JP6130247B2 - Abrasive electrodeposition liquid, method for producing fixed abrasive saw wire, and fixed abrasive saw wire - Google Patents
Abrasive electrodeposition liquid, method for producing fixed abrasive saw wire, and fixed abrasive saw wire Download PDFInfo
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本発明はシリコン，水晶，サファイア，チタンカーバイト等の硬質脆性材料のインゴット等から，シリコンウェハーや水晶振動子，基板等の製品を切り出す際に使用するソーワイヤであって，ワイヤの表面に砥粒が固定されている固定砥粒型ソーワイヤの製造に適した砥粒電着液，前記砥粒電着液を使用した固定砥粒型ソーワイヤの製造方法，及び前記方法で製造された固定砥粒型ソーワイヤに関する。 The present invention relates to a saw wire used for cutting a product such as a silicon wafer, a crystal resonator, or a substrate from an ingot of a hard brittle material such as silicon, quartz, sapphire, titanium carbide or the like. Abrasive Electrodeposition Liquid Suitable for Production of Fixed Abrasive Type Saw Wire with Fixed Abrasion, Method for Producing Fixed Abrasive Type Saw Wire Using Abrasive Electrodeposition Liquid, and Fixed Abrasive Mold Produced by the Method Related to saw wire.
シリコン，水晶，サファイア，チタンカーバイトのインゴット等の硬質脆性材料からシリコンウェハー，水晶振動子，基板等の製品を切り出すに際しては，従来から「ソーワイヤ」が使用されている。 Conventionally, when cutting products such as silicon wafers, crystal resonators, and substrates from hard brittle materials such as silicon, quartz, sapphire, titanium carbide ingots, etc., "saw wire" has been used.
このようなソーワイヤとしては，表面に砥粒が固定されていないピアノ線等から成り，砥粒と水や油の懸濁液であるスラリーをかけながら使用される遊離砥粒型ソーワイヤと，ワイヤの表面に予めダイヤモンド等の砥粒を付着させてある固定砥粒型ソーワイヤがある。 Such a saw wire is composed of a piano wire or the like that has no abrasive grains fixed on its surface, and is a free abrasive type saw wire that is used while applying abrasive grains and a slurry of water or oil suspension, There is a fixed-abrasive saw wire in which abrasive grains such as diamond are previously attached to the surface.
固定砥粒型のソーワイヤでは，遊離砥粒型ソーワイヤに比べて切り出し速度を向上させることができると共に，ソーワイヤの使用量を大幅に減少させることができ，しかも，砥粒を含むスラリーの使用を必要としないために廃棄物の発生を大幅に減少できる利点があることから，その利用が普及しつつあるが，その一方で，固定砥粒型ソーワイヤは，遊離砥粒型ソーワイヤに比較して製造コストが高いことから，低価格で，より切断能力が高く，しかも，長寿命である固定砥粒型ソーワイヤの開発が要望されている。 The fixed-abrasive saw wire can improve the cutting speed as compared to the free-abrasive saw wire, greatly reduce the amount of saw wire used, and requires the use of slurry containing abrasive grains. However, the use of fixed-abrasive saw wires is less expensive than the free-abrasive saw wires. Therefore, there is a demand for the development of a fixed-abrasive saw wire that is low in price, has a higher cutting ability, and has a longer life.
固定砥粒型ソーワイヤを製造するためには，ワイヤの表面に砥粒を固着させることが必要で，このような固着方法の一例としてダイヤモンドやＣＢＮ等の硬質の砥粒を分散させためっき浴中でめっきを行うことにより，めっき層の形成と共に砥粒を付着させる「分散めっき法」と呼ばれる方法が提案されている。 In order to manufacture a fixed-abrasive saw wire, it is necessary to fix the abrasive grains to the surface of the wire. As an example of such a fixing method, in a plating bath in which hard abrasive grains such as diamond and CBN are dispersed. A method called “dispersion plating method” has been proposed in which the abrasive grains are adhered together with the formation of the plating layer by plating with the use of the above method.
このような分散めっき法の一例として，Ｎｉめっき浴中に表面をＮｉ等の金属被膜で覆ったダイヤモンド砥粒を投入しておき，このめっき浴中でワイヤに対しＮｉめっきを行うことにより，ワイヤの表面に形成されたＮｉめっき層中に前述の金属被覆ダイヤモンドを埋設することで，ワイヤの表面に砥粒を付着させる方法が提案されている（特許文献１参照）。 As an example of such a dispersion plating method, diamond abrasive grains whose surfaces are covered with a metal film such as Ni are placed in a Ni plating bath, and Ni plating is performed on the wire in this plating bath. There has been proposed a method of attaching abrasive grains to the surface of a wire by embedding the above-mentioned metal-coated diamond in a Ni plating layer formed on the surface of the wire (see Patent Document 1).
また，砥粒の付着量の多いソーワイヤを高速で製造することを目的とし，前述の分散めっき法とは別の方法として，砥粒を１００質量部以上１００００質量部以下，酸化チタンまたは酸化ジルコニウムの少なくとも一方のコロイド粒子を５０質量部以上１００質量部以下含有し，電気伝導度が１０mS/cm未満のソーワイヤ電着液を使用してワイヤの表面に砥粒を付着させ，その後，Ｎｉめっき層を形成して砥粒を固定する，固定粒子型のソーワイヤの製造方法も提案されている（特許文献２参照）。 Also, for the purpose of producing a saw wire with a large amount of attached abrasive grains at a high speed, as a method different from the above-described dispersion plating method, the abrasive grains are made into 100 parts by weight or more and 10,000 parts by weight or less of titanium oxide or zirconium oxide. At least one colloidal particle is contained in an amount of 50 parts by mass or more and 100 parts by mass or less, and an abrasive is attached to the surface of the wire using a saw wire electrodeposition liquid having an electric conductivity of less than 10 mS / cm. There has also been proposed a method for manufacturing a fixed particle type saw wire that is formed and fixed with abrasive grains (see Patent Document 2).
以上で説明した従来の固定砥粒式ソーワイヤの製造方法中，特許文献１に記載の製造方法では，金属被覆された砥粒をめっき浴中に添加した状態でワイヤに対しめっきを行うことで，砥粒を埋設しためっき層を成長させることができ，これにより，めっき層によって砥粒をワイヤ表面に強固に固着できるものとなっている。 Among the conventional fixed abrasive saw wire manufacturing methods described above, in the manufacturing method described in Patent Document 1, plating is performed on the wire with the metal-coated abrasive grains added to the plating bath. A plating layer in which the abrasive grains are embedded can be grown, whereby the abrasive grains can be firmly fixed to the wire surface by the plating layer.
しかし，めっき浴中に添加した砥粒は比較的短時間で沈降してしまうために，めっき浴中の砥粒の濃度を一定の状態に管理することが難しく，沈降と共にワイヤ表面に対する砥粒の析出量も減少してしまうために，砥粒の析出量を一定に維持することが難しい。 However, since the abrasive grains added to the plating bath settle in a relatively short time, it is difficult to control the concentration of the abrasive grains in the plating bath to a constant state. Since the precipitation amount is also reduced, it is difficult to keep the precipitation amount of the abrasive grains constant.
このような砥粒の沈降によって生じる析出量変化を防止するためには，ワイヤに対し絶えず一定量の砥粒を供給できるようにする必要があり，前掲の特許文献１に記載の発明ではこのような方法として，めっき浴を行う電着槽内に砥粒沈降領域を設け，この砥粒沈降領域内にあるワイヤに向かって，上方から，砥粒を含むめっき液を供給する構成を採用しており，砥粒の析出量を一定量に維持するためには，このような特別な構造を備えた製造装置が必要となる。 In order to prevent such a change in the precipitation amount caused by the settling of the abrasive grains, it is necessary to be able to constantly supply a certain amount of abrasive grains to the wire. In the invention described in the above-mentioned Patent Document 1, this is the case. As a simple method, a configuration is adopted in which an abrasive settling region is provided in an electrodeposition bath for performing a plating bath, and a plating solution containing abrasive grains is supplied from above toward the wire in the abrasive settling region. Therefore, in order to maintain the precipitation amount of abrasive grains at a constant amount, a manufacturing apparatus having such a special structure is required.
また，金属被覆された砥粒は，Ｎｉイオンに比較して大きな質量を持つことから，砥粒は，めっき浴中を自由に移動することができず，そのため，特許文献１に記載の方法では，沈降時にワイヤの近くを通過する僅かな量の砥粒のみがワイヤに付着し，その他の砥粒はワイヤに付着することなく余剰の砥粒として回収される（特許文献１［0046］）。 In addition, since the metal-coated abrasive grains have a large mass compared to Ni ions, the abrasive grains cannot move freely in the plating bath. Therefore, in the method described in Patent Document 1, Only a small amount of abrasive grains passing near the wire during sedimentation adhere to the wire, and the other abrasive grains are recovered as excess abrasive grains without adhering to the wire (Patent Document 1 [0046]).
そのため，分散めっき法で砥粒の付着を行う場合，砥粒の析出速度が遅く，ワイヤに対する砥粒の固着量を増大させるためには，ワイヤの送り速度を低下させて砥粒沈降領域にワイヤを長く止めておくか，砥粒沈降領域を長い距離設ける等して，砥粒が分散されためっき浴に対するワイヤの浸漬時間を長くする必要があり，いずれの場合にも，ソーワイヤの製造速度が遅くなると共に，砥粒沈降領域を長距離設ける場合には，製造装置も大型化する。 Therefore, when depositing abrasive grains by the dispersion plating method, the deposition rate of the abrasive grains is slow, and in order to increase the amount of abrasive grains fixed to the wire, the wire feed rate is lowered and the wire is placed in the abrasive grain settling region. It is necessary to lengthen the dipping time of the wire in the plating bath in which the abrasive grains are dispersed, for example, by holding the wire for a long time, or by providing a long distance for the abrasive grain settling region. When the abrasive sedimentation region is provided for a long distance, the manufacturing apparatus becomes larger.
しかも，分散めっき法によって砥粒の析出とめっき層の成長を同時に行う場合，めっき層の成長初期でワイヤの表面に付着した砥粒と，めっき層の成長終期でワイヤ表面に付着した砥粒では，めっき層に対する埋没状態が異なり，砥粒の粒径をある程度揃えておいたとしてもワイヤ表面（めっき層の表面）より露出する砥粒の高さを均一化することが難しく，このようなソーワイヤを使用して切断を行う場合，露出の大きい砥粒は脱落し易くソーワイヤの寿命を縮めることとなると共にワークに対し必要以上のダメージを与えるおそれがある。 Moreover, when the precipitation of the abrasive grains and the growth of the plating layer are performed simultaneously by the dispersion plating method, the abrasive grains adhering to the wire surface at the initial stage of the plating layer growth and the abrasive grains adhering to the wire surface at the end of the plating layer growth are However, it is difficult to equalize the height of the exposed abrasive grains from the wire surface (plated layer surface) even if the buried state of the plated layer is different and the grain size of the abrasive grains is uniform to some extent. When cutting is performed using, abrasive grains with large exposure are likely to fall off, reducing the life of the saw wire and possibly causing damage to the workpiece more than necessary.
以上で説明した課題を有する分散めっき法によるソーワイヤの製造に対し，特許文献２に記載のソーワイヤの製造方法では，砥粒と共に帯電したコロイド粒子を含有する電着液を使用することで，この電着液中にワイヤを浸漬させた状態でワイヤと，電着液を貯留する電着槽との間に電圧を印加すると，帯電したコロイド粒子がワイヤの表面に析出する際に，コロイド粒子が砥粒をワイヤに向かって押す等して砥粒をワイヤ表面に付着させることができるものとなっており（特許文献２［0030］），その結果，砥粒に対し金属等を被覆することなしに，砥粒の析出量の増大と，ソーワイヤの製造速度の向上を得ている。 In contrast to the manufacture of saw wire by the dispersion plating method having the above-described problems, the saw wire manufacturing method described in Patent Document 2 uses this electrodeposition liquid containing colloidal particles charged together with abrasive grains. When a voltage is applied between the wire and the electrodeposition tank in which the electrodeposition liquid is stored while the wire is immersed in the landing liquid, the colloidal particles are ground when the charged colloidal particles are deposited on the surface of the wire. Abrasive grains can be attached to the wire surface by pushing the grains toward the wire (Patent Document 2 [0030]). As a result, the abrasive grains are not coated with metal or the like. , Increase in the amount of precipitation of abrasive grains and improvement in the production rate of saw wire.
また，前述の電着液を使用して砥粒を付着させたワイヤは，更に，ワイヤの表面にＮｉめっきを施すことにより砥粒の固定を行うことでソーワイヤとして完成するものであり（特許文献２［0044］，［0045］），このように砥粒の付着と，Ｎｉめっき層の形成を別工程として行うようにしたことで，砥粒の粒径を揃えておくことにより，Ｎｉめっき層より露出する砥粒の高さについても揃えることができるものとなっている。 Further, the wire on which the abrasive grains are adhered using the above-mentioned electrodeposition liquid is completed as a saw wire by further fixing the abrasive grains by applying Ni plating to the surface of the wire (Patent Document) 2 [0044] and [0045]), the adhesion of the abrasive grains and the formation of the Ni plating layer are performed as separate processes in this manner, so that the grain size of the abrasive grains is made uniform so that the Ni plating layer The height of the more exposed abrasive grains can also be made uniform.
しかし，前掲の特許文献２に記載の発明では，コロイド粒子を帯電させるためにリン酸や縮合リン酸などの水溶性リン化合物を添加するだけでなく，アルカリ成分の添加によって電着液のpH調整を行う等の煩雑な作業が必要となる。 However, in the invention described in Patent Document 2, the pH of the electrodeposition solution is adjusted not only by adding a water-soluble phosphorus compound such as phosphoric acid or condensed phosphoric acid to charge the colloidal particles, but also by adding an alkali component. Complicated work such as carrying out is required.
また，このような電着液において電気伝導度が低い程，砥粒の電着速度を速めることができるが（特許文献２［0010］），特許文献２に記載の方法で製造された電着液には多くのイオンが存在しているため，その電気伝導度は０．５〜８mS/cm（５００〜８０００μS/cm）程度であり（特許文献２の［表１］），電気伝導度の低下，従って砥粒の電着速度の向上には一定の限界がある。 Moreover, the lower the electric conductivity in such an electrodeposition liquid, the faster the electrodeposition speed of the abrasive grains (Patent Document 2 [0010]), but the electrodeposition produced by the method described in Patent Document 2 Since many ions are present in the liquid, its electric conductivity is about 0.5 to 8 mS / cm (500 to 8000 μS / cm) (Table 1 of Patent Document 2). There is a certain limit to the reduction and hence the improvement of the electrodeposition rate of the abrasive grains.
このような電気伝導度を低下させるためには，電着液中のイオンを除去することも考えられるが，前述した複雑な工程を経て製造された特許文献２に記載の電着液に対し，更に，イオン除去のための工程を付与すれば，その製造方法は更に複雑となる。 In order to reduce such electrical conductivity, it is conceivable to remove ions in the electrodeposition solution. However, with respect to the electrodeposition solution described in Patent Document 2 manufactured through the complicated process described above, Furthermore, if a process for removing ions is added, the manufacturing method becomes more complicated.
しかも，前述した特許文献２に記載のソーワイヤの製造方法では，電解液で砥粒の付着を行ったワイヤをそのままＮｉめっき浴中に浸漬すると，Ｎｉめっき浴中にコロイド粒子が溶出してめっき浴を劣化させることから，Ｎｉめっき層の形成前に乾燥炉による加熱乾燥によってコロイド粒子を脱水縮合することが必要であり（特許文献２［0044］，［0045］），この点も生産性の向上に対する足枷となっている。 In addition, in the saw wire manufacturing method described in Patent Document 2 described above, when the wire on which the abrasive grains are adhered with the electrolytic solution is immersed in the Ni plating bath as it is, colloidal particles are eluted in the Ni plating bath, and the plating bath Therefore, before forming the Ni plating layer, it is necessary to dehydrate and condense the colloidal particles by heating and drying in a drying furnace (Patent Documents 2 [0044] and [0045]), which also improves productivity. It has become a footstep against.
このように，特許文献２に記載の発明は，前掲の特許文献１として紹介した方法で砥粒の析出を行う場合に比較して，種々の優れた点を有するものの，依然として改良の余地が認められる。 As described above, the invention described in Patent Document 2 has various excellent points as compared with the case where the precipitation of the abrasive grains is performed by the method introduced as Patent Document 1 described above, but still has room for improvement. It is done.
そこで本発明は，上記従来技術の欠点を解消するために成されたものあり，砥粒とコロイドを共に含有するソーワイヤ製造用の電着液において，pH調整等の煩雑な作業を必要とせず，また，イオン除去等の追加の工程を必要とすることなしに，より一層の電気伝導度の低下，従って，砥粒の析出速度の向上が得られると共に，砥粒付着後の乾燥工程を経ることなしにＮｉめっき等の金属めっき層の形成による砥粒の固着工程を実施することができ，長寿命で，且つ，切断能力に優れた固定砥粒型ソーワイヤの製造に使用することができる砥粒電着液，前記砥粒電着液を使用した固定砥粒型ソーワイヤの製造方法，及び前記方法で製造された固定砥粒型ソーワイヤを提供することを目的とする。 Therefore, the present invention has been made to solve the above-mentioned disadvantages of the prior art, and does not require complicated operations such as pH adjustment in the electrodeposition liquid for saw wire production containing both abrasive grains and colloids. Further, without requiring an additional step such as ion removal, the electrical conductivity can be further lowered, and hence the deposition rate of the abrasive grains can be improved, and the drying step after the abrasive grains have been attached. Abrasive grains that can be used in the manufacture of fixed-abrasive saw wires with a long service life and excellent cutting ability. It is an object of the present invention to provide an electrodeposition liquid, a method for producing a fixed abrasive saw wire using the above-mentioned abrasive electrodeposition liquid, and a fixed abrasive saw wire manufactured by the method.
上記課題を達成するために，本発明の砥粒電着液は，脱イオン水，純水，超純水等のイオンが除去された水１００００質量部と，酸化チタン，酸化ジルコニウム等の粒径６〜４０nmの酸化物粉末１〜５０質量部，アクリル酸エステル０．５〜２５質量部，及び，砥粒５０〜７００質量部を含み，電気伝導度が５００μS/cm以下であることを特徴とする（請求項１）。 In order to achieve the above object, the abrasive electrodeposition liquid of the present invention comprises 10000 parts by mass of water from which ions such as deionized water, pure water, and ultrapure water have been removed, and particle sizes of titanium oxide, zirconium oxide, and the like. It includes 1 to 50 parts by mass of oxide powder of 6 to 40 nm, 0.5 to 25 parts by mass of acrylate ester, and 50 to 700 parts by mass of abrasive grains, and has an electric conductivity of 500 μS / cm or less. (Claim 1).
なお，本発明の砥粒電着液は，後述する固定砥粒型ソーワイヤの製造に適したものであるが，固定砥粒型ソーワイヤの製造に限定されず，ワイヤ以外の他の基材の表面に砥粒を付着させる作業，例えば砥石車の製造に際し金属製ディスクの表面に砥粒を付着させる際に使用することも可能である。 The abrasive electrodeposition liquid of the present invention is suitable for the production of a fixed abrasive saw wire, which will be described later, but is not limited to the production of a fixed abrasive saw wire. It is also possible to use it when attaching abrasive grains to the surface of a metal disk in the operation of attaching abrasive grains to the surface, for example, in manufacturing a grinding wheel.
また，本発明の固定砥粒型ソーワイヤの製造方法は，
脱イオン水，純水，超純水等のイオンが除去された水１００００質量部に，酸化チタン，酸化ジルコニウム等の粒径６〜４０nmの酸化物粉末１〜５０質量部と，砥粒５０〜７００質量部を添加すると共に，電気伝導度が５００μS/cm以下となるようにアクリル酸エステルを０．５〜２５質量部の範囲で添加して電着液を得る工程と，
前記電着液を使用した電着により，ワイヤの表面に砥粒を付着させる砥粒付着工程と，
前記砥粒付着工程で砥粒が付着されたワイヤの表面に，電気めっきにより金属めっき層を形成する砥粒固定工程を含むことを特徴とする（請求項２）。
The method for producing the fixed abrasive saw wire of the present invention is as follows:
To 10000 parts by mass of water from which ions such as deionized water, pure water, and ultrapure water have been removed, 1 to 50 parts by mass of oxide powder having a particle diameter of 6 to 40 nm, such as titanium oxide and zirconium oxide, and 50 to 50 abrasive grains. Adding 700 parts by mass and adding an acrylate ester in the range of 0.5 to 25 parts by mass so that the electric conductivity is 500 μS / cm or less;
Abrasive grain attachment step of attaching abrasive grains to the surface of the wire by electrodeposition using the electrodeposition liquid,
An abrasive grain fixing step of forming a metal plating layer by electroplating on the surface of the wire to which the abrasive grains are adhered in the abrasive grain adhesion step is included (claim 2).
更に，本発明の固定砥粒型ソーワイヤは，
ワイヤの外周面に砥粒が固定された固定砥粒ソーワイヤにおいて，
前記砥粒が，アクリル酸エステル，及びアクリル酸エステルで被覆された粒径６〜４０nmの酸化物粉末を表面に付着させた状態で，前記ワイヤの表面に形成されたＮｉめっき等の金属めっき層に一部露出した状態で埋設されることにより前記ワイヤの表面に固定されていることを特徴とする（請求項３）。
Furthermore, the fixed abrasive saw wire of the present invention is
In a fixed abrasive saw wire in which abrasive grains are fixed to the outer peripheral surface of the wire,
A metal plating layer such as a Ni plating formed on the surface of the wire in a state where the abrasive grains are adhered to the surface with an acrylate ester and an oxide powder having a particle size of 6 to 40 nm coated with the acrylate ester. The wire is fixed to the surface of the wire by being embedded in a state of being partially exposed to the wire (claim 3).
以上説明した本発明の構成により，以下の顕著な効果を得ることができた。 With the configuration of the present invention described above, the following remarkable effects can be obtained.
溶媒として脱イオン水，純水，超純水等のイオンが除去された水を使用すると共に，砥粒の電着に使用する砥粒電着液にコロイド粒子として添加される酸化物粉末を帯電させるための分散剤としてアクリル酸エステルを使用したことで，コロイド粒子が完全分散された砥粒電着液が得られるだけでなく，pH調整等を行うことなしに，中性乃至は略中性である砥粒電着液を簡単に製造することができた。 Use water from which ions have been removed, such as deionized water, pure water, and ultrapure water, as a solvent, and charge oxide powder that is added as colloidal particles to the abrasive electrodeposition liquid used for electrodeposition of abrasive grains. By using acrylic acid ester as a dispersing agent, it is possible not only to obtain an abrasive electrodeposition liquid in which colloidal particles are completely dispersed, but also neutral or almost neutral without adjusting pH. It was possible to easily produce an abrasive electrodeposition liquid.
また，このようにして得られた砥粒電着液にあっては，イオンが除去された水に，酸化物粉末，砥粒及びアクリル酸エステルを添加するだけで容易に製造することができ，余分なイオンを含める必要が無いために，アクリル酸エステルの添加量を，０．５〜２５質量部の範囲内で調整するだけで，３０〜５００μS/cmという極めて低い電気伝導度を実現することができた。 In addition, the abrasive electrodeposition liquid thus obtained can be easily produced by simply adding oxide powder, abrasive grains, and acrylic acid ester to water from which ions have been removed. Since it is not necessary to include extra ions, an extremely low electrical conductivity of 30 to 500 μS / cm should be realized by adjusting the amount of acrylate added within the range of 0.5 to 25 parts by mass. I was able to.
従って，このような低い電気伝導度の実現により，本発明の砥粒電着液を使用することで，砥粒の析出速度を大幅に向上させることができ，その結果，固定砥粒型ソーワイヤの製造速度を向上させることができた。 Therefore, by realizing such low electrical conductivity, the abrasive deposition rate can be greatly improved by using the abrasive electrodeposition liquid of the present invention. As a result, the fixed abrasive saw wire The production speed could be improved.
また，アクリル酸エステルは酸化物粉末と結合した際に，酸化物粉末の表面を覆うと共に，粘着性を有する物質であるアクリル酸エステルは，その粘着性によって砥粒表面に対する酸化物粉末の付着，砥粒とワイヤ間の付着，及びワイヤに対する酸化物粉末の付着を補助する役目を有する。その結果，ダイヤモンド等の高価な砥粒のロスが発生しない。 In addition, the acrylic ester covers the surface of the oxide powder when combined with the oxide powder, and the acrylic ester, which is a sticky substance, adheres the oxide powder to the abrasive grain surface due to its adhesiveness. It has a role of assisting adhesion between the abrasive grains and the wire and adhesion of the oxide powder to the wire. As a result, loss of expensive abrasive grains such as diamond does not occur.
更に，このアクリル酸エステルが持つ粘着性により，本発明の砥粒電着液で砥粒の付着を行った場合には，砥粒を付着させた後のワイヤに対し，加熱や乾燥による脱水縮合によるコロイド粒子の固定を行うことなしにめっき浴に浸漬して金属めっき層の成膜を行った場合であっても，コロイド粒子である酸化物粉末がめっき浴中に溶出することを防止でき，その結果，コロイド粒子によってワイヤに付着されていた砥粒の脱落も無く，前掲の特許文献２に記載の発明において必要としていた砥粒電着後の加熱，乾燥工程が省略可能であることから，固定砥粒型ソーワイヤの生産速度をより一層向上させることができた。 Furthermore, due to the adhesiveness of the acrylate ester, when the abrasive grains are deposited with the abrasive electrodeposition liquid of the present invention, the wire after the abrasive grains are deposited is dehydrated and condensed by heating or drying. Even when the metal plating layer is formed by immersing in the plating bath without fixing the colloidal particles, the colloidal particles can be prevented from eluting into the plating bath. As a result, there is no loss of the abrasive grains adhered to the wire by the colloidal particles, and the heating and drying steps after the electrodeposition of the abrasive grains, which are necessary in the invention described in the above-mentioned Patent Document 2, can be omitted. The production rate of the fixed abrasive saw wire could be further improved.
なお，前述した砥粒電着液を使用して砥粒の電着を行う場合，後掲の実施例に記載の条件において，９μmの砥粒使用時において１秒の浸漬で最大１０００個/mm2迄，砥粒の析出速度を向上させることができたことから，この電着液を使用して固定砥粒型ソーワイヤを製造することで，電圧の制御により１秒あたりの浸漬による砥粒の析出量を１００〜１０００個/mm2の範囲で自由に調整することが可能である。 In addition, when electrodeposition of abrasive grains using the above-described abrasive electrodeposition liquid, under the conditions described in the examples below, a maximum of 1000 particles / mm is obtained with a 1-second immersion when using 9 μm abrasive grains. Since the deposition rate of the abrasive grains was improved up to 2 , by using this electrodeposition liquid to produce a fixed-abrasive saw wire, it was possible to control the abrasive grains by immersion per second by controlling the voltage. The amount of precipitation can be freely adjusted within the range of 100 to 1000 / mm 2 .
また，このような析出速度の向上が得られたことで，全長５m程度の短い製造ラインによっても，２０m/minという速い生産速度で固定砥粒型ソーワイヤを製造することが可能である。 In addition, since such an improvement in the deposition rate is obtained, it is possible to manufacture a fixed abrasive saw wire at a high production rate of 20 m / min even with a short production line having a total length of about 5 m.
なお，前述した本発明の砥粒電着液を使用して製造された固定砥粒型ソーワイヤでは，高密度で砥粒を付着させることが可能であること，めっき層より突出する砥粒の突出長さが揃っていることに加え，他の方法で製造された固定砥粒型ソーワイヤに比較して砥粒の固定強度を高めることができることから，長寿命であると共に，切断中，ワイヤ表面からの砥粒の露出状態，付着密度が大きく変化することが無く，また，めっき層から露出した部分の砥粒表面に付着している，アクリル酸エステルで被覆された酸化物粉末の存在が切断時に発生する切り粉の排出を促進する効果があると考えられ，その結果，切断速度が速く，被切断材に与えるダメージを小さくすることができ，単結晶シリコンは勿論，多結晶シリコンについてもダメージを与えることなく切断することができた。また，Ｎｉめっき後すなわち最終製品にもアクリル酸エステルは残り，それが砥粒の固着強度のアップにつながるとともに，砥粒と砥粒の隙間に析出したナノサイズの酸化チタンもアクリル酸エステルで固着され切断時の切粉の排出に役立つ。 In the fixed abrasive saw wire manufactured by using the above-described abrasive electrodeposition liquid of the present invention, it is possible to attach the abrasive grains at a high density, and the protrusion of the abrasive grains protruding from the plating layer. In addition to having a uniform length, the fixed strength of the abrasive grains can be increased compared to fixed abrasive saw wires manufactured by other methods, so it has a long life and can be removed from the wire surface during cutting. The presence of oxide powder coated with acrylic acid ester that is attached to the surface of the abrasive grains exposed from the plating layer does not change significantly during the cutting. It is thought that it has the effect of promoting the discharge of the generated chips. As a result, the cutting speed is fast and the damage to the material to be cut can be reduced. It could be cut without obtain. In addition, the acrylic ester remains in the final product after Ni plating, which leads to an increase in the adhesive strength of the abrasive grains, and the nano-sized titanium oxide deposited in the gap between the abrasive grains and the abrasive grains also adheres with the acrylic ester. It helps to discharge chips when cutting.
次に，本発明の実施形態につき以下説明する。 Next, an embodiment of the present invention will be described below.
〔本発明の概要〕
本発明の固定砥粒型ソーワイヤは，図１に示すように，所定の組成を有する砥粒電着液を使用してワイヤの表面に砥粒を付着させる砥粒付着工程と，この砥粒付着工程によって砥粒の付着が行われた後のワイヤ表面に対し，Ｎｉめっき等の金属めっきを行うことで，砥粒をワイヤの表面に固定する，砥粒固定工程の二工程を経て製造される。
[Outline of the Invention]
As shown in FIG. 1, the fixed abrasive saw wire according to the present invention includes an abrasive adhesion process for attaching abrasive grains to the surface of a wire using an abrasive electrodeposition liquid having a predetermined composition, and this abrasive adhesion. Manufactured through two steps of the abrasive grain fixing process, which fixes the abrasive grains to the surface of the wire by performing metal plating such as Ni plating on the wire surface after the abrasive grains are adhered by the process. .
〔被処理対象〕（ワイヤ）
母材となるワイヤとしては，固定砥粒型ソーワイヤの芯線として一般的に使用されているピアノ線や硬鋼線等の鋼線を使用することができるが，砥粒の電着時，及び後述する電気めっきに際し，ワイヤは電極として機能するものであることから，少なくともその表面が導電性を有することが必要である。
[Target] (Wire)
As the base wire, steel wires such as piano wire and hard steel wire, which are generally used as the core wire of fixed abrasive saw wires, can be used. At the time of electroplating, since the wire functions as an electrode, it is necessary that at least its surface has conductivity.
ワイヤは，一種類の金属あるいは合金で構成したものであっても良いが，例えば，表面に付着させる砥粒や，後述するめっき層との馴染みを良くするために，表面にめっきが施されたもの等についても使用可能である。 The wire may be composed of one type of metal or alloy, but for example, the surface was plated to improve familiarity with the abrasive grains that adhere to the surface and the plating layer described below. It can also be used for things.
使用可能なワイヤの線径等は特に限定されず，ソーワイヤとして使用可能な範囲であれば，如何なる太さのものであっても使用可能である。 The wire diameter and the like of the wire that can be used are not particularly limited, and any wire having a thickness that can be used as a saw wire can be used.
このようなワイヤは，必要に応じて脱脂等の処理が行われた後，後述の砥粒付着工程に付される。 Such a wire is subjected to a degreasing process or the like as necessary, and then subjected to an abrasive grain adhesion process described later.
〔砥粒付着工程〕
脱脂等の処理により表面に付着した汚れが除去された前述のワイヤは，本発明の砥粒電着液に浸漬されて，砥粒の電着が行われる。
[Abrasive adhesion process]
The above-mentioned wire from which the dirt adhering to the surface is removed by a process such as degreasing is immersed in the abrasive electrodeposition liquid of the present invention, and the electrodeposition of the abrasive grains is performed.
（１）砥粒電着液
ここで使用する砥粒電着液は，脱イオン水，純水，超純水等のイオンが除去された水を溶媒とし，この水１００００質量部に６〜４０nmの酸化物粉末１〜５０質量部と，砥粒５０〜７００質量部，及び，出来上がりの砥粒電着液の電気伝導度が３０〜５００μS/cmとなるようにアクリル酸エステルを０．５〜２５質量部の範囲で添加したものであり，このような配合により，コロイド粒子である酸化物粉末が所定の極性に帯電して安定した分散状態を有すると共に，中性あるいは略中性である砥粒電着液が得られる。
(1) Abrasive electrodeposition liquid The abrasive electrodeposition liquid used here uses water from which ions such as deionized water, pure water, and ultrapure water have been removed as a solvent, and 6 to 40 nm in 10000 parts by mass of this water. 1 to 50 parts by mass of the oxide powder, 50 to 700 parts by mass of the abrasive grains, and 0.5 to 0.5 acrylate so that the electrical conductivity of the finished abrasive electrodeposition liquid is 30 to 500 μS / cm. By adding such an amount in the range of 25 parts by mass, the oxide powder, which is colloidal particles, is charged with a predetermined polarity and has a stable dispersion state, and is a neutral or substantially neutral abrasive. A grain electrodeposition solution is obtained.
(1-1) 溶媒
本発明の砥粒電着液では，溶媒としてイオンが除去された水を使用する。このような水は，一例として不純物を濾過した水道水中のイオンを，更にイオン交換樹脂によって除去して得た脱イオン水，あるいは純水，脱イオン水や純水では除去対象としない有機物や微粒子，気体などについても更に除去して得た超純水等はいずれも使用可能であり，前述したように水道水より精製して得る他，市販されている脱イオン水，純水（精製水），超純水を購入して使用しても良い。本実施形態にあっては，水道水よりイオン交換樹脂を用いて生成した脱イオン水を使用した。
(1-1) Solvent In the abrasive electrodeposition liquid of the present invention, water from which ions are removed is used as a solvent. Such water is, for example, deionized water obtained by further removing ions in tap water from which impurities have been filtered with an ion exchange resin, or organic substances and fine particles that are not subject to removal by pure water, deionized water, or pure water. Any ultra-pure water, etc. obtained by further removing gas, etc. can be used. It can be purified from tap water as described above, and is also commercially available deionized water, pure water (purified water) , Ultrapure water may be purchased and used. In this embodiment, deionized water produced from tap water using an ion exchange resin was used.
なお，溶媒として使用する水は，イオンが除去された，イオンを殆ど含まないものであれば良く，pH７の中性であることが好ましいが，これに限定されず，弱酸性，弱アルカリ性等の，略中性，あるいは中性に近いものであっても使用可能である。 The water used as a solvent may be any water from which ions are removed and contains almost no ions, and is preferably neutral at pH 7. However, it is not limited to this, and it may be weakly acidic or weakly alkaline. , Almost neutral, or near neutral can be used.
(1-2) 酸化物粉末(コロイド粒子)
ナノレベルの粒径を有する酸化物粉末としては，酸化チタンや，酸化ジルコニウムの粉末を使用することができる。
(1-2) Oxide powder (colloidal particles)
As the oxide powder having a nano-level particle size, titanium oxide or zirconium oxide powder can be used.
このうち酸化チタン（ＴｉＯ2）としては，アナターゼ型，ルチル型，ブルッカイト型があるが，これらのいずれ共に使用可能であるが，析出速度の点でルチル型，他に対しより優れているアナターゼ型の使用が好ましい。 Among these, as titanium oxide (TiO 2 ), there are anatase type, rutile type, and brookite type, and any of these can be used, but in terms of precipitation rate, rutile type, anatase type which is superior to others. Is preferred.
使用する酸化物粉末の粒径は，６〜４０nmの範囲で，酸化物粉末の粒径は小さすぎても大きすぎても完全分散が難しくなる。 The particle size of the oxide powder used is in the range of 6 to 40 nm. If the particle size of the oxide powder is too small or too large, complete dispersion becomes difficult.
(1-3) 砥粒
砥粒電着液に添加する砥粒としては，ソーワイヤの用途に応じて各種の材質の砥粒を使用することができ，ダイヤモンド砥粒（Ｎｉ被覆，Ｔｉ被覆その他の金属被覆も含む），ｃＢＮ（立方晶窒化硼素）砥粒等の超硬質砥粒の他，切断対象とするワークの材質に対応し，Ａｌ2Ｏ3，ＳｉＣ等のセラミック系砥粒を使用することも可能であり，本実施形態にあっては，ダイヤモンド砥粒を使用している。
(1-3) Abrasive grains As the abrasive grains to be added to the abrasive electrodeposition liquid, various types of abrasive grains can be used depending on the purpose of saw wire, and diamond abrasive grains (Ni coating, Ti coating, etc. In addition to super hard abrasive grains such as cBN (cubic boron nitride) abrasive grains, etc., ceramic type abrasive grains such as Al 2 O 3 and SiC are used in accordance with the workpiece material to be cut. In this embodiment, diamond abrasive grains are used.
使用する砥粒の粒径も，ソーワイヤの用途や切削対象とするワークとの関係で適宜決定可能であるが，粒径が過度に小さい砥粒を使用する場合，切断に時間がかかり切断性能が低下する一方，粒径の大きな砥粒では，砥粒電着液内で分散させることが難しくなることから，粒径８〜１２０μm程度の粒径の使用が好ましい。 The grain size of the abrasive grains used can be determined as appropriate depending on the use of the saw wire and the workpiece to be cut. However, when abrasive grains with excessively small grain sizes are used, it takes time to cut and the cutting performance is reduced. On the other hand, in the case of abrasive grains having a large particle diameter, it is difficult to disperse them in the electrodeposition liquid for abrasive grains. Therefore, it is preferable to use a particle diameter of about 8 to 120 μm.
(1-4) アクリル酸エステル
アクリル酸エステルには，代表的なものとしてアクリル酸メチル，アクリル酸エチル，アクリル酸ブチル，アクリル酸2-エチルヘキシル，アクリル酸2-ジメチルアミノエチル，アクリル酸2-ヒドロキシエチルがあるが，これらは全て，本発明における分散剤として使用可能であると共に，その他のアクリル酸エステルについても使用可能である。
(1-4) Acrylic acid esters Typical acrylic acid esters include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-dimethylaminoethyl acrylate, 2-hydroxy acrylate. Although there are ethyls, all of these can be used as dispersants in the present invention, as well as other acrylic esters.
このアクリル酸エステルは分散剤として添加するもので，コロイド粒子である酸化物粉末（酸化チタン粉末）を負に帯電させる本実施形態にあっては，アニオン系のアクリル酸エステルを使用した。 This acrylic ester is added as a dispersant. In the present embodiment in which the oxide powder (titanium oxide powder), which is colloidal particles, is negatively charged, an anionic acrylic ester is used.
アクリル酸エステルは，最終的に得られる砥粒分散液の電気伝導度が３０〜５００μS/cmの範囲となるよう，０．５〜２５質量部の範囲内で添加量を調整する。 The amount of the acrylate ester is adjusted within the range of 0.5 to 25 parts by mass so that the electrical conductivity of the finally obtained abrasive dispersion is in the range of 30 to 500 μS / cm.
溶媒であるイオンが除去された水に，前述した酸化チタン粉末及び砥粒が添加されている状態で更に分散剤であるアクリル酸エステルを添加すると，添加されたアクリル酸エステルは，液体中の酸化物粉末及び砥粒に吸着し，これらの粒子の表面を覆うと共に，酸化チタン粉末を負に帯電させて酸化チタン粉末同士の反発によって粒子同士が凝集することを防ぐことで，分散剤として機能する。 If the acrylic acid ester, which is a dispersant, is further added to the water from which the ions, which are the solvent, have been removed, with the titanium oxide powder and abrasive grains added, the added acrylic acid ester is oxidized in the liquid. Adsorbs to the object powder and abrasive grains, covers the surface of these particles, and functions as a dispersant by negatively charging the titanium oxide powder and preventing the particles from aggregating due to the repulsion between the titanium oxide powders .
（２）砥粒の電着
以上のようにして得られた砥粒電着液を入れた電着層内にワイヤを浸漬すると共に，ワイヤと電着層内の電極間に電圧，一例として５〜５０Vを印加することで，ワイヤの表面に対する砥粒の付着が行われる。
(2) Electrodeposition of abrasive grains While immersing a wire in the electrodeposition layer containing the abrasive electrodeposition liquid obtained as described above, the voltage between the wire and the electrode in the electrodeposition layer is, for example, 5 By applying ˜50 V, the abrasive grains adhere to the surface of the wire.
前述したように，アニオン系のアクリル酸エステルの添加によって酸化チタン粉末を負に帯電させた本実施形態にあっては，ワイヤを正，電着層内の電極に負の電圧を印加すると，ワイヤの表面に酸化チタン粉末が引き寄せられる。 As described above, in the present embodiment in which the titanium oxide powder is negatively charged by the addition of an anionic acrylic ester, when the wire is positive and a negative voltage is applied to the electrode in the electrodeposition layer, the wire Titanium oxide powder is attracted to the surface.
この酸化チタン粉末は，図２中に拡大図で示すように吸着したアクリル酸エステルで覆われていると共に，砥粒も同様にアクリル酸エステルで覆われている。 The titanium oxide powder is covered with adsorbed acrylic ester as shown in an enlarged view in FIG. 2, and the abrasive grains are similarly covered with acrylic ester.
このように，酸化チタン粉末及び砥粒を覆うアクリル酸エステルは，粘接着剤等としても使用される高い粘着性を備えた材質であることから，コロイド液中ではアクリル酸エステルで覆われた砥粒表面に負に帯電した酸化チタン粉末が付着している。電圧をかけると負に帯電した酸化チタンとともに，負帯電の酸化チタンの付着した砥粒もワイヤに向かって引き寄せられ，ワイヤの表面に付着する結果，高い析出速度を実現することが可能となり，本発明の砥粒電着液を使用した砥粒の電着では，電極間に印加する電圧と，浸漬時間の調整により，ワイヤの表面に対する砥粒の析出量を１００〜１０００個/mm2の範囲で調整することができる。 In this way, the acrylic ester covering the titanium oxide powder and abrasive grains is a highly tacky material that is also used as an adhesive, so it was covered with the acrylic ester in the colloidal liquid. Negatively charged titanium oxide powder adheres to the abrasive grain surface. When voltage is applied, the negatively charged titanium oxide and the abrasive particles with negatively charged titanium oxide are attracted toward the wire and adhere to the surface of the wire. As a result, a high deposition rate can be realized. In the electrodeposition of abrasive grains using the electrodeposited abrasive liquid of the invention, the precipitation amount of abrasive grains on the surface of the wire is in the range of 100 to 1000 / mm 2 by adjusting the voltage applied between the electrodes and the dipping time. Can be adjusted.
このようにして，ワイヤの表面に付着した砥粒や酸化チタン粉体は，単にワイヤの表面に堆積しているだけでなく，アクリル酸エステルが持つ粘着力によってもワイヤ表面に付着された状態となっている。 In this way, the abrasive grains and titanium oxide powder adhering to the surface of the wire are not only deposited on the surface of the wire, but also adhered to the surface of the wire due to the adhesive strength of the acrylate ester. It has become.
その結果，このようにしてワイヤの表面に付着した酸化チタン粉末や砥粒は，その後のめっき浴に対する浸漬によっても溶出や脱落がなく，ワイヤの表面に付着した状態が維持される。 As a result, the titanium oxide powder and abrasive grains adhering to the surface of the wire in this way are not eluted or dropped by subsequent immersion in the plating bath, and remain attached to the surface of the wire.
〔砥粒固定工程〕
以上のようにしてワイヤ表面に付着した砥粒は，アクリル酸エステルの粘着力によってワイヤ表面に付着されているとは言え，大きな力を加えれば，ワイヤの表面より脱落してしまう。
[Abrasive fixing process]
Although the abrasive grains adhering to the wire surface as described above are adhering to the wire surface due to the adhesive force of the acrylate ester, if a large force is applied, they will fall off the surface of the wire.
従って，前述した砥粒付着工程によって砥粒が表面に付着されたワイヤを固定砥粒型ソーワイヤとして完成させるためには，更に金属めっきを行い，前述した方法でワイヤ表面に付着させた砥粒を，金属めっき層の形成によってワイヤの表面に対し強力に固定する必要がある（砥粒固定工程）。 Therefore, in order to complete the wire with the abrasive grains attached to the surface by the above-described abrasive adhesion process as a fixed abrasive saw wire, metal plating is further performed, and the abrasive grains adhered to the wire surface by the above-described method are used. , It is necessary to strongly fix to the surface of the wire by forming a metal plating layer (abrasive fixing process).
但し，前述した砥粒付着工程で付着させた砥粒は，金属めっきによる砥粒固定工程中，砥粒をワイヤ表面に付着させておくに十分な付着力を有し，めっき浴に浸漬した場合であっても酸化チタン粉末の溶出や砥粒の脱落が生じないことから，加熱や乾燥などの他に別段の処理を行うことなく，これをそのまま砥粒固定工程に付すことが可能である。 However, the abrasive grains deposited in the above-mentioned abrasive grain adhesion process have sufficient adhesion to keep the abrasive grains attached to the wire surface during the metal grain fixing process and are immersed in a plating bath. However, since the elution of the titanium oxide powder and the falling off of the abrasive grains do not occur, this can be directly applied to the abrasive grain fixing step without performing a separate process other than heating and drying.
本工程（砥粒固定工程）で形成する金属めっき層は，前述した方法でワイヤの表面に付着させた砥粒を，ワイヤの表面に強固に固定することができるものであれば，各種の金属めっきを形成することができ，形成する金属めっき層の材質は特に限定されず，本実施形態では，一例としてＮｉめっき層を形成することにより，砥粒の固定を行っている。 The metal plating layer formed in this step (abrasive fixing step) can be any metal as long as the abrasive particles adhered to the wire surface by the above-described method can be firmly fixed to the wire surface. Plating can be formed, and the material of the metal plating layer to be formed is not particularly limited. In this embodiment, as an example, an Ni plating layer is formed to fix the abrasive grains.
このニッケルめっき層の電着は，既知の各種の電気めっき法により行うことが可能である。もっとも，ニッケルめっきは，めっき浴の種類に応じて得られるニッケルめっき膜の硬さに違いが生じるが，本発明において得られるニッケルめっき膜は硬質である程好ましく，本実施形態にあっては，高硬度のめっき層を得ることができるスルファミン酸浴中でＮｉめっき層を形成した。 The electrodeposition of the nickel plating layer can be performed by various known electroplating methods. However, the nickel plating is different in the hardness of the nickel plating film obtained according to the type of the plating bath, but the nickel plating film obtained in the present invention is preferably as hard as possible. In the present embodiment, The Ni plating layer was formed in a sulfamic acid bath capable of obtaining a high hardness plating layer.
めっき層の形成は，砥粒の全体がめっき層中に埋没するまで行うことなく，その一部が，めっき層の表面より露出する程度に行い，好ましくは，砥粒の直径に対し，めっき層の厚さが２０〜８０％程度となるように行う。 The plating layer is not formed until the entire abrasive grains are buried in the plating layer, and a part thereof is exposed from the surface of the plating layer. Preferably, the plating layer is formed with respect to the diameter of the abrasive grains. The thickness is about 20 to 80%.
このようにしてめっき層を形成することで，砥粒はワイヤの表面に強固に固着されて，本発明の固定砥粒型ソーワイヤが完成する。 By forming the plating layer in this manner, the abrasive grains are firmly fixed to the surface of the wire, and the fixed abrasive type saw wire of the present invention is completed.
本発明の方法による固定砥粒型ソーワイヤの製造実施例，及び製造された固定砥粒型ソーワイヤの性能確認試験を行った結果を以下に示す。 Examples of production of fixed abrasive saw wires by the method of the present invention and results of performance confirmation tests of the produced fixed abrasive saw wires are shown below.
〔製造実施例〕
（１）前処理工程
ブラスめっきが施された直径０．１２mmのワイヤを，市販の電解脱脂剤（株式会社ムラタ製「ＲＣＳ−２１」）に常温で６秒間浸漬した後，水洗して脱脂を行った。
[Production Examples]
(1) Pretreatment step A 0.12 mm diameter wire subjected to brass plating is immersed in a commercially available electrolytic degreasing agent ("RCS-21" manufactured by Murata Co., Ltd.) for 6 seconds at room temperature, and then washed with water to degrease. went.
（２）砥粒の付着
脱脂後のワイヤを，砥粒を含んだ電着液がそれぞれ入った電着槽に浸漬し，砥粒の付着を行った。
(2) Adhesion of abrasive grains The degreased wire was immersed in an electrodeposition bath containing an electrodeposition solution containing abrasive grains to adhere abrasive grains.
電着は，ワイヤを正，電着槽内に設けたＳＵＳ製の電極を負として，所定の電圧を印加した状態でワイヤを電着液内に所定時間浸漬することにより行った。 The electrodeposition was performed by immersing the wire in the electrodeposition liquid for a predetermined time with a predetermined voltage applied, with the wire being positive and the SUS electrode provided in the electrodeposition tank being negative.
各実施例及び比較例における砥粒付着の際の処理条件を下記の表１及び表２に示す。 The processing conditions at the time of adhering abrasive grains in each Example and Comparative Example are shown in Table 1 and Table 2 below.
（３）砥粒の固定
実施例１〜８，及び比較例１，２の方法で砥粒の付着を行ったワイヤに対し，スルファミン酸Ｎｉめっき浴により，実施例１〜５では５μm，実施例６〜７では１０μm，実施例８では２５μｍ厚のＮｉめっきを施すことにより，砥粒をワイヤの表面に固着して，固定砥粒型ソーワイヤを得た。
(3) Abrasive Grain Fixation For the wires on which the abrasive grains were adhered by the methods of Examples 1 to 8 and Comparative Examples 1 and 2, using a sulfamic acid Ni plating bath, Examples 1 to 5 had a thickness of 5 μm. In 6 to 7, Ni plating of 10 μm and in Example 8 having a thickness of 25 μm was applied to fix the abrasive grains to the surface of the wire, thereby obtaining a fixed abrasive saw wire.
実施例１〜８では，前工程で砥粒の付着を行ったワイヤの表面にそのままＮｉめっきを施した。 In Examples 1 to 8, Ni plating was directly applied to the surface of the wire on which the abrasive grains were adhered in the previous step.
一方，比較例１，２では，Ｎｉめっきを行う前に，前工程で砥粒が付着されたワイヤを１５０℃で１０秒間，加熱，乾燥させてワイヤ表面に付着した酸化チタン粉末の脱水縮合を行った。 On the other hand, in Comparative Examples 1 and 2, before performing Ni plating, the wire on which the abrasive grains were adhered in the previous process was heated and dried at 150 ° C. for 10 seconds to dry-condense the titanium oxide powder adhered to the wire surface. went.
なお，比較例３については，本工程を経ることなく，前掲の表１に示す条件でのスルファミン酸ニッケルめっき浴による分散めっきで，固定砥粒型ソーワイヤを完成させた。 In Comparative Example 3, a fixed abrasive saw wire was completed by performing dispersion plating using a nickel sulfamate plating bath under the conditions shown in Table 1 above without passing through this step.
〔性能確認試験〕
以上のようにして得られた実施例１〜８及び比較例１〜３の固定砥粒型ソーワイヤについて，以下の点を評価した。評価結果を，表３に示す。
[Performance confirmation test]
The following points were evaluated for the fixed abrasive saw wires of Examples 1 to 8 and Comparative Examples 1 to 3 obtained as described above. Table 3 shows the evaluation results.
（１）砥粒電着液の性能評価
砥粒電着液毎の砥粒の析出速度を評価するため，各ソーワイヤ毎の砥粒の付着密度（１mm2あたりの砥粒の付着数）を測定した。
(1) Performance evaluation of abrasive electrodeposition liquid In order to evaluate the deposition rate of abrasive grains for each abrasive electrodeposition liquid, the adhesion density of abrasive grains for each saw wire (number of abrasive grains deposited per 1 mm 2 ) was measured. did.
測定は，ＳＥＭによって得たソーワイヤの表面拡大像に基づいて目視で砥粒の付着数をカウントすることにより行い，１mm2あたりの砥粒の付着数が２５０個以上のものを「Ａ」，２５０個未満のものを「Ｂ」と評価した。 The measurement is performed by visually counting the number of attached abrasive grains based on the enlarged surface image of the saw wire obtained by SEM, and “A”, 250 for the number of adhered abrasive grains of 250 or more per 1 mm 2. Those less than one were evaluated as “B”.
但し，砥粒の粒径が３５μｍのもの（実施例６，７）は２０〜５０個のものを「Ａ」と，砥粒の粒径が１００μmのもの（実施例８）は２〜１０個のものを「Ａ」と評価した。 However, when the abrasive grain size is 35 μm (Examples 6 and 7), 20 to 50 are “A”, and when the abrasive grain size is 100 μm (Example 8) are 2 to 10 pieces. Was rated “A”.
（２）ソーワイヤの性能試験
実施例１〜５及び比較例１〜３のソーワイヤ５０cmを一定の張力を付与した状態で切断機に取り付けると共に単結晶シリコン及び多結晶シリコンのインゴットに押し当て，１往復／１秒のペースで３０分間往復させて，各ソーワイヤにおける「砥粒の固着強度」と，「切断性能」を評価した。
(2) Performance test of saw wire 50 cm of saw wires of Examples 1 to 5 and Comparative Examples 1 to 3 are attached to a cutting machine with a constant tension applied and pressed against an ingot of single crystal silicon and polycrystalline silicon and reciprocated once. The sample was reciprocated at a pace of 1 second for 30 minutes to evaluate the “abrasive bond strength” and “cutting performance” of each saw wire.
砥粒の固着強度は，使用前の砥粒量に対する使用後の砥粒残存率に基づいて評価し，使用後の砥粒残存率が９５％以上のものを「○」，９５％未満のものを「×」と評価した。 Adhesive strength of abrasive grains is evaluated based on the residual ratio of abrasive grains after use with respect to the amount of abrasive grains before use. Was evaluated as “×”.
切断性能は，前述のインゴットの切断深さと，切断面に対するダメージに基づいて評価し，切断深さは，２mm以上を「Ａ」，１．５mm以上２mm未満を「Ｂ」，１．５mm未満を「Ｃ」と評価し，切断面に対するダメージは，目視によりダメージが無いものを「○」，ダメージがあったものを「×」と評価した。 The cutting performance is evaluated based on the ingot cutting depth and damage to the cut surface. The cutting depth is 2A or more, "A", 1.5mm or more and less than 2mm, "B", and less than 1.5mm. “C” was evaluated, and the damage to the cut surface was evaluated as “◯” when there was no damage by visual inspection, and “X” when there was damage.
なお，砥粒の粒径を３５μm以上とした実施例（実施例６〜８）のソーワイヤは，シリコン切断用では無いことから，切断性能試験は行っていない。 In addition, since the saw wire of the Example (Examples 6-8) which made the particle size of the abrasive grain 35 micrometers or more is not a thing for silicon | silicone cutting | disconnection, it has not performed the cutting performance test.
〔試験結果の考察〕
（１）砥粒電着液の性能
本発明の砥粒電着液を使用した実施例１〜５では，いずれも，１秒以下という短い処理時間で２５０個/mm2以上という高い付着密度で砥粒を付着させることができた。
[Consideration of test results]
(1) Performance of Abrasive Electrodeposition Liquid In Examples 1 to 5 using the abrasive electrodeposition liquid of the present invention, all have a high adhesion density of 250 pieces / mm 2 or more in a short processing time of 1 second or less. Abrasive grains could be deposited.
これに対し，分散剤として，水溶性リン化合物（ヘキサメタリン酸ナトリウム）を使用した比較例１では，浸漬時間２秒でも２５０個/mm2以上という砥粒の付着密度を得ることができず，本発明の砥粒電着液に比較して，析出速度が遅いことが確認された。 In contrast, in Comparative Example 1 using a water-soluble phosphorus compound (sodium hexametaphosphate) as a dispersant, an adhesion density of abrasive grains of 250 particles / mm 2 or more could not be obtained even with an immersion time of 2 seconds. It was confirmed that the deposition rate was slow compared to the abrasive electrodeposition liquid of the invention.
なお，比較例２では分散剤として水溶性リン化合物（ヘキサメタリン酸ナトリウム）を使用するものでありながら２５０個/mm2以上という砥粒の付着密度を達成しているが，この結果は，酸化チタン粉末の添加量を実施例１〜５の砥粒電着液に比較して増大させると共に，浸漬時間を実施例１〜５に比較して長い，２秒とした結果得られたもので，水溶性リン化合物を分散剤とした砥粒電着液において，本発明の砥粒電着液と同等の性能を得ようとした場合には，酸化チタンの添加量増加が必要なことと，浸漬時間の長大化と砥粒付着後の乾燥工程が必要なため生産速度が実施例のものと比べ遅く製造コストが上昇する。 In Comparative Example 2, a water-soluble phosphorus compound (sodium hexametaphosphate) was used as a dispersant, but an abrasive density of 250 particles / mm 2 or more was achieved. The amount of powder added was increased as compared to the abrasive electrodeposition liquids of Examples 1 to 5, and the immersion time was longer than that of Examples 1 to 5, and was obtained as a result of 2 seconds. In the case of an abrasive electrodeposition liquid containing a soluble phosphorus compound as a dispersant, when it is intended to obtain the same performance as the abrasive electrodeposition liquid of the present invention, it is necessary to increase the amount of titanium oxide added, and the immersion time And a drying process after adhering abrasive grains is required, so that the production rate is slower than that of the embodiment and the manufacturing cost is increased.
また，スルファミン酸ニッケルめっき浴によって砥粒の付着を行った比較例３においても，実施例同様，２５０個/mm2以上という砥粒の付着密度を達成されているが，この結果は，浸漬時間を１００秒としたことで得られたものであり，砥粒の析出速度は，実施例の砥粒電着液に比較して遅いものとなっている。 Further, in Comparative Example 3 in which the abrasive grains were deposited using a nickel sulfamate plating bath, an abrasive density of 250 particles / mm 2 or more was achieved as in the Example. This is obtained by setting the time to 100 seconds, and the precipitation rate of the abrasive grains is slower than that of the abrasive electrodeposition liquid of the examples.
よって，本発明の砥粒電着液を使用することで，従来の方法に比較して砥粒の析出速度を向上させることができ，ソーワイヤの生産速度の向上，あるいは生産ラインの短縮化等に貢献し得るものであることが確認できた。 Therefore, by using the abrasive electrodeposition liquid of the present invention, the deposition rate of the abrasive grains can be improved compared to the conventional method, so that the production speed of the saw wire can be improved or the production line can be shortened. It was confirmed that it can contribute.
なお，本発明の砥粒電着液を使用する場合には，印加電圧や浸漬時間を調整することで，粒径１００μmの砥粒についても付着させることが可能であり（実施例８），使用可能な砥粒の最大粒径を６０μmとしている特許文献２（特許文献２［0028］欄）に比較して大きな粒径の砥粒が使用可能で，ソーワイヤに付着させる砥粒の選択の幅を拡げることができた。 When the abrasive electrodeposition liquid of the present invention is used, it is possible to attach abrasive grains having a particle size of 100 μm by adjusting the applied voltage and immersion time (Example 8). Compared to Patent Document 2 (Patent Document 2 [0028] column) in which the maximum particle size of possible abrasive grains is 60 μm, abrasive grains having a larger particle diameter can be used, and the selection range of the abrasive grains to be attached to the saw wire is wide. I was able to expand.
（２）ソーワイヤの性能
比較例１〜３のソーワイヤでは，いずれも砥粒残存率９５％以上を達成できたものが存在しなかった。
(2) Performance of saw wire None of the saw wires of Comparative Examples 1 to 3 achieved an abrasive grain residual ratio of 95% or more.
一方，実施例１〜５のソーワイヤは，全てで砥粒残存率９５％以上を実現しており，本発明の方法でソーワイヤを製造することで，砥粒の固定強度の高く，従って，長寿命のソーワイヤを提供できることが明らかとなっており，砥粒の表面に付着したアクリル酸エステルの存在が，砥粒の固定強度の向上に貢献しているものと考えられる。 On the other hand, all of the saw wires of Examples 1 to 5 achieve an abrasive grain residual ratio of 95% or more, and by producing the saw wire by the method of the present invention, the fixed strength of the abrasive grains is high, and therefore, a long service life. It is clear that the saw wire can be provided, and the presence of acrylate adhering to the surface of the abrasive grains is thought to contribute to the improvement of the fixing strength of the abrasive grains.
また，切断性能については，実施例１〜５のソーワイヤは，比較例１〜３のソーワイヤに比較して，全てで切断深さが深くなっていると共に，切断面に対するダメージも確認できなかった。 Regarding the cutting performance, the saw wires of Examples 1 to 5 were all deeper than the saw wires of Comparative Examples 1 to 3, and the damage to the cut surface could not be confirmed.
すなわち，実施例１〜５のソーワイヤでは，高い付着密度で砥粒が固定されているために切断性能が良いだけでなく，砥粒の固定強度が高いために砥粒の脱落に伴う切断性能の低下が抑制されていることで，比較例のソーワイヤに比較してより大きな切断深さが得られたものと考えられる。 That is, in the saw wires of Examples 1 to 5, not only the cutting performance is good because the abrasive grains are fixed at a high adhesion density, but also the cutting performance due to the dropping of the abrasive grains because of the high fixing strength of the abrasive grains. It is considered that a larger cutting depth was obtained than the saw wire of the comparative example because the decrease was suppressed.
また，実施例１〜５のソーワイヤでは，砥粒の付着密度が高いことに加え，砥粒電着液を使用して砥粒の付着を行った後，電気めっきによる金属めっき層を形成して砥粒を固定したことで，金属めっき層の表面より突出する砥粒の突出長さを揃えることができると共に，前述した砥粒の付着強度の向上によって，砥粒の突出長さが揃った状態が維持されることで，切断面に対し全体的に略均一な加工を行えることと，砥粒と砥粒の隙間に析出した酸化チタンの粒子が切断時の切り粉の排出を助けることで，部分的に過度の負荷が加わること等により生じるダメージの発生を防止することができたものと考えられる。 In addition, in the saw wires of Examples 1 to 5, in addition to the high adhesion density of the abrasive grains, after the abrasive grains were deposited using the abrasive electrodeposition liquid, a metal plating layer was formed by electroplating. By fixing the abrasive grains, the protruding lengths of the abrasive grains protruding from the surface of the metal plating layer can be made uniform, and the above-mentioned improvement in the adhesion strength of the abrasive grains makes the protruding lengths of the abrasive grains uniform. Is maintained, so that the cutting surface can be processed substantially uniformly as a whole, and the titanium oxide particles deposited in the gaps between the abrasive grains help the discharge of chips during cutting. It is considered that it was possible to prevent the occurrence of damage caused by an excessive load being applied partially.
しかも，単結晶シリコンインゴットに比較してより切断面にあれが生じ易い，多結晶シリコンインゴットの切断では，比較例１〜３のソーワイヤでは，いずれもダメージ無しで切断することはできなかったが，実施例１〜５のソーワイヤを使用した切断では，いずれも切断面に対するダメージは確認できず，この点においても，本発明の方法で製造された固定砥粒型ソーワイヤの高性能性が確認できた。 Moreover, in the cutting of the polycrystalline silicon ingot, the saw wires of Comparative Examples 1 to 3 could not be cut without any damage in the cutting of the polycrystalline silicon ingot more easily than the single crystal silicon ingot. In the cutting using the saw wires of Examples 1 to 5, no damage to the cut surface could be confirmed, and also in this respect, the high performance of the fixed abrasive saw wire manufactured by the method of the present invention could be confirmed. .
Claims (3)
前記電着液を使用した電着により，ワイヤの表面に砥粒を付着させる砥粒付着工程と，
前記砥粒付着工程で砥粒が付着されたワイヤの表面に，電気めっきにより金属めっき層を形成する砥粒固定工程を含むことを特徴とする固定砥粒ソーワイヤの製造方法。 Add 1-50 parts by weight of 6-40 nm oxide powder and 50-700 parts by weight of abrasive powder to 10000 parts by weight of water from which ions have been removed, and add acrylic so that the electrical conductivity is 500 μS / cm or less. Adding an acid ester in the range of 0.5 to 25 parts by mass to obtain an electrodeposition solution;
Abrasive grain attachment step of attaching abrasive grains to the surface of the wire by electrodeposition using the electrodeposition liquid,
A method of manufacturing a fixed abrasive saw wire, comprising an abrasive grain fixing step of forming a metal plating layer by electroplating on the surface of the wire to which abrasive grains are adhered in the abrasive grain adhesion step.
前記砥粒が，アクリル酸エステル，及びアクリル酸エステルで被覆された粒径６〜４０nmの酸化物を表面に付着させた状態で，前記ワイヤの表面に形成された金属めっき層に一部露出した状態で埋設されることにより前記ワイヤの表面に固定されていることを特徴とする，固定砥粒型ソーワイヤ。
In a fixed abrasive saw wire in which abrasive grains are fixed to the outer peripheral surface of the wire,
The abrasive grains are partially exposed to the metal plating layer formed on the surface of the wire in a state where an acrylate ester and an oxide having a particle diameter of 6 to 40 nm coated with the acrylate ester are attached to the surface. A fixed-abrasive saw wire fixed on the surface of the wire by being embedded in a state.
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