JP2007152858A - Method of cutting or grinding brittle material and chip-sticking preventive agent - Google Patents
Method of cutting or grinding brittle material and chip-sticking preventive agent Download PDFInfo
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Abstract
Description
本発明は、高脆性材料の切削又は研削加工方法及び切り屑付着抑制剤に関する。更に詳しくは、本発明は、ガラス、セラミックス及びシリコン等の高脆性材料の加工時に発生する切り屑や研磨粉等の被加工材料への付着を抑制し、加工後の洗浄を容易にして洗浄不良による歩留まりの低減を解消することができる高脆性材料の切削又は研削加工方法及び切り屑付着抑制剤に関する。 The present invention relates to a cutting or grinding method of a highly brittle material and a chip adhesion inhibitor. More specifically, the present invention suppresses the adhesion of chips and abrasive powders generated during processing of highly brittle materials such as glass, ceramics, and silicon, and facilitates post-processing cleaning and poor cleaning. The present invention relates to a highly brittle material cutting or grinding method and a chip adhesion inhibitor capable of eliminating the yield reduction due to the above.
近年、半導体材料、ＭＥＭＳデバイス材料及び磁気記録材料等の分野において、ガラス、セラミックス及びシリコン等の高脆性材料が多用されている。これらの材料は硬く脆い性質があり、また、かかる高脆性材料の切削又は研削加工を行うと、微細な切り屑又は研磨粉に由来するパーティクルと呼ばれる微細な粒子が被加工材に付着することがある。かかるパーティクルが被加工材に付着すると、後工程で特性不良や配線不良等の不具合が発生するおそれがある。そのため、切削又は研削加工後、かかるパーティクルを速やかに除去する必要がある。特に、ダイシング加工では、微細な素子や回路が形成されたデバイスを切断対象とするため、切り屑、コンタミネーション及び金属汚染に対する要求が格段に高い。更に、デジタルカメラなどで使用されるイメージセンサ等では、その受光面となる表面に、かかるパーティクルが残留すると撮像時の妨げとなり、近年の高画素化や小型化を目指した受光素子部の微細化とも相まって、その要求は難化の一途を辿っている。また、ダイシング加工では、デバイスに損傷を与えないために、使用する砥粒が細かい。このため、発生する切り屑は非常に細かく、一旦デバイス表面に付着してしまうと除去しづらい。そこで、従来より、切削水のかけ方を工夫したり、切削水に二酸化炭素を混入して静電気の発生を抑えたりすることにより、汚れの付着を少なくする工夫をしている。また、加工後の洗浄工程を工夫したりしている。 In recent years, highly brittle materials such as glass, ceramics, and silicon are frequently used in the fields of semiconductor materials, MEMS device materials, and magnetic recording materials. These materials are hard and brittle, and when such highly brittle materials are cut or ground, fine particles called particles derived from fine chips or abrasive powder may adhere to the workpiece. is there. If such particles adhere to the workpiece, there is a risk that problems such as characteristic failure and wiring failure may occur in a later process. Therefore, it is necessary to quickly remove such particles after cutting or grinding. In particular, in the dicing process, a device in which fine elements and circuits are formed is targeted for cutting. Therefore, the demand for chips, contamination, and metal contamination is extremely high. Furthermore, in image sensors used in digital cameras and the like, if such particles remain on the light-receiving surface, they interfere with imaging, and the size of the light-receiving element has been reduced in recent years with the aim of increasing the number of pixels and downsizing. Together with that, the demand is becoming increasingly difficult. In the dicing process, the abrasive grains used are fine so as not to damage the device. For this reason, the generated chips are very fine and once attached to the device surface, it is difficult to remove. Therefore, conventionally, a method for reducing the adhesion of dirt is devised by devising how to apply the cutting water or by suppressing the generation of static electricity by mixing carbon dioxide into the cutting water. Also, the cleaning process after processing is devised.
例えば、下記特許文献１及び２には、固体材料をダイシング後、切断されたワークに向けて高圧で洗浄液を噴射すると共に、洗浄液に超音波振動を与えて切り屑の除去性を向上させる技術が開示されている。また、下記特許文献３には、ダイシング後の固体材料を真空吸着により固定し、その後、ロールブラシで洗浄して切り屑の残留を防ぐ技術が開示されている。更に、下記特許文献４には、ダイシング前の固体材料表面に界面活性剤を塗布してからダイシングし、その後、ダイシングされた固体材料を洗浄することによりチッピング、クラックの減少や切り屑の付着低減を可能にする技術が開示されている。 For example, in Patent Documents 1 and 2 below, there is a technique for improving the chip removal performance by spraying a cleaning liquid at a high pressure toward a cut workpiece after dicing a solid material and applying ultrasonic vibration to the cleaning liquid. It is disclosed. Further, Patent Document 3 below discloses a technique in which a solid material after dicing is fixed by vacuum suction, and then washed with a roll brush to prevent residual chips. Furthermore, in Patent Document 4 below, a surface active agent is applied to the surface of the solid material before dicing and then dicing, and then the dicing solid material is washed to reduce chipping, cracks, and chip adhesion. Techniques that enable this are disclosed.
また、ダイシング時の切削水に関する技術として、下記特許文献５及び６には、ダイシング時の切削水に、界面活性剤、炭酸若しくは酢酸等の無機酸、又は低級カルボン酸と、アンモニア塩基の化合物とからなる塩を添加して、切削水の電気伝導度を上げて、回路素子の静電破壊を抑制する技術が紹介されている。しかしながら、これらの文献には、ダイシング時の切り屑の除去効果についての言及はない。 In addition, as technologies relating to cutting water at the time of dicing, the following Patent Documents 5 and 6 include a surfactant, an inorganic acid such as carbonic acid or acetic acid, or a compound of a lower carboxylic acid and an ammonia base. A technique has been introduced in which a salt consisting of is added to increase the electrical conductivity of cutting water and suppress electrostatic breakdown of circuit elements. However, these documents do not mention the chip removal effect during dicing.
しかしながら、装置及び方法の面から被加工材表面からのパーティクルの除去を改善する方法では、相応の設備が必要である。その結果、装置が大型化、複雑化するのに加えて、装置自体の費用増の問題がある。また、いずれの方法も、活性剤塗布・洗浄工程等の加工以外の工程を増やすことになるため、コストの面からも不利な点が挙げられていた。更に、加工用油剤の組成から被加工材表面からのパーティクルの除去を改善する方法についても、従来の加工用油剤は、材料の帯電防止又は金属イオンによる汚染の除去に重点が置かれており、切り屑の付着防止を考慮した組成物は報告されていなかった。 However, methods that improve the removal of particles from the workpiece surface in terms of apparatus and method require corresponding equipment. As a result, there is a problem in that the cost of the device itself is increased in addition to the increase in size and complexity of the device. In addition, each method increases the number of processes other than the processing such as the activator application / cleaning process, and thus has a disadvantage from the viewpoint of cost. Furthermore, with regard to a method for improving the removal of particles from the surface of the work material from the composition of the processing oil, the conventional processing oil is focused on antistaticing the material or removing contamination by metal ions, No composition considering the prevention of chip adhesion has been reported.
本発明は、上記実情に鑑みてなされたものであり、ガラス、セラミックス及びシリコン等の高脆性材料の加工時に発生する切り屑や研磨粉等の被加工材料への付着を抑制し、加工後の洗浄を容易にして洗浄不良による歩留まりの低減を解消することができる高脆性材料の切削又は研削加工方法及び切り屑付着抑制剤を提供することを目的とする。 The present invention has been made in view of the above circumstances, and suppresses adhesion of chips, polishing powder, and other work materials generated during processing of highly brittle materials such as glass, ceramics, and silicon, It is an object of the present invention to provide a highly brittle material cutting or grinding method and a chip adhesion inhibitor capable of facilitating cleaning and eliminating reduction in yield due to poor cleaning.
本発明者らは、高脆性材料の加工、特に半導体材料に用いられるダイシング加工において、加工水の面から種々検討を行った。その結果、水に特定の添加剤を加えることにより、水溶性でありながら切り屑、研磨粉又はパーティクルに対する高い付着防止効果を奏し、高脆性材料の加工、特に半導体材料に用いられる脆性材料の切削又は研削加工、特にダイシング加工等の切断加工又は精密研磨加工において、高い生産性を実現できることを見出し、本発明を完成した。 The present inventors have made various studies from the viewpoint of processing water in the processing of highly brittle materials, particularly in dicing processing used for semiconductor materials. As a result, by adding a specific additive to water, it has a high anti-adhesion effect on chips, abrasive powders or particles while being water-soluble, processing of highly brittle materials, especially cutting of brittle materials used in semiconductor materials Alternatively, the inventors have found that high productivity can be realized in grinding processing, particularly cutting processing such as dicing processing or precision polishing processing, and the present invention has been completed.
本発明は、以下に示す通りである。
〔１〕水と、重量平均分子量７０〜７００００の高分子量水溶性カチオンポリマーと、を混合することにより得られ、且つ該高分子量水溶性カチオンポリマーの含有量が５〜１００００ｐｐｍである高脆性材料加工用剤を用いて、高脆性材料の切削又は研削加工を行うことを特徴とする高脆性材料の切削又は研削加工方法。
〔２〕水と、重量平均分子量７０〜７００００の高分子量水溶性カチオンポリマーと、を混合することにより得られ、該高分子量水溶性カチオンポリマーの含有量が５〜１００００ｐｐｍであり、且つ遊離砥粒を含まない高脆性材料加工用剤を用いて、該高脆性材料加工用剤と遊離砥粒とを混合せずに、高脆性材料の切削又は研削加工を行うことを特徴とする高脆性材料の切削又は研削加工方法。
〔３〕上記高脆性材料加工用剤は、上記切削又は研削加工の際に生じる切り屑が被加工材に付着するのを抑制する切り屑付着抑制剤である上記〔１〕又は〔２〕に記載の高脆性材料の切削又は研削加工方法。
〔４〕上記高分子量水溶性カチオンポリマーは、ポリエチレンイミン、ジシアンジアミド及び４級化アンモニウム塩のうちの少なくとも１種である上記〔１〕乃至〔３〕のいずれかに記載の高脆性材料の切削又は研削加工方法。
〔５〕上記高脆性材料加工用剤のｐＨが６〜９である上記〔１〕乃至〔４〕のいずれかに記載の高脆性材料の切削又は研削加工方法。
〔６〕上記高脆性材料が、ガラス、セラミックス又はシリコンを含む高脆性材料である上記〔１〕乃至〔５〕のいずれかに記載の高脆性材料の切削又は研削加工方法。
〔７〕上記高脆性材料が半導体ウエハである上記〔１〕乃至〔６〕のいずれかに記載の高脆性材料の切削又は研削加工方法。
〔８〕上記切削又は研削加工が、切断加工又は精密研磨加工である上記〔１〕乃至〔７〕のいずれかに記載の高脆性材料の切削又は研削加工方法。
〔９〕上記切削又は研削加工が、ダイシング加工である上記〔１〕乃至〔７〕のいずれかに記載の高脆性材料の切削又は研削加工方法。
〔１０〕高脆性材料の切削又は研削加工に用いられる切り屑付着抑制剤であって、
水と、重量平均分子量７０〜７００００の高分子量水溶性カチオンポリマーと、を混合することにより得られ且つ該高分子量水溶性カチオンポリマーの含有量が５〜１００００ｐｐｍであり、上記切削又は研削加工の際に生じる切り屑が被加工材に付着するのを抑制することを特徴とする切り屑付着抑制剤。
〔１１〕高脆性材料の切削又は研削加工に用いられる切り屑付着抑制剤であって、
水と、重量平均分子量７０〜７００００の高分子量水溶性カチオンポリマーと、を混合することにより得られ、該高分子量水溶性カチオンポリマーの含有量が５〜１００００ｐｐｍであり且つ遊離砥粒を含んでおらず、上記切削又は研削加工の際に生じる切り屑が被加工材に付着するのを抑制することを特徴とする切り屑付着抑制剤。
〔１２〕上記高分子量水溶性カチオンポリマーは、ポリエチレンイミン、ジシアンジアミド及び４級化アンモニウム塩のうちの少なくとも１種である上記〔１０〕又は〔１１〕に記載の切り屑付着抑制剤。
〔１３〕上記切削又は研削加工が、ダイシング加工である上記〔１０〕乃至〔１２〕のいずれかに記載の切り屑付着抑制剤。
The present invention is as follows.
[1] High brittle material processing obtained by mixing water and a high molecular weight water-soluble cationic polymer having a weight average molecular weight of 70 to 70000, and having a content of the high molecular weight water-soluble cationic polymer of 5 to 10,000 ppm A method for cutting or grinding a highly brittle material, comprising cutting or grinding a highly brittle material using an agent.
[2] It is obtained by mixing water and a high molecular weight water-soluble cationic polymer having a weight average molecular weight of 70 to 70000, the content of the high molecular weight water-soluble cationic polymer is 5 to 10,000 ppm, and free abrasive grains Of a highly brittle material characterized by cutting or grinding a highly brittle material without mixing the highly brittle material processing agent and free abrasive grains using a highly brittle material processing agent not containing Cutting or grinding method.
[3] The above-mentioned highly brittle material processing agent is the above-mentioned [1] or [2], which is a chip adhesion inhibitor that suppresses chips generated during the cutting or grinding process from adhering to a workpiece. A method of cutting or grinding the described brittle material.
[4] The high-molecular-weight water-soluble cationic polymer is a cutting of the highly brittle material according to any one of the above [1] to [3], which is at least one of polyethyleneimine, dicyandiamide, and quaternized ammonium salt. Grinding method.
[5] The highly brittle material cutting or grinding method according to any one of [1] to [4], wherein the high brittle material processing agent has a pH of 6 to 9.
[6] The highly brittle material cutting or grinding method according to any one of [1] to [5], wherein the highly brittle material is a highly brittle material containing glass, ceramics, or silicon.
[7] The cutting or grinding method for a highly brittle material according to any one of [1] to [6], wherein the highly brittle material is a semiconductor wafer.
[8] The highly brittle material cutting or grinding method according to any one of [1] to [7], wherein the cutting or grinding process is a cutting process or a precision polishing process.
[9] The highly brittle material cutting or grinding method according to any one of [1] to [7], wherein the cutting or grinding is dicing.
[10] A chip adhesion inhibitor used for cutting or grinding of highly brittle materials,
It is obtained by mixing water and a high molecular weight water-soluble cationic polymer having a weight average molecular weight of 70 to 70000, and the content of the high molecular weight water-soluble cationic polymer is 5 to 10,000 ppm. The chip adhesion inhibitor characterized by suppressing that the chip which arises adheres to a workpiece.
[11] A chip adhesion inhibitor used for cutting or grinding of highly brittle materials,
It is obtained by mixing water and a high molecular weight water-soluble cationic polymer having a weight average molecular weight of 70 to 70,000. The content of the high molecular weight water-soluble cationic polymer is 5 to 10,000 ppm and contains free abrasive grains. The chip adhesion inhibitor characterized by suppressing that the chip produced in the said cutting or grinding process adheres to a workpiece.
[12] The chip adhesion inhibitor according to [10] or [11], wherein the high molecular weight water-soluble cationic polymer is at least one of polyethyleneimine, dicyandiamide, and a quaternized ammonium salt.
[13] The chip adhesion inhibitor according to any one of [10] to [12], wherein the cutting or grinding is dicing.
本発明の高脆性材料の切削又は研削加工方法は、上記構成を有することにより、高脆性材料の加工時に発生する切り屑や研削粉等の付着を抑制し、加工後の洗浄を容易にして洗浄不良による歩留まりの低減することができる。
他の本発明の高脆性材料の切削又は研削加工方法は、上記構成を有することにより、遊離砥粒の付着を防いで切削又は研削加工を行うことができる。その結果、加工後の洗浄を容易にして洗浄不良による歩留まりの低減することができる。
本発明の高脆性材料の切削又は研削加工方法において、上記高分子量水溶性カチオンポリマーが、ポリエチレンイミン、ジシアンジアミド及び４級化アンモニウム塩のうちの少なくとも１種であると、より優れた切り屑や研削粉等の付着抑制効果を奏する。
本発明の高脆性材料の切削又は研削加工方法において、上記高脆性材料加工用剤のｐＨを６〜９とすると、より優れた切り屑や研削粉等の付着抑制効果を奏する。
本発明の高脆性材料の切削又は研削加工方法では、ガラス、セラミックス又はシリコンを含む高脆性材料、例えば半導体ウエハの切削又は研削において、上記の好適な作用効果を奏する。
本発明の高脆性材料の切削又は研削加工方法では、切断加工又は精密研磨加工において、上記の好適な作用効果を奏する。更には、ダイシング加工において、上記の好適な作用効果を奏する。
本発明の切り屑付着抑制剤は、上記構成を有することにより、切削又は研削加工の際に生じる切り屑や研削粉等が被加工材に付着するのを十分に抑制することができる。
他の本発明の切り屑付着抑制剤は、上記構成を有することにより、切削又は研削加工の際に生じる切り屑や研削粉等が被加工材に付着するのを十分に抑制することができる。
本発明の切り屑付着抑制剤において、上記高分子量水溶性カチオンポリマーが、ポリエチレンイミン、ジシアンジアミド及び４級化アンモニウム塩のうちの少なくとも１種であると、より優れた切り屑や研削粉等の付着抑制効果を奏する。
本発明の切り屑付着抑制剤は、ダイシング加工において、上記の好適な作用効果を奏する。
The highly brittle material cutting or grinding method of the present invention has the above-described configuration, thereby suppressing adhesion of chips and grinding powder generated during processing of the highly brittle material, and facilitating cleaning after processing. The yield due to defects can be reduced.
Another cutting method or grinding method of a highly brittle material according to the present invention can perform cutting or grinding processing while preventing the adhesion of loose abrasive grains by having the above-described configuration. As a result, cleaning after processing can be facilitated and the yield due to poor cleaning can be reduced.
In the cutting or grinding method of a highly brittle material of the present invention, when the high molecular weight water-soluble cationic polymer is at least one of polyethyleneimine, dicyandiamide and quaternized ammonium salt, more excellent chips and grinding There is an effect of suppressing adhesion of powder or the like.
In the highly brittle material cutting or grinding method of the present invention, when the pH of the highly brittle material processing agent is set to 6 to 9, a more excellent effect of suppressing adhesion of chips, grinding powder, and the like is achieved.
In the cutting or grinding method of the highly brittle material of the present invention, the above-mentioned preferred effects are obtained in cutting or grinding of highly brittle materials including glass, ceramics or silicon, for example, semiconductor wafers.
The highly brittle material cutting or grinding method of the present invention has the above-described advantageous effects in cutting or precision polishing. Furthermore, in the dicing process, the above-described preferable effects are exhibited.
By having the said structure, the chip adhesion inhibitor of this invention can fully suppress that the chip, grinding powder, etc. which arise in the case of cutting or grinding process adhere to a workpiece.
By having the said structure, the other chip adhesion inhibitor of this invention can fully suppress that the chip, the grinding powder, etc. which arise in the case of cutting or grinding process adhere to a workpiece.
In the chip adhesion inhibitor of the present invention, when the high molecular weight water-soluble cationic polymer is at least one of polyethyleneimine, dicyandiamide, and quaternized ammonium salt, more excellent adhesion of chips, grinding powder, etc. There is an inhibitory effect.
The chip adhesion inhibitor of the present invention has the above-mentioned preferred effects in the dicing process.
本発明の高脆性材料の切削又は研削加工方法は、水と、重量平均分子量７０〜７００００の高分子量水溶性カチオンポリマーと、を混合することにより得られ、且つ該高分子量水溶性カチオンポリマーの含有量が５〜１００００ｐｐｍである高脆性材料加工用剤を用いて、高脆性材料の切削又は研削加工を行う。
また、他の本発明の高脆性材料の切削又は研削加工方法は、水と、重量平均分子量７０〜７００００の高分子量水溶性カチオンポリマーと、を混合することにより得られ、該高分子量水溶性カチオンポリマーの含有量が５〜１００００ｐｐｍであり、且つ遊離砥粒を含まない高脆性材料加工用剤を用いて、該高脆性材料加工用剤と遊離砥粒とを混合せずに、高脆性材料の切削又は研削加工を行う。
更に、本発明の切り屑付着抑制剤は、高脆性材料の切削又は研削加工に用いられ、水と、重量平均分子量７０〜７００００の高分子量水溶性カチオンポリマーと、を混合することにより得られ且つ該高分子量水溶性カチオンポリマーの含有量が５〜１００００ｐｐｍであり、上記切削又は研削加工の際に生じる切り屑が被加工材に付着するのを抑制する。
また、他の本発明の切り屑付着抑制剤は、高脆性材料の切削又は研削加工に用いられ、水と、重量平均分子量７０〜７００００の高分子量水溶性カチオンポリマーと、を混合することにより得られ、該高分子量水溶性カチオンポリマーの含有量が５〜１００００ｐｐｍであり且つ遊離砥粒を含んでおらず、上記切削又は研削加工の際に生じる切り屑が被加工材に付着するのを抑制する。
The method of cutting or grinding a highly brittle material of the present invention is obtained by mixing water and a high molecular weight water-soluble cationic polymer having a weight average molecular weight of 70 to 70000, and contains the high molecular weight water-soluble cationic polymer. A highly brittle material is cut or ground using a highly brittle material processing agent having an amount of 5 to 10,000 ppm.
Further, another highly brittle material cutting or grinding method of the present invention is obtained by mixing water and a high molecular weight water-soluble cationic polymer having a weight average molecular weight of 70 to 70000, and the high molecular weight water-soluble cation is obtained. Using a highly brittle material processing agent having a polymer content of 5 to 10000 ppm and not containing free abrasive grains, the high brittle material processing agent and free abrasive grains are not mixed, Perform cutting or grinding.
Furthermore, the chip adhesion inhibitor of the present invention is used for cutting or grinding a highly brittle material, and is obtained by mixing water and a high-molecular weight water-soluble cationic polymer having a weight average molecular weight of 70 to 70000 and The content of the high-molecular-weight water-soluble cationic polymer is 5 to 10,000 ppm, and suppresses chips generated during the cutting or grinding process from adhering to the workpiece.
Another chip adhesion inhibitor of the present invention is used for cutting or grinding a highly brittle material, and is obtained by mixing water and a high molecular weight water-soluble cationic polymer having a weight average molecular weight of 70 to 70000. The content of the high-molecular-weight water-soluble cationic polymer is 5 to 10,000 ppm and does not contain free abrasive grains, and suppresses chips generated during the cutting or grinding process from adhering to the workpiece. .
上記高分子量水溶性カチオンポリマーとしては、第４級窒素原子及び／又は４級化可能な窒素原子を合計で２個以上有するものが好ましい。具体的には、例えば、ポリエチレンイミン、ポリエチレンイミンエトキシレート、ポリビニルピロリドン、ビニルピロリドンとビニルイミダゾールの共重合体、ポリアリルアミン、ポリアルキレンポリアミン、カチオン化セルロース、ジシアンジアミド、４級化アンモニウム塩及びこれらの誘導体等が挙げられる。上記４級化アンモニウム塩としては、例えば、モノアルキルアンモニウムクロライド、アルキルジメチルベンジルアンモニウムクロライド等が挙げられる。
これらの高分子量水溶性カチオンポリマーのなかでも、ポリエチレンイミン、ジシアンジアミド、４級化アンモニウム塩が好ましく、ポリエチレンイミンが特に好ましい。
上記高分子量水溶性カチオンポリマーは、単独で用いてよいし、２種以上を混合して用いてもよい。
The high molecular weight water-soluble cationic polymer is preferably one having a total of two or more quaternary nitrogen atoms and / or quaternized nitrogen atoms. Specifically, for example, polyethyleneimine, polyethyleneimine ethoxylate, polyvinylpyrrolidone, copolymer of vinylpyrrolidone and vinylimidazole, polyallylamine, polyalkylenepolyamine, cationized cellulose, dicyandiamide, quaternized ammonium salt and derivatives thereof Etc. Examples of the quaternized ammonium salt include monoalkylammonium chloride and alkyldimethylbenzylammonium chloride.
Among these high molecular weight water-soluble cationic polymers, polyethyleneimine, dicyandiamide, and quaternized ammonium salts are preferable, and polyethyleneimine is particularly preferable.
The high molecular weight water-soluble cationic polymer may be used alone or in combination of two or more.
上記高分子量水溶性カチオンポリマーの重量平均分子量は７０〜７００００、好ましくは１００〜３００００、更に好ましくは２００〜１５０００、より好ましくは２５０〜７０００、特に好ましくは２５０〜２０００である。上記高分子量水溶性カチオンポリマーの重量平均分子量が７０未満では、高脆性材料の加工性及びパーティクルの洗浄性を向上させるのに十分でなく、上記高分子量水溶性カチオンポリマーの重量平均分子量が７００００を超えると、粘度の上昇により作業性が低下してしまうので好ましくない。 The weight average molecular weight of the high molecular weight water-soluble cationic polymer is 70 to 70000, preferably 100 to 30000, more preferably 200 to 15000, more preferably 250 to 7000, and particularly preferably 250 to 2000. If the weight average molecular weight of the high molecular weight water-soluble cationic polymer is less than 70, it is not sufficient to improve the workability of the highly brittle material and the cleaning property of the particles, and the weight average molecular weight of the high molecular weight water soluble cationic polymer is 70,000. Exceeding this is not preferable because the workability deteriorates due to an increase in viscosity.
上記高分子量水溶性カチオンポリマーの含有量は５〜１００００ｐｐｍ、好ましくは１０〜５０００ｐｐｍ、更に好ましくは２０〜４０００ｐｐｍ、より好ましくは３０〜３０００ｐｐｍ、特に好ましくは５０〜１５００ｐｐｍである。上記高分子量水溶性カチオンポリマーの含有量が５ｐｐｍ未満では、加工性・洗浄性を向上させるには不十分であるので好ましくなく、含有量が１００００ｐｐｍを超えると、高脆性材料加工用剤又は切り屑付着抑制剤への溶解性に劣る上、加工対象である高脆性材料に対して悪影響を与えるほど、高脆性材料加工用剤等のｐＨが上昇することがあるので好ましくない。一方、上記高分子量水溶性カチオンポリマーの含有量を上記範囲とすると、加工性・洗浄性を向上させることができる。また、上記高分子量水溶性カチオンポリマーの含有量を上記範囲とすると、微量の含有量であることから、加工後の廃液処理が容易、あるいは不要とすることができるという長所もある。 The content of the high molecular weight water-soluble cationic polymer is 5 to 10,000 ppm, preferably 10 to 5000 ppm, more preferably 20 to 4000 ppm, more preferably 30 to 3000 ppm, and particularly preferably 50 to 1500 ppm. If the content of the high-molecular weight water-soluble cationic polymer is less than 5 ppm, it is not preferable because it is insufficient for improving the workability / cleanability, and if the content exceeds 10,000 ppm, the highly brittle material processing agent or chips In addition to being poor in solubility in the adhesion inhibitor, the pH of the highly brittle material processing agent and the like may increase so as to adversely affect the highly brittle material to be processed. On the other hand, when the content of the high molecular weight water-soluble cationic polymer is within the above range, processability and detergency can be improved. Further, if the content of the high molecular weight water-soluble cationic polymer is within the above range, it is a very small amount of content, so that there is an advantage that the waste liquid treatment after processing can be easily or unnecessary.
上記高脆性材料加工用剤又は切り屑付着抑制剤の溶媒として、高脆性材料に対する影響の観点から、通常は水（純水、精製水）が使用されるが、必要に応じて水と油剤等の水以外の媒体とを混合して使用することもできる。かかる混合溶媒の場合、水の配合量については特に限定はないが、通常は、上記高脆性材料加工用剤又は切り屑付着抑制剤１００質量％中、１０〜９９．５質量％、好ましくは４０〜９９．５質量％、更に好ましくは６０〜９９．５質量％である。かかる範囲とすることにより、上記高分子量水溶性カチオンポリマーの添加による効果が十分に発揮されるので好ましい。尚、上記高脆性材料加工用剤又は切り屑付着抑制剤は、上記のように最初から水を配合したものとするだけでなく、使用時に水を加えて所定の水系加工用として使用することもできる。また、必要に応じて、使用の際に更に水で稀釈して使用することもできる。 As a solvent for the above highly brittle material processing agent or chip adhesion inhibitor, water (pure water, purified water) is usually used from the viewpoint of the influence on the highly brittle material. It is also possible to use a mixture with a medium other than water. In the case of such a mixed solvent, the amount of water is not particularly limited, but is usually 10 to 99.5% by mass, preferably 40% in 100% by mass of the highly brittle material processing agent or chip adhesion inhibitor. ˜99.5 mass%, more preferably 60 to 99.5 mass%. By setting it as this range, since the effect by addition of the said high molecular weight water-soluble cationic polymer is fully exhibited, it is preferable. In addition, the high brittle material processing agent or the chip adhesion inhibitor is not only formulated from the beginning as described above, but can also be used for predetermined aqueous processing by adding water during use. it can. If necessary, it can be further diluted with water before use.
上記高脆性材料加工用剤又は切り屑付着抑制剤のｐＨは６〜９であることが好ましく、より好ましくは６〜７である。かかる範囲とすることにより、より優れた切り屑や研削粉等の付着抑制効果を奏する。
また、上記高脆性材料加工用剤等のｐＨの調整には、ｐＨ調整剤を用いることができる。
上記ｐＨ調整剤は、上記高脆性材料加工用剤等の加工性能・洗浄性能を著しく低下させない限り特に限定されず、例えば、安息香酸、フタル酸及びトリメリット酸などの芳香族酸、プロピオン酸、ブチル酸、バレリアン酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ウンデカン酸、ラウリン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、クエン酸及びリンゴ酸などの脂肪族酸、並びに、硝酸、塩酸及びリン酸などの無機酸等を挙げることができる。
The pH of the highly brittle material processing agent or chip adhesion inhibitor is preferably 6-9, more preferably 6-7. By setting it as this range, there exists more excellent adhesion inhibitory effect, such as a chip and grinding powder.
Moreover, a pH adjuster can be used for adjustment of pH, such as the said highly brittle material processing agent.
The pH adjuster is not particularly limited as long as the processing performance and cleaning performance of the highly brittle material processing agent and the like are not significantly reduced. For example, aromatic acids such as benzoic acid, phthalic acid and trimellitic acid, propionic acid, Butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, citric acid And aliphatic acids such as malic acid, and inorganic acids such as nitric acid, hydrochloric acid and phosphoric acid.
上記高脆性材料加工用剤又は切り屑付着抑制剤には、その加工性能・洗浄性能を著しく低下させない限り、一般的な加工油剤に添加されている種々の添加剤の１種又は２種以上を必要に応じて適宜含有させることができる。上記添加剤としては、例えば、一般的な加工油剤に添加されている公知の防錆剤、消泡剤、防食剤、防腐剤及び着色剤等が挙げられる。また、上記高脆性材料加工用剤には、必要に応じて遊離砥粒を含有させてもよいが、遊離砥粒を含まないものとしてもよい。 The above highly brittle material processing agent or chip adhesion inhibitor includes one or more of various additives added to general processing oils unless the processing performance and cleaning performance are significantly reduced. It can be suitably contained as required. As said additive, the well-known rust preventive agent, antifoamer, anticorrosive agent, antiseptic | preservative, coloring agent etc. which are added to the general processing oil agent are mentioned, for example. Moreover, although the said highly brittle material processing agent may contain a free abrasive grain as needed, it is good also as what does not contain a free abrasive grain.
また、本発明における上記高脆性材料加工用剤は、上記切削又は研削加工の際に生じる切り屑が被加工材に付着するのを抑制するための切り屑付着抑制剤として用いることができる。 Moreover, the said highly brittle material processing agent in this invention can be used as a chip adhesion inhibitor for suppressing that the chip produced in the said cutting or grinding process adheres to a workpiece.
上記高脆性材料加工用剤の使用形態は、切削又は研削加工に応じて適宜の使用形態とすることができる。例えば、必要に応じて、使用の際に更に水で稀釈してもよい。また、必要に応じて遊離砥粒を含有させてもよいが、遊離砥粒を含まないものとしてもよい。例えば、遊離砥粒を含まない上記高脆性材料加工用剤を用いて、該高脆性材料加工用剤と遊離砥粒とを混合せずに、高脆性材料の切削又は研削加工を行うことができる。この方法の場合、砥石からの脱落砥粒が若干含まれることは不可避であるが、切削又は研削加工における遊離砥粒の量を減らすことができる。そのため、かかる遊離砥粒が付着することを防いで切削又は研削加工を行うことができ、その結果、加工後の洗浄を容易にして洗浄不良による歩留まりの低減することができる。 The usage form of the agent for processing a highly brittle material can be an appropriate usage form according to cutting or grinding. For example, if necessary, it may be further diluted with water at the time of use. Moreover, although you may contain a loose abrasive as needed, it is good also as what does not contain a loose abrasive. For example, using the above-mentioned agent for processing a highly brittle material that does not contain free abrasive grains, the highly brittle material can be cut or ground without mixing the agent for processing a highly brittle material and free abrasive grains. . In the case of this method, it is inevitable that some abrasive grains fall off from the grindstone are included, but the amount of loose abrasive grains in cutting or grinding can be reduced. Therefore, cutting or grinding can be performed while preventing such loose abrasive particles from adhering, and as a result, cleaning after processing can be facilitated and yield due to poor cleaning can be reduced.
本発明の高脆性材料の切削又は研削加工方法をより良好に行うため、上記高脆性材料加工用剤の液温、供給量及び加工速度等の諸条件を適宜調整することができる。例えば、上記高脆性材料加工用剤の供給量は、通常０．５リットル／ｍｉｎ以上、好ましくは０．７リットル／ｍｉｎ以上、更に好ましくは１．２リットル／ｍｉｎ以上とすることができる。 In order to perform the highly brittle material cutting or grinding method of the present invention more satisfactorily, various conditions such as the liquid temperature, supply amount, and processing speed of the highly brittle material processing agent can be appropriately adjusted. For example, the supply amount of the high brittle material processing agent is usually 0.5 liter / min or more, preferably 0.7 liter / min or more, more preferably 1.2 liter / min or more.
本発明の高脆性材料の切削又は研削加工方法において、上記高脆性材料の種類、材質及び形状等には特に限定はない。上記高脆性材料として具体的には、例えば、ガラス、セラミックス、又はシリコンを含む高脆性材料等が挙げられる。より具体的には、例えば、シリコン、ガリウムヒ素、酸化珪素などを含む半導体ウエハ等の半導体材料、水晶、サファイア等を含む電子デバイス基板材料、酸化アルミニウムなどの金属酸化物からなるセラミックス材料、及び、フェライト、ネオジム磁石、サマリウム・コバルト磁石などの各種磁性材料等が挙げられる。尚、上記半導体材料には、その表面が樹脂製の保護膜やマイクロレンズに覆われているものも含まれる。 In the highly brittle material cutting or grinding method of the present invention, the kind, material and shape of the highly brittle material are not particularly limited. Specific examples of the highly brittle material include a highly brittle material containing glass, ceramics, or silicon. More specifically, for example, a semiconductor material such as a semiconductor wafer containing silicon, gallium arsenide, silicon oxide, etc., an electronic device substrate material containing quartz, sapphire, etc., a ceramic material made of a metal oxide such as aluminum oxide, and Examples thereof include various magnetic materials such as ferrite, neodymium magnet, samarium / cobalt magnet, and the like. The semiconductor material includes one whose surface is covered with a resin protective film or a microlens.
上記切削又は研削加工の具体的種類には特に限定はない。上記切削又は研削加工として具体的には、例えば、切断加工、精密研磨加工、又はダイシング加工等が挙げられる。また、上記切削又は研削加工を行う装置についても特に限定はなく、公知の切削又は研削加工装置を適宜使用することができる。更に、上記切削又は研削加工の具体的な方法についても特に限定はなく、公知の方法により行うことができる。 There is no limitation in particular in the specific kind of the said cutting or grinding process. Specific examples of the cutting or grinding process include a cutting process, a precision polishing process, and a dicing process. Moreover, there is no limitation in particular also about the apparatus which performs the said cutting or grinding process, A well-known cutting or grinding apparatus can be used suitably. Furthermore, the specific method of the cutting or grinding is not particularly limited, and can be performed by a known method.
以下、実施例により本発明を具体的に説明する。
（１）高脆性材料加工用剤（切り屑付着抑制剤）の調製
表１及び表２に記載の各成分を、表１及び表２に示す割合で純水に配合することにより、高脆性材料加工用剤を調製した。
尚、実施例８及び比較例１〜６で添加した各成分の詳細を以下に記載する。
<１>「４級化アンモニウム塩」；三愛石油株式会社製、「ビューサン７７」
<２>「カチオン活性剤」；塩化ベンザルコニウム
<３>「ノニオン活性剤Ａ」；エチレンジアミンのポリオキシアルキレン縮合物
<４>「ノニオン活性剤Ｂ」；ポリオキシエチレンポリオキシプロピレングリコール
<５>「市販品Ａ」；ポリオキシエチレンポリオキシプロピレン共重合体
<６>「市販品Ｂ」；ポリオキシエチレンポリオキシプロピレンアルキルエーテル
<７>「市販品Ｃ」；ポリオキシエチレンオクチルフェニルエーテル
Hereinafter, the present invention will be described specifically by way of examples.
(1) Preparation of high brittle material processing agent (chip adhesion inhibitor) By blending each component shown in Table 1 and Table 2 into pure water in the proportions shown in Table 1 and Table 2, highly brittle material A processing agent was prepared.
In addition, the detail of each component added in Example 8 and Comparative Examples 1-6 is described below.
<1> “Quaternized ammonium salt”; manufactured by Sanai Oil Co., Ltd., “View Sun 77”
<2> “Cationic activator”; benzalkonium chloride
<3> “Nonion Activator A”; Polyoxyalkylene condensate of ethylenediamine
<4>"Nonion activator B"; polyoxyethylene polyoxypropylene glycol
<5>"Commercially available product A"; polyoxyethylene polyoxypropylene copolymer
<6> “Commercially available product B”; polyoxyethylene polyoxypropylene alkyl ether
<7>"Commercially available product C"; polyoxyethylene octyl phenyl ether
（２）高脆性材料のダイシング加工及びその性能評価
Ｓｉウエハ（φ６"，ｔ；０．６３５ｍｍ）をダイシングテープで固定し、次いで、上記高脆性材料用加工剤を用いてダイシング加工を行った（実施例１〜８及び比較例１〜６）。尚、参考例として、純水を高脆性材料加工用剤としてダイシング加工を行った。ダイシング条件は以下に示す通りである。
使用装置：「ＤＦＤ６４１ ＦＵＬＬＹ ＡＵＴＯＭＡＴＩＣ ＤＩＣＩＮＧ ＳＡＷ」（ディスコ社製）
切断条件：送り速度；５０ｍｍ／ｓ、切り込み深さ；ダイシングテープへ３０μｍ、スピンドル回転数；４００００ｒｐｍ
切削水流量：０．７リットル／ｍｉｎ（ブレードノズル）、１．０リットル／ｍｉｎ（シャワーノズル）、スピンナ洗浄なし
(2) Dicing processing of highly brittle material and performance evaluation thereof A Si wafer (φ6 ″, t; 0.635 mm) was fixed with a dicing tape, and then dicing processing was performed using the processing agent for highly brittle materials ( Examples 1 to 8 and Comparative Examples 1 to 6. In addition, as a reference example, dicing was performed using pure water as a highly brittle material processing agent, and the dicing conditions are as follows.
Device used: “DFD641 FULL AUTOMATIC DICING SAW” (manufactured by Disco)
Cutting conditions: Feed rate: 50 mm / s, cutting depth: 30 μm to dicing tape, spindle rotation speed: 40000 rpm
Cutting water flow rate: 0.7 l / min (blade nozzle), 1.0 l / min (shower nozzle), no spinner cleaning
上記ダイシング加工後、ダイシングした際に切り分けられた個々のチップの表面及びカーフ部について、切り屑の残存状態を目視にて観察し、以下の４水準に区別した。この結果を以下の表１に示す。
<切り屑残存基準>
◎：個々のチップ及びカーフ部に切り屑は認められない。
○：個々のチップ及びカーフ部に僅かに切り屑の残留が認められる。
△：個々のチップ及びカーフ部に切り屑の残留が認められる。
×：個々のチップ及びカーフ部に切り屑の残留が多量に認められる。
After the dicing process, the remaining state of the chips was visually observed on the surface and kerf portion of each chip cut when dicing, and was classified into the following four levels. The results are shown in Table 1 below.
<Cut residual criteria>
A: Chips are not observed in individual chips and kerf parts.
○: Slight chip residue is observed in each chip and kerf.
(Triangle | delta): The residue of a chip | tip is recognized by each chip | tip and a kerf part.
X: A large amount of chips remained in each chip and kerf.
（３）実施例の効果
表２によれば、単なる純水を用いた参考例では、ダイシングした際に切り分けられた個々のチップの表面及びカーフ部の切り屑の残存状態は「×」であり、高脆性材料の加工時に発生する切り屑の付着を十分抑制していないことが分かる。
また、本発明の範囲外であるカチオン活性剤（アルキルアミン塩酸塩）を用いた比較例１、ノニオン系活性剤（エチレンジアミンのポリオキシアルキレン縮合物）を用いた比較例２、ノニオン系活性剤（ポリオキシエチレンポリオキシプロピレングリコール）を用いた比較例３、ポリオキシエチレンポリオキシプロピレン共重合体を用いた比較例４、ポリオキシエチレンポリオキシプロピレンアルキルエーテルを用いた比較例５及びポリオキシエチレンオクチルフェニルエーテルを用いた比較例６では、ダイシングした際に切り分けられた個々のチップの表面及びカーフ部の切り屑の残存状態は「×」であり、高脆性材料の加工時に発生する切り屑の付着抑制効果の向上が認められていないことが分かる。
(3) Effects of Examples According to Table 2, in the reference example using pure water, the remaining state of chips on the surface of each chip and the kerf portion that were cut when dicing was “×”. It can be seen that the adhesion of chips generated during processing of the highly brittle material is not sufficiently suppressed.
Further, Comparative Example 1 using a cationic activator (alkylamine hydrochloride) which is outside the scope of the present invention, Comparative Example 2 using a nonionic activator (polyoxyalkylene condensate of ethylenediamine), Nonionic activator ( Comparative Example 3 using polyoxyethylene polyoxypropylene glycol), Comparative Example 4 using polyoxyethylene polyoxypropylene copolymer, Comparative Example 5 using polyoxyethylene polyoxypropylene alkyl ether, and polyoxyethylene octyl In Comparative Example 6 using phenyl ether, the remaining state of chips on the surface and kerf of each chip cut when dicing is “x”, and the adhesion of chips generated when processing highly brittle materials It turns out that the improvement of the suppression effect is not recognized.
これに対し、表１より、本発明の範囲内である実施例１〜８では、いずれもダイシング後、ダイシングした際に切り分けられた個々のチップの表面及びカーフ部の切り屑の残存状態は「◎」、「○」及び「△」のいずれかであった。特に、実施例１〜５及び７〜８では、含まれる水溶性カチオンポリマーの濃度が１００ｐｐｍ以上であると、切り屑の残存状態は「◎」か「○」であり、残存する切り屑はほとんど認められず、より優れた切り屑の付着抑制効果を奏することが分かる。 On the other hand, from Table 1, in Examples 1 to 8, which are within the scope of the present invention, after dicing, the remaining state of the chip surface and the chips on the kerf portion separated when dicing is “ ◎ ”,“ ◯ ”and“ △ ”. In particular, in Examples 1 to 5 and 7 to 8, when the concentration of the water-soluble cationic polymer contained is 100 ppm or more, the remaining state of the chips is “◎” or “◯”, and most of the remaining chips are It is not recognized and it turns out that there exists a more excellent chip adhesion inhibitory effect.
尚、本発明においては、上記具体的実施例に示すものに限られず、目的、用途に応じて本発明の範囲内で種々変更した実施例とすることができる。 The present invention is not limited to the specific examples described above, and can be variously modified examples within the scope of the present invention depending on the purpose and application.
Claims (13)
水と、重量平均分子量７０〜７００００の高分子量水溶性カチオンポリマーと、を混合することにより得られ且つ該高分子量水溶性カチオンポリマーの含有量が５〜１００００ｐｐｍであり、上記切削又は研削加工の際に生じる切り屑が被加工材に付着するのを抑制することを特徴とする切り屑付着抑制剤。 A chip adhesion inhibitor used for cutting or grinding of highly brittle materials,
It is obtained by mixing water and a high molecular weight water-soluble cationic polymer having a weight average molecular weight of 70 to 70,000, and the content of the high molecular weight water-soluble cationic polymer is 5 to 10,000 ppm. The chip adhesion inhibitor characterized by suppressing that the chip which arises adheres to a workpiece.
水と、重量平均分子量７０〜７００００の高分子量水溶性カチオンポリマーと、を混合することにより得られ、該高分子量水溶性カチオンポリマーの含有量が５〜１００００ｐｐｍであり且つ遊離砥粒を含んでおらず、上記切削又は研削加工の際に生じる切り屑が被加工材に付着するのを抑制することを特徴とする切り屑付着抑制剤。 A chip adhesion inhibitor used for cutting or grinding of highly brittle materials,
It is obtained by mixing water with a high molecular weight water-soluble cationic polymer having a weight average molecular weight of 70 to 70,000. The content of the high molecular weight water-soluble cationic polymer is 5 to 10,000 ppm and contains free abrasive grains. The chip adhesion inhibitor characterized by suppressing that the chip produced in the said cutting or grinding process adheres to a workpiece.
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| JP2005354069A JP2007152858A (en) | 2005-12-07 | 2005-12-07 | Method of cutting or grinding brittle material and chip-sticking preventive agent |
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| JP2005354069A JP2007152858A (en) | 2005-12-07 | 2005-12-07 | Method of cutting or grinding brittle material and chip-sticking preventive agent |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009013301A (en) * | 2007-07-05 | 2009-01-22 | Adeka Corp | Additive for dicing cutting water and cutting work method using its additive |
| JP2009096146A (en) * | 2007-10-19 | 2009-05-07 | Ngk Insulators Ltd | Manufacturing method of ceramic sintered body |
| JP2009279710A (en) * | 2008-05-23 | 2009-12-03 | Olympus Corp | Centering and edging method and centering and edging device |
| JP2011222716A (en) * | 2010-04-08 | 2011-11-04 | Fujimi Inc | Polishing composition and polishing method |
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| JPH07331229A (en) * | 1994-06-06 | 1995-12-19 | Bayer Ag | Suspension for cutting |
| JPH08164517A (en) * | 1994-12-14 | 1996-06-25 | Nikon Corp | Washing water repellent and dicing method using the same |
| JPH08298250A (en) * | 1995-04-26 | 1996-11-12 | Oki Electric Ind Co Ltd | Splitting method of semiconductor wafer |
| JPH10102042A (en) * | 1996-09-27 | 1998-04-21 | Kao Corp | Processing auxiliary composition, abrasive composition and surface processing |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009013301A (en) * | 2007-07-05 | 2009-01-22 | Adeka Corp | Additive for dicing cutting water and cutting work method using its additive |
| JP2009096146A (en) * | 2007-10-19 | 2009-05-07 | Ngk Insulators Ltd | Manufacturing method of ceramic sintered body |
| JP2009279710A (en) * | 2008-05-23 | 2009-12-03 | Olympus Corp | Centering and edging method and centering and edging device |
| JP2011222716A (en) * | 2010-04-08 | 2011-11-04 | Fujimi Inc | Polishing composition and polishing method |
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