JP5935159B2 - Polishing holding pad - Google Patents

Polishing holding pad Download PDF

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JP5935159B2
JP5935159B2 JP2010085300A JP2010085300A JP5935159B2 JP 5935159 B2 JP5935159 B2 JP 5935159B2 JP 2010085300 A JP2010085300 A JP 2010085300A JP 2010085300 A JP2010085300 A JP 2010085300A JP 5935159 B2 JP5935159 B2 JP 5935159B2
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base material
polishing
polished
urethane sheet
surface roughness
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JP2011212822A (en
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範幸 世良
範幸 世良
前田 裕司
裕司 前田
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NHK Spring Co Ltd
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Description

本発明は、ハードディスク基板、半導体基板または半導体ウエハ、液晶ディスプレイ用のガラス基板などの各種基板、LCDなどの表面を研磨する際に、研磨テーブルと研磨対象物との間に介在されて、前記研磨対象物を保持する研磨保持用パッドに関する。   In the present invention, when polishing the surface of a hard disk substrate, a semiconductor substrate or a semiconductor wafer, various substrates such as a glass substrate for a liquid crystal display, an LCD or the like, the polishing table is interposed between a polishing table and an object to be polished. The present invention relates to a polishing holding pad for holding an object.

コンピュータの記憶手段として用いられるハードディスク基板、シリコーン棒から切り出したシリコンウエハ、液晶ディスプレイ用のガラス基板などの研磨対象物を製造する場合には、高い精度での平坦性が求められる。このため、これらの基板の表面は研磨粒子を用いて研磨加工される。この研磨加工では研磨対象物を保持する必要があるが、研磨対象物と研磨テーブルを直接接触させると研磨対象物に傷が発生してしまう。この様な傷の発生を回避するために、従来から研磨対象物の保持に適する多孔質型のポリウレタン発泡体からなる研磨保持用パッドが広く用いられている(例えば、特許文献1、2参照)。   When manufacturing an object to be polished such as a hard disk substrate used as a storage means of a computer, a silicon wafer cut out from a silicone rod, or a glass substrate for a liquid crystal display, flatness with high accuracy is required. For this reason, the surface of these substrates is polished using abrasive particles. In this polishing process, it is necessary to hold the object to be polished. However, if the object to be polished and the polishing table are brought into direct contact, the object to be polished is damaged. In order to avoid the occurrence of such scratches, polishing holding pads made of a porous polyurethane foam suitable for holding an object to be polished have been widely used (see, for example, Patent Documents 1 and 2). .

また、前記ポリウレタン発泡体は、研磨対象物の吸着面に緻密で、しかも内部より密度の高い発泡表面層(スキン層)を持つことが好ましく、従って、このポリウレタン発泡体は、水混和性の有機溶媒に溶解させた樹脂溶液をシート状の成膜基板に塗布した後、水系凝固液中で凝固再生させる、いわゆる湿式成膜法で製造されている(例えば、特許文献1
参照)。
The polyurethane foam preferably has a foam surface layer (skin layer) that is dense on the surface to be polished and has a higher density than the inside. Therefore, the polyurethane foam is a water-miscible organic layer. A resin solution dissolved in a solvent is applied to a sheet-like film formation substrate, and then coagulated and regenerated in a water-based coagulation liquid.
reference).

一方、ポリエステルポリオール類、ポリイソシアネート類、発泡剤、触媒および撥水付与剤を含むポリウレタン発泡体の原料を反応させ、発泡および硬化させるに際して、発泡時における温度を低く設定することにより、衷面に密度の高い前記スキン層を形成する研磨保持用パッドが提案されている(例えば、特許文献2参照)。   On the other hand, when the polyurethane foam raw material containing polyester polyols, polyisocyanates, foaming agent, catalyst and water repellency imparting agent is reacted, foamed and cured, by setting the temperature during foaming low, A polishing holding pad for forming the skin layer having a high density has been proposed (see, for example, Patent Document 2).

更に、被着体とバッキング材との間に空気の咬み込みを防止すると共に、バッキング内部への水と研磨粒子のスラリーの侵入しない保持パッドとして、基材の上に弾性体を積層し、次いでこの弾性体の表面を研磨により平滑加工し、その平滑化された面に粘着性の樹脂をコーティングし、その樹脂が完全に硬化する前に凹凸を有するフィルムを圧着し、樹脂の硬化後フィルムを剥離することにより製造する研磨保持用パッドが提案されている(例えば、特許文献3参照)。   Furthermore, while preventing the biting of air between the adherend and the backing material, an elastic body is laminated on the base material as a holding pad from which water and slurry of abrasive particles do not enter the backing, The surface of this elastic body is smoothed by polishing, and an adhesive resin is coated on the smoothed surface, and a film having unevenness is pressure-bonded before the resin is completely cured, and the film is cured after the resin is cured. A polishing holding pad produced by peeling is proposed (see, for example, Patent Document 3).

特開2006−062059JP2006-062059 特開2006−334745JP 2006-334745 A 特開2002−355755JP 2002-355755 A

しかしながら、前記従来の(例えば、特許文献1に記載のような)湿式成膜法は湿式であるため発泡層の密度が高いものしかできず、また厚み精度も悪いために研磨を行う必要があった。さらに塗布された樹脂が水混和性有機溶媒の30%液で現場発泡方式によって製造されたためか圧縮した場合の復元回復性が悪く、いわゆる「へたり」が生じ、その結果長期間の使用ができないばかりでなく、製造方法が湿式のため低密度のものはできないという不都合があった。また、生産性が悪く、コストが高くなるという課題もあった。   However, since the conventional wet film forming method (for example, as described in Patent Document 1) is wet, only the foam layer has a high density, and the thickness accuracy is poor, so that polishing is necessary. It was. Furthermore, because the applied resin was manufactured by an in-situ foaming method using a 30% solution of a water-miscible organic solvent, the recovery recovery is poor when compressed, so-called “sagging” occurs, and as a result it cannot be used for a long time. In addition, since the manufacturing method is wet, there is a disadvantage that a low-density one cannot be made. In addition, there is a problem that productivity is low and cost is high.

また、前記従来の低温での(例えば、特許文献2に記載のような)スキン形成技術にあっては、連続気泡のため表面皮膜がポーラスとなるため研磨砥粒が皮膜の気孔内に入り込んでしまう。このため、皮膜の密度を上げるために整泡剤を用いない組成でパッド体を製造しているが、密度が600〜800kg/mと極めて高い製品となってしまい、重量大でしかも原料費が高くなるという課題があった。 Further, in the conventional skin formation technique at a low temperature (for example, as described in Patent Document 2), since the surface film becomes porous due to open cells, the abrasive grains enter the pores of the film. End up. For this reason, in order to increase the density of the film, the pad body is manufactured with a composition that does not use a foam stabilizer, but the density is 600 to 800 kg / m 3 and the product is extremely high, and the weight is large and the material cost is high. There was a problem of increasing the cost.

さらに、前記従来の(例えば、特許文献3に記載のような)被着体とバッキング材との間に空気の咬み込みを防いで平らなバッキング面を得ようとするバッキング材では、前記の粘着性樹脂表面の凹凸形状により、被研磨物と、保持パッド間に噛み込まれたエアーはある程度分散される。しかし、上記弾性体の研磨加工面がスキン層の様に平滑で均一で無い為、樹脂コーティングが平滑にならない。更に、凹凸形状の圧着が場所によりバラツキがある為、出来た保持パッドの平滑性・均一性は劣る。その結果、披研磨物と保持パッドの間に噛み込まれたエアー量が大きくなるとエアーの貯留が発生する。また、被研磨物と保持パッドの間の水量が一定で無い為、一定の保持力が発現できないという課題があった。   Further, in the conventional backing material (for example, as described in Patent Document 3) which prevents air from being caught between the adherend and the backing material, a flat backing surface is obtained. The air entrained between the object to be polished and the holding pad is dispersed to some extent due to the uneven shape on the surface of the conductive resin. However, since the polished surface of the elastic body is not as smooth and uniform as the skin layer, the resin coating is not smooth. Furthermore, since the uneven crimping varies depending on the location, the smoothness and uniformity of the resulting holding pad is poor. As a result, when the amount of air caught between the polished article and the holding pad increases, air is stored. Moreover, since the amount of water between the object to be polished and the holding pad is not constant, there is a problem that a constant holding force cannot be expressed.

本発明は、上述した課題に鑑みてなされたものであり、その目的は、生産コストを低減でき、低密度でありながら研磨塗粒を含むスラリーが気孔内に浸透することがなく、復元性に優れるため長期使用可能で、溶剤使用量が削減できるので環境汚染を改善できる研磨保持用パッドを提供することにある。   The present invention has been made in view of the above-mentioned problems, and its purpose is to reduce production cost, and the slurry containing abrasive coating particles does not permeate into the pores while being low in density, so that it can be restored. An object of the present invention is to provide a polishing holding pad that can be used for a long time because it is excellent, and can reduce the amount of solvent used, thereby improving environmental pollution.

前記目的を達成するため、本発明の請求項1に係る研磨保持用パッドは、可塑性ポリウレタン樹脂からなる非発泡ウレタンシートの一面側に熱硬化性ポリウレタン樹脂からなるウレタン発泡体が形成されており、研磨対象物を保持するための定盤に前記ウレタン発泡体の他面側を固着させて前記非発泡ウレタンシートの他面側が前記研磨対象物に当接する研磨保持用パッドにおいて、前記非発泡ウレタンシートは表面粗さRaが0.5〜17μmであり、水との接触角が90°以上であり、圧縮応力が0.05〜0.5MPaであり、厚みが5〜30μmであって、前記ウレタン発泡体は70℃オーブンにて促進した、50%圧縮永久歪が10%以下の独立気泡型ポリウレタン発泡体であることを特徴とする。 To achieve the above object, a polishing retaining pad according to claim 1 of the present invention, urethane foam made of a thermosetting polyurethane resin on one side of the non-foamed urethane sheet made of a thermoplastic polyurethane resin is formed In the polishing holding pad, the other surface side of the urethane foam is fixed to a surface plate for holding the object to be polished, and the other surface side of the non-foamed urethane sheet is in contact with the object to be polished. The sheet has a surface roughness Ra of 0.5 to 17 μm, a contact angle with water of 90 ° or more, a compressive stress of 0.05 to 0.5 MPa, and a thickness of 5 to 30 μm, The urethane foam is a closed-cell polyurethane foam having a 50% compression set of 10% or less promoted in a 70 ° C. oven .

この構成の研磨保持用パッドによれば、研磨対象物(被研磨物)に当接する非発泡ウレタンシートは表面粗さ(Ra)が0.5〜17μmの微少な凹凸を有するので、研磨対象物に対する吸着度合を制御できると共に、パッドに研磨対象物を貼着する際に、この凹凸を通して空気を外部へ逃がすことができ、空気の咬み込みを防止することができる。
また、水との接触角が90°以上の前記非発泡ウレタンシートは、撥水性(疎水性)が高く、吸水性及び水膨潤もなく、水(研磨砥粒を含むスラリー)の下面側に位置するウレタン発泡体への浸入を防止できる。
According to the polishing holding pad of this configuration, the non-foamed urethane sheet that comes into contact with the object to be polished (the object to be polished) has minute irregularities with a surface roughness (Ra) of 0.5 to 17 μm. It is possible to control the degree of adsorption to the air and to allow air to escape to the outside through the irregularities when sticking an object to be polished to the pad, thereby preventing air biting.
The non-foamed urethane sheet having a contact angle with water of 90 ° or more has high water repellency (hydrophobicity), no water absorption and no water swelling, and is located on the lower surface side of water (a slurry containing abrasive grains). Can be prevented from entering the urethane foam.

また、本発明の請求項2に係る研磨保持用パッドは、前記ウレタン発泡体の定盤への固着面が厚み調整平滑処理され、その平滑面に粘着剤が塗工されていることを特徴とする。
この構成により、その表面は比較的平滑であるので、表面精度が良く、基材付き粘着層が確実に貼着でき、ひいては定盤への装着性が向上する。
Further, the polishing holding pad according to claim 2 of the present invention is characterized in that the surface fixed to the surface plate of the urethane foam is subjected to thickness adjustment smoothing treatment, and an adhesive is applied to the smooth surface. To do.
With this configuration, since the surface is relatively smooth, the surface accuracy is good, the adhesive layer with a base material can be reliably attached, and the mounting property to the surface plate is improved.

本発明の研磨保持用パッドによれば、次のような効果を奏する。
(1)研磨時にパッド内部に水やスラリーが浸入しないので、研磨後の洗浄・乾燥時間の短縮が可能である。また、研磨中の吸水による研磨性能の変動も少ない。
(2)軽く扱い易く、低硬度パッドの要求に対応出来る。
(3)復元性に優れ長期使用でも「へたり」が少ない為、コスト低減が出来る。
(4)生産時のN、N−ジメチルホルムアミドなどの溶剤使用量を削減できるので、環境面での寄与が出来る。
(5)発泡層は低密度のウレタン発泡体でよいので、安価に提供できる。
The polishing holding pad according to the present invention has the following effects.
(1) Since water and slurry do not enter the pad during polishing, cleaning and drying time after polishing can be shortened. In addition, there is little variation in polishing performance due to water absorption during polishing.
(2) It is light and easy to handle and can meet the demand for low hardness pads.
(3) Since it has excellent recoverability and has less “hang” even during long-term use, cost can be reduced.
(4) Since the amount of solvent used such as N, N-dimethylformamide during production can be reduced, environmental contributions can be made.
(5) Since the foam layer may be a low-density urethane foam, it can be provided at a low cost.

本発明に係る研磨保持用パッドの製造工程を工程順(a)(b)(c)(d)に示す断面説明図である。It is sectional explanatory drawing which shows the manufacturing process of the pad for polishing holding | maintenance which concerns on this invention in process order (a) (b) (c) (d). 使用形態の一例を示す断面説明図である。It is sectional explanatory drawing which shows an example of a usage pattern.

以下、本発明の実施形態にかかる研磨保持用パッドについて、図面を参照して詳細に説明する。
まず、工程1として図1(a)においてウレタンシートの作製について説明する。表面粗さ(Ra)0・5〜17μmの微小な凹凸の表面形状を持つ基材1(リンテック株式会社製FN、R8、108SG、PETLSM−100GSなど)に熟可塑性ポリウレタン樹脂(DlC株式会社製ゾルテックスPX−550など)をスキージを用いて塗工し、例えば、70℃×5min間乾燥させ、非発泡ウレタンシート2を得る。あるいは、基材1に熟硬化性ポリウレタン原料を塗布したものを加熱し、反応硬化させ、非発泡のウレタンシート2を得る。
なお、図1中で1としては、片面をサンドマット処理し、更に離型処理を行ったポリエチレンテレフタレート(以下PETと略す)フイルム、紙+ポリプロピレンラミネート品(微小な凹凸を持つ表面形状)などが使用でき、2は非発泡ウレタンシート(熟可塑性ポリウレタン樹脂又は熟硬化性ポリウレタン樹脂)である。
Hereinafter, a polishing holding pad according to an embodiment of the present invention will be described in detail with reference to the drawings.
First, production of a urethane sheet will be described as step 1 in FIG. Ripe plastic polyurethane resin (DLC Co., Ltd. Zoltex Co., Ltd.) on the base material 1 (FN, R8, 108SG, PETLSM-100GS, etc. manufactured by Lintec Co., Ltd.) having a minute uneven surface shape with a surface roughness (Ra) of 0.5 to 17 μm. PX-550 or the like) is applied using a squeegee and dried, for example, at 70 ° C. for 5 minutes to obtain a non-foamed urethane sheet 2. Alternatively, a material obtained by applying a mature curable polyurethane raw material to the substrate 1 is heated and reaction-cured to obtain a non-foamed urethane sheet 2.
1 in FIG. 1 includes a polyethylene terephthalate (hereinafter abbreviated as PET) film, a paper + polypropylene laminate (surface shape with minute irregularities), etc., which has been subjected to sand mat treatment on one side and further subjected to release treatment. 2 is a non-foamed urethane sheet (mature plastic polyurethane resin or mature curable polyurethane resin).

次に図1(b)の工程2のウレタン発泡体の一体成形工程としては、基材1付き非発泡ウレタンシート2の表面にポリウレタン原料を塗布し、さらに基材4を被せ、加熱し(80℃×2min、120℃×4min)弾性体3を得る。又は、基材4にポリウレタン原料を塗布し、更に基材1を被せ、加熱し(80℃×2min、120℃×4min)発泡させても良い。
図1において、弾性体3は熱硬化性ポリウレタン発泡体である。圧縮永久歪を10以下にし、長期使用でも「へたり」を少なくするために、このタイプのウレタン発泡体を使用する。なお、4は弾性体から剥離可能な基材であって、ポリエチレンテレフタレート(PET)フイルムが好ましく使用され、この外にポリ塩化ビニル(PVC)、ナイロンフィルム等を使用可能な基材に挙げられる。
Next, as an integral molding process of the urethane foam in step 2 of FIG. 1B, a polyurethane raw material is applied to the surface of the non-foamed urethane sheet 2 with the base material 1, and the base material 4 is further covered and heated (80 (° C. × 2 min, 120 ° C. × 4 min) to obtain the elastic body 3. Or you may apply | coat a polyurethane raw material to the base material 4, and also cover the base material 1 and heat (80 degreeC * 2min, 120 degreeC * 4min), and you may make it foam.
In FIG. 1, the elastic body 3 is a thermosetting polyurethane foam. This type of urethane foam is used to reduce the compression set to 10 or less and reduce “sagging” even during long-term use. In addition, 4 is a base material which can be peeled from the elastic body, and polyethylene terephthalate (PET) film is preferably used, and besides this, examples of the base material which can use polyvinyl chloride (PVC), nylon film and the like.

次の図1(c)の工程3のウレタン発泡体研磨工程においては、基材4を剥離して取除き、弾性体3の表面を研磨して均一厚みにする。
続く工程4(図1(d))の粘着テープ貼り付け工程においては、研磨加工されたウレタン発泡体(弾性体)3の被研磨面に基材付き粘着層5を貼り合わせる。なお、基材付き粘着層は、粘着剤−PETフィルム−粘着剤−セパレータによって構成されている。
In the urethane foam polishing step of step 3 in the next FIG. 1 (c), the base material 4 is peeled and removed, and the surface of the elastic body 3 is polished to a uniform thickness.
In the subsequent adhesive tape attaching step of Step 4 (FIG. 1 (d)), the adhesive layer 5 with the substrate is attached to the polished surface of the polished urethane foam (elastic body) 3. In addition, the adhesion layer with a base material is comprised by the adhesive-PET film-adhesive-separator.

更に、使用形態の一例を図2に示す。
前記図1(d)の工程4で作成した研磨保持用パッドを所定の形状に切り取り、切断面(端部)を防水処理7する。なお、使用条件によってはこの端部の防水処理7は不要である。
このパッドを使用する際には、先ず基材1を剥離し、次いで基材付き粘着層5のセパレータを剥離したもの5’を定盤6に貼り付ける。そして、基材1が剥離された非発泡ウレタンシート2上に水を介して研磨対象物として、例えば、ガラス基盤を水の表面張力により吸着させ、研磨に付される。
Furthermore, an example of the usage pattern is shown in FIG.
The polishing holding pad created in Step 4 of FIG. 1D is cut into a predetermined shape, and the cut surface (end) is waterproofed 7. Depending on the use conditions, the waterproof treatment 7 at the end is not necessary.
When using this pad, first, the substrate 1 is peeled off, and then 5 ′ from which the separator of the adhesive layer 5 with the substrate is peeled off is attached to the surface plate 6. And as a grinding | polishing target object through water on the non-foaming urethane sheet 2 from which the base material 1 was peeled off, for example, a glass substrate is adsorbed by the surface tension of water and subjected to polishing.

前記研磨保持用パッドの研磨対象物(被研磨物)と当接する非発泡低硬度ウレタンシートは、請求項1に記載の特徴を有するものであれば、ジイソシアナートとポリオールの重付加で作られるポリウレタンである限り熱可塑性、熱硬化性のどちらの樹脂であってもよい。   The non-foamed low-hardness urethane sheet that comes into contact with the object to be polished (the object to be polished) of the polishing holding pad is made by polyaddition of diisocyanate and polyol as long as it has the characteristics of claim 1. As long as it is polyurethane, it may be either thermoplastic or thermosetting resin.

この非発泡ウレタンシートと定盤の間に介在させるポリウレタン発泡体(弾性体)3は、請求項1に記載した圧縮永久歪が10以下の熱硬化性ポリウレタン発泡体でなければならない。そのためには、密度が300kg/m近辺である必要がある。こうすることで、研磨保持用パッドとしての好適な圧縮応力や長期使用での「へたり」の少なさを維持できるばかりでなく、低吸水性にもなる。密度が300kg/mを可成り下回る場合にはフォーム体の吸水量が増加し、被研磨物との吸着性が低下する。さらに、密度が低くなるほど単位面積当りの塗布量が少なくなり、また発泡倍率も増すため、厚み精度が悪くなる。また、密度が300kg/mを大幅に超えると、フォーム体が硬くなり、十分なクッション性を得ることができなくなる。結果として、研磨時の衝撃で研磨対象のガラス基板が外れる惧れがある。従って、密度は300kg/m前後が好ましい。 The polyurethane foam (elastic body) 3 interposed between the non-foamed urethane sheet and the surface plate must be a thermosetting polyurethane foam having a compression set of 10 or less according to claim 1. For this purpose, the density needs to be around 300 kg / m 3 . By doing so, not only can a compressive stress suitable as a polishing holding pad and a small amount of “sagging” in long-term use be maintained, but also low water absorption can be achieved. When the density is well below 300 kg / m 3 , the water absorption amount of the foam body increases and the adsorptivity with the object to be polished decreases. Furthermore, the lower the density, the smaller the coating amount per unit area and the higher the expansion ratio, resulting in poor thickness accuracy. On the other hand, if the density greatly exceeds 300 kg / m 3 , the foam body becomes hard and sufficient cushioning properties cannot be obtained. As a result, there is a concern that the glass substrate to be polished may come off due to impact during polishing. Accordingly, the density is preferably around 300 kg / m 3 .

前記ポリウレタン発泡体(弾性体)3は、ポリオール、ポリイソシアネート、発泡剤、触媒および必要に応じ架橋剤、着色剤、樹脂改質剤、難然剤、紫外線吸収剤、耐久性改良剤から選択される添加剤、等の配合物を混合撹拌して得られた反応原料を、剥離処理を施した工程紙(基材)4の剥離面に均一に塗布した後、この塗布原料の上面に剥離面がくるように工程紙を被せて加熱発泡して硬化させ、自己スキン層を形成したエアリークの無い独立気泡性ポリウレタン発泡体を形成することで製造できる。   The polyurethane foam (elastic body) 3 is selected from polyols, polyisocyanates, foaming agents, catalysts and, if necessary, cross-linking agents, colorants, resin modifiers, refractory agents, ultraviolet absorbers, and durability improvers. After the reaction raw material obtained by mixing and stirring a compound such as an additive is uniformly applied to the release surface of the process paper (base material) 4 subjected to the release treatment, the release surface is applied to the upper surface of the application raw material. It is possible to manufacture by forming a closed-cell polyurethane foam having no air leak and having a self-skin layer formed by covering the process paper so as to be heated and foaming and curing.

前記ポリオール類としては、ポリエステルポリオールあるいはポリエーテルポリオールがあるが、疎水性のポリオールを用いることで、水との接触角が90°以上のポリウレタン発泡体を得ることができ好ましい。例えば、ポリブタジエン系ポリオール、ダイマー酸系ポリオール、ヒマシ油系ポリオール、ポリカーボネート系ポリオール或いはポリプロピレングリコール、ポリテトラメチレングリコールなどが挙げられる。この中でも、ポリテトラメチレングリコールは強度が出て、長期使用に耐えるため好ましい。また、ダイマー酸系ポリオールは特に疎水性が高くなり好ましい。   Examples of the polyols include polyester polyols and polyether polyols, and using a hydrophobic polyol is preferable because a polyurethane foam having a contact angle with water of 90 ° or more can be obtained. For example, polybutadiene-based polyol, dimer acid-based polyol, castor oil-based polyol, polycarbonate-based polyol, polypropylene glycol, polytetramethylene glycol and the like can be mentioned. Among these, polytetramethylene glycol is preferable because it has high strength and can withstand long-term use. In addition, dimer acid-based polyols are particularly preferred because of their high hydrophobicity.

また、多官能性イソシアナートとしては、分子中にイソシアナート基を2個以上含有する芳香族イソシアナートおよび脂肪酸族イソシアナートそれらの変成物を用いることができる。具体的には、トルエンジイソシアナート(TDI)、ジフェニルメタンジイソシアナート(MDI)、イソホロンジイソシアナート(IPDI)、ヘキサメチレンジイソシアナート(HDI)、キシレンジイソシアナート(XDI)、テトラメチルキシリレンジイソシアナート(TMXDI)等、およびこれらの混合物等を用いることができるが、これらに限定されるものではない。また、これらをプレポリマーにすることで伸びおよび強度、耐久性が向上し、長期の使用が可能になる。   Moreover, as a polyfunctional isocyanate, the aromatic isocyanate which contains two or more isocyanate groups in a molecule | numerator, and fatty acid group isocyanate those modified products can be used. Specifically, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), tetramethylxylylene diene Isocyanate (TMXDI) and the like, and mixtures thereof can be used, but are not limited thereto. Further, by using these as prepolymers, the elongation, strength and durability are improved, and long-term use becomes possible.

前記発泡剤として、水、常圧で気体の窒素ガス、炭酸ガスおよび空気等の不活性ガス、モノフッ化トリ塩化メタンや塩化メタン等のハロゲン化アルカン、ブタンやペンタン等の低沸点アルカン、分解窒素ガス等を発生するアゾビスイソブチルニトリル等およびこれらの混合物が用いられるが、これらに限定されるものではない。   Examples of the blowing agent include water, nitrogen gas at normal pressure, inert gas such as carbon dioxide and air, halogenated alkanes such as monofluorinated trichloromethane and chloromethane, low-boiling alkanes such as butane and pentane, and decomposed nitrogen Azobisisobutylnitrile and the like that generate gas and the like and mixtures thereof are used, but are not limited thereto.

この発明の研磨保持用パッドの固定定盤6に装着するための弾性体としてのポリウレタン発泡体3は、前記実施の形態に示した製造方法だけでなく、前記のような諸原料を使用して、従来から知られているワンショット法、部分プレポリマー法等の方法によって製造してもよい。製造されるポリウレタン発泡体は、モールド成形、連続シート成形等によってシート状に成形すると、研磨保持用パッドのクッション材に使用するのに好都合となるので好ましい。特に、前記実施の形態で示した上下面の離型紙と非発泡ポリウレタンシートとの間にポリウレタン原液を挟み込んで発泡させる「シート状発泡法」が最も適する方法である。   The polyurethane foam 3 as an elastic body to be attached to the fixed surface plate 6 of the polishing holding pad of the present invention is not limited to the manufacturing method shown in the above embodiment, but uses the above-mentioned various raw materials. Alternatively, it may be produced by a conventionally known method such as a one-shot method or a partial prepolymer method. When the polyurethane foam to be produced is molded into a sheet by molding, continuous sheet molding or the like, it is preferable to use it as a cushioning material for a polishing holding pad. In particular, the “sheet-like foaming method” in which the polyurethane stock solution is sandwiched between the release paper on the upper and lower surfaces and the non-foamed polyurethane sheet shown in the above embodiment and foamed is the most suitable method.

次に、本発明を実施例及び比較例により詳細に説明する。以下において、「部」及び「%」は重量基準の単位とする。
表面粗さ(Ra)11μmの微小な凹凸の表面形状を持つ基材1(リンテック株式会社製FN)にメチルエチルケトン:トルエンの1:2の有機溶剤で熱可塑性ポリウレタン樹脂2(DIC株式会社製ゾルテックスPX−550)の固形分が20%になるように希釈したものを40μm間隙のスキージを用いて塗工し、70℃×5min間乾燥させ、厚み5μm、表面粗さ(Ra)6μmの非発泡ウレタンシート2を作製した。
次にポリウレタン原料として、ポリオールとしてダイマー酸ポリエステルジオール(分子量1236、水酸基価104.4、DIC株式会社製UA2812)100部とポリイソシアネートとして4,4−ジフェニルメタンジイソシアネートとPPGとのプレポリマー(イソシアネート含有量13.1wt%、日本ポリウレタン株式会社製DC6974)をNCO/OH比率=1.05で混合し、35℃に温調した。更に触媒として1,8−ジアザ・ビシクロ[5,4,0]ウンデセン・7有機酸塩(三洋化成製SA102)を0.4部、発泡剤として水を0.5部添加し、よく攪拌した後に基材4上に塗布し、基材1付き非発泡ウレタンシート2を被せ、80℃×2min、120℃×4minn加温し、厚み1mm、密度;300kg/mの弾性体を得た。更に基材4を取除き、弾性体3の表面を平滑研磨し、厚み公差±0.01mmに調整した後に基材付き粘着層5を貼り付けた。
Next, the present invention will be described in detail with reference to examples and comparative examples. In the following, “part” and “%” are units based on weight.
Thermoplastic polyurethane resin 2 (Zoltex PX manufactured by DIC Corporation) with a 1: 2 organic solvent of methylethylketone: toluene on a base material 1 (FN manufactured by Lintec Corporation) having a surface roughness (Ra) of 11 μm and fine irregularities. -550) diluted to a solid content of 20% using a 40 μm gap squeegee, dried for 70 ° C. × 5 min, non-foamed urethane having a thickness of 5 μm and a surface roughness (Ra) of 6 μm Sheet 2 was produced.
Next, as a polyurethane raw material, 100 parts of dimer acid polyester diol (molecular weight 1236, hydroxyl value 104.4, DIC Corporation UA2812) as polyol and prepolymer (isocyanate content) of 4,4-diphenylmethane diisocyanate and PPG as polyisocyanate 13.1 wt%, Nippon Polyurethane Co., Ltd. DC6974) was mixed at an NCO / OH ratio = 1.05, and the temperature was adjusted to 35 ° C. Further, 0.4 part of 1,8-diaza-bicyclo [5,4,0] undecene-7 organic acid salt (SA102 manufactured by Sanyo Chemical Industries) was added as a catalyst, and 0.5 part of water was added as a blowing agent, and the mixture was stirred well. after coating onto the substrate 4, covered with a base material 1 with a non-foamed urethane sheet 2, 80 ℃ × 2min, 120 ℃ × 4minn warmed, thickness 1 mm, density: obtain an elastic body 300 kg / m 3. Further, the base material 4 was removed, the surface of the elastic body 3 was smooth polished, and after adjusting the thickness tolerance to ± 0.01 mm, the base material-attached adhesive layer 5 was attached.

表面粗さ(Ra)17μmの微小な凹凸の表面形状を持つ基材1(リンテック株式会社製108SG)にメチルエチルケトン:トルエンの1:2の有機溶剤で熱可塑性ポリウレタン樹脂2(DIC株式会社製クリスボンNB−637N)の固形分が20%になるように希釈したものを200μm間隙のスキージを用いて塗工し、70℃×5min間乾燥させ、表面粗さ(Ra)15μm、厚み23μmの非発泡ウレタンシート2を作製した。以降は実施例1と同じ作業を行い、粘着テープ付きウレタンシートを作製した。   Thermoplastic polyurethane resin 2 (Chrisbon NB manufactured by DIC Corporation) with a 1: 2 organic solvent of methyl ethyl ketone: toluene on a base material 1 (108 SG manufactured by Lintec Corporation) having a surface roughness (Ra) of 17 μm. -637N) diluted to a solid content of 20%, coated with a squeegee with a gap of 200 μm, dried for 70 ° C. × 5 min, and non-foamed urethane having a surface roughness (Ra) of 15 μm and a thickness of 23 μm Sheet 2 was produced. Thereafter, the same operation as in Example 1 was performed to produce a urethane sheet with an adhesive tape.

表面粗さ(Ra)4.6μmの微小な凹凸の表面形状を持つ基材1(リンテック株式会社製R8)にメチルエチルケトン:トルエンの1:2の有機溶剤で熱可塑性ポリウレタン樹脂2(DIC株式会社製ゾルテックスPX−550)の固形分が20%になるように希釈したものを200μm間隙のスキージを用いて塗工し、70℃×5min間乾燥させ、表面粗さ(Ra)6μm、厚み20μmの非発泡ウレタンシート2を作製した。以降は実施例1と同じ作業を行い、粘着テープ付きウレタンシートを作製した。   Thermoplastic polyurethane resin 2 (manufactured by DIC Corporation) with a 1: 2 organic solvent of methyl ethyl ketone: toluene on a base material 1 (R8 manufactured by Lintec Corporation) having a surface roughness (Ra) of 4.6 μm and a minute unevenness. Zoltex PX-550) diluted to a solid content of 20% is coated using a squeegee with a gap of 200 μm, dried for 70 ° C. × 5 min, and has a surface roughness (Ra) of 6 μm and a thickness of 20 μm. A foamed urethane sheet 2 was produced. Thereafter, the same operation as in Example 1 was performed to produce a urethane sheet with an adhesive tape.

表面粗さ(Ra)11μmの微小な凹凸の表面形状を持つ基材1(リンテック株式会社製FN)に熱硬化性ポリウレタン樹脂としてポリオールとしてダイマー酸ポリエステルジオール(分子量1236、水酸基価104.4、DIC株式会社製UA2812)100部とポリイソシアネート成分のカルボジイミド変性4、4−ジフェニルメタンジイソシアネート(イソシアネート含有量29.5wt%、日本ポリウレタン株式会社製C−98)をNCO/OH比率=1.05で混合し、35℃で温調し、更に触媒としてジブチルチンジラウレート(U−100)を0.35部添加し、よく攪拌及び脱泡した後にポリウレタン原料を250μm間隙のスキージを用いて塗工し、100℃×10min間加温し、表面粗さ(Ra)7.1μm、厚み24μmの非発泡ウレタンシート2を作製した。
次に、ポリオール成分のポリテトレメチレングリコール(分子量2000、水酸基価57、三菱化学株式会社製PTMG2000)100部及びトリメチロールプロパントリメタクリレート(IR94)5部とポリイソシアネートとして4,4−ジフェニルメタンジイソシアネートとPPGとのプレポリマー(イソシアネート含有量13.1wt%、日本ポリウレタン株式会社製DC6974)をNCO/OH比率=1.05で混ぜ、35℃に温調した。更に触媒として1,8−ジアザ・ビシクロ[5,4,0]ウンデセン・7有機酸塩(三洋化成製SA102)0.4部、発泡剤として水を0.5部添加し、よく攪拌した後にポリウレタン原料を基材4上に塗布し、基材1付非発泡ウレタンシート2を被せ、80℃×2min、120℃×4minn加温し、厚み1mm、密度;300kg/mの弾性体を得た。更に基材4を取除き、弾性体3の表面を平滑研磨し、厚み公差±0.01mmに調整した後に基材付き粘着層5を貼り付けた。
Dimer acid polyester diol (molecular weight 1236, hydroxyl value 104.4, DIC) as a polyol as a thermosetting polyurethane resin on a base material 1 (FN) manufactured by Lintec Corporation having a surface roughness (Ra) of 11 μm and fine irregularities. 100 parts of UA2812 manufactured by Co., Ltd. and carbodiimide-modified 4,4-diphenylmethane diisocyanate (isocyanate content 29.5 wt%, C-98 manufactured by Nippon Polyurethane Co., Ltd.) of polyisocyanate component were mixed at an NCO / OH ratio = 1.05. The temperature was adjusted at 35 ° C., 0.35 part of dibutyltin dilaurate (U-100) was further added as a catalyst, and after stirring and defoaming, the polyurethane raw material was applied using a squeegee with a gap of 250 μm. Heated for 10 min, surface roughness (Ra) 7.1 μm, thickness To prepare a non-foamed urethane sheet 2 of 4μm.
Next, 100 parts of polyol component polytetramethylene glycol (molecular weight 2000, hydroxyl value 57, PTMG 2000 manufactured by Mitsubishi Chemical Corporation) and 5 parts of trimethylolpropane trimethacrylate (IR94) and 4,4-diphenylmethane diisocyanate and PPG as polyisocyanate The prepolymer (isocyanate content 13.1 wt%, DC6974 manufactured by Nippon Polyurethane Co., Ltd.) was mixed at an NCO / OH ratio = 1.05, and the temperature was adjusted to 35 ° C. Further, 0.4 part of 1,8-diaza-bicyclo [5,4,0] undecene-7 organic acid salt (SA102 manufactured by Sanyo Chemical Industries) as a catalyst and 0.5 part of water as a blowing agent were added and stirred well. A polyurethane raw material is coated on the base material 4 and covered with the non-foamed urethane sheet 2 with the base material 1 and heated at 80 ° C. × 2 min, 120 ° C. × 4 minn to obtain an elastic body having a thickness of 1 mm and a density of 300 kg / m 3. It was. Further, the base material 4 was removed, the surface of the elastic body 3 was smooth polished, and after adjusting the thickness tolerance to ± 0.01 mm, the base material-attached adhesive layer 5 was attached.

表面粗さ(Ra)0.5μmの微小な凹凸の表面形状を持つ基材1(リンテック株式会社製PETLSM100GS)にメチルエチルケトン:トルエンの1:2の有機溶剤で熱可塑性ポリウレタン樹脂2(DIC株式会社製ゾルテックスPX−550)の固形分が20%になるように希釈したものを250μm間隙のスキージを用いて塗工し、70℃×5min間乾燥させ、表面粗さ(Ra)0.8μm、厚み30μmの非発泡ウレタンシート2を作製した。
次に実施例1と同様にその上に弾性体を発泡させた。更に基材4を取除き、弾性体3の表面を平滑研磨し、厚み公差±0.01mmに調整した後に基材付き粘着層5を貼り付けた。
Thermoplastic polyurethane resin 2 (manufactured by DIC Corporation) with a 1: 2 organic solvent of methylethylketone: toluene on a base material 1 (PETLSM100GS manufactured by Lintec Corporation) having a surface roughness (Ra) of 0.5 μm and minute irregularities. Zoltex PX-550) diluted to a solid content of 20% is coated using a squeegee with a gap of 250 μm, dried for 70 ° C. × 5 min, surface roughness (Ra) 0.8 μm, thickness 30 μm A non-foamed urethane sheet 2 was prepared.
Next, an elastic body was foamed thereon as in Example 1. Further, the base material 4 was removed, the surface of the elastic body 3 was smooth polished, and after adjusting the thickness tolerance to ± 0.01 mm, the base material-attached adhesive layer 5 was attached.

比較例1Comparative Example 1

表面粗さ(Ra)0μmの表面形状を持つ基材1(リンテック株式会社製PET100GS)にメチルエチルケトン:トルエンの1:2の有機溶剤で熱可塑性ポリウレタン樹脂2(DIC株式会社製ゾルテックスPX−550)の固形分が20%になるように希釈したものを200μm間隙のスキージを用いて塗工し、70℃×5min間乾燥させ、表面粗さ(Ra)0.3μm、厚み20μmの非発泡ウレタンシート2を作製した。更に実施例1と同様にその上に弾性体を発泡させたあと更に基材4を取除き、弾性体3の表面を平滑研磨し、厚み公差±0.01mmに調整した後に基材付粘着層5を貼り付けた。   The surface of the base material 1 (PET100GS manufactured by Lintec Corporation) having a surface roughness (Ra) of 0 μm is coated with a thermoplastic polyurethane resin 2 (Zoltex PX-550 manufactured by DIC Corporation) with a 1: 2 organic solvent of methyl ethyl ketone: toluene. Non-foamed urethane sheet 2 having a surface roughness (Ra) of 0.3 μm and a thickness of 20 μm, coated with a squeegee having a gap of 200 μm and dried at 70 ° C. for 5 minutes. Was made. Further, after the elastic body was foamed thereon as in Example 1, the base material 4 was further removed, the surface of the elastic body 3 was smooth polished, and the thickness tolerance was adjusted to ± 0.01 mm, and then the adhesive layer with the base material was used. 5 was pasted.

比較例2Comparative Example 2

表面粗さ(Ra)11μmの表面形状を持つ基材1(リンテック株式会社製FN)にポリオールEP551C(分子量3000、水酸基価57、三井化学株式会社製)100部とカルボジイミド変性4、4−ジフェニルメタンジイソシアネート(イソシアネート含有量29.5wt%、日本ポリウレタン株式会社製C・98)を15部、触媒として1,8−ジアザ・ビシクロ[5,4,0]ウンデセン・7有機酸塩(三洋化成製SA102)を0.4部混合し脱泡したものを100μm間隙のスキージを用いて塗工し、80℃×3min、120℃×4min間加温させ、表面粗さ(Ra)5.5μm、厚み25μmの非発泡ウレタンシート2を作製した。
次に、ポリオール成分の分子量2000のポリテトレメチレングリコール(分子量2000、水酸基価57、三菱化学株式会社製PTMG2000)とトリメチロールプロパントリメタクリレート(IR−94)5部とポリイソシアネート成分のカルボジイミド変性4,4−ジフェニルメタンジイソシアネート(イソシアネート含有量29.5wt%、日本ポリウレタン株式会社製C・98)をNCO/OH比率=1.05で混合し、35℃に温調した。触媒として1,8−ジアザ・ビシクロ[5,4,0]ウンデセン・7有機酸塩(三洋化成製SA102)を0.4部、発泡剤として水を0.5部添加し、よく攪拌した後に非発泡ウレタンシート上にポリウレタン原料を塗布し、更に塗布後にその上から別の基材4を被せ、80℃×2min、120℃×4min加温し、ポリウレタン熱硬化性ポリウレタン発泡体を作製した。更に基材4を取除き、弾性体3の表面を平滑研磨し、厚み公差±0.01mmに調整した後に基材付き粘着層5を貼り付けた。
Substrate 1 having a surface roughness (Ra) of 11 μm (FNTech's FN) and polyol EP551C (molecular weight 3000, hydroxyl value 57, Mitsui Chemicals) 100 parts and carbodiimide-modified 4, 4-diphenylmethane diisocyanate (Isocyanate content 29.5 wt%, Nippon Polyurethane Co., Ltd. C / 98) 15 parts, 1,8-diaza-bicyclo [5,4,0] undecene-7 organic acid salt (Sanyo Chemical Industries SA102) as a catalyst The mixture was defoamed with 0.4 parts using a squeegee with a gap of 100 μm, heated for 80 ° C. × 3 min, 120 ° C. × 4 min, surface roughness (Ra) 5.5 μm, thickness 25 μm A non-foamed urethane sheet 2 was produced.
Next, polytetramethylene glycol having a molecular weight of 2000 (molecular weight 2000, hydroxyl value 57, Mitsubishi Chemical Co., Ltd. PTMG 2000) and 5 parts of trimethylolpropane trimethacrylate (IR-94) and carbodiimide modification of the polyisocyanate component 4, 4-Diphenylmethane diisocyanate (isocyanate content 29.5 wt%, Nippon Polyurethane Co., Ltd. C · 98) was mixed at an NCO / OH ratio = 1.05, and the temperature was adjusted to 35 ° C. After adding 0.4 parts of 1,8-diaza-bicyclo [5,4,0] undecene-7 organic acid salt (SA102 manufactured by Sanyo Chemical Industries) as a catalyst and 0.5 parts of water as a blowing agent, the mixture was stirred well. A polyurethane raw material was applied onto a non-foamed urethane sheet, and after the application, another base material 4 was placed thereon and heated at 80 ° C. × 2 min, 120 ° C. × 4 min to prepare a polyurethane thermosetting polyurethane foam. Further, the base material 4 was removed, the surface of the elastic body 3 was smooth polished, and after adjusting the thickness tolerance to ± 0.01 mm, the base material-attached adhesive layer 5 was attached.

比較例3Comparative Example 3

表面粗さ(Ra)20μmの表面形状を持つ基材1(リンテック株式会社製R80N2)にメチルエチルケトン:トルエンの1:2の有機溶剤で熱可塑性ポリウレタン樹脂2(DIC株式会社製ゾルテックスPX−550)の固形分が20%になるように希釈したものを200μm間隙のスキージ等を用いて塗工し、70℃×5min間乾燥させ、表面粗さ(Ra)19μm、厚み23μmの非発泡ウレタンシート2を作製した。
次に、熱硬化性ポリウレタン樹脂としてポリオールとしてダイマー酸ポリエステルジオール(分子量1236、水酸基価104.4、DIC株式会社製UA2812)100部とポリイソシアネートとして4、4−ジフェニルメタンジイソシアネート(イソシアネート含有量13.1wt%、日本ポリウレタン株式会社製DC6974)をNCO/OH比率=1.05で混合し、35℃に温調した。触媒として1,8−ジアザ・ビシクロ[5,4,0]ウンデセン・7有機酸塩(三洋化成製SA102)を0.4部、発泡剤として水を0.5部添加し、よく攪拌した後に非発泡ウレタンシート上にポリウレタン原料を塗布し、更に塗布後にその上から別の基材4を被せ、80℃×2min、120℃×4min加温し、ポリウレタン熱硬化性ポリウレタン発泡体を作製した。更に基材4を取除き、弾性体3の表面を平滑研磨し、厚み公差±0.01mmに調整した後に基材付粘着層5を貼り付けた。
Surface roughness (Ra) of base material 1 having a surface shape of 20 μm (R80N2 manufactured by Lintec Corporation) and thermoplastic polyurethane resin 2 (Zoltex PX-550 manufactured by DIC Corporation) with a 1: 2 organic solvent of methyl ethyl ketone: toluene. A non-foamed urethane sheet 2 having a surface roughness (Ra) of 19 μm and a thickness of 23 μm is applied by coating with a squeegee with a gap of 200 μm, and the like so that the solid content becomes 20%, and drying for 70 minutes at 70 ° C. Produced.
Next, dimer acid polyester diol (molecular weight 1236, hydroxyl value 104.4, UA2812 manufactured by DIC Corporation) as a polyol as a thermosetting polyurethane resin and 4,4-diphenylmethane diisocyanate (isocyanate content 13.1 wt as polyisocyanate) %, Nippon Polyurethane Co., Ltd. DC6974) was mixed at an NCO / OH ratio = 1.05, and the temperature was adjusted to 35 ° C. After adding 0.4 parts of 1,8-diaza-bicyclo [5,4,0] undecene-7 organic acid salt (SA102 manufactured by Sanyo Chemical Industries) as a catalyst and 0.5 parts of water as a blowing agent, the mixture was stirred well. A polyurethane raw material was applied onto a non-foamed urethane sheet, and after the application, another base material 4 was placed thereon and heated at 80 ° C. × 2 min, 120 ° C. × 4 min to prepare a polyurethane thermosetting polyurethane foam. Furthermore, the base material 4 was removed, the surface of the elastic body 3 was smooth polished, and after adjusting the thickness tolerance to ± 0.01 mm, the base material-attached adhesive layer 5 was attached.

比較例4Comparative Example 4

ポリオールとしてダイマー酸ポリエステルジオール(DIC株式会社製分子量1259、水酸基価89.1、DIC株式会社製UA2701)とポリイソシアネートとして4,4−ジフェニルメタンジイソシアネート(イソシアネート含有量13.1%、日本ポリウレタン株式会社製DC6974)をNCO/OH比率=1.05で混合し、35℃に温調した。更に触媒として1,8−ジアザ・ビシクロ[5,4,0]ウンデセン・7有機酸塩(三洋化成製SA102)0.4部、発泡剤として水を0.5部添加し、よく攪拌した後にポリウレタン原料を表面粗さ(Ra)0.8μmの表面形状を持つ基材1(リンテック株式会社製TP−SG)上に塗布し、更に塗布後にその上から別の基材4を被せ、80℃×2min、120℃×4min加温し、表面粗さ(Ra)10.2μmの微小な凹凸の表面形状を接触角105度、厚み1mm、密度;300kg/mの熱硬化性ポリウレタン発泡体を作製した。弾性体3の表面を平滑研磨し、厚み公差±0.01mmに調整した後に基材付き粘着層5を貼り付けた。 Dimer acid polyester diol (molecular weight 1259 manufactured by DIC Corporation, hydroxyl value 89.1, UA 2701 manufactured by DIC Corporation) as polyol and 4,4-diphenylmethane diisocyanate (isocyanate content 13.1%, manufactured by Nippon Polyurethane Co., Ltd.) as polyisocyanate DC6974) was mixed at an NCO / OH ratio = 1.05, and the temperature was adjusted to 35 ° C. Further, 0.4 part of 1,8-diaza-bicyclo [5,4,0] undecene-7 organic acid salt (SA102 manufactured by Sanyo Chemical Industries) as a catalyst and 0.5 part of water as a blowing agent were added and stirred well. A polyurethane raw material is coated on a base material 1 (TP-SG manufactured by Lintec Co., Ltd.) having a surface shape with a surface roughness (Ra) of 0.8 μm. X2 min, 120 ° C. x 4 min heated, surface roughness (Ra) 10.2 μm fine uneven surface shape with a contact angle of 105 degrees, thickness 1 mm, density; 300 kg / m 3 thermosetting polyurethane foam Produced. After smooth-polishing the surface of the elastic body 3 and adjusting the thickness tolerance to ± 0.01 mm, the adhesive layer 5 with a substrate was attached.

比較例5Comparative Example 5

表面粗さ(Ra)11μmの表面形状を持つ基材1(リンテック株式会社製FN)にメチルエチルケトン:トルエンの1:2の有機溶剤で熱可塑性ポリウレタン樹脂2(DIC株式会社製ゾルテックスPX−550)の固形分が20%になるように希釈したものを200μm間隙のスキージを用いて塗工し、70℃×5min間乾燥させ、表面粗さ(Ra)4.9μm、厚み26μmの非発泡ウレタンシート2を作製した。
次に、熱硬化性ポリウレタン樹脂としてポリオール成分の分子量2000のポリテトレメチレングリコール(分子量2000、水酸基価57、三菱化学株式会社製PTMG2000)とポリイソシアネート成分のトルエンジイソシアネート(イソシアネート含有量30%、日本ポリウレタン株式会社製T−65)をNCO/OH比率=1.0で混合し、35℃に温調した。触媒としてジブチルチンジラウレート(日東化成株式会社製ネオスタンU−100)を0.15部添加し、トリエチレンジアミン(花王株式会社製カオーライザーNo.30P)を0.15部、発泡剤として水を0.5部添加し、よく攪拌した後に非発泡ウレタンシート上にポリウレタン原料を塗布し、更に塗布後にその上から別の基材4を被せ、80℃×2min、120℃×4min加温し、密度280kg/mの熱硬化性ポリウレタン発泡体を作製した。弾性体3の表面を平滑研磨し、厚み公差±0.01mmに調整した後に基材付き粘着層5を貼り付けた。
Surface roughness (Ra) of base material 1 having a surface shape of 11 μm (FNTech's FN) and 1: 2 organic solvent of methyl ethyl ketone: toluene and thermoplastic polyurethane resin 2 (DIC Corporation's Zortex PX-550) Non-foamed urethane sheet 2 having a surface roughness (Ra) of 4.9 μm and a thickness of 26 μm, coated with a squeegee with a gap of 200 μm and dried for 70% × 5 min. Was made.
Next, as a thermosetting polyurethane resin, a polytetramethylene glycol having a molecular weight of 2000 (molecular weight 2000, hydroxyl value 57, Mitsubishi Chemical Co., Ltd. PTMG2000) as a thermosetting polyurethane resin and toluene diisocyanate as a polyisocyanate component (isocyanate content 30%, Nippon Polyurethane) T-65) was mixed at an NCO / OH ratio = 1.0, and the temperature was adjusted to 35 ° C. 0.15 parts of dibutyltin dilaurate (Neostan U-100 manufactured by Nitto Kasei Co., Ltd.) was added as a catalyst, 0.15 parts of triethylenediamine (Caorizer No. 30P manufactured by Kao Corporation), and water as a foaming agent was added in an amount of 0.15. After adding 5 parts and stirring well, a polyurethane raw material is coated on a non-foamed urethane sheet, and after coating, another base material 4 is placed thereon, heated at 80 ° C. × 2 min, 120 ° C. × 4 min, and a density of 280 kg. A thermosetting polyurethane foam of / m 3 was produced. After smooth-polishing the surface of the elastic body 3 and adjusting the thickness tolerance to ± 0.01 mm, the adhesive layer 5 with a substrate was attached.

比較例6Comparative Example 6

表面粗さ(Ra)11μmの表面形状を持つ基材1(リンテック株式会社製FN)にメチルエチルケトン:トルエンの1:2の有機溶剤で熱可塑性ポリウレタン樹脂2(DIC株式会社製ゾルテックスPX−550)の固形分が20%になるように希釈したものを60μm間隙のスキージを用いて塗工し、70℃×5min間乾燥させ、表面粗さ(Ra)7μm、厚み2.5μmの非発泡ウレタンシート2を作製した。
次に、熱硬化性ポリウレタン樹脂としてポリオールとしてダイマー酸ポリエステルジオール(分子量1236、水酸基価104.4、DIC株式会社製UA2812)100部とポリイソシアネートとして4,4−ジフェニルメタンジイソシアネート(イソシアネート含有量13.1wt%、日本ポリウレタン株式会社製DC6974)をNCO/OH比率=1.05で混合し、35℃に温調した。触媒として1,8−ジアザ・ビシクロ[5,4,0]ウンデセン・7有機酸塩(三洋化成製SA102)を0.4部、発泡剤として水を0.5部添加し、よく攪拌した後に非発泡ウレタンシート上にポリウレタン原料を塗布し、更に塗布後にその上から別の基材4を被せ、80℃×2min、120℃×4min加温し、ポリウレタン熱硬化性ポリウレタン発泡体を作製した。更に基材4を取除き、弾性体3の表面を平滑研磨し、厚み公差±0.01mmに調整した後に基材付き粘着層5を貼り付けた。
Surface roughness (Ra) of base material 1 having a surface shape of 11 μm (FNTech's FN) and 1: 2 organic solvent of methyl ethyl ketone: toluene and thermoplastic polyurethane resin 2 (DIC Corporation's Zortex PX-550) Non-foamed urethane sheet 2 having a surface roughness (Ra) of 7 μm and a thickness of 2.5 μm, coated with a squeegee with a gap of 60 μm and dried for 70 minutes for 5 minutes. Was made.
Next, dimer acid polyester diol (molecular weight 1236, hydroxyl value 104.4, UA2812 manufactured by DIC Corporation) as a polyol as a thermosetting polyurethane resin and 4,4-diphenylmethane diisocyanate (isocyanate content 13.1 wt as polyisocyanate) %, Nippon Polyurethane Co., Ltd. DC6974) was mixed at an NCO / OH ratio = 1.05, and the temperature was adjusted to 35 ° C. After adding 0.4 parts of 1,8-diaza-bicyclo [5,4,0] undecene-7 organic acid salt (SA102 manufactured by Sanyo Chemical Industries) as a catalyst and 0.5 parts of water as a blowing agent, the mixture was stirred well. A polyurethane raw material was applied onto a non-foamed urethane sheet, and after the application, another base material 4 was placed thereon and heated at 80 ° C. × 2 min, 120 ° C. × 4 min to prepare a polyurethane thermosetting polyurethane foam. Further, the base material 4 was removed, the surface of the elastic body 3 was smooth polished, and after adjusting the thickness tolerance to ± 0.01 mm, the base material-attached adhesive layer 5 was attached.

比較例7Comparative Example 7

表面粗さ(Ra)11μmの表面形状を持つ基材1(リンテック株式会社製FN)にメチルエチルケトン:トルエンの1:2の有機溶剤で熱可塑性ポリウレタン樹脂2(DIC株式会社製ゾルテックスPX−550)の固形分が20%になるように希釈したものを400μm間隙のスキージを用いて塗工し、70℃×5min間乾燥させ、表面粗さ(Ra)5μm、厚み50μmの非発泡ウレタンシート2を作製した。
以降は比較例6と同じ作業を行い、粘着テープ付きウレタンシートを作製した。
Surface roughness (Ra) of base material 1 having a surface shape of 11 μm (FNTech's FN) and 1: 2 organic solvent of methyl ethyl ketone: toluene and thermoplastic polyurethane resin 2 (DIC Corporation's Zortex PX-550) Coated with a squeegee with a gap of 400 μm so that the solid content is 20%, and dried for 70 ° C. for 5 minutes to produce a non-foamed urethane sheet 2 having a surface roughness (Ra) of 5 μm and a thickness of 50 μm. did.
Thereafter, the same operation as in Comparative Example 6 was performed to produce a urethane sheet with an adhesive tape.

比較例8Comparative Example 8

表面粗さ(Ra)11μmの表面形状を持つ基材1(リンテック株式会社製FN)にメチルエチルケトン:トルエンの1:2の有機溶剤で熱可塑性ポリウレタン樹脂2(DIC株式会社製ゾルテックスPX−550)の固形分が20%になるように希釈し、ポリブテン(新日本石油株式会社製LV−100)を5部添加し、混合したものを200μm間隙のスキージ等を用いて塗工し、70℃×5min間乾燥させ、表面粗さ(Ra)6.1μm、厚み22μmの非発泡ウレタンシート2を作製した。
以降は比較例6と同じ作業を行い、粘着テープ付きウレタンシートを作製した。
Surface roughness (Ra) of base material 1 having a surface shape of 11 μm (FNTech's FN) and 1: 2 organic solvent of methyl ethyl ketone: toluene and thermoplastic polyurethane resin 2 (DIC Corporation's Zortex PX-550) Dilute so that the solid content is 20%, add 5 parts of polybutene (LV-100, Nippon Oil Corporation), apply the mixture using a squeegee with a gap of 200 μm, etc., 70 ° C. × 5 min The non-foamed urethane sheet 2 having a surface roughness (Ra) of 6.1 μm and a thickness of 22 μm was produced.
Thereafter, the same operation as in Comparative Example 6 was performed to produce a urethane sheet with an adhesive tape.

比較例9Comparative Example 9

表面粗さ(Ra)11μmの表面形状を持つ基材1(リンテック株式会社製FN)にメチルエチルケトン:トルエンの1:2の有機溶剤で熱可塑性ポリウレタン樹脂2(DIC株式会社製ゾルテックスPX−550)の固形分が20%になるように希釈し、イソシアネートプレポリマー(DIC株式会社製ゾルテックスCL−15)を3部、有機錫触媒(DIC株式会社製ゾルテックスT・81E)を3部添加し、混合したものを200μm間隙のスキージを用いて塗工し、70℃×5min間乾燥させ、表面粗さ(Ra)6.1μm、厚み24μmの非発泡ウレタンシート2を作製した。
以降は比較例6と同じ作業を行い、粘着テープ付きウレタンシートを作製した。
Surface roughness (Ra) of base material 1 having a surface shape of 11 μm (FNTech's FN) and 1: 2 organic solvent of methyl ethyl ketone: toluene and thermoplastic polyurethane resin 2 (DIC Corporation's Zortex PX-550) Diluted to a solid content of 20%, 3 parts of isocyanate prepolymer (DIC Corporation Zortex CL-15) and 3 parts of organotin catalyst (DIC Corporation Zortex T.81E) were added and mixed. This was coated using a squeegee with a gap of 200 μm and dried for 70 ° C. × 5 min to produce a non-foamed urethane sheet 2 having a surface roughness (Ra) of 6.1 μm and a thickness of 24 μm.
Thereafter, the same operation as in Comparative Example 6 was performed to produce a urethane sheet with an adhesive tape.

Figure 0005935159
Figure 0005935159

Figure 0005935159
Figure 0005935159



Figure 0005935159
Figure 0005935159

表1、表2及び表3における各用語の意味を以下に示す。
表面粗さ(Ra):各工程紙で作製した非発泡ウレタンシート表面の表面粗さRaを表面粗さ計で測定した値を示す。表面粗さ計は、株式会社東京精密製SURFCOM110Aを使用した。
保持力:試験治具に50×50mm角のサンプル片を貼付け、8g/cmの荷重がかかるように調整する。50μLの水をガラス上に滴下し、その上にサンプル片を馴染ませ、静値させる。ガラス板と水平方向にサンプル片を引張り、サンプル片がずれる時の引張力のピーク値を測定した。単位;N(ニュートン) 引張速度;100mm/min。試験機;UT4−5KN
エアー残留性:100×100mm角のガラス板を0.1mlの霧状の水で濡らした保持パッド材上に5°の傾きをつけた状態から静かに置く。ガラス上に400gのおもりを1分置いた後、おもりを外し、エアーの有無を確認する。
吸水量:100×100mm角のガラス板上に1mlの水を滴下し、その上に50×50mm角のサンプル片を静置させる。80g/cmの荷重を繰返し10回かけ、吸水した水の量を測定した。単位;mg
スラリー残留性:100×100mm角のガラス板上に0.1mlの研磨用スラリー液を滴下し、その上に50×50mm角のサンプル片を静置させる。80g/cmの荷重を繰返し10回かけた後、流水でスラリーを洗い流す。保持パッド材表面にスラリー(研磨砥粒)を目視にて確認できなければ○、スラリーを目視にて確認できた場合を×とした。
The meaning of each term in Table 1, Table 2 and Table 3 is shown below.
Surface roughness (Ra): A value obtained by measuring the surface roughness Ra of the surface of the non-foamed urethane sheet prepared with each process paper with a surface roughness meter. As the surface roughness meter, SURFCOM110A manufactured by Tokyo Seimitsu Co., Ltd. was used.
Holding power: A 50 × 50 mm square sample piece is attached to the test jig and adjusted so that a load of 8 g / cm 2 is applied. 50 μL of water is dropped on the glass, and the sample piece is conditioned on it and allowed to settle. The sample piece was pulled horizontally with the glass plate, and the peak value of the tensile force when the sample piece was displaced was measured. Unit: N (Newton) Tensile speed: 100 mm / min. Testing machine: UT4-5KN
Air persistence: A 100 × 100 mm square glass plate is gently placed on a holding pad material wetted with 0.1 ml of mist-like water from a 5 ° tilted state. After placing a 400 g weight on the glass for 1 minute, remove the weight and check for air.
Water absorption: 1 ml of water is dropped on a 100 × 100 mm square glass plate, and a 50 × 50 mm square sample piece is allowed to stand on it. A load of 80 g / cm 2 was repeatedly applied 10 times, and the amount of absorbed water was measured. Unit: mg
Slurry persistence: 0.1 ml of slurry liquid for polishing is dropped on a 100 × 100 mm square glass plate, and a 50 × 50 mm square sample piece is allowed to stand on it. After repeatedly applying a load of 80 g / cm 2 10 times, the slurry is washed away with running water. The case where the slurry (abrasive grains) could not be visually confirmed on the surface of the holding pad material was evaluated as “◯”, and the case where the slurry was visually confirmed was evaluated as “x”.

乾燥時間:50×50mm角のガラス板を一定量の霧状の水で濡らした保持パッド材上に静置する。50%圧縮率でガラス板を10回/分で4分間上下した後、80℃のオーブン中に1分間入れ、乾燥しているか否かを確認する。
復元性:70℃オーブンにて促進した、50%圧縮永久歪。
非発泡ウレタンシート樹脂:熱可塑性とは熱可塑性ポリウレタン樹脂を用いて作製したものをいい、熱硬化とは熱硬化性ポリウレタン樹脂を用いて作製したシートを言う。
厚み;非発泡ウレタンシートを株式会社ミツトヨ製ID−Hで測定した値である。単位;μm
接触角:鏡面仕上げのPET上に各ポリウレタン原料を塗布、乾燥し、平滑なフィルム状となしたものを接触角計で測定した値である。接触角計としては協和接触角計CA―A型(協和科学社製)を使用した。
ポリウレタン発泡体:エステルとは、各種ポリエステルポリオール原料を使用し、所定の条件で発泡させたポリウレタン発泡体をいい、エーテルとはポリエーテルポリオール原料を使用し、所定の条件で発泡させたポリウレタン発泡体いう。
圧縮応力:30×30mmのサンプルを10枚積層し、1mm/minの速度で25%圧縮したときの圧縮応力値(JIS K6400−2準拠)。測定機は島津製作所製autographAG−Xを使用した。単位;MPa
耐磨耗性;JIS K5600・5・9<塗膜・機械的性質(第9節;耐磨耗性(磨耗輪法))準拠
磨耗輪;H・18、荷重250gを用い、試験サンプルの重量減少率(%)を測定した値である。耐磨耗試験機はティーバー式(東洋精機製)を使用した。
Drying time: A glass plate of 50 × 50 mm square is left on a holding pad material wetted with a certain amount of mist water. The glass plate is moved up and down at a rate of 50% at 10 times / minute for 4 minutes, and then placed in an oven at 80 ° C. for 1 minute to check whether it is dry.
Restorability: 50% compression set promoted in a 70 ° C. oven.
Non-foamed urethane sheet resin: Thermoplastic means a material made using a thermoplastic polyurethane resin, and thermosetting means a sheet made using a thermosetting polyurethane resin.
Thickness: A value obtained by measuring a non-foamed urethane sheet with ID-H manufactured by Mitutoyo Corporation. Unit: μm
Contact angle: A value obtained by measuring each polyurethane raw material on a mirror-finished PET and drying it to form a smooth film with a contact angle meter. As a contact angle meter, Kyowa contact angle meter CA-A type (manufactured by Kyowa Science Co., Ltd.) was used.
Polyurethane foam: An ester refers to a polyurethane foam that is foamed under specified conditions using various polyester polyol raw materials. An ether is a polyurethane foam that is foamed under predetermined conditions using a polyether polyol raw material. Say.
Compressive stress: Compressive stress value (according to JIS K6400-2) when 10 samples of 30 × 30 mm are stacked and compressed by 25% at a speed of 1 mm / min. The measuring machine used was autograph AG-X manufactured by Shimadzu Corporation. Unit: MPa
Wear resistance; JIS K5600 ・ 5 ・ 9 <Paint / Mechanical properties (Section 9; Wear resistance (wear ring method)) compliant wear wheel; Weight of test sample using H · 18 and load 250g It is a value obtained by measuring the reduction rate (%). A tea bar type (manufactured by Toyo Seiki) was used as an abrasion resistance tester.

表1に示した結果から、実施例1〜5は、研磨対象物を吸着保持する非発泡ウレタンシートの厚み、圧縮応力、接触角及び表面粗さ、並びにポリウレタン発泡体のタイプ、エステルタイプ又はエーテルタイプにより保持力、復元性、耐摩耗性などに若干のバラツキが見られるものの、エアー残留性(空気の咬み込み)、吸水量、スラリー残留性、乾燥時間において十分満足できる結果が得られている。   From the results shown in Table 1, in Examples 1 to 5, the thickness, compression stress, contact angle and surface roughness of the non-foamed urethane sheet that adsorbs and holds the object to be polished, and the type of polyurethane foam, ester type or ether Although there is some variation in holding power, resilience, wear resistance, etc. depending on the type, satisfactory results have been obtained in terms of air persistence (air bite), water absorption, slurry persistence, and drying time. .

一方、表2及び表3に示した結果から比較例1は表面粗さ(Ra)が0.3と小さすぎて表面がほぼ平坦なため保持力が0.8と極めて小さくなるだけでなく、エアー残留性も悪化し不合格と言える。比較例2は接触角が80°と低いため親水性が生じ、そのため吸水量が大きく乾燥時間が長くなり実用的に非効率的になるばかりでなく、非発泡ウレタンシートの厚みが25μmと厚いため圧縮応力も大きくなり、表面粗さが5.5とそこそこの値を有するものの保持力が2.1Nと言う不満足で不合格な結果になる。比較例3は、非発泡ウレタンシートの厚みが23μmと厚いため、表面粗さ(Ra)が19もあっても保持力が2Nと言う不満足で不合格なものになる。比較例4はポリウレタン発泡体だけからなるために、当然想到されることであるが吸水量が妥当な値であるにもかかわらず乾燥時間が長くなり、しかも耐摩耗性が悪化するだけでなく保持力も2.5Nと言う不満足で不合格となる結果を生じる。比較例5はポリウレタン発泡体の密度が280kg/mと若干低いため復元性(圧縮永久歪)が30と大きく長期間の使用に耐えないだけでなく、吸水量も大きく乾燥時長時間要し実用性に劣るという不合格となる結果に終わる。 On the other hand, from the results shown in Tables 2 and 3, Comparative Example 1 not only has a surface roughness (Ra) as small as 0.3 and the surface is almost flat, so that the holding force is extremely small as 0.8, Air persistence deteriorates and it can be said that it is rejected. In Comparative Example 2, the contact angle is as low as 80 °, so that hydrophilicity is generated. Therefore, not only is the water absorption amount large and the drying time becomes long and practically inefficient, but also the thickness of the non-foamed urethane sheet is as thick as 25 μm. Although the compressive stress is increased, the surface roughness is 5.5 or so, but the holding force is 2.1 N, which is an unsatisfactory and unsatisfactory result. In Comparative Example 3, since the thickness of the non-foamed urethane sheet is as thick as 23 μm, even if the surface roughness (Ra) is 19, the holding power is 2N, which is unsatisfactory and unacceptable. Since Comparative Example 4 is composed only of polyurethane foam, it is naturally conceived that although the water absorption amount is a reasonable value, the drying time becomes longer and the wear resistance is not only deteriorated but also retained. The result is an unsatisfactory and unsatisfactory force of 2.5N. In Comparative Example 5, the density of the polyurethane foam is slightly low at 280 kg / m 3 , so that the resilience (compression set) is 30 and not only can withstand long-term use, but also has a large water absorption and requires a long time for drying. The result is a rejected result of inferior utility.

比較例6は非発泡ウレタンシートの厚みが2.5μmと薄すぎたため、表面粗さ(Ra)が7であったので保持力も4.5Nと言う良好な性能を有し、エアー残留性から復元性まで良好な性能を示したにもかかわらず、耐摩耗性(重量減少率)が0.5%という実施例に比べて見劣りするという不満足な結果になる。比較例7は比較例6とは反対に非発泡ウレタンシートの厚みが50μmと極めて厚過ぎたため、保持力以下耐摩耗性に至るまで良好な性能が得られたにもかかわらず非発泡ウレタンシートが破れるという不合格な結果となる。比較例7は非発泡ウレタンシートの厚みが22μmとやや厚かったため表面粗さ(Ra)が6.1という程良い粗さであったにもかかわらず、保持力が2.7Nというやや見劣りする結果で不合格となる。比較例9は比較例8と同様に非発泡ウレタンシートの厚みが24μmと少々厚かったため表面粗さ(Ra)が6.3という良好な粗さであったにもかかわらず、保持力が2Nと言う不満足で不合格な数値になる。   In Comparative Example 6, since the thickness of the non-foamed urethane sheet was too thin, 2.5 μm, the surface roughness (Ra) was 7, so the holding power was 4.5 N, and the performance was restored from the air residual property. In spite of the good performance, the abrasion resistance (weight reduction rate) is inferior to that of the example of 0.5%. In contrast to Comparative Example 6, the thickness of the non-foamed urethane sheet was 50 μm, which was very thick, so that the non-foamed urethane sheet was obtained even though good performance was obtained up to the holding force and the wear resistance. The result is an unacceptable failure. In Comparative Example 7, the thickness of the non-foamed urethane sheet was slightly thick at 22 μm, so the surface roughness (Ra) was as good as 6.1 but the holding power was 2.7 N. Will be rejected. In Comparative Example 9, as in Comparative Example 8, the thickness of the non-foamed urethane sheet was slightly thick at 24 μm, so the surface roughness (Ra) was 6.3, but the holding power was 2N. It becomes an unsatisfactory and unacceptable number.

1 基材
2 非発泡ウレタンシート
3 ポリウレタン発泡体
4 基材
5 基材付き粘着層(セパレータを付けた状態)
5’ 基材付き粘着層(セパレータで剥離した状態)
6 定盤
7 端部の防水処理加工
DESCRIPTION OF SYMBOLS 1 Base material 2 Non-foaming urethane sheet 3 Polyurethane foam 4 Base material 5 Adhesive layer with a base material (The state which attached the separator)
5 'Adhesive layer with substrate (peeled with a separator)
6 Surface plate 7 Waterproof treatment of the edge

Claims (2)

可塑性ポリウレタン樹脂からなる非発泡ウレタンシートの一面側に熱硬化性ポリウレタン樹脂からなるウレタン発泡体が形成されており、研磨対象物を保持するための定盤に前記ウレタン発泡体の他面側を固着させて前記非発泡ウレタンシートの他面側が前記研磨対象物に当接する研磨保持用パッドにおいて、前記非発泡ウレタンシートは表面粗さRaが0.5〜17μmであり、水との接触角が90°以上であり、圧縮応力が0.05〜0.5MPaであり、厚みが5〜30μmであって、前記ウレタン発泡体は70℃オーブンにて促進した、50%圧縮永久歪が10%以下の独立気泡型ポリウレタン発泡体であることを特徴とする研磨保持用パッド。 A urethane foam made of a thermosetting polyurethane resin is formed on one side of a non-foamed urethane sheet made of a thermoplastic polyurethane resin, and the other side of the urethane foam is placed on a surface plate for holding an object to be polished. In the polishing holding pad that is fixed and the other surface side of the non-foamed urethane sheet comes into contact with the object to be polished, the non-foamed urethane sheet has a surface roughness Ra of 0.5 to 17 μm and a contact angle with water. 90 ° or more, compressive stress is 0.05 to 0.5 MPa, thickness is 5 to 30 μm, and the urethane foam is accelerated in an oven at 70 ° C., 50% compression set is 10% or less A polishing holding pad characterized by being a closed-cell polyurethane foam. 前記ウレタン発泡体の定盤への固着面が厚み調整平滑処理され、その平滑面に粘着剤が塗工されていることを特徴とする請求項1記載の研磨保持用パッド。   The polishing holding pad according to claim 1, wherein a surface of the urethane foam fixed to the surface plate is subjected to a thickness adjustment smoothing treatment, and an adhesive is applied to the smooth surface.
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