201211235 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種固定 十工一 / 研磨粒細線切割器用水溶性加工 液，洋細而&，係關於一 石夕晶圓進行切斷加卫時所:藉由蚊研磨粒細線切割器對 π使用之固定研磨粒細線切割器用 水溶性加工液。 【先前技術】 ，重要的是提高矽晶圓之 ，雖利用游離研磨粒方式 為實現矽晶圓之製造成本之降低 切斷加工技術。於矽晶圓之加工中 之細線切割器所進行之切斷為主流，但於游離研磨粒方式之 加工中，存在以下各種問題。 指出有以下等負面效果之問題：（1)@使用於油劑中分散 有研磨粒之漿料作為加工液，故游離研磨粒與切屑之分離較 為困難。（2)細線行走速度有限制，且於加工效率之提高方 面有極限。（3)為減少截口損失(kerf loss)而使細線細線化之 情形時，加工中發生斷線，良率降低。（4)為減少截口損失 而使研磨粒微粒化之情形時，漿料黏度上升，使截口損失增 多。 對於此種問題，最近開發有於鋼琴線等細線表面，藉由電 鍍或樹脂黏合劑等而固定有金剛石研磨粒之固走研磨粒細 線切割器（專利文獻1)。使用固定研磨粒細線切割器加工脆 性材料之情形時，以潤滑、冷卻、所產生之切屑之分散為目 100127516 4 201211235 的而使用加讀。作為該加工液’若亦結合賴性 々 考慮’則較佳為使用水溶性加工液。鈇 續等 …、句，於被切材料A a 之情形時，與一般材料相比，切屑與加 •石夕 „ 工液之反應性較离 石夕屬（切屑）與加讀巾之水分級起反應㈣生氫。 之虞。因此，理想的是財之反應性得到抑制二易燃 就此觀點而言，提出有如專利文獻2所示之加工液。之’自 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特願2〇〇1_〇5485〇 [專利文獻2]曰本專利特願2〇〇3_〇82334 【發明内容】 (發明所欲解決之問題) 然而’已知近年來藉由提高加工精度，而使切屬變細，如 專利文獻2所示之加I液無法得到充分之穩定性。尤其是: 知此入有切屑之加工液之黏度上升而產生各種問題。又，於 大里地s有水分且pH為驗性之加工液之情形時不僅存在 產生乳之問題，而且存在產生增黏、凝膠化之問題。 加工液之增黏、凝膠化產生下述問題： ⑴由細―人之導人油量發生變化，厚度不均變大 品品質之劣化）。 (2) 產生細線滑動，細線發生斷線（良率之降低）。 (3) 下-步驟中之清潔變得困難（晶圓間之切屑、油劑之除 100127516 201211235 去困難）。 ()油;^之可命而更換液量增加(成本增加 於本么明中，其課題在於提供—種固定研磨粒細線 切割裔用水溶性加工液，其可抑制混人有切屑之加工液之增 黏’抑制加工液與切叙反應而可抑制氫之產生，進而可抑 制加工液之增黏、凝膠化。 (解決問題之手段） 發現以下 本發明者等人為解決±述問題而進行努力研究， 之事項： ⑴由S1切屑之混人所致之黏度上升係由於混人之S1_ 係微粉，又Si切屑之分散性差所致。 /上述黏度之上升可I!由使加工液中含有既定之水溶性 南分子來提高Si切屑之分散性而解決。 (3)於加工液中含有&切屑之愔 月 形時，存在Si切屑與加工 液反應而產生氫之情形。 W於大量地含有水分之加工液之情形時，因含有以切 屑，故存在產生增黏、凝膠化之情形。 (5)上述（3)及(4)之問題可藉由使 一 尺加工液中含有既定之水 溶性高分子而解決。 發明 本發明者等人針對上述問題進行努力研究’從而完成以下 明。 第1本發明係—翻定研贿細線切抑用水溶性加工 100127516 6 201211235 液（以下有時稱為「本發明之加工液」）’其含有：（A)自聚 乙烯0比咯。定酮及包含乙烯基°比"各咬3同之共聚合物中選擇之 至少一耩以上之水溶性高分子、及(B)水。 . 本發明之加工液藉由含有既定之水溶性高分子作為(A)成 分，而於加工液中含有石夕粉之情形時，可提高石夕粉之分散 性，可抑制含有矽粉之加工液之黏度上升。又’可抑制加工 液與矽粉反應而產生氫，同時可抑制含有矽粉之加工液之增 黏、凝膠化。 於第1本發明中，較佳為上述(A)成分之重量平均分子量 為 2,000〜1，〇〇〇,〇〇〇。 於第1本發明中，較佳為將固定研磨粒細線切割器用水溶 性加工液整體之質量設為100質量％，上述(A)成分之含量 設為0.02質量％以上7質量％以下。 第1本發明之固定研磨粒細線切割器用水溶性加工液，較 佳為其更含有（C)多元叛酸之驗金屬鹽（aikali salt)。較佳為 將固定研磨粒細線切割器用水溶性加工液整體之質量設為 100質量％ ’則上述(C)成分之含量為0.01質量％以上1〇質 量％以下。本發明之加工液藉由含有多元羧酸之鹼金屬鹽作 為(C)成分，而容易賦予分散性、洗淨性、财腐姓性。 第1本發明之固定研磨粒細線切割器用水溶性加工液，較 佳為其更含有（D)自一醇類、一醇_1類及聚氧伸烧二醇類所 組成之群組中選擇之一種以上。較佳為將固定研磨粒細線切 100127516 7 201211235201211235 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a water-soluble processing fluid for a fixed work-in-one/abrasive fine wire cutter, which is cut and reinforced with respect to a stone wafer. At the time: a water-soluble working fluid for a fixed abrasive fine wire cutter used for π by a mosquito abrasive fine wire cutter. [Prior Art] It is important to improve the ruthenium wafer, although the use of the free abrasive granule method is to reduce the manufacturing cost of the ruthenium wafer. The cutting by the fine wire cutter in the processing of the wafer is the mainstream, but in the processing of the free abrasive grain method, the following various problems exist. It is pointed out that there are the following negative effects: (1) @Used in the oil agent to disperse the slurry of abrasive grains as the processing liquid, it is difficult to separate the free abrasive grains from the chips. (2) The travel speed of the thin wire is limited, and there is a limit to the improvement of the processing efficiency. (3) In the case where the fine line is thinned to reduce the kerf loss, the wire breakage occurs during processing, and the yield is lowered. (4) When the abrasive grains are atomized in order to reduce the kerf loss, the viscosity of the slurry rises and the kerf loss increases. In order to solve such a problem, a solid-grinding abrasive fine wire cutter having a diamond abrasive grain fixed by a plating or a resin adhesive or the like on the surface of a fine wire such as a piano wire has been developed (Patent Document 1). When a brittle material is processed using a fixed abrasive fine wire cutter, the addition is performed by lubrication, cooling, and dispersion of the generated chips for the purpose of 100127516 4 201211235. It is preferred to use a water-soluble working fluid as the working fluid 'in consideration of the dependence 赖. Continuation, etc., in the case of the material A a being cut, compared with the general material, the reactivity of the chip with the Jia Shishi „ working fluid is higher than that of the genus (chip) and the water of the reading towel. The reaction (4) is hydrogen generation. Therefore, it is desirable that the reactivity of the financial property is suppressed and the flammability is flammable. In view of this, a processing liquid as disclosed in Patent Document 2 is proposed. [From [Previous Technical Literature] [Patent Literature [Patent Document 1] Japanese Patent Application No. 2〇〇1_〇5485〇 [Patent Document 2] Japanese Patent Application No. 2〇〇3_〇82334 [Summary of the Invention] (The problem to be solved by the invention) In recent years, it has been known that the cutting precision is reduced by the improvement of the processing precision, and the addition of the liquid I shown in Patent Document 2 does not provide sufficient stability. In particular, it is known that the viscosity of the processing liquid in which the chips are added increases. In addition, in the case of Dali s water with a pH and an experimental solution, there is not only a problem of milk production, but also a problem of viscosity increase and gelation. The following questions: (1) The amount of oil introduced by the thin person is changed. Degree of unevenness deteriorates the quality of the product. (2) Thin line slip occurs, and the thin line breaks (the yield decreases). (3) The cleaning in the next step becomes difficult (chips and oil between wafers) In addition to 100127516 201211235 to the difficulty). () oil; ^ can be replaced by the increase in liquid volume (cost increase in this Ming, the subject is to provide a fixed abrasive fine wire cutting liquid water-soluble processing fluid, which can inhibit It is possible to suppress the generation of hydrogen and suppress the formation of hydrogen in the processing liquid by suppressing the viscosity of the processing liquid mixed with the cutting liquid. The method of solving the problem is as follows. Efforts to solve the problems described by humans, the following matters: (1) The increase in viscosity caused by the mixing of S1 chips is due to the mixed S1_ micropowder and the poor dispersibility of Si chips. It is solved by increasing the dispersibility of Si chips by containing a predetermined water-soluble southern molecule in the processing liquid. (3) When the processing liquid contains a & chip shape, the Si chips react with the processing liquid to generate hydrogen. The situation In the case of a working fluid containing water in a large amount, since it contains chips, it may cause sticking and gelation. (5) The problems of the above (3) and (4) may be solved by one-step processing liquid. The inventors of the present invention have made efforts to study the above problems, and have completed the following description. The first invention is a method for determining the thickness of a bribe and using a water-soluble processing 100127516 6 201211235 liquid (below It is sometimes referred to as "the processing liquid of the present invention"), which contains: (A) at least one selected from the group consisting of polyethylene, ketone, and vinyl group ratio. The above water-soluble polymer and (B) water. When the processing liquid of the present invention contains a predetermined water-soluble polymer as the component (A) and contains Shishi powder in the working liquid, the dispersibility of the powder of Shishi powder can be improved, and the processing containing the tantalum powder can be suppressed. The viscosity of the liquid rises. Further, it is possible to suppress the reaction of the processing liquid with the tantalum powder to generate hydrogen, and at the same time, it is possible to suppress the viscosity and gelation of the processing liquid containing the tantalum powder. In the first invention, it is preferred that the component (A) has a weight average molecular weight of 2,000 to 1, 〇〇〇, 〇〇〇. In the first aspect of the invention, the mass of the water-soluble working fluid of the fixed abrasive fine wire cutter is preferably 100% by mass, and the content of the component (A) is 0.02% by mass or more and 7% by mass or less. The water-soluble working fluid for a fixed abrasive fine wire cutter of the first aspect of the present invention preferably further contains (C) a multi-vitamin acid aikali salt. In the case where the mass of the water-soluble working fluid for the fixed abrasive fine wire cutter is 100% by mass, the content of the component (C) is preferably 0.01% by mass or more and 1% by mass or less. The processing liquid of the present invention can easily impart dispersibility, detergency, and stagnation property by using an alkali metal salt containing a polyvalent carboxylic acid as the component (C). The water-soluble working fluid for a fixed abrasive fine wire cutter according to the first aspect of the invention preferably comprises (D) a group consisting of an alcohol, an alcohol-1, and a polyoxyalkylene glycol. More than one. Preferably, the fixed abrasive grain is cut into thin lines. 100127516 7 201211235
成分之含量為0·1質量％以上95質量％以下。 第1本發明之固定研磨粒細線切割器用水溶性加工夜 黏度七佳為於25t：為5〇mPa.s以下。若加工液本身= 度較高’料树粉之加卫敎減進—步變高。因此，= 佳為加工液本身之黏度為既定之值以下。 乂 中添加10質量％之平均粒徑1 5 之加工液(模擬使用液）之黏度，肩 於第1本發明之固定研磨粒細線切割器用水溶性加工液 ：)之矽粉並攪拌而形成 較佳為於25它為i00mPa.s 以下。衫有既定之㈣之模擬制液之黏度較高，則有產 生上述課題之欄中所揭示之各種問題之虞。 (發明效果） 藉由本發明之固定研磨粒細線切割器用水溶性加工液，因 含有既定之水溶性高分子，故於該加錢含有作為㈣屑之 石夕粉之情形時’可使該”分散於加工液中。因此，可抑制The content of the component is from 0.1% by mass to 95% by mass. In the first aspect of the invention, the fixed abrasive fine wire cutter has a water-soluble processing night viscosity of preferably 75t: 5 〇 mPa.s or less. If the working fluid itself = a higher degree, the addition of the tree powder is reduced. The step becomes higher. Therefore, it is preferable that the viscosity of the working fluid itself is below a predetermined value. Adding 10% by mass of the viscosity of the processing liquid (simulated use liquid) having an average particle diameter of 15% to the crucible, and forming the powder of the water-soluble working fluid for the fixed abrasive fine wire cutter of the first invention of the present invention and stirring Good for 25 it is below i00mPa.s. If the shirt has a high viscosity of the simulated liquid (4), it will cause various problems revealed in the column of the above-mentioned subject. (Effect of the Invention) The water-soluble working fluid for a fixed abrasive fine wire cutter of the present invention contains a predetermined water-soluble polymer, so that when the money is contained as a stone powder of (4), it can be dispersed. In the processing fluid. Therefore, it can be suppressed
氫’又可抑制含有矽粉之加工液之增黏、凝膠化。 【實施方式】 <固定研磨粒細線切割器用水溶性加工液〉 本發明之固定研磨粒細線切割器用水溶性加工液含有：（A) 自聚乙稀吼咯咬酮及包含乙烯基吡咯啶酮之共聚合物中選 100127516 8 201211235 擇之至少一種以上之水溶性高分子、及(B)水。 (⑷成分） 本發明之加工液含有自聚乙烯吡咯啶酮及包含乙烯基吡 各定S同之共聚合物中選擇之至少一種以上之水溶性高分子 作為(A)成分。藉由使加工液中含有該水溶性高分子，可於 έ有石夕私而成之加工液中提高該石夕粉之分散性。因此，可抑 制έ有石夕粉而成之加工液之黏度之上升。又，可抑制石夕粉與 夜之反應’而於含有石夕粉而成之加工液中抑制氳產生。 進而可抑制含有矽粉而成之加工液之增黏、凝膠化。 利用凝膠渗透色譜法/多角度雷射光散射檢測器法所得之 ()成刀之水，奋性向分子之重量平均分子量下限較佳為 2,000以上…圭為以㈨以上:上限較佳為^澤娜以下、 更L為7GG,GGG以下，進而較佳為5gq，_以下。若超出該 ^請而分子量過小，則有不會表現出加人⑷成分之效果之 ^ 若分子量過大，則有凝聚或加工液之黏度過高之 虞0 ^ ° 〇用水溶性加工液整體之皙詈· 為基準_質量%)’則(Α)成分…液“之質里 量％以上’更佳為_ f量％以3 ,里之下限較佳為㈣^ 以上；上限較佳為7質量％以°下上’進而較佳為 而較佳為3質量％以下。若超^更佳為5質量％以下，i 少，則有增黏之抑制效果、定°垓範圍而（A)成分之含量i _516 4 效果變得不充分3 201211235 虞。相反，若過多則有加工液之黏度變得過高之虞。 (A)成分之水溶性高分子係聚乙烯吼咯啶酮或包含乙烯基 吡咯啶酮之共聚合物，該等亦可混合兩種以上使用。包含乙 烯基°比°各。定酮之共聚合物之乙稀基π比σ各α定嗣單元之比率，以 共聚合物整體為基準，較佳為60莫耳％以上。作為與乙烯 基吡咯啶酮共聚合之單體，可舉出乙酸乙烯酯。 ((C)成分） 本發明之加工液亦可更含有多元羧酸之鹼金屬鹽作為（C) 成分。藉由添加（C)成分並調整其添加量，而有所謂賦予分 散性、洗淨性、对腐姓性之效果。 作為多元叛酸，可舉出：己二酸、草酸、十二院二酸、檸 檬酸、蘋果酸等。作為鹼，可舉出：氫氧化鉀、氫氧化鈉等 鹼金屬之氫氧化物；三乙醇胺、三異丙醇胺、乙二胺、Ν-(2-胺基乙基)-2-胺基乙醇等胺。 將本發明之加工液整體之質量作為基準（100質量％)，則 (C)成分之含量之下限較佳為0.01質量％以上，更佳為0.1 質量％以上；上限較佳為10質量％以下，更佳為2質量％以 下，進而較佳為1質量％以下。若非上述範圍，（C)成分之 含量過少則難以發揮添加（C)成分之效果，相反，若過多則 有增黏、凝膠化或自原液之析出之虞。 ((D)成分） 本發明之加工液亦可更含有自二醇類、二醇醚類及聚氧伸 100127516 10 201211235 烷二醇類所組成之群組中選擇之一種以上作為（D)成分。藉 由含有（D)成分，而有所謂賦予潤滑性、濕潤性之效果。 作為二醇類，可舉出：丙二醇、二乙二醇、乙二醇、丁二 - 醇等。作為二醇醚類，可舉出上述二醇類之烷基醚。作為烷 , 基，可舉出：甲基、乙基、丁基等。再者，二醇類之羥基之 一部分亦有成為烷基醚，亦可全部成為烷基醚。作為二醇醚 類之具體例，可舉出：二乙二醇單乙醚、二乙二醇二乙醚、 丙二醇單乙醚等。 作為聚氧伸烷二醇類，可舉出：聚乙二醇、聚丙二醇、聚 氧乙烯與聚氧丙烯之共聚合物等’較佳為使用重量平均分子 量(使用凝膠滲透色讀法之聚苯乙烯換算）為1〇_以下、較 佳為5000以下、進而較佳為400以下者。 將本發明之加工液整體之質量作為基準_質量％)，則 (D)成分之含量為之下限較佳為〇」f量％以上、更佳為〇 5 質量％以上，進而較佳為i f量％以上、進而較佳為3質量 %以上，特佳為質量％以上；上限較佳為％質量％以下， 更佳為9〇質量％以下，進而較佳為8〇質量％以下。若#上 述範圍，（D)成分之含量過少則不會表現出加入⑼成分之效 果，相反，若(灌分之含量過大則有冷卻性下降之虞。 本發明之加工液含有上述⑷成分，視情況更含有(c)成分 及(D)成分’剩餘部分(B)為水。 水可為蒸餾水、自來水等， 其種類無特別限定。再者，於*人 水之含量較多之加工液中， 100127516 201211235 3有石夕叔之加工液易增黏、 士 焚疹化。相對於此，於本發明 加工液中，即便於水之含量 之 之質量作為基準，水為例如以加工液整發 有石夕粉之加工液之增黏、凝^从上之組成’亦可抑制含 <加工液之特性> 本發明之加工液之黏度於 Ώ 為5〇mpa.s以下，較佳 25 mPa.s以下，更佳為2〇 為 x .. , x P 以下。又，於本發明之a 工液中分散有既定之石夕粉 力0 . 1ΛΛ 心力口工液（模擬使用液）之黏度 25C 為 10〇mpa.s 以下，較 馮55 mPa.s以下、更佳暮 mPa.s以下、進而較佳為乜 為5〇 系n Pa.s以下。該模擬使用液才 黏度係針對在本發明之加 之 夜中添加1〇質量％之矽粉⑷ 徑.1.5 #m)攪拌混合後，放 (板 取入不鏽鋼鋼球（直徑2 ， 以職㈣㈣Η)小時，且過遽分離該不鏽鋼鋼球所得之 模擬使用液而測定者。若上述加Μ自身之黏度過高，則含 有石夕粉之碰使職之減亦㈣衫。又，若難使用液 之黏度過高，則有產生上述課題之攔中所述之各種問題之 虞。再者’加工液及模擬使用液之勒度可利用布氏黏度計 (Brookfield viscometer )測定。 加工液之PH較佳為5.0以上9.〇以下。於加工液之阳值 過低之情形時，有產生該加工液所接觸之鐵材或細線的腐蝕 Μ ’相反’於加工液之#過高之情形時’有加工液與石夕 粉反應而產生氫之虞’本發明之加工液亦可稀釋於水中使 ^0127516 12 201211235 用，但該情形時，較佳為稀釋後之加工液之pH亦為上述範 圍。 [實施例] - <實施例1〜13、比較例1〜5〉 * 以成為表1〜3所示之組成之方式，製作本發明之固定研 磨粒細線切割态用水溶性加工液(實施例丨〜13)及本發明以 外之固定研磨粒細線切割器用水溶性加工液（實施例i〜 5)。測定所製作之加工液之pH，同時利用布氏黏度計測定 其於25°C之黏度。 進而，於各加工液中添加10質量％之矽粉（平均粒徑：15 #m)，攪拌混合後’放入不鏽鋼鋼球（直徑2 ，以1〇〇〇 rpm攪拌10小時而形成模擬使用液。自該模擬使用液中， 用金屬絲網(50目）過濾分離不鏽鋼鋼球後，利用布氏黏度計 測定該模擬使用液之黏度(mPa.s、25°C)。又，將10 ml模 擬使用液之黏度加熱至50。(：，測定30分鐘所產生之氮量 (ml)。 « 再者，聚乙烯。比咯啶酮(PVP)之重量平均分子量PVPK_15 • 為 9700 ’ PVP K-30 為 70000，PVP Κ·60 為 400000。又， PVPA/A係乙烯基吡咯啶酮與乙酸乙烯酯之共聚合物，重量 平均分子量為32,000,共聚合物中之乙烯基吡咯σ定酮之比率 為70莫耳％。 100127516 13 201211235 [表i] 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 PVP(M=2500) PVP(K-15) PVP(K-30) 0.3 0.3 0.3 1 3 5 PVP(K-60) PVP/VA 丙二醇 20 20 20 二乙二醇 聚氧伸烷二醇 (Mw=3000 ' 環氧乙炫/環氧丙烷 =50%/50%) 5 二乙二醇單乙醚 水 99.7 98.9 94 78.4 76.4 74.4 檸檬酸 0.3 0.3 0.3 0.3 0.3 十二烷二酸 0.1 氫氧化鉀 0.2 0.1 0.3 0.3 0.3 三乙醇胺 0.3 N~(2-胺基乙基)-2-胺基乙醇 0.2 總計 100 100 100 100 100 100 加工液黏度(mPa-s) 1.1 1.2 1.7 2.8 4.4 6.0 pH Ί2 7.1 8.8 6.2 6.2 6.3 模擬使用液黏度(mPa · s) 8 9 12 14 17 25 氫產生量(ml) 4.8 4.7 4.1 2.7 2.1 1.8 備註 稀釋10倍 稀釋10倍 稀釋10倍 14 100127516 201211235 [表2] 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 PVP(M=2500) 0.5 PVP(K-15) 0.5 PW(K-30) 0.5 0.05 0.5 PVP(K-60) 0.5 PVP/VA 0.5 丙二醇 70 70 70 70 70 70 二乙二醇 50 聚氧伸烧二醇 (Mw=3000 ' 環氧乙炫/環氧丙烷 =50%/50%) 二乙二醇單乙醚 20 水 28.9 28.9 28.9 28.9 28.9 29.35 29 檸樣酸 0.4 0.4 0.4 0.4 0.4 0.4 03 十二烷二酸 氫氧化鉀 0.2 0.2 0.2 0.2 0.2 0.2 0.2 三乙醇胺 N<2-胺基乙基)-2-胺基乙醇 總計 100 100 100 100 100 100 100 加工液黏度(mPa. s) 11.5 1L8 12.1 12.2 12.0 11.9 11.2 pH 6.0 6.0 5.9 6.0 6.0 5.9 6.1 樹疑使用液黏度(mPa · s) 35 35 26 30 32 40 33 氫產生量(ml) 2.1 1.6 1.3 0.9 1.5 2.5 1.6 15 100127516 201211235 [表3] 比較例1 比較例2 比較例3 比較例4 比較例5 PVP(M = 2500) PVP(K-15) PVP(K-30) PVP(K-60) PVP/VA 丙二醇 20 70 二乙二醇 50 聚氧伸统二醇 (Mw=3000、 環氧乙炫;環氧丙烷 =50%/50°/〇) 5 二乙二醇單乙醚 20 水 99.2 94.3 79.4 29.4 29.5 檸檬酸 0.3 0.3 0.3 0.4 0.3 十二烷二酸 0.1 氫氧化鉀 0.2 0.1 0.3 0.2 0.2 三乙醇胺 0.3 N-(2-胺基乙基)-2-胺基乙醇 0.2 總計 100 100 100 100 100 加工液黏度(mPa · s) 1.1 1.7 2.0 11.8 11.2 PH 7.9 8.8 6.2 6.0 6.1 模擬使用液黏度(mPa · s) 520 410 350 80 71 氫產生量(ml) 18.5 16.7 15.1 3.4 3.3 備註 稀釋10倍 稀釋10倍 於比較例之加工液中，模擬使用液黏度皆上升，且超過 55 mPa’s。相對於此，本發明之加工液（實施例1〜13)即便 於模擬使用液中，黏度變化亦較小，皆為45 mPa · s以下。 實施例1〜3、比較例1 ' 2係將原液稀釋10倍者。因此， 原液之組成中各化合物為10倍量。 (組I) 組I為實施例1〜6及比較例1〜3，係水分量較多之加工 液之例。於比較例之加工液中，水分量之較多之組成（比較 16 100127516 201211235 例1〜3)皆增黏、凝膠化，但添加有PVP之本發明之加工液 (實施例1〜6)無凝膠化，幾乎未增黏。 又，關於氫產生量，相對於在實施例1〜6中氫產生量為5 ml以下，於比較例1〜3中氫產生量為15 ml以上，非常多。 (組Π) 組Π為實施例7〜12及比較例4，係統一（C)成分及(D)成 分之種類及量而改變(A)成分者。藉此，顯示出各種聚乙烯 吼咯啶酮（PVP)、乙烯基吡咯啶酮/乙酸乙烯酯之共聚合物 (PVP/VA)之增黏抑制效果。 又’關於虱產生量，若比較實施例7〜12與比較例4，則 包含聚乙稀°比η各η定酮等之本發明之加工液之氫產生量較少。 (組m) 組瓜為實施例13及比較例5，係包含與組I、組Π不同 之(D)成分者。藉此，不論(D)成分之種類而顯示出聚乙烯吡 咯啶酮(PVP)之增黏抑制效果。 又，若比較實施例13與比較例5 ,則包含聚乙烯吡咯啶 嗣之實施例13之IU生量較少。 由以上内令顯示出，含有聚乙烯町卜各咬酉同及包含乙稀基口比 各定-同之/、聚5物之本發明之加工液，於分散有矽粉之模擬 使用液中有抑制勘度上升，同時抑制氫產生之效果。 以上’聯繫目前被認為最具實踐性且最佳之實施形態對本 1月進灯了明本發明並不限定於本案說明書中所揭示 100127516 17 201211235 之實施形態，可在不違背自申請專利範圍及說明書整體所理 解之發明之主旨或思想之範圍内進行適當變更，伴隨此種變 更之固定研磨粒細線切割器用水溶性加工液亦必須理解為 包含於本發明之技術範圍内者。 (產業上之可利用性） 本發明之固定研磨粒細線切割器用水溶性加工液可於使 用固定研磨粒細線切割器切斷矽晶圓時使用。 100127516 18Hydrogen can inhibit the thickening and gelation of the processing liquid containing the powder. [Embodiment] <Water-soluble processing liquid for fixed abrasive fine wire cutter> The water-soluble processing liquid for fixed abrasive fine wire cutter of the present invention contains: (A) self-polyethylene ketone ketone and vinyl pyrrolidone Among the copolymers, 100127516 8 201211235 is selected from at least one of the water-soluble polymers and (B) water. (Component (4)) The working fluid of the present invention contains at least one or more water-soluble polymers selected from the group consisting of polyvinylpyrrolidone and a copolymer containing vinylpyrrolidine S as the component (A). By containing the water-soluble polymer in the processing liquid, the dispersibility of the powder can be improved in the processing liquid which is formed by Shixia. Therefore, it is possible to suppress the increase in the viscosity of the working fluid obtained by the stone powder. Further, it is possible to suppress the reaction of the stone powder with the night, and to suppress the generation of cockroaches in the working fluid containing the stone powder. Further, it is possible to suppress the viscosity increase and gelation of the working fluid containing the tantalum powder. The lower limit of the weight average molecular weight of the excitatory molecule is preferably 2,000 or more by the gel permeation chromatography/multi-angle laser light scattering detector method, and the lower limit of the weight average molecular weight is preferably 2,000 or more. Below N, L is 7GG, GGG or less, and further preferably 5gq, _ or less. If the molecular weight is too small, the effect of adding the component (4) will not be exhibited. If the molecular weight is too large, the viscosity of the coagulation or the processing liquid is too high. ^0 ^ ° 整体 The whole of the water-soluble working fluid詈· For the reference _ mass%)' (Α) component... The liquid "% or more of the mass" is more preferably _ f% is 3, the lower limit is preferably (four) ^ or more; the upper limit is preferably 7 mass % is more preferably 3% by mass or less, and more preferably 3% by mass or less. If the amount of super is more preferably 5% by mass or less, if i is small, the effect of suppressing viscosity is increased, and the range of 垓 垓 is obtained (A) Content i _516 4 The effect becomes insufficient 3 201211235 虞. Conversely, if too much, the viscosity of the working fluid becomes too high. (A) The water-soluble polymer of the component is polyvinylpyrrolidone or contains ethylene. a copolymer of a pyrrolidone, which may be used in combination of two or more kinds, including a vinyl group ratio, a ratio of a vinyl group of a ketone, a π ratio of σ, and a ratio of each α unit to a copolymerization unit. The content of the whole material is preferably 60 mol% or more. As a monomer copolymerized with vinylpyrrolidone, (V) component (The component (C)) The working fluid of the present invention may further contain an alkali metal salt of a polyvalent carboxylic acid as the component (C). By adding the component (C) and adjusting the amount thereof, there is a so-called imparting. Dispersibility, detergency, and effect on rot. As a plurality of retinoic acids, adipic acid, oxalic acid, diterpene diacid, citric acid, malic acid, etc. may be mentioned. As the base, hydrogen may be mentioned. An alkali metal hydroxide such as potassium oxide or sodium hydroxide; an amine such as triethanolamine, triisopropanolamine, ethylenediamine or hydrazine-(2-aminoethyl)-2-aminoethanol. When the mass of the entire processing liquid is 100% by mass, the lower limit of the content of the component (C) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and the upper limit is preferably 10% by mass or less, more preferably 2% by mass or less, more preferably 1% by mass or less. If the content of the component (C) is too small, it is difficult to exhibit the effect of adding the component (C), and if it is too large, it is thickened, gelled or self-suppressed. The precipitate of the stock solution ((D) component) The processing liquid of the present invention may further contain self-diols, Alcohol ethers and polyoxyl extensions 100127516 10 201211235 One or more selected from the group consisting of alkanediols is the component (D). By containing the component (D), there is an effect of imparting lubricity and wettability. Examples of the diols include propylene glycol, diethylene glycol, ethylene glycol, and butyl diol. Examples of the glycol ethers include alkyl ethers of the above diols. Further, a methyl group, an ethyl group, a butyl group, etc. may be mentioned, and a part of the hydroxyl group of the diol may be an alkyl ether, and all of them may be an alkyl ether. Specific examples of the glycol ethers include a glycol ether. Diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monoethyl ether, etc. As the polyoxyalkylene glycols, polyethylene glycol, polypropylene glycol, polyoxyethylene and polyoxypropylene are mentioned. The polymer or the like is preferably used in a weight average molecular weight (in terms of polystyrene by gel permeation chromatography) of 1 Å or less, preferably 5,000 or less, and more preferably 400 or less. In the case where the mass of the entire processing liquid of the present invention is used as a reference _ mass%, the lower limit of the content of the component (D) is preferably 〇"f or more, more preferably 5% by mass or more, and still more preferably if The amount is not less than 5% by mass, more preferably 3% by mass or more, particularly preferably 7% by mass or more, more preferably 9% by mass or less, still more preferably 9% by mass or less, still more preferably 8% by mass or less. When the content of the component (D) is too small, the effect of adding the component (9) is not exhibited, and if the content of the component is too large, the cooling property is lowered. The working fluid of the present invention contains the above component (4). Further, the component (c) and the component (D) may be contained as water. The water may be distilled water or tap water, and the type thereof is not particularly limited. Further, the working fluid having a high content of * human water is used. In the process liquid of the present invention, even if the mass of the water is used as a reference, the water is, for example, processed. The viscosity-increasing and condensing composition of the processing liquid of the powder of Shishi powder can also suppress the inclusion of <characteristics of the processing liquid> The viscosity of the processing liquid of the present invention is less than 5 〇 mPa.s, preferably 25 mPa.s or less, more preferably 2 〇 is x.., x P or less. Further, in the working fluid of the present invention, a predetermined Shishi powder strength is dispersed. 0 ΛΛ Xinlikougong liquid (simulated use liquid) The viscosity of 25C is below 10 〇mpa.s, which is lower than von 55 mPa.s, and better than 暮mPa.s. Further, it is preferable that the enthalpy is 5 n n Pa.s or less. The simulation uses the liquid viscosity system for the addition of 1 〇 mass% of the 矽 powder (4) diameter. 1.5 #m) in the night of the present invention, and then mixes and releases ( The plate is taken into a stainless steel ball (diameter 2, for (4) (four) Η) hours, and is measured by separating the simulated use liquid obtained by separating the stainless steel ball. If the viscosity of the above-mentioned twisting itself is too high, the stone powder is included. In addition, if the viscosity of the difficult-to-use liquid is too high, there are various problems described in the above-mentioned problems. In addition, the processing fluid and the simulated use liquid can be utilized by Brinell. Measured by a Brookfield viscometer. The pH of the working fluid is preferably 5.0 or more and 9. 〇 or less. When the positive value of the working fluid is too low, there is corrosion of the iron or fine wire which is contacted by the working fluid. Conversely, 'when the processing liquid is too high, 'there is a reaction between the processing liquid and the Shiyan powder to produce hydrogen.' The processing liquid of the present invention can also be diluted in water to make ^0127516 12 201211235, but in this case, The pH of the processing fluid after the dilution is also [Examples] - <Examples 1 to 13 and Comparative Examples 1 to 5> * The water-soluble processing liquid for the fixed abrasive fine-wire cut state of the present invention was produced in such a manner as to have the compositions shown in Tables 1 to 3 ( Example 丨~13) and a water-soluble working fluid for fixed abrasive fine wire cutters other than the present invention (Examples i to 5). The pH of the produced working fluid was measured while measuring at 25 ° C by a Brookfield viscometer. Further, 10% by mass of cerium powder (average particle diameter: 15 #m) was added to each working solution, and after stirring and mixing, 'a stainless steel ball was placed (diameter 2, and stirred at 1 rpm for 10 hours). A simulated use solution is formed. From the simulated use liquid, the stainless steel balls were separated by filtration using a wire mesh (50 mesh), and the viscosity (mPa.s, 25 ° C) of the simulated use liquid was measured by a Brookfield viscometer. Also, heat the viscosity of 10 ml of the simulated liquid to 50. (:, measure the amount of nitrogen (ml) produced in 30 minutes. « Furthermore, polyethylene. The weight average molecular weight of piracetone (PVP) is PVPK_15 • 9700 'PVP K-30 is 70,000, PVP Κ·60 is 400000. Further, the PVPA/A copolymer of vinylpyrrolidone and vinyl acetate has a weight average molecular weight of 32,000 and a ratio of vinylpyrrolidone in the copolymer of 70 mol%. 100127516 13 201211235 [Table i] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 PVP (M = 2500) PVP (K-15) PVP (K-30) 0.3 0.3 0.3 1 3 5 PVP (K- 60) PVP/VA Propylene glycol 20 20 20 Diethylene glycol polyoxyalkylene glycol (Mw=3000 'epoxyethylene/propylene oxide=50%/50%) 5 Diethylene glycol monoethyl ether 99.7 98.9 94 78.4 76.4 74.4 Citric acid 0.3 0.3 0.3 0.3 0.3 Dodecanedioic acid 0.1 Potassium hydroxide 0.2 0.1 0.3 0.3 0.3 Triethanolamine 0.3 N~(2-Aminoethyl)-2-aminoethanol 0.2 Total 100 100 100 100 100 100 Process Fluid Viscosity (mPa-s) 1.1 1.2 1.7 2.8 4.4 6.0 pH Ί2 7.1 8.8 6.2 6.2 6.3 Mode Proposed liquid viscosity (mPa · s) 8 9 12 14 17 25 Hydrogen generation amount (ml) 4.8 4.7 4.1 2.7 2.1 1.8 Remarks Dilution 10 times dilution 10 times dilution 10 times 14 100127516 201211235 [Table 2] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 PVP (M=2500) 0.5 PVP(K-15) 0.5 PW(K-30) 0.5 0.05 0.5 PVP(K-60) 0.5 PVP/VA 0.5 Propylene glycol 70 70 70 70 70 70 Diethylene glycol 50 polyoxyalkylene diol (Mw=3000 'epoxyethylene/propylene oxide=50%/50%) Diethylene glycol monoethyl ether 20 water 28.9 28.9 28.9 28.9 28.9 29.35 29 Lime acid 0.4 0.4 0.4 0.4 0.4 0.4 03 Potassium dodecanoate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Triethanolamine N<2-aminoethyl)-2-aminoethanol Total 100 100 100 100 100 100 100 viscosity of processing fluid (mPa. s) 11.5 1L8 12.1 12.2 12.0 11.9 11.2 pH 6.0 6.0 5.9 6.0 6.0 5.9 6.1 Tree viscosity (mPa · s) 35 35 26 30 32 40 33 Hydrogen production (ml) 2.1 1.6 1.3 0.9 1.5 2.5 1.6 15 100127516 201211235 [Table 3] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 PVP (M = 2500) PVP (K-15) PVP (K-30) PVP (K-60) PVP/VA Propylene glycol 20 70 Diethylene glycol 50 polyoxylated diol (Mw=3000, epoxy bromide; propylene oxide=50%/50°/〇) 5 Diethylene glycol monoethyl ether 20 Water 99.2 94.3 79.4 29.4 29.5 Citric acid 0.3 0.3 0.3 0.4 0.3 Dodecanedioic acid 0.1 Hydrogen Potassium Oxide 0.2 0.1 0.3 0.2 0.2 Triethanolamine 0.3 N-(2-Aminoethyl)-2-aminoethanol 0.2 Total 100 100 100 100 100 Processing Fluid Viscosity (mPa · s) 1.1 1.7 2.0 11.8 11.2 PH 7.9 8.8 6.2 6.0 6.1 Simulated liquid viscosity (mPa · s) 520 410 350 80 71 Hydrogen production (ml) 18.5 16.7 15.1 3.4 3.3 Remarks Dilute 10 times and dilute 10 times in the working fluid of the comparative example, the simulated liquid viscosity increases, and More than 55 mPa's. On the other hand, in the working fluids of the present invention (Examples 1 to 13), even in the simulated use liquid, the viscosity change was small, and all were 45 mPa·s or less. Examples 1 to 3 and Comparative Example 1 ' 2 The system was diluted 10 times. Therefore, each compound in the composition of the stock solution was 10 times the amount. (Group I) Group I is Examples 1 to 6 and Comparative Examples 1 to 3, and is an example of a processing liquid having a large amount of water. In the working fluid of the comparative example, the composition of the water content (compared to 16 100127516 201211235, Examples 1 to 3) was thickened and gelled, but the working fluid of the present invention to which PVP was added (Examples 1 to 6) No gelation, almost no viscosity. In addition, the amount of hydrogen generated was 5 ml or less with respect to Examples 1 to 6, and the amount of hydrogen generated in Comparative Examples 1 to 3 was 15 ml or more. (Group) The group (A) was changed according to the types and amounts of the system (C) component and the (D) component of Examples 7 to 12 and Comparative Example 4. Thereby, the viscosity-inhibiting effect of various polyvinylpyrrolidone (PVP), vinylpyrrolidone/vinyl acetate copolymer (PVP/VA) was exhibited. Further, in the case of comparing Examples 7 to 12 and Comparative Example 4, the amount of hydrogen generated in the working fluid of the present invention including the polyethylene sulphur ratio η and the η decyl ketone was small. (Group m) The group melons were the same as those of the group (I) and the group (I) which were different from the group I and the group (III). Thereby, the viscosity-inhibiting effect of polyvinylpyrrolidone (PVP) is exhibited regardless of the type of the component (D). Further, when Example 13 and Comparative Example 5 were compared, the amount of IU produced in Example 13 containing polyvinylpyrrolidine was small. It is shown in the above-mentioned generals that the processing liquid of the present invention containing the polyethylene singly and the singly-containing and the sulphur-based sulphate is in the simulated use liquid in which the bismuth powder is dispersed. It has the effect of suppressing the increase in the degree of investigation while suppressing the generation of hydrogen. The above 'contact' is currently considered to be the most practical and best implementation form. This invention is not limited to the implementation of 100127516 17 201211235 disclosed in the present specification, and may not violate the scope of the patent application. It is to be understood that the water-soluble working fluid for a fixed abrasive fine wire cutter is also included in the technical scope of the present invention as appropriate within the scope of the gist of the invention or the scope of the invention. (Industrial Applicability) The water-soluble working fluid for a fixed abrasive fine wire cutter of the present invention can be used when a silicon wafer is cut by a fixed abrasive fine wire cutter. 100127516 18