上 1.0以下 ο 實施例 +5以下 23以下 1.2以上 8.5以上 1.5以下 ο Δ 實施例 +10以下 25以下 1.2以上 8.5以上 2.0以下 Δ 比較例 +30以下 30以下 1.0以上 X 比較例 +50以下 40以下 0.8以上 XX 比較例 50以下 0.6以上 1)結晶度在本發明中，關於水溶性樹脂組成物的結晶度測量方法，係對所版付之水浴性樹脂組成物使用DSC (示差掃描熱量計，Untreated N/mmJ 50°C, llii. After N/mm2 Untreated N/mm2, Post prl ο Π N/ Comprehensive judgment -112 -110 -111 1.02 0.98 1.00 [Table 4] Comprehensive judgment benchmark effect effect claim claim Requirement opening position accuracy change rate (%, opening position accuracy (μιη) crystallinity surface hardness (N/mm2) 50 C, 50°C after lhr, untreated untreated Ανβ. + 3σ Ave. + 3o Ave after 1hr σ ◎ Example '**'·*—0 below 21, 1.3 or more, 8.5 or more, 1.0 or less. Example +5 or less, 23 or less, 1.2 or more, 8.5 or more and 1.5 or less. Δ Example +10 or less, 25 or less, 1.2 or more, 8.5 or more. The following Δ Comparative Example + 30 or less 30 or less 1.0 or more X Comparative Example + 50 or less 40 or less 0.8 or more XX Comparative Example 50 or less 0.6 or more 1) Crystallinity In the present invention, the method for measuring the crystallinity of the water-soluble resin composition is DSC (differential scanning calorimeter) is used for the water-based resin composition to be applied.

Nano technology .製 DSC6220 )。 ^條件為：從3(TC升溫到100t：之後，在lOOt：保持3分鐘，指著’從UKTC冷卻到3(TC之後，在30°C保持3分鐘，此時升溫道度f+π：/分，冷卻速度為一3。(：/分。將該循環實施2次，算，第2次降溫時的固化熱量。此時，用1〇mg的水溶性樹脂組成彩試，進行測量’從所得到的資料算出每lmg試料的固化熱量，網其當作水溶性樹脂組成物試料的固化熱量。 …' 另一方面，對重量平均分子量（Mw) 110,000的聚環氧乙尸 23 201247761 (明成工業化學股份有限公司製ALK〇XU1) 100重量色2號5重量份，將其當作標準樹脂組成物（A) 成物的結晶度’ _用DSC，算出第2次降溫量’將該固化熱量定義為結晶度1.0。 … 接著’將該水雜樹驗成赋料_化歸除組成物（A)的固化熱量，算出水溶性樹脂組成物試料的社晶产。試料的結晶度=試料的固化熱量+標準樹脂組成物（A) ^固化熱量 2) 固化溫度在本發明中，水溶性樹脂組成物的固化溫度的測量條件，係使用與1)的結晶度相同的條件，將第2姆溫發峰的峰頂溫度當作固化溫度使用。 …尖峄 3) 表面硬度 f本發明中，關於水溶性樹脂組成物層的表面硬度，係從鑽孔用蓋板的垂直上部，用動態超微小硬度計（島津製作份限f司製DUH-211)，在壓頭：Triangularll5、試料受力：1〇_、負荷速度：0.7316mN/sec、負荷保持時間：1()sec、帕松比：〇〇7 ，條件下’從鑽孔用蓋板的垂直上部測量任意1〇點的水溶性樹脂，成物層的表面硬纟（馬氏硬度）。算出此時所得到的表面硬度的平均値與標準偏差σ。 4) 鑽孔加工在本發明中，對各樣本按照以下條件進行鑽孔加工。堆疊度〇.2mm的銅箔堆疊板（CCL—HU32，銅箔兩 =2μηι ’二菱瓦斯化學股份有限公司製），在其上以水溶性樹脂，、且成物層在上的方式配置鑽孔用蓋板’在所堆疊之銅箔堆疊板的 :側配置抵板（背板），使用〇_2mm(p (CFU〇2〇s，Tungal〇y股份 ^限公司製）的鑽頭，以轉速·· 200,000rpm、進給速度：2 6m/min 的加工條件，在鑽頭1支3,000hits的情況下進行鑽孔加工。 5) 開孔位置精度在本發明中，鑽孔用蓋板的開孔位置精度，係用開孔分析儀 24 201247761 (日立ViaMechanics製ΠΑ-1ΑΜ)測量在所堆疊之的最下層板的背面上的3，_個開孔位置與缺座標 j 1支鑽頭的平均値與標準偏差⑷，算財均値+ 3讀==鼻之後’算出鑽頭的「平均値+ 3σ」的平均値作為鑽孔加工整^ .開孔位置精度，並表列記錄之。算式如下：豆、 [式1] 鑽孔加工整體的開孔位置精度（μηχ) 鑽頭支數 Σ鑽頭的「平均値+3σ 圖式簡單說明】圖式圖1係實施例以及比較例的蓋板的結晶度對開孔位置精度的圖2係貫施例以及比較例的蓋板的表面硬度的標準偏差〇開孔位置精度的圖式。曰 rfr 日日度圖3係實施例以及比較例的蓋板的開孔位置精度Α對結的圖式。度的圖式圖4係實施例以及比較例的蓋板的開孔位置精度△對表面硬【主要元件符號說明】盖 25Nano technology. DSC6220). ^ The condition is: from 3 (TC warming to 100t: after, at lOOt: hold for 3 minutes, pointing to 'cooling from UKTC to 3 (after TC, hold at 30 ° C for 3 minutes, then warming the degree f + π: /min, the cooling rate is one. (: / min. This cycle is carried out twice, and the heat of curing at the second cooling is calculated. At this time, a color test is performed with 1 〇mg of water-soluble resin, and measurement is performed' From the obtained data, the curing heat per 1 mg of the sample was calculated, and the net was used as the curing heat of the sample of the water-soluble resin composition. ... On the other hand, the polyethylene oxide body 23 with a weight average molecular weight (Mw) of 110,000 was 201247761 ( ALK〇XU1 by Mingcheng Industrial Chemical Co., Ltd.) 5 parts by weight of 100% by weight of No. 2, which is regarded as the standard resin composition (A) Crystallinity of the product ' _ using DSC to calculate the second cooling amount ' The heat of curing is defined as the degree of crystallinity of 1.0. Then, the water is mixed with the heat of the composition (A), and the heat of the composition of the water-soluble resin composition is calculated. The crystallinity of the sample = Curing heat of the sample + standard resin composition (A) ^ curing heat 2) curing temperature at In the present invention, the curing temperature of the water-soluble resin composition is measured under the same conditions as the crystallinity of 1), and the peak top temperature of the second temperature peak is used as the curing temperature. In the present invention, the surface hardness of the water-soluble resin composition layer is from the vertical upper portion of the drilling cover plate by a dynamic ultra-fine hardness tester (Shimadzu production limit F-DUH-211), in the indenter : Triangularll5, sample force: 1〇_, load speed: 0.7316mN/sec, load holding time: 1 () sec, Passon's ratio: 〇〇7, under the condition 'measured from the vertical upper part of the drilling cover 1 point of water-soluble resin, the surface of the layer is hard (Martens hardness). The average 値 and standard deviation σ of the surface hardness obtained at this time were calculated. 4) Drilling processing In the present invention, each sample was subjected to drilling processing under the following conditions. A copper foil stacking plate (CCL-HU32, copper foil two = 2μηι' manufactured by Mitsubishi Gas Chemical Co., Ltd.) with a stacking degree of 22 mm, with a water-soluble resin thereon, and a drill layer is placed thereon. The hole cover plate 'is disposed on the side of the stacked copper foil stacking plate (back plate), using a drill bit of 〇_2 mm (p (CFU〇2〇s, manufactured by Tungal〇y Co., Ltd.)) The machining conditions of the rotation speed··200,000 rpm and the feed rate: 2 6 m/min are drilled in the case of one 3,000 hits of the drill. 5) Hole position accuracy In the present invention, the drilling cover is opened. Hole position accuracy, using the hole analyzer 24 201247761 (Hitachi ViaMechanics ΠΑ-1ΑΜ) to measure the average 値 of the 3,_open position on the back side of the stacked lowermost board and the missing bit j 1 bit Calculate the average value of the "average 値 + 3σ" of the drill as the standard deviation (4), calculate the balance of the money + 3 read = = after the nose. The calculation formula is as follows: Bean, [Formula 1] Overall hole position accuracy (μηχ) of the drilling process. Drill count ΣDrill bit "Average 値+3σ Schematic diagram" FIG. 1 is a cover of the embodiment and the comparative example. Fig. 2 is a diagram showing the accuracy of the opening position and the standard deviation of the surface hardness of the cover sheet of the comparative example, and the accuracy of the opening position. 曰rfr Day and day Fig. 3 is a cover of the embodiment and the comparative example. The accuracy of the hole position of the plate is the pattern of the knot. The figure of the figure is the accuracy of the opening position of the cover plate of the embodiment and the comparative example. △ The surface is hard [Description of main component symbols] Cover 25

Claims

201247761 VII. Patent application scope: : l. A drilling cover plate for stacking boards or multi-layer boards, and presenting the water-soluble resin composition cage of the metal support _ at least one side - ΐίΓ Containing water-soluble resin, water-soluble lubricant, and hydrazine, 3, basal ice [(4·weil-1-naphthyl)azo], trisodium salt (red 2, water-soluble resin composition layer' At the temperature of 25^ ΐ, the temperature starts from 12GC to 16G °C to the end of the cooling temperature. In the second state, the crystallinity of the water-soluble resin composition is cooled at a cooling rate of hunger/second or more. The crystallinity of the composition is 1.2 or more. The standard deviation of the surface hardness is below β 2 , and the surface hardness is 8.5 N/mm 2 or less / mm 2 or less. 2. For the drilling cover plate according to the scope of the patent application, the oxygen and the polyolefin B The water-soluble lubricant is a polyethylene glycol, and the water-soluble lubricant is polyethylene glycol. The drilling cover plate according to item j of the patent application scope, wherein the addition amount is relative to the a water-soluble resin and the water-soluble lubricant. The weight of 0.01 part by weight is 0.01 part by weight or more and 1 〇 The following are the following: j. For the drilling cover plate of the patent model _ ί, the water-soluble resin composition in the basin further contains sodium formate. 5. The drilling cover plate according to item 4 of the patent application scope, in the basin The water-soluble resin and the water-soluble lubricant are more than 0.01 parts by weight and not more than 15 parts by weight. f. The drilling cover plate of the fourth aspect of the patent scope of claim 4, Lizhong, ; J Jinghe _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 0.05m or more 03mm (p below 26 201247761 stacking plate or multi-layer plate iron hole processing. 8. The drilling cover plate according to claim 1 of the patent scope, wherein the metal support box has a thickness of 0.05 mm or more The thickness of the water-soluble resin composition layer of 0.5 mm or less is 0.01 mm or more and 0.3 mm or less.