201042028 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種脆性材料用加工液及硬質材料用加工 液’更詳細而言，係關於一種可較好地用於藉由利用游離 研磨粒之線鋸或固定研磨粒線鋸來切割脆性材料及硬質材 料時之脆性材料用及硬質材料用含水加工液。 【先前技術】201042028 VI. Description of the Invention: [Technical Field] The present invention relates to a working fluid for a brittle material and a working fluid for a hard material. More specifically, it relates to a method for utilizing free abrasive grains. A wire saw or a fixed abrasive wire saw for cutting brittle materials and hard materials for brittle materials and hard materials for aqueous processing fluids. [Prior Art]
半導體製品之製造中重要的是高精度地加工作為脆性材 料之石夕晶錠’就於其開槽或切割中其加工精度及生產性之 觀點而言’一般係利用線鋸加工。 力一方面，於陶瓷、石英、藍寶石等作為難削材之硬質 材料的開槽或切割中，係利用使用例如金剛石研磨粒或立 方晶氮化棚（cBN)研磨粒等超硬研磨粒之線鋸加工。 作為線鋸加工方法，有一邊向被加工物與切割線之滑動 部供給游離研磨粒，—邊進行開槽、㈣或内表面研磨加 工$之方式；及使用於切割線之表面直接固著有研磨粒之 固定研磨粒線鋸之方式。 前者之游離研磨粒方式之線鋸加工中使用使游離研磨粒 分散於加工液中之漿料，藉由包含鋼琴線等之線鑛來切割 =材料或硬質材料。因此，關於該加卫液，除潤滑性能 :"生月b之外’亦需要游離研磨粒之分散性能及加工後 之容易性等。特別是近年來半導體製品等有大型 昇。π»積體度化之傾向’隨之需要加工液之性能進一步提 147069.doc 201042028 另一方面，後者之使用固定研磨粒線鋸之方式中，係使 用it由電鑛而於鋼灵綠望+ + 7線等心線上固足有研磨粒之電鍍線 鋸、或以高分子材料作為點合劑來固定研磨粒之樹脂黏合 劑線鑛等作為線鑛。於使用此種固定研磨粒線鑛之方式 中，作為加工液，特別是為防止固定研磨粒之剝離而需要 摩擦係數較低者。 又，於兩方式之線鋸加工中，需要如下加工液，其切屑 之清洗、分散性優異，切屑不易阻塞喷嘴或加工間隙等， 且可進行穩定之加工處理。 迄今為止作為用於該等用途中之加工液，主要係使用加 工油（使用礦物油或合成油作為基礎油之油系加工液）。妖 而’由於加工油有環境問題及安全性之問題，故近年來期 望的是水系加工液、特另,】是含水率高之加工液。 關於含有水之加卫液’例如於專利文獻！中揭示有含有 水分1〜20質量％之非水溶性分散介質組合物，於專利文獻 2中揭示有含有特定胺類化合物之水溶性金屬加工油劑組 合物。該等為含有水之加工液，但係使用礦物油等基礎油 作為主成分者’並未完全解決上述環境問題及安全性之問 題。又，於專利文獻3中揭示有含有膨土之水分散液及特 定添加劑之切削液，於專利文獻4中揭示有於含有親水性 多兀醇系化合物、親油性多元醇系化合物及水之分散介質 中分散石夕酸膠粒子而成之水性組合物。該等並非含有礦物 油等基礎油者’但含水率不高。特別是於專利文獻*之實 施例中，在增加水之情況下發現性能下降。 147069.doc 201042028 先前技術文獻 專利文獻 專利文獻1 :日本專利特開平11 _ 1 〇〇590號公報 專利文獻2 :日本專利特開2002-285186號公報 專利文獻3 :曰本專利特開平8_6〇 176號公報 專利文獻4:日本專利特開平u_3〇2681號公報 【發明内容】In the manufacture of a semiconductor article, it is important to process a stone ingot as a brittle material with high precision, and it is generally processed by a wire saw from the viewpoint of its processing accuracy and productivity in its grooving or cutting. On the one hand, in the grooving or cutting of hard materials such as ceramics, quartz, sapphire, etc., which are hard materials, use a line of superhard abrasive grains such as diamond abrasive grains or cubic nitride sheds (cBN). Saw processing. As a wire saw processing method, there is a method in which a free abrasive grain is supplied to a workpiece and a sliding portion of a cutting line, and a groove is formed, (4) or an inner surface is polished, and the surface is directly fixed to the surface of the wire. The method of fixing the abrasive grain saw by the abrasive grain. In the wire sawing process of the former free-grain type, a slurry in which free abrasive grains are dispersed in a working fluid is used, and a material or a hard material is cut by a wire ore containing a piano wire or the like. Therefore, regarding the reinforcing liquid, in addition to the lubricating property: "raw month b, the dispersion property of the free abrasive grains and the easiness after processing are required. In particular, semiconductor products and the like have risen in large numbers in recent years. The tendency of π»integration is followed by the performance of the processing fluid. 147069.doc 201042028 On the other hand, the latter uses the fixed abrasive wire saw method, which uses it from the electric mine and the steel spirit + + 7-line and other core wires are fixed with an electroplated wire saw with abrasive grains, or a resin binder wire ore with a polymer material as a point agent to fix the abrasive particles. In the method of using such a fixed abrasive granule, it is necessary to use a lower friction coefficient as a working fluid, particularly to prevent peeling of the fixed abrasive grains. Further, in the wire sawing process of the two types, the following machining liquid is required, and the chips are excellent in cleaning and dispersibility, and the chips are less likely to block the nozzle or the machining gap, and the stable processing can be performed. Conventionally, as a working fluid used in such applications, a processing oil (an oil-based working fluid using mineral oil or synthetic oil as a base oil) is mainly used. Demon and because the processing oil has environmental problems and safety problems, it is expected that water processing fluids, in particular, are processing fluids with high water content. Regarding the water-containing accelerator solution, for example, in the patent literature! A water-insoluble dispersion medium composition containing 1 to 20% by mass of water is disclosed, and Patent Document 2 discloses a water-soluble metalworking oil composition containing a specific amine compound. These are the processing liquids containing water, but the use of base oils such as mineral oil as the main component' does not completely solve the above environmental problems and safety problems. Further, Patent Document 3 discloses a cutting fluid containing an aqueous dispersion of benton and a specific additive, and Patent Document 4 discloses a dispersion containing a hydrophilic polyhydric alcohol compound, a lipophilic polyol compound, and water. An aqueous composition obtained by dispersing a mixture of aspartic acid particles in a medium. These are not those containing base oils such as mineral oils, but the moisture content is not high. Particularly in the embodiment of Patent Document*, a decrease in performance was observed in the case of increasing water. 147 069 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Patent Document 4: Japanese Patent Laid-Open Publication No. Hei No. Hei. No. 2681
發明所欲解決之問題 如上所述含有水之加工液先前亦已知PROBLEM TO BE SOLVED BY THE INVENTION The processing liquid containing water as described above is also known previously.
加工液來提南含水率，則於游 得易沈降而難以將研磨粒均句 預期猎由间加工液之毒占度而 於此情況下，若黏度過大則難 加工間隙。又，若使用先前之 擦係數會變高，於使用固定研 磨粒變得易剝離。 但右使用先前之 離研磨粒方式中，研磨粒變 地供給至加工間隙。又，可 使研磨粒變得難以沈降，但 以將充分量之加工液供給至 加工液來提南含水率，則摩 磨粒線鋸之方式中，固定研 環境問題及安全性之問題 本發明係鑒於上述情況而成者， ^ ,、私外^ 成者其目的在於提供一種含 水加工液’該含水加工液於 裡3 充分地供給至加工間隙， 了將漿枓 %應杻分散穩定性優 屑之清洗、分散性優異；另外本 2、並且切 含水加工液，該含水加工液於 杈仏種 中，固定研磨粒不易剝離，且 、之方式 肖之0洗、分散性優異。 147069.doc 201042028 解決間題之技術手段 結果發現藉由調配特 題。本發明係基於相 本發明者等人反覆進行銳意研究， 定添加劑而成之加工液可解決上述問 關知識而完成者。 即本發明提供 下述成分（A)〜(〇調配 1_ 一種硬脆性材料用加工液，其係將 而成： (A) 水， (B) 具有含乳基且數量平約分；旦斗 十g刀子置為6,000〜3,000,000之水 溶性南分子化合物， (CM質量。/。水溶液之濁點為1G〜7Gt之非離子界面活性劑； 2+上述！之硬脆性材料m，其中上述成分⑻中之 含氧基係自m基、經基、氧乙烯基及氧丙烯基中選擇之任 一基團； 3. 如上述W2之硬脆性材料用加工液，其中上述成分(b)係 羧酸系高分子化合物及/或烷二醇系高分子化合物； 4. 如上述3之硬脆性材料用加工液，其中上述成分（B)係羧 酸系高分子化合物及烷二醇系高分子化合物之組合； 5. 如上述1至4中任一之硬脆性材料用加工液，其中上述成 分（C)係含有氧丙烯基且數量平均分子量為70〜5,000之非離 子界面活性劑； 6. 如上述1至5中任一之硬脆性材料用加工液，其中以加工 液總量為基準’上述成分之調配量為5〇〜99質量％，上 述成分（B)之調配量為0.01-3 0質量。/。，上述成分（C)之調配 147069.doc 201042028 述成分（B)之調配量為〇.〇1〜3〇質量％，上述成分（c)之調配 量為0.1〜20質量％ ; 7. 如上述1至6中任一之硬脆性材料用加工液，其中pH為 2〜10 ;及 8. 如上述7之硬脆性材料用加工液，其包含酸成分與鹼成 刀且藉由調整上述酸成分與鹼成分之調配比來調整pJJ而 獲得。 發明之效果 〇 藉由本發明，可k供一種含水加工液，其於線雜加工之 游離研磨粒方式中，可將漿料充分地提供至加工間隙，研 磨粒分散穩定性優異，並且切屑之清洗（分散）性優異；另 外可提供-種含水加工液，其於使用固定研磨粒線錯之方 式中，固定研磨粒不易剝離，且切屑之清洗（分散）性優 異。 【實施方式】 〇 纟發明之硬質材料及脆性材料（以下，有時稱為「硬脆 性材料」）用加工液，係將（A)水、（B)特定之水溶性高分子 化合物、（C)特定之非離子界面活性劑調配而成之加工 液。 作為本發明之硬脆性材料用加工液之成分（A)的水，可 無特定限制地使用，較好的是使用純化水，特別好的是去 離子水。水之調配量’以加工液總量為基準通常為50〜99 質量％，較好的是60〜95質量％。藉由使水之調配量為5〇質 量％以上，可使易燃性下降，因此安全性提高，並且就環 147069.doc 201042028 境方面而言亦較好。關於上限並無特別原目，與其他成分 之調配量之關係通常為99質量％。 而 作為本發明之硬脆性材料用加工液之成分(B)的水溶性 分子化合物係具有含氧基且數量平均分子量為 6，_〜3，刪，_之水溶性高分子化合物。於本發明中，藉 由調配成分(B)來調整加工液之黏度，藉由該黏度調整： 而於游離研磨粒方式中，可«料中之研磨粒之分散穩定 性及切屑之清洗性提高，於使用固定研磨粒線鋸之方式 中’加工液易附著於切割線上，向加工間隙浸透，切割速 度變快’且T抑制研磨纟之㈣。若數量平均&子量未達 6,_，則難以獲得該黏度調整效果1超過3，_，000, 則於游離研磨粒方式中，點庚鐵p、風丄^此 、τ黏度變仵過大而難以將漿料充分 地供給至加工間隙。就马·迦 丨糸就及硯點而言，數量平均分子量較好 的是 10,000〜1，500,000。 作為上述含氧基， 及氧丙稀基。此處， 中和而變為陰離子者 例如可列舉羧基、羥基及氧乙烯基、 該羧基及羥基亦包含藉由去質子化或 再者，所t胃水純高分子化合物，係指溶於水之高分子 化合物’通常係指對水之溶解度⑽。〇為(U g/水⑽㈣ 上之高分子化合物。又，於本說明書中，所謂漿料係指含 有加工液及研磨粒之混合物。 成分（B)巾，於不僅黏度調整效果優異、作為分散 劑或切屑之清洗性提昇劑亦優異之方面，較好的是竣酸率 南分子化合物或烷二醇系高分子化合物。 I47069.doc 201042028 上述羧酸系兩分子化合物係使具有聚合性基之不飽和羧 酸聚合而獲得之高分子化合物。作為不飽和羧酸，例如可 列舉丙烯酸、甲基丙烯酸、順丁烯二酸酐、順丁烯二酸、 反丁烯二酸、丁烯酸及亞甲基丁二酸等。作為羧酸系高分 子化合物之具體例，可列舉聚丙烯酸、聚甲基丙烯酸、聚 ‘ 丁烯酸、聚亞甲基丁二酸、聚順丁烯二酸、聚反丁烯二 酸、丙浠酸-甲基丙烯酸共聚物、丙烯酸-亞曱基丁二酸共 ❹ 聚物丙稀酸_順丁稀二酸共聚物、丙烯酸-丙稀醢胺共聚 物、丙烯酸·丙烯酸醋共聚物、丙烯酸_甲基丙烯酸醋共聚 物、丙烯酸-磺酸系單體共聚物、丙烯酸_乙烯基吡咯啶酮 共聚物等。X’缓酸系高分子化合物亦可為該等聚合物之 鹽’例如可列舉聚丙烯酸鈉、聚丙烯酸鉀、聚丙烯酸銨 等。 上述烷二醇系高分子化合物為烷二醇之聚合物例如可 舉出聚炫二醇或其衍生物等M乍為烧二醇系高分子化合物 ❹之/、體例可列舉聚乙二醇、聚丙二醇、環氧乙烷及環氧 丙燒之叙段共聚物、以及該等聚合物之衍生物（例如醋衍 生物、趟衍生物等）。該等之中較好的是具有氧乙稀基之 聚合物。 本發明中，成分（B)中水溶性高分子化合物既可單獨使 用-種，亦可組合使用兩種以上。尤其是於游離研磨粒方 式中，為使研磨粒分散穩定性或料研磨粒流動性大幅产 提高，較好的是將羧酸系高分子化合物及烷二醇系高 化合物組合使用。 147069.doc 201042028 一於本發明之硬脆性材料用加工液中，成分（B)之水溶性 间分子化合物之調配量，以加工液總量為基準通常為 1 30質量./。，較好的是〇1〜2〇質量％。藉由使調配量為 〇.〇1質量％以上，可獲得充分之黏度調整效果藉由使調 配量為30質量％以下，黏度不會變得過大，於游離研磨粒 方式中’可將漿料充分地供給至加工間隙，於使用固定研 磨粒線鋸之方式中，可將加工液充分地供給至加工間隙。 作為本發明之硬脆性材料用加工液之成分（c)的非離子 界面活性劑，其】質量％水溶液之濁點為1〇〜7〇。〇，較好的 是25〜6〇°C。本發明中藉由調配成分（C)，於游離研磨粒方 式中’可提高研磨粒之分散穩錢及切屬之清洗性，於使 用固定研磨粒線鑛之方式中，可提高切層之清洗性，並且 加工液之摩擦係數變小，可抑制固定研磨粒之剝離。若濁 點未達1G°C則溶解性差’若超過7()。⑽起泡性變高。 作為上述成分（C) ’較好者可舉出含有氧丙烯基之非離 子界面活性劑（以下’彳時簡稱為含P〇之非離子界面活性 劑)。作為含PO之非離子界面活性劑，例如可列舉聚丙二 醇、丙二醇或聚丙二醇之8旨衍生物、丙二醇或聚丙二醇之 鍵衍生物、及環氧丙院與環氧乙貌之嵌段共聚物（ΕΟ·ΡΟ嵌 段共聚物），就分散性及低起泡性之觀點而言特別好的是 ΕΟ-ΡΟ嵌段共聚物。 含ΡΟ之非離子界面活性劍齡杯认& β f削較好的的是數量平均分子量 為70〜5,000之化合物，更好的s 丈奸的疋100〜4,000之化合物。含 ΡΟ之非離子界面活性劑，較妊 权好的疋氧丙烯基佔分子整體的 147069.doc -10- 201042028 40〜90質量％，更好的是佔50〜80質量％。 本發明中’成分（C)之非離子界面活性 一锸n 劑既可單獨使用 種，亦可組合使用兩種以上。成分（C) ,½細—M 非離子界面活 劑之調配量，以加工液總量為基準通常為01〜20質量When the working fluid comes to the water content of the south, it is easy to settle and it is difficult to collect the granules of the inter-processed liquid. In this case, if the viscosity is too large, it is difficult to process the gap. Further, if the previous rubbing coefficient is increased, the use of the fixed abrasive grains becomes easy to peel off. However, in the case of using the previous abrasive particle method, the abrasive grains are supplied to the processing gap. Further, the abrasive grains can be made difficult to settle, but the problem is that the grinding solution is supplied to the working fluid to increase the water content of the south, and the problem of the environment and safety of the fixed abrasive is obtained. In view of the above situation, ^,, privately, the purpose is to provide an aqueous processing fluid 'the aqueous processing fluid is fully supplied to the processing gap in the inner 3, and the pulp has a good dispersion stability. The cleaning and dispersibility of the chips are excellent. In addition, the aqueous processing liquid is cut in the aqueous processing liquid, and the fixed abrasive grains are not easily peeled off, and the method is excellent in the method of washing and dispersing. 147069.doc 201042028 The technical means of solving the problem was found by deploying the topic. The present invention is based on the fact that the inventors and the like have repeatedly conducted intensive studies to determine that the processing fluid obtained by the additive can solve the above-mentioned knowledge. That is, the present invention provides the following components (A) to (〇1) a processing fluid for a hard and brittle material, which is obtained by: (A) water, (B) having a milk-containing group and having a number of equal parts; g knife is set to 6,000~3,000,000 water-soluble southern molecular compound, (CM mass. /. The cloud point of the aqueous solution is 1G~7Gt nonionic surfactant; 2+ above! The hard brittle material m, wherein the above component (8) The oxygen-containing one is selected from the group consisting of a m group, a trans group, an oxyethylene group and an oxypropylene group; 3. The working fluid for a hard and brittle material according to the above W2, wherein the component (b) is a carboxylic acid system 4. The polymer compound and/or the alkanediol-based polymer compound, wherein the component (B) is a combination of a carboxylic acid-based polymer compound and an alkanediol-based polymer compound. 5. The working fluid for a hard and brittle material according to any one of the above 1 to 4, wherein the component (C) is a nonionic surfactant having an oxypropylene group and having a number average molecular weight of 70 to 5,000; a working fluid for hard and brittle materials of any of 5, wherein the total processing fluid For the reference, the amount of the above components is 5 〇 to 99% by mass, and the amount of the above component (B) is 0.01 to 30,000. The composition of the above component (C) is 147069.doc 201042028 The component (B) The compounding amount of the component (c) is 0.1 to 20% by mass, and the working fluid for a hard and brittle material according to any one of the above 1 to 6, wherein the pH is 2 to 10; and 8. The working fluid for a hard and brittle material according to the above 7, which comprises obtaining an acid component and a base, and adjusting the ratio of the acid component to the alkali component to adjust pJJ to obtain the effect of the invention. According to the present invention, it is possible to provide an aqueous processing liquid which can sufficiently supply the slurry to the processing gap in the form of the free abrasive grains processed by the wire miscellaneous processing, has excellent dispersion stability of the abrasive particles, and is excellent in cleaning (dispersion) of the chips. Further, in the method of using a fixed abrasive grain line, the fixed abrasive grains are not easily peeled off, and the cleaning (dispersion) of the chips is excellent. [Embodiment] The hard material and brittleness of the invention are Material (hereinafter, sometimes The working fluid for the "hard brittle material" is a working fluid obtained by blending (A) water, (B) a specific water-soluble polymer compound, and (C) a specific nonionic surfactant. The water of the component (A) of the working fluid for hard and brittle materials can be used without particular limitation, and it is preferred to use purified water, particularly preferably deionized water. The amount of water is usually based on the total amount of the working fluid. It is 50 to 99% by mass, preferably 60 to 95% by mass. By setting the amount of water to 5% by mass or more, the flammability is lowered, so the safety is improved, and the ring is 147069.doc 201042028 It is also better in terms of the environment. There is no special purpose for the upper limit, and the relationship with the other components is usually 99% by mass. Further, the water-soluble molecular compound as the component (B) of the working fluid for a hard and brittle material of the present invention has a water-soluble polymer compound having an oxygen-containing group and having a number average molecular weight of 6, _ to 3, and _. In the present invention, the viscosity of the working fluid is adjusted by blending the component (B), and the viscosity is adjusted: In the free abrasive grain method, the dispersion stability of the abrasive grains in the material and the cleaning property of the chips are improved. In the method of using a fixed abrasive wire saw, 'the processing fluid is easy to adhere to the cutting line, soaked into the machining gap, the cutting speed becomes faster' and T suppresses the grinding flaw (4). If the number average & sub-quantity is less than 6, _, it is difficult to obtain the viscosity adjustment effect 1 more than 3, _, 000, then in the free abrasive grain mode, point hep iron p, wind 丄 ^ this, τ viscosity change 仵It is too large to sufficiently supply the slurry to the processing gap. In terms of horses and scorpions, the average molecular weight is preferably 10,000 to 1,500,000. The above-mentioned oxygen-containing group and oxypropylene group. Here, examples of the neutralization and the anion include, for example, a carboxyl group, a hydroxyl group, and an oxyethylene group, and the carboxyl group and the hydroxyl group also include deprotonated or further, a pure polymer compound of the stomach water, which means dissolved in water. The polymer compound 'generally refers to the solubility in water (10). 〇 is a polymer compound (U g/water (10) (4). In the present specification, the slurry means a mixture containing a working fluid and abrasive grains. The component (B) towel is excellent in not only the viscosity adjustment effect but also dispersion. The agent or the chip cleaning improver is also excellent, and the phthalic acid rate is a south molecular compound or an alkanediol polymer compound. I47069.doc 201042028 The above carboxylic acid two-molecule compound has a polymerizable group. A polymer compound obtained by polymerization of an unsaturated carboxylic acid. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic anhydride, maleic acid, fumaric acid, crotonic acid, and arsenic acid. Methyl succinic acid, etc. Specific examples of the carboxylic acid-based polymer compound include polyacrylic acid, polymethacrylic acid, poly-butenoic acid, polymethylene succinic acid, polymaleic acid, and poly Fumaric acid, propionic acid-methacrylic acid copolymer, acrylic acid-mercapto succinic acid conjugated acrylic acid _ butyl succinic acid copolymer, acrylic acid acrylamide copolymer, acrylic acid ·Acrylic vinegar copolymer Acrylic acid-methacrylic acid vinegar copolymer, acrylic acid-sulfonic acid monomer copolymer, acrylic acid-vinylpyrrolidone copolymer, etc. X's slow acid polymer compound may also be a salt of such polymers', for example The sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, etc. The above-mentioned alkanediol type polymer compound is a polymer of an alkane diol, for example, a polyglycol diol or a derivative thereof, etc. Examples of the molecular compound may include polyethylene glycol, polypropylene glycol, a copolymer of ethylene oxide and propylene propylene, and derivatives of the polymers (for example, vinegar derivatives, anthraquinone derivatives, etc.) Among these, a polymer having an oxyethylene group is preferred. In the present invention, the water-soluble polymer compound in the component (B) may be used singly or in combination of two or more. In the free abrasive method, in order to improve the dispersion stability of the abrasive particles or the fluidity of the abrasive particles, it is preferred to use a combination of a carboxylic acid polymer compound and an alkanediol compound. 147069.doc 201042028 Yu Benfa In the working fluid for a hard and brittle material, the amount of the water-soluble inter-molecular compound of the component (B) is usually 1 to 30 mass% based on the total amount of the working fluid, preferably 〇1 to 2% by mass. When the blending amount is 〇.〇1% by mass or more, a sufficient viscosity adjustment effect can be obtained. When the blending amount is 30% by mass or less, the viscosity does not become excessive, and in the free abrasive method, the slurry can be obtained. The material is sufficiently supplied to the processing gap, and the machining liquid can be sufficiently supplied to the machining gap in the manner of using the fixed abrasive grain saw. The nonionic interface activity of the component (c) of the working fluid for hard and brittle materials of the present invention. The physico-% aqueous solution has a cloud point of 1 〇 to 7 〇. 〇, preferably 25 to 6 〇 ° C. In the present invention, by blending the component (C), it can be improved in the form of free abrasive grains. The dispersion of the abrasive grains and the cleaning property of the granules can improve the cleaning property of the dicing layer in the method of using the fixed abrasive granules, and the friction coefficient of the working fluid becomes small, and the peeling of the fixed abrasive grains can be suppressed. If the cloud point is less than 1 G ° C, the solubility is poor, if it exceeds 7 (). (10) The foaming property becomes high. The component (C)' is preferably a nonionic surfactant containing an oxypropylene group (hereinafter, simply referred to as a P-containing nonionic surfactant). Examples of the PO-containing nonionic surfactant include a derivative of polypropylene glycol, propylene glycol or polypropylene glycol, a bond derivative of propylene glycol or polypropylene glycol, and a block copolymer of epoxy propylene and epoxy. (ΕΟ·ΡΟ block copolymer), a ruthenium-iridium block copolymer is particularly preferable from the viewpoint of dispersibility and low foaming property. The non-ionic interfacial activity of the sputum-containing cups is better than the compound with a number average molecular weight of 70 to 5,000, and the better s 丈 100 to 4,000 compounds. The bismuth-containing nonionic surfactant has a better total weight of oxime propylene groups than 147069.doc -10- 201042028 40 to 90% by mass, more preferably 50 to 80% by mass. In the present invention, the nonionic surfactant of the component (C) may be used singly or in combination of two or more. Ingredient (C), 1⁄2 fine-M non-ionic interface agent, usually based on the total amount of processing fluid, 01 to 20 mass
%，較好的是0.5〜10質量％。藉由使調配量為〇1⑼質量 % ’而於游離研磨粒方式中，可獲得充分之研磨粒分散效 果及切屑之清洗、分散效果’於使用固定研磨粒線鑛之方 式中，可獲得加卫液之摩擦係數變小，抑制固定研磨粒之 彔J離，並且提咼切屑之清洗、分散性等效果。 本發明之硬脆性材料用加工液中，於不違背本發明之目 的之範圍内可調配防銹劑、消泡劑、抗氧化劑、金屬鈍化 劑、及殺_、防腐劑等公知之添加劑。作為防錄劑，可 列舉烷基苯磺酸鹽、二壬基萘磺酸鹽、烯基丁二酸酯、多 元醇酯等。作為消泡劑’可列舉矽油、氟矽酮油及氟烷基 喊等。作為抗氧化劑，可列舉紛系抗氧化劑或胺系抗氧化 劑。作為’金屬鈍化劑，可列舉咪唑啉、嘧啶衍生物、噻一 坐知并二唾及嗟二唾等。作為殺菌劑、防腐劑，除對經 基苯甲酸酯類（paraben)外，亦可列舉苯甲酸、水揚酸、己 二烯酸、去氫乙酸、對曱苯磺酸及該等之鹽類、笨氧基乙 醇等。 土 該等添加劑之調配量可視目的適當選定，以加工液總量 為基準’該等添加劑之合計通常為〇 〇1〜5質量％左右。 本發明之硬脆性材料用加工液，較好的是pH為2〜10，更 好的是pH為4〜8。藉由使pH為2以上，抗鏽性良好，藉由 147069.doc 201042028 使pH為10以下，可避免矽等之腐蝕。1?11可藉由調整加入 至硬脆性材料用加工液中之酸成分與鹼成分之調配比來調 整。上述各種添加劑中，有符合酸成分或鹼成分者，例如 酸成分可列舉聚丙烯酸、異壬酸，鹼成分可列舉N-曱基二 乙醇胺、環己基二乙醇胺。 本發明之硬脆性材料用加工液之製造方法並無特定限 疋例如可舉出如下態樣：製備水含量較之濃縮狀態下的 硬脆性材料用加工液，於使用前添加水而調整濃度。此種 形態就搬運、販賣等之容易度或使用時濃度調節之容易度 的觀而。較好。作為此種處於濃縮狀態下之硬脆性材料 用加工液，例如可舉出如下加工液：相對於成分（B)1質量 伤含有成分（C) 〇.〇01〜5〇質量份（較好的是〇 〇1〜3〇質量份， 更好的疋0_1〜15質量份）’以該加工液總量為基準成分 (B)與成分（C)之合計含有量χ(質量％)為5 $ χ<⑽(較好的是 8〇Sx$99)。 3有本心明之硬脆性材料用加工液之漿料之黏度通常於 25 C為40〜200 mpa.s ’更好的是5〇〜i8〇 。藉由使衆 料之黏度為上述範圍’可將均句性高之漿料充分地供給至 加工間隙，可獲得優異之加工性。 如上所述含有本發明之硬脆性材料用加卫液之漿料係呈 有相對較低之黏度者，χ，通常含水率變高。一般於此種 情況下，於游離研磨船古山 粒方式中研磨粒變得易於沈降，本發 月之硬脆性材料用加工液係併用上述成分⑻與成分⑹ 者’藉此可獲得優異之研磨粒分散穩定性。 147069.doc 201042028 或多線鋸等對脆性材料或硬質材料進行線錯加工時。作為 脆1·生材料，可列舉石夕、水晶及石岌等，作為硬質材料，可列 舉陶竟；5英、藍寶石等。於線錯加工中之游離研磨粒方 式中，將本發明之硬脆性材料用加工液及游離研磨粒混合 而製備硬脆性材料加王液組合物（毁料）。作為游離研磨 粒，可無特定限制地使肖，例如可列舉Sic(碳化石幻研磨 粒、氧化鋁研磨粒、cBN研磨粒、金剛石研磨粒等。游離 ❹研磨粒之調配畺可根據目的適當決定，通常以質量比計硬 脆性材料用加工液：游離研磨粒為95:5〜10:90，較好的是 90:10〜30:70。 實施例 繼而，藉由實施例更詳細地說明本發明，本發明並不受 該等實施例任何限定。 實施例1〜4及比較例1〜6% is preferably from 0.5 to 10% by mass. By making the blending amount 〇1 (9) mass%', in the free abrasive granule method, sufficient abrasive particle dispersion effect and chip cleaning and dispersing effect can be obtained, and in the manner of using fixed abrasive granules, it is possible to obtain reinforcement. The friction coefficient of the liquid becomes small, and the effect of fixing the abrasive grains and the dispersibility of the chips is suppressed. In the working fluid for a hard and brittle material of the present invention, a known additive such as a rust preventive, an antifoaming agent, an antioxidant, a metal passivating agent, a killing agent, a preservative, or the like can be blended in a range not departing from the object of the present invention. The anti-recording agent may, for example, be an alkylbenzenesulfonate, a dinonylnaphthalenesulfonate, an alkenyl succinate or a polyhydric alcohol ester. Examples of the antifoaming agent include eucalyptus oil, fluoroketone oil, and fluoroalkyl group. As the antioxidant, a wide range of antioxidants or amine-based antioxidants can be mentioned. Examples of the metal deactivator include an imidazoline, a pyrimidine derivative, a thiophene, and a disazone and a bismuth. As a bactericide and a preservative, in addition to paraben, benzoic acid, salicylic acid, hexadienoic acid, dehydroacetic acid, p-toluenesulfonic acid, and the like, and stupid oxygen may also be mentioned. Base ethanol and the like. The amount of the additives may be appropriately selected depending on the purpose, and the total amount of the additives is usually about 1 to 5 mass%. The working fluid for a hard and brittle material of the present invention preferably has a pH of from 2 to 10, more preferably a pH of from 4 to 8. By setting the pH to 2 or higher, the rust resistance is good, and the pH is 10 or less by 147069.doc 201042028, and corrosion such as ruthenium can be avoided. 1 to 11 can be adjusted by adjusting the ratio of the acid component to the alkali component added to the working fluid for hard and brittle materials. Among the above various additives, those which are in accordance with an acid component or an alkali component, for example, polyacrylic acid or isodecanoic acid may be mentioned, and examples of the alkali component include N-mercaptodiethanolamine and cyclohexyldiethanolamine. The method for producing the working fluid for a hard and brittle material of the present invention is not particularly limited. For example, a working fluid for a hard and brittle material having a water content in a concentrated state is prepared, and water is added to adjust the concentration before use. Such a form is easy to handle, sell, etc., or the ease of concentration adjustment at the time of use. better. Examples of the working fluid for a hard and brittle material in a concentrated state include the following processing liquid: a component containing a mass of the component (B) 〇.〇01 to 5〇 by mass with respect to the component (B) (better) It is 〇〇1 to 3 〇 parts by mass, more preferably _10_1 to 15 parts by mass) 'The total content of the processing liquid (B) and the total content of the component (C) χ (% by mass) is 5 $ χ < (10) (preferably 8 〇 Sx $ 99). 3 The viscosity of the slurry of the working fluid with the hard and brittle material of the present invention is usually 40 to 200 mpa.s </ br> at 25 C, and more preferably 5 〇 to i8 〇. By setting the viscosity of the mass to the above range, a slurry having a high uniformity can be sufficiently supplied to the processing gap, and excellent workability can be obtained. As described above, the slurry containing the accelerator liquid for the hard and brittle material of the present invention exhibits a relatively low viscosity, and the water content generally becomes high. Generally, in this case, in the free-grinding ship, the abrasive grains become easy to settle, and the hard and brittle material used in the present month is used in combination with the above components (8) and (6) to obtain excellent abrasive grains. Dispersion stability. 147069.doc 201042028 Or multi-wire saws for wire-wound machining of brittle or hard materials. As the brittle material, it is exemplified by Shi Xi, crystal, and stone enamel. As a hard material, it can be listed as Tao Jing; 5 ying, sapphire, etc. In the free abrasive grain method in the wire-cut processing, the hard brittle material of the present invention is mixed with the working fluid and the free abrasive grains to prepare a hard brittle material plus king liquid composition (detergent). The free abrasive grains can be obtained without any particular limitation, and examples thereof include Sic (carbon carbide pseudo-abrasive grains, alumina abrasive grains, cBN abrasive grains, diamond abrasive grains, etc., and the preparation of free ❹ abrasive grains can be appropriately determined depending on the purpose) The working fluid for the hard and brittle material is usually 95:5 to 10:90, preferably 90:10 to 30:70 in terms of mass ratio. EXAMPLES Next, the present embodiment will be described in more detail by way of examples. The present invention is not limited by these examples. Examples 1 to 4 and Comparative Examples 1 to 6
製備表1所示之組成之加工液。再者，表中之值表示質 量份。 [表1] 表1 實施例 比較例 1 2 3 4 I 2 3 4 5 6 水 89.84 83.54 92.79 89.84 100.00 20.00 88 36 93.09 83.54 90.09 水 >容性高分子化合物1 3.00 7.⑻ 3.00 7.00 水溶性高分子化合物2 0.25 0.30 0.25 水落性高分子化合物3 - • • _ 7.00 非離子界面活性劑1 4.00 7.50 4.00 4.00 7.50 非離子界面活性劑2 - • • 4.00 丙二酵 - - - - - 80.00 • - - - 147069.doc -13- 201042028 異壬酸 0.07 0.04 0.07 0.07 0.28 0.07 0 04 Π Π7 十二烧二酸 1.11 1.05 1.11 1.11 • _ 4.44 l.li ]〇5 1 11 N·甲基二乙酵胺 1.03 0.52 1.03 1.03 麵 4.12 1.03 0 52 1 0¾ 環己基二乙醇胺 0.70 0.35 0.70 0.70 _ 2.80 0.70 0 35 η 7Π 合計 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100 00 1ΠΛ ΛΠ 省資源性(水之含量） A A A A A c A A A 1 w. w pH 6.7 7.5 6.3 6.7 7.0 7.0 8.2 8.2 Ί·Ί 8.2 水溶性高分子化合物1 :聚烷二醇衍生物[日油股份有限公 司製造，商品名Unilube 75DE-3800](數量平均分子量 18,200，重量平均分子量18,500)A working fluid having the composition shown in Table 1 was prepared. Furthermore, the values in the table indicate the mass fraction. [Table 1] Table 1 Example Comparative Example 1 2 3 4 I 2 3 4 5 6 Water 89.84 83.54 92.79 89.84 100.00 20.00 88 36 93.09 83.54 90.09 Water > Capacitive Polymer Compound 1 3.00 7.(8) 3.00 7.00 High water solubility Molecular Compound 2 0.25 0.30 0.25 Waterborne Polymer Compound 3 - • • _ 7.00 Nonionic Surfactant 1 4.00 7.50 4.00 4.00 7.50 Nonionic Surfactant 2 - • • 4.00 Propionate - - - - - 80.00 • - - - 147069.doc -13- 201042028 Isophthalic acid 0.07 0.04 0.07 0.07 0.28 0.07 0 04 Π Π7 12-burned diacid 1.11 1.05 1.11 1.11 • _ 4.44 l.li ]〇5 1 11 N·methyldiethylamine 1.03 0.52 1.03 1.03 Face 4.12 1.03 0 52 1 03⁄4 Cyclohexyldiethanolamine 0.70 0.35 0.70 0.70 _ 2.80 0.70 0 35 η 7Π Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100 00 1ΠΛ ΛΠ Provincial resources (water content) AAAAA c AAA 1 w. w pH 6.7 7.5 6.3 6.7 7.0 7.0 8.2 8.2 Ί·Ί 8.2 Water-soluble polymer compound 1: Polyalkylene glycol derivative [Manufactured by Nippon Oil Co., Ltd., trade name Unilube 75DE -3800] (number average molecular weight 18,200, weight average molecular weight 18,500)
水溶性高分子化合物2 :聚丙烯酸[日本觸媒股份有限公司 製造，商品名Aqualic AS58](數量平均分子量1〇6,〇〇〇，重 量平均分子量798,000) 水溶性高分子化合物3 :聚丙烯酸鈉[日本觸媒股份有限公 司製造，商品名Aqualic DL365](數量平均分子量2,5〇〇， 重量平均分子量5,400) 非離子界面活性劑i : i質量％水溶液之濁點為3〇它之£〇_ PO截段共聚物，分子整體中之氧丙烯基之比例為79質量％Water-soluble polymer compound 2: polyacrylic acid [manufactured by Nippon Shokubai Co., Ltd., trade name Aqualic AS58] (number average molecular weight: 1〇6, 〇〇〇, weight average molecular weight: 798,000) Water-soluble polymer compound 3: sodium polyacrylate [Manufactured by Nippon Shokubai Co., Ltd., trade name Aqualic DL365] (quantitative molecular weight 2,5〇〇, weight average molecular weight 5,400) Nonionic surfactant i : i mass % aqueous solution has a cloud point of 3 〇 _ PO segment copolymer, the ratio of oxypropylene groups in the entire molecule is 79% by mass
[三洋化成工業股份有限公司製造，商品名 PE62](數量平均分子量2,5〇〇) 非離子界面活性劑2 : 1晳暑％ 士、'六v & 1貝重/〇水溶液之濁點為56t之ΕΟ- Ρ⑽段共聚物’分子整體中氧丙烯基之比例心質量％ [三洋化成工業股份有限公司製造商品名 PE74](數量平均分子量34〇〇) 147069.doc -14- 201042028 表1中之省資源性（水之含量）之評價標準 A :水分80質量％以上 B ··水分40質量％以上、未達80質量％ C :水分未達40質量％ [研磨粒分散穩定性試驗] ，關於所得加卫液，利用以下所示之方法進行研磨粒分散 穩定性試驗。 將研磨粒（Fujimi Incorporated股份有限公司製造GC # :5〇〇)與加工液以1:1之質量比混合而製備漿料。將剛製備 後之漿料100 ml裝入量筒（内徑：28 mm、容量12〇 内， 於3〇°C下靜置。5小時後，根據以下算式求得液分離層（研 磨粒與加工液分離之層）之比例。 液分離層之比率（％)=液分離層之體積（ml)/總體之體積 (ml)xl〇〇 結果示於表2。 [沈降研磨粒之流動性試驗] 藉由與研磨粒分散穩定性試驗同樣之方法製備聚料，將 100 ml漿料裝入量筒（内徑：28 mm、容量12〇 ml)内靜置。 24小時後使量筒反轉，1小時後測定堆積之研磨粒流動之 量（ml)。結果示於表2。 [漿料之黏度] 研磨粒（Fujimi Incorporated股份有限公司製造gc # 1500)與加工液以1:1之質量比混合而製備漿料。使用b型 旋轉黏度計[東機產業股份有限公司製造TVB-1〇]測定剛製 147069.doc -15- 201042028 備後之漿料之25°C下之黏度。結果示於表2。 [往復動摩擦試驗] 試驗條件 試驗機：Orientec股份有限公司製造「F-2100」[Made in Sanyo Chemical Industry Co., Ltd., trade name PE62] (quantitative average molecular weight 2,5〇〇) Nonionic surfactant 2: 1 clear heat %, 'six v & 1 ballast / 〇 aqueous solution of cloud point The ratio of the mass percentage of the oxypropylene group in the molecular weight of the copolymer of the 56(10) segment of the 56(10) segment [Sanyo Chemical Industry Co., Ltd. Manufactured under the trade name PE74] (quantitative average molecular weight 34 〇〇) 147069.doc -14- 201042028 Table 1 Evaluation criteria for resource (water content) in the province A: moisture 80% by mass or more B · moisture 40% by mass or less, less than 80% by mass C: moisture less than 40% by mass [abrasive dispersion stability test] Regarding the obtained accelerator liquid, the abrasive particle dispersion stability test was carried out by the method shown below. A slurry was prepared by mixing abrasive grains (GC #: 5 制造 manufactured by Fujimi Incorporated Co., Ltd.) with a working liquid at a mass ratio of 1:1. 100 ml of the slurry immediately after preparation was placed in a graduated cylinder (inner diameter: 28 mm, volume 12 Torr, and allowed to stand at 3 ° C. After 5 hours, the liquid separation layer was obtained according to the following formula (abrasive grain and processing) The ratio of the liquid separation layer (%) = the volume of the liquid separation layer (ml) / the volume of the whole (ml) x l 〇〇 The results are shown in Table 2. [Liquidity test of sedimentation abrasive grains] The aggregate was prepared by the same method as the abrasive particle dispersion stability test, and 100 ml of the slurry was placed in a graduated cylinder (inner diameter: 28 mm, capacity: 12 〇 ml), and the cylinder was inverted for one hour after 24 hours. The amount (ml) of the accumulated abrasive particles was measured, and the results are shown in Table 2. [Slurry of the slurry] The abrasive grains (gc # 1500 manufactured by Fujimi Incorporated Co., Ltd.) and the working fluid were mixed at a mass ratio of 1:1. The slurry was prepared. The viscosity of the prepared slurry was measured at 25 ° C using a b-type rotary viscometer [TVB-1 制造 manufactured by Toki Sangyo Co., Ltd.]. The results are shown in Table 2. [Reciprocating friction test] Test condition test machine: Orientec Co., Ltd. manufactures "F-2100"
球：3/16英吋SUJ2 試驗板：多晶矽 滑動速度：20mm/s 滑動距離：2 cm 荷重：1.96 N 以上述試驗條件進行往復動摩擦試驗，測定摩擦係數。 結果不於表2。 [表2] 表2 實施例 比較例 1 2 3 4 1 2 3 4 5 6 研磨粒分散穩定性試驗ί〇/·Λ 8.5 14.5 16.0 8.0 54.0 14 0 54 0 54.0 45.0 25.0 1伞研磨粒之流動性試驗 53 47 45 52 0 0 0 45 50 40 水竹挪度(mPa · s) 84 110 140 82 110 . 200 枝復動摩擦試驗(摩擦係數） 0.11 0.12 0.10 0.11 0.39 0.27 0.08 0.09 0.10 0.12 如表2所明不，由於實施例之加工液之研磨粒分散穩定 性良好，㈣黏度低，故以游離研磨粒方式進行線鑛加工 時之加工精度及加工效率高，操作性亦優異。X，漿料攪 拌停止後，沈降之研磨粒之再分散性亦優異。 又’實施例之加工液之往復動摩擦試驗之摩擦係數較低 為0.HMM2’因此，於使用固^研磨粒線鑛之方 抑制固定研磨粒之剝離，且切斷阻力亦減小。 產業上之可利用性 147069.doc 201042028 本發明之硬雜材料用含水加玉液具有如下特徵：於游 研磨粒方式之線鋸加工中，可將漿料充分地供給至加工 間隙’研磨粒分散穩定性優異，並且切肩之清洗（分散）性 優異，另外於使用固定研磨粒方式之使用線鋸之方式中， 固疋研磨粒不易剝離，且切屑之清洗、分散性優異；並且 可解決環境問題及安全性之問題。 147069.doc -17-Ball: 3/16 inch SUJ2 test plate: polycrystalline 矽 sliding speed: 20 mm/s sliding distance: 2 cm load: 1.96 N The reciprocating dynamic friction test was carried out under the above test conditions, and the coefficient of friction was measured. The results are not in Table 2. [Table 2] Table 2 Example Comparative Example 1 2 3 4 1 2 3 4 5 6 Abrasive dispersion stability test 〇 〇 Λ 8.5 14.5 16.0 8.0 54.0 14 0 54 0 54.0 45.0 25.0 1 The mobility of the umbrella abrasive grains Test 53 47 45 52 0 0 0 45 50 40 Water bamboo levitation (mPa · s) 84 110 140 82 110 . 200 branch reciprocating friction test (friction coefficient) 0.11 0.12 0.10 0.11 0.39 0.27 0.08 0.09 0.10 0.12 As shown in Table 2 In addition, since the polishing liquid of the working fluid of the example has good dispersion stability and (4) the viscosity is low, the processing precision and the processing efficiency in the processing of the line ore by the free abrasive grains are high, and the workability is also excellent. X, after the slurry stirring is stopped, the re-dispersibility of the settled abrasive grains is also excellent. Further, the friction coefficient of the reciprocating dynamic friction test of the working fluid of the embodiment was as low as 0.HMM2'. Therefore, the peeling of the fixed abrasive grains was suppressed by using the solid abrasive ore, and the cutting resistance was also reduced. Industrial Applicability 147069.doc 201042028 The aqueous jade liquid for hard materials of the present invention has the following characteristics: in the wire sawing process of the abrasive grain method, the slurry can be sufficiently supplied to the processing gap 'abrasive particle dispersion Excellent in stability and excellent in cleaning (dispersion) of the shoulder cutting, and in the method of using a wire saw with a fixed abrasive method, the solid abrasive grains are not easily peeled off, and the cleaning and dispersibility of the chips are excellent; and the environment can be solved. Problem and security issues. 147069.doc -17-