JP6697931B2 - Polishing pad, polishing pad manufacturing method and polishing method - Google Patents
Polishing pad, polishing pad manufacturing method and polishing method Download PDFInfo
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- JP6697931B2 JP6697931B2 JP2016074460A JP2016074460A JP6697931B2 JP 6697931 B2 JP6697931 B2 JP 6697931B2 JP 2016074460 A JP2016074460 A JP 2016074460A JP 2016074460 A JP2016074460 A JP 2016074460A JP 6697931 B2 JP6697931 B2 JP 6697931B2
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- woven fabric
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- 238000005498 polishing Methods 0.000 title claims description 243
- 238000000034 method Methods 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 229920005989 resin Polymers 0.000 claims description 171
- 239000011347 resin Substances 0.000 claims description 171
- 239000004745 nonwoven fabric Substances 0.000 claims description 93
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 68
- 239000000243 solution Substances 0.000 claims description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 44
- 238000005470 impregnation Methods 0.000 claims description 41
- 239000002904 solvent Substances 0.000 claims description 39
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 36
- 229920001281 polyalkylene Polymers 0.000 claims description 34
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 32
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 238000007598 dipping method Methods 0.000 claims description 22
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
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- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- PIODVRGFECLUSY-UHFFFAOYSA-N 2,6-diamino-4-[2-(3,5-diamino-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C(N)=C(O)C(N)=CC=1C(C)(C)C1=CC(N)=C(O)C(N)=C1 PIODVRGFECLUSY-UHFFFAOYSA-N 0.000 description 1
- KIAWNCIDEJNMPR-UHFFFAOYSA-N 2,6-diamino-4-methylphenol Chemical compound CC1=CC(N)=C(O)C(N)=C1 KIAWNCIDEJNMPR-UHFFFAOYSA-N 0.000 description 1
- WGFYAPLOOOHKPS-UHFFFAOYSA-N 2-(butan-2-ylamino)-4-[2-[3-(butan-2-ylamino)-4-hydroxyphenyl]propan-2-yl]phenol Chemical compound C1=C(O)C(NC(C)CC)=CC(C(C)(C)C=2C=C(NC(C)CC)C(O)=CC=2)=C1 WGFYAPLOOOHKPS-UHFFFAOYSA-N 0.000 description 1
- DPYAEAOFIKXXMM-UHFFFAOYSA-N 2-(hexan-2-ylamino)-4-[2-[3-(hexan-2-ylamino)-4-hydroxyphenyl]propan-2-yl]phenol Chemical compound CC(CCCC)NC=1C=C(C=CC=1O)C(C)(C)C1=CC(=C(C=C1)O)NC(CCCC)C DPYAEAOFIKXXMM-UHFFFAOYSA-N 0.000 description 1
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- UHIDYCYNRPVZCK-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(N)=CC=1C(C)(C)C1=CC=C(O)C(N)=C1 UHIDYCYNRPVZCK-UHFFFAOYSA-N 0.000 description 1
- TXDBDYPHJXUHEO-UHFFFAOYSA-N 2-methyl-4,6-bis(methylsulfanyl)benzene-1,3-diamine Chemical compound CSC1=CC(SC)=C(N)C(C)=C1N TXDBDYPHJXUHEO-UHFFFAOYSA-N 0.000 description 1
- GNBPEYCZELNJMS-UHFFFAOYSA-N 2-methylbutane-1,3-diol Chemical compound CC(O)C(C)CO GNBPEYCZELNJMS-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、研磨パッド、研磨パッドの製造方法及び研磨方法に関する。 The present invention relates to a polishing pad, a method for manufacturing the polishing pad, and a polishing method.
シリコンウェハや、ＳｉＣウェハ等の半導体材料の表面には平坦性が求められるため、研磨パッドを用いた化学機械研磨（Ｃｈｅｍｉｃａｌ Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉｎｇ：ＣＭＰ）が行われている。 Since a surface of a semiconductor material such as a silicon wafer or a SiC wafer is required to have flatness, chemical mechanical polishing (CMP) using a polishing pad is performed.
ＣＭＰには、不織布にポリウレタン樹脂を含浸した研磨パッドが用いられることがあり、平坦性の向上を目的として、当該研磨パッドの硬度を向上させる技術が種々提案されている。例えば、特許文献１では、不織布にポリウレタン樹脂を含浸し、凝固浴で樹脂を湿式凝固させた後、発泡を溶剤で処理し、さらに硬化剤で硬化させることにより、得られる研磨パッドの硬度が向上することが記載されている。また、研磨パッドの硬度を向上させるため、不織布に樹脂を複数回含浸させた研磨パッド及びその製造方法も知られている（例えば、特許文献２，３参照）。 A polishing pad obtained by impregnating a nonwoven fabric with a polyurethane resin may be used for CMP, and various techniques for improving the hardness of the polishing pad have been proposed for the purpose of improving flatness. For example, in Patent Document 1, a nonwoven fabric is impregnated with a polyurethane resin, the resin is wet-coagulated in a coagulation bath, and then foaming is treated with a solvent and further cured with a curing agent to improve the hardness of a polishing pad obtained. It is described to do. Further, in order to improve the hardness of the polishing pad, a polishing pad in which a non-woven fabric is impregnated with resin a plurality of times and a method for manufacturing the same are also known (for example, refer to Patent Documents 2 and 3).
特許文献１〜３に記載の技術によれば、硬度を上昇させることはできるが、研磨液との馴染みが悪く、十分な研磨効率（研磨レート）を確保することができない。特に、特許文献１の技術では、湿式含浸した樹脂に含まれるＯＨ基等の親水基が、次いで含浸される硬化剤の組成物と反応するため、親水性が不十分となり、結果として研磨レートが不十分となる。 According to the techniques described in Patent Documents 1 to 3, the hardness can be increased, but the compatibility with the polishing liquid is poor and a sufficient polishing efficiency (polishing rate) cannot be secured. In particular, in the technique of Patent Document 1, hydrophilic groups such as OH groups contained in the wet-impregnated resin react with the composition of the curing agent to be subsequently impregnated, resulting in insufficient hydrophilicity, resulting in a polishing rate. Will be insufficient.
本発明は、上記事情に鑑みてなされたものであり、研磨レートに優れ、研磨時の目詰まり及びスクラッチの発生を防止できる研磨パッド、研磨パッドの製造方法及び研磨方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a polishing pad that has an excellent polishing rate and that can prevent clogging and scratches during polishing, a method for manufacturing the polishing pad, and a polishing method. To do.
本発明者らは、鋭意研究を重ねた結果、特定の構成を有する研磨パッドが上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that a polishing pad having a specific structure can solve the above problems, and have completed the present invention.
すなわち、本発明は、以下の態様を包含する。
［１］
不織布と、第１の樹脂と、当該第１の樹脂とは異なる第２の樹脂と、を有する研磨パッドであって、
前記第２の樹脂が、ＮＣＯ当量５００以下のウレタンプレポリマーと、２官能以上かつＯＨ当量５００〜１００００であるポリアルキレンエーテルグリコールと、硬化剤との反応物であり、
前記ウレタンプレポリマーにおけるＮＣＯ基の量に対する前記ポリアルキレンエーテルグリコールにおけるＯＨ基の量のモル比が、０．０１〜０．１５である、研磨パッド。
［２］
前記研磨パッドの引張強度に対する、３質量％の過マンガン酸カリウム水溶液に硝酸を加えてｐＨ２に調整した溶液に前記研磨パッドを２５℃で４８時間浸漬した後の前記研磨パッドの引張強度の比が、４５％以上である、［１］に記載の研磨パッド。
［３］
前記不織布、前記第１の樹脂及び前記第２の樹脂の合計に対して、前記不織布の含有量が１０〜５０質量％であり、かつ、前記第１の樹脂の含有量が１０〜６０質量％であり、かつ、前記第２の樹脂の含有量が１０〜７０質量％である、［１］又は［２］に記載の研磨パッド。
［４］
前記ウレタンプレポリマーにおけるＮＣＯ基の量に対する前記ポリアルキレンエーテルグリコールにおけるＯＨ基の量及び前記硬化剤におけるＮＨ2基の量の合計のモル比が、０．８〜１．０である、［１］〜［３］のいずれかに記載の研磨パッド。
［５］
不織布に第１の樹脂を含む樹脂溶液を含浸させ、湿式凝固を行うことにより、樹脂含浸不織布を得る１次含浸工程と、
前記樹脂含浸不織布を、前記第１の樹脂が可溶な溶媒に浸漬する浸漬工程と、
前記浸漬工程の後の前記樹脂含浸不織布を、ＮＣＯ当量５００以下のウレタンプレポリマーと、２官能以上かつＯＨ当量５００〜１００００であるポリアルキレンエーテルグリコールと、硬化剤とを含む溶液に含浸する２次含浸工程と、
を有し、
前記ウレタンプレポリマーにおけるＮＣＯ基の量に対する前記ポリアルキレンエーテルグリコールにおけるＯＨ基の量のモル比が、０．０１〜０．１５である、研磨パッドの製造方法。
［６］
前記第１の樹脂が、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルアセトアミド及びメチルエチルケトンからなる群より選ばれる１種以上の溶媒に可溶である、［５］に記載の研磨パッドの製造方法。
［７］
前記溶媒が、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルアセトアミド及びメチルエチルケトンからなる群より選ばれる１種以上の溶媒を含む、［５］又は［６］に記載の研磨パッドの製造方法。
［８］
化合物半導体ウェハを、過マンガン酸カリウムを含む溶液に接触させながら［１］〜［４］のいずれかに記載の研磨パッドにより研磨する、研磨方法。
That is, the present invention includes the following aspects.
[1]
A polishing pad having a non-woven fabric, a first resin, and a second resin different from the first resin,
The second resin is a reaction product of a urethane prepolymer having an NCO equivalent of 500 or less, a polyalkylene ether glycol having a functionality of 2 or more and an OH equivalent of 500 to 10,000, and a curing agent,
The polishing pad, wherein the molar ratio of the amount of OH groups in the polyalkylene ether glycol to the amount of NCO groups in the urethane prepolymer is 0.01 to 0.15.
[2]
The ratio of the tensile strength of the polishing pad after immersing the polishing pad in a solution in which nitric acid is added to a 3% by mass potassium permanganate aqueous solution to adjust the pH to 2 with respect to the tensile strength of the polishing pad at 25° C. for 48 hours. , 45% or more, the polishing pad according to [1].
[3]
The content of the non-woven fabric is 10 to 50 mass% and the content of the first resin is 10 to 60 mass% with respect to the total of the non-woven fabric, the first resin, and the second resin. And the content of the second resin is 10 to 70 mass%, the polishing pad according to [1] or [2].
[4]
The total molar ratio of the amount of OH groups in the polyalkylene ether glycol and the amount of NH 2 groups in the curing agent to the amount of NCO groups in the urethane prepolymer is 0.8 to 1.0, [1] ~ The polishing pad according to any one of [3].
[5]
A primary impregnation step of obtaining a resin-impregnated nonwoven fabric by impregnating the nonwoven fabric with a resin solution containing a first resin and performing wet coagulation;
A dipping step of dipping the resin-impregnated nonwoven fabric in a solvent in which the first resin is soluble;
Secondary impregnation of the resin-impregnated non-woven fabric after the dipping step with a solution containing a urethane prepolymer having an NCO equivalent of 500 or less, a polyalkylene ether glycol having a functionality of 2 or more and an OH equivalent of 500 to 10,000, and a curing agent. Impregnation process,
Have
The method for producing a polishing pad, wherein the molar ratio of the amount of OH groups in the polyalkylene ether glycol to the amount of NCO groups in the urethane prepolymer is 0.01 to 0.15.
[6]
The method for producing a polishing pad according to [5], wherein the first resin is soluble in one or more solvents selected from the group consisting of N,N-dimethylformamide, dimethylacetamide and methylethylketone.
[7]
The method for producing a polishing pad according to [5] or [6], wherein the solvent contains at least one solvent selected from the group consisting of N,N-dimethylformamide, dimethylacetamide and methyl ethyl ketone.
[8]
A polishing method in which a compound semiconductor wafer is polished with the polishing pad according to any one of [1] to [4] while being brought into contact with a solution containing potassium permanganate.
本発明によれば、研磨レートに優れ、研磨時の目詰まり及びスクラッチの発生を防止できる研磨パッド、研磨パッドの製造方法及び研磨方法を提供することが可能となる。 According to the present invention, it is possible to provide a polishing pad that has an excellent polishing rate and can prevent clogging and scratches during polishing, a method for manufacturing the polishing pad, and a polishing method.
以下、本発明を実施するための形態（以下、単に「本実施形態」という。）について詳細に説明する。なお、本実施形態は、本発明を説明するための例示であり、本発明は以下の実施形態のみに限定されない。 Hereinafter, modes for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The present embodiment is an example for explaining the present invention, and the present invention is not limited to the following embodiments.
［研磨パッド］
本実施形態の研磨パッドは、不織布と、第１の樹脂と、当該第１の樹脂とは異なる第２の樹脂と、を有する研磨パッドであって、当該第２の樹脂が、ＮＣＯ当量５００以下のウレタンプレポリマーと、２官能以上かつＯＨ当量５００〜１００００であるポリアルキレンエーテルグリコールと、硬化剤との反応物であり、当該ウレタンプレポリマーにおけるＮＣＯ基の量に対する当該ポリアルキレンエーテルグリコールにおけるＯＨ基の量のモル比が、０．０１〜０．１５である。このように構成されているため、本実施形態の研磨パッドは、研磨レートに優れ、研磨時の目詰まり及びスクラッチの発生を防止できる。
[Polishing pad]
The polishing pad of the present embodiment is a polishing pad having a nonwoven fabric, a first resin, and a second resin different from the first resin, and the second resin has an NCO equivalent of 500 or less. Of the urethane prepolymer, a polyalkylene ether glycol having a functionality of 2 or more and an OH equivalent of 500 to 10,000, and a curing agent, wherein the OH groups in the polyalkylene ether glycol with respect to the amount of NCO groups in the urethane prepolymer. The molar ratio of the amount of is 0.01 to 0.15. With this configuration, the polishing pad of this embodiment has an excellent polishing rate and can prevent clogging and scratches during polishing.
（不織布）
本実施形態における不織布は、特に限定されるものではなく、種々公知のものを採用できる。上記不織布の例としては、ポリアミド系、ポリエステル系等の不織布を挙げることができる。また、不織布を得る際に繊維を交絡させる方法としても特に限定されず、例えば、ニードルパンチであってもよく、水流交絡であってもよい。不織布は上述した中から１種を単独で用いることができ、２種以上を組み合わせて用いることもできる。
(Nonwoven fabric)
The nonwoven fabric in this embodiment is not particularly limited, and various known ones can be adopted. Examples of the above-mentioned non-woven fabric include polyamide-based and polyester-based non-woven fabrics. The method of entanglement of fibers when obtaining a nonwoven fabric is not particularly limited, and may be, for example, needle punching or hydroentanglement. As the non-woven fabric, one kind may be used alone from the above-mentioned ones, and two or more kinds may be used in combination.
本実施形態における不織布の厚さは、特に限定されないが、研磨パッド厚さの観点から、２〜５ｍｍであることが好ましい。 The thickness of the nonwoven fabric in the present embodiment is not particularly limited, but is preferably 2 to 5 mm from the viewpoint of the polishing pad thickness.
本実施形態における不織布の繊度は、特に限定されないが、研磨時のスクラッチ発生減少の観点から、２〜６ｄであることが好ましい。 The fineness of the non-woven fabric in the present embodiment is not particularly limited, but is preferably 2 to 6 d from the viewpoint of reducing scratch generation during polishing.
本実施形態における不織布の目付けは、特に限定されないが、研磨パッド密度や不織布と樹脂の比率の観点から、２００〜１０００ｇ／ｍ2であることが好ましい。 The basis weight of the nonwoven fabric in this embodiment is not particularly limited, but is preferably 200 to 1000 g/m 2 from the viewpoint of the polishing pad density and the ratio of the nonwoven fabric to the resin.
（第１の樹脂）
本実施形態における第１の樹脂としては、いわゆる湿式含浸により不織布に含浸できるものであれば特に限定されず、種々公知のものを適用できる。そのような樹脂（以下、単に「湿式樹脂」ともいう。）の例としては、以下に限定されないが、ポリウレタン、ポリウレタンポリウレア等のポリウレタン系、ポリアクリレート、ポリアクリロニトリル等のアクリル系、ポリ塩化ビニル、ポリ酢酸ビニル、ポリフッ化ビニリデン等のビニル系、ポリサルホン、ポリエーテルサルホン等のポリサルホン系、アセチル化セルロース、ブチリル化セルロース等のアシル化セルロース系、ポリアミド系及びポリスチレン系が挙げられる。ポリウレタン樹脂としては、以下に限定されないが、例えば、ポリエステル系ポリウレタン樹脂、ポリエーテル系ポリウレタン樹脂、及びポリカーボネート系ポリウレタン樹脂が挙げられる。樹脂の１００％モジュラスは、５ＭＰａ〜３０ＭＰａであると好ましく、１０ＭＰａ〜２０ＭＰａであるとより好ましい。樹脂の１００％モジュラスは、その樹脂からなるシートを１００％伸ばしたとき、すなわち元の長さの２倍に伸ばしたとき、に掛かる荷重を単位面積で割った値である。
(First resin)
The first resin in the present embodiment is not particularly limited as long as it can impregnate the nonwoven fabric by so-called wet impregnation, and various known resins can be applied. Examples of such a resin (hereinafter, also simply referred to as “wet resin”) include, but are not limited to, polyurethanes such as polyurethane and polyurethane polyurea, acrylics such as polyacrylate and polyacrylonitrile, polyvinyl chloride, Examples thereof include vinyl type such as polyvinyl acetate and polyvinylidene fluoride, polysulfone type such as polysulfone and polyether sulfone, acylated cellulose type such as acetylated cellulose and butyrylized cellulose, polyamide type and polystyrene type. Examples of the polyurethane resin include, but are not limited to, polyester-based polyurethane resin, polyether-based polyurethane resin, and polycarbonate-based polyurethane resin. The 100% modulus of the resin is preferably 5 MPa to 30 MPa, more preferably 10 MPa to 20 MPa. The 100% modulus of a resin is a value obtained by dividing the load applied when a sheet made of the resin is stretched 100%, that is, when the sheet is stretched to twice its original length, divided by a unit area.
（第２の樹脂）
本実施形態における第２の樹脂としては、ＮＣＯ当量５００以下のウレタンプレポリマーと、２官能以上かつＯＨ当量５００〜１００００であるポリアルキレンエーテルグリコールと、硬化剤との反応物であり、いわゆる乾式含浸により不織布に含浸できるものである。すなわち、第２の樹脂（以下、単に「乾式樹脂」ともいう。）は、例えば、末端にイソシアネート基を有するウレタンプレポリマーと、ポリアルキレンエーテルグリコールと、硬化剤であるアミン化合物及び／又は多価アルコール化合物と、それらを溶解可能な溶媒とを含む溶液を用い、乾式法によって得ることができる。
(Second resin)
The second resin in the present embodiment is a reaction product of a urethane prepolymer having an NCO equivalent of 500 or less, a polyalkylene ether glycol having a functionality of 2 or more and an OH equivalent of 500 to 10,000, and a curing agent, so-called dry impregnation. The non-woven fabric can be impregnated with. That is, the second resin (hereinafter, also simply referred to as “dry resin”) is, for example, a urethane prepolymer having an isocyanate group at a terminal, a polyalkylene ether glycol, an amine compound as a curing agent, and/or a polyvalent resin. It can be obtained by a dry method using a solution containing an alcohol compound and a solvent capable of dissolving them.
ＮＣＯ当量５００以下のウレタンプレポリマーとしては、以下に限定されないが、例えば、ヘキサメチレンジイソシアネートとヘキサントリオールとの付加物、２，４−トリレンジイソシアネートとプレンツカテコールとの付加物、トリレンジイソシアネートとヘキサントリオールとの付加物、トリレンジイソシアネートとトリメチロールプロパンとの付加物、キシリレンジイソシアネートとトリメチロールプロパンとの付加物、ヘキサメチレンジイソシアネートとトリメチロールプロパンとの付加物、及びイソシアヌル酸とヘキサメチレンジイソシアネートとの付加物が挙げられる。 Examples of the urethane prepolymer having an NCO equivalent of 500 or less include, but are not limited to, an adduct of hexamethylene diisocyanate and hexanetriol, an adduct of 2,4-tolylene diisocyanate and prenzcatechol, and tolylene diisocyanate. Addition product with hexanetriol, addition product with tolylene diisocyanate and trimethylol propane, addition product with xylylene diisocyanate and trimethylol propane, addition product with hexamethylene diisocyanate and trimethylol propane, and isocyanuric acid and hexamethylene diisocyanate And the adduct with.
２官能以上かつＯＨ当量５００〜１００００であるポリアルキレンエーテルグリコールとしては、以下に限定されないが、例えば、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリオキシテトラメチレングリコール、並びにこれらのグリセロール、ソルビトール及びマンニトール等の多価アルコール誘導体が挙げられる。 The polyalkylene ether glycol having two or more functional groups and an OH equivalent of 500 to 10,000 is not limited to the following, and examples thereof include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and glycerol, sorbitol, and mannitol. And other polyhydric alcohol derivatives.
硬化剤のうち、アミン化合物としては、例えば、多官能ポリアミン化合物が挙げられる。多官能ポリアミン化合物としては、以下に限定されないが、例えば、３，３’−ジクロロ−４，４’−ジアミノジフェニルメタン、４−メチル−２，６−ビス（メチルチオ）−１，３−ベンゼンジアミン、２−メチル−４，６−ビス（メチルチオ）−１，３−ベンゼンジアミン、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、２，２−ビス［３−（イソプロピルアミノ）−４−ヒドロキシフェニル］プロパン、２，２−ビス［３−（１−メチルプロピルアミノ）−４−ヒドロキシフェニル］プロパン、２，２−ビス［３−（１−メチルペンチルアミノ）−４−ヒドロキシフェニル］プロパン、２，２−ビス（３，５−ジアミノ−４−ヒドロキシフェニル）プロパン、２，６−ジアミノ−４−メチルフェノール、トリメチルエチレンビス−４−アミノベンゾネート、及びポリテトラメチレンオキサイド−ｄｉ−ｐ−アミノベンゾネートが挙げられる。多価アルコール化合物としては、以下に限定されないが、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、トリメチレングリコール、テトラエチレングリコール、トリエチレングリコール、ジプロピレングリコール、１，４−ブタンジオール、１，３−ブタンジオール、２，３−ブタンジオール、１，２−ブタンジオール、３−メチル−１，２−ブタンジオール、１，２−ペンタンジオール、１，４−ペンタンジオール、２，４−ペンタンジオール、２，３−ジメチルトリメチレングリコール、テトラメチレングリコール、３−メチル−４，３−ペンタンジオール、３−メチル−４，５−ペンタンジオール、２，２，４−トリメチル−１，３−ペンタンジオール、１，６−ヘキサンジオール、１，５−ヘキサンジオール、１，４−ヘキサンジオール、２，５−ヘキサンジオール、１，４−シクロヘキサンジメタノール、ネオペンチルグリコール、グリセリン、トリメチロールプロパン、トリメチロールエタン、トリメチロールメタンが挙げられる。上記した中でも、多官能ポリアミン化合物を硬化剤として用いることが好ましく、より好ましくは２官能のアミン化合物である。 Among the curing agents, examples of the amine compound include polyfunctional polyamine compounds. Examples of polyfunctional polyamine compounds include, but are not limited to, for example, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4-methyl-2,6-bis(methylthio)-1,3-benzenediamine, 2-Methyl-4,6-bis(methylthio)-1,3-benzenediamine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis[3-(isopropylamino)- 4-hydroxyphenyl]propane, 2,2-bis[3-(1-methylpropylamino)-4-hydroxyphenyl]propane, 2,2-bis[3-(1-methylpentylamino)-4-hydroxyphenyl ] Propane, 2,2-bis(3,5-diamino-4-hydroxyphenyl)propane, 2,6-diamino-4-methylphenol, trimethylethylenebis-4-aminobenzoate, and polytetramethylene oxide-di -P-aminobenzoate may be mentioned. Examples of the polyhydric alcohol compound include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3- Butanediol, 2,3-butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 1,2-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2 , 3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4,3-pentanediol, 3-methyl-4,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1 ,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, glycerin, trimethylolpropane, trimethylolethane, tri Methylolmethane is mentioned. Among the above, a polyfunctional polyamine compound is preferably used as a curing agent, and more preferably a bifunctional amine compound.
上述したウレタンプレポリマー、ポリアルキレンエーテルグリコール及び硬化剤は、それぞれ、１種を単独で又は２種以上を組み合わせて用いられる。なお、溶媒としては、特に限定されないが、例えば、Ｎ，Ｎ−ジメチルホルムアミド、及びＮ，Ｎ−ジメチルアセトアミドが挙げられる。 The above-mentioned urethane prepolymer, polyalkylene ether glycol and curing agent may be used alone or in combination of two or more. The solvent is not particularly limited, but examples thereof include N,N-dimethylformamide and N,N-dimethylacetamide.
本実施形態において、研磨パッドに良好な耐薬品性を付与する観点から、ウレタンプレポリマーのＮＣＯ当量は５００以下である。同様の観点から、上記ＮＣＯ当量は４５０以下であることが好ましく、２００以上であることがより好ましい。なお、本明細書中において、「ＮＣＯ当量」とは、該当樹脂溶液中のウレタンプレポリマーの平均ＮＣＯ当量を意味する。また、ＮＣＯ当量は周知の方法で測定でき、例えばＪＩＳ Ｋ ７３０１に準拠して測定することができる。上記ＮＣＯ当量は、例えば、原料及びその配合比等により上記した範囲に調整することができる。 In the present embodiment, the NCO equivalent of the urethane prepolymer is 500 or less from the viewpoint of imparting good chemical resistance to the polishing pad. From the same viewpoint, the NCO equivalent is preferably 450 or less, more preferably 200 or more. In addition, in this specification, "NCO equivalent" means the average NCO equivalent of the urethane prepolymer in the corresponding resin solution. The NCO equivalent can be measured by a known method, and can be measured, for example, according to JIS K7301. The NCO equivalent can be adjusted within the above range depending on, for example, the raw materials and the mixing ratio thereof.
本実施形態において、研磨パッドの研磨液に対する親和性を良好なものとする観点から、ポリアルキレンエーテルグリコールは２官能以上であり、かつ、そのＯＨ当量は５００〜１００００である。同様の観点から、ポリアルキレンエーテルグリコールは３官能であることが好ましい。また、ポリアルキレンエーテルグリコールのＯＨ当量は５００〜３０００であることが好ましく、５００〜２０００であることがより好ましい。なお、本明細書中において、「ＯＨ当量」とは、該当樹脂溶液中のポリアルキレンエーテルグリコールの平均ＯＨ当量を意味する。また、ＯＨ当量は周知の方法で測定でき、例えば、ポリアルキレンエーテルグリコールの重合度によりコントロールすることができる。 In the present embodiment, from the viewpoint of improving the affinity of the polishing pad for the polishing liquid, the polyalkylene ether glycol is bifunctional or higher, and its OH equivalent is 500 to 10,000. From the same viewpoint, the polyalkylene ether glycol is preferably trifunctional. The OH equivalent of the polyalkylene ether glycol is preferably 500 to 3000, more preferably 500 to 2000. In addition, in this specification, "OH equivalent" means the average OH equivalent of the polyalkylene ether glycol in the corresponding resin solution. The OH equivalent can be measured by a known method, and can be controlled by, for example, the degree of polymerization of polyalkylene ether glycol.
本実施形態において、ウレタンプレポリマーにおけるＮＣＯ基の量に対するポリアルキレンエーテルグリコールにおけるＯＨ基の量のモル比は、０．０１〜０．１５である。上記モル比が０．０１以上であることにより、乾式樹脂表面のＯＨ基の量が十分に確保されるため、研磨パッドの研磨液に対する親和性が向上する。また、上記モル比が０．１５以下であることにより、乾式樹脂表面のＯＨ基の量が過剰となることに起因する、研磨機の研磨定盤に対する研磨パッドの接着性の低下を防止することができる。上記と同様の観点から、上記モル比は、０．０２〜０．１２が好ましく、より好ましくは０．０３〜０．１０である。
上記モル比は、後述する実施例に記載の方法で得られたＯＨ当量、ＮＣＯ当量から計算により求めることができ、それぞれの当量と配合比により上記した範囲に調整することができる。
In this embodiment, the molar ratio of the amount of OH groups in the polyalkylene ether glycol to the amount of NCO groups in the urethane prepolymer is 0.01 to 0.15. When the above molar ratio is 0.01 or more, the amount of OH groups on the surface of the dry resin is sufficiently secured, so that the affinity of the polishing pad with the polishing liquid is improved. Further, when the above molar ratio is 0.15 or less, it is possible to prevent a decrease in the adhesiveness of the polishing pad to the polishing plate of the polishing machine due to an excessive amount of OH groups on the surface of the dry resin. You can From the same viewpoint as above, the molar ratio is preferably 0.02 to 0.12, more preferably 0.03 to 0.10.
The above molar ratio can be calculated from the OH equivalents and NCO equivalents obtained by the method described in Examples below, and can be adjusted to the above range by the respective equivalents and blending ratios.
本実施形態において、研磨パッドの研磨液に対する親和性と研磨機の研磨定盤に対する研磨パッドの接着性とのバランスの観点から、ウレタンプレポリマーにおけるＮＣＯ基の量に対するポリアルキレンエーテルグリコールにおけるＯＨ基の量及び硬化剤におけるＮＨ2基の量の合計のモル比が、０．８〜１．０であることが好ましい。
上記モル比は、後述する実施例に記載の方法で得られたＯＨ当量、ＮＣＯ当量、ＮＨ2当量から計算により求めることができ、それぞれの当量と配合比により上記した範囲に調整することができる。
In the present embodiment, from the viewpoint of the balance between the affinity of the polishing pad for the polishing liquid and the adhesion of the polishing pad to the polishing plate of the polishing machine, the OH groups in the polyalkylene ether glycol relative to the amount of NCO groups in the urethane prepolymer are The total molar ratio of the amount and the amount of NH 2 groups in the curing agent is preferably 0.8 to 1.0.
The above molar ratio can be calculated from the OH equivalents, NCO equivalents, and NH 2 equivalents obtained by the method described in the examples below, and can be adjusted to the above range by the respective equivalents and blending ratios. ..
本実施形態の研磨パッドにおいて、研磨中の引張強度保持の観点から、不織布、第１の樹脂及び第２の樹脂の合計に対して、不織布の含有量が１０〜５０質量％であり、かつ、第１の樹脂の含有量が１０〜６０質量％であり、かつ、第２の樹脂の含有量が１０〜７０質量％であることが好ましい。同様の観点から、不織布の含有量が２０〜４０質量％であり、かつ、第１の樹脂の含有量が２０〜６０質量％であり、かつ、第２の樹脂の含有量が２０〜５０質量％であることがより好ましい。研磨パッドにおける不織布、第１の樹脂及び第２の樹脂の各含有量は、極性溶媒への溶解性(極性)の差や、アミン分解性の差を利用して、溶出する成分の質量又は残渣の質量より、求めることができる。また、後述する１次含浸工程後の研磨パッドの密度と、後述する浸漬工程後の研磨パッドの密度と、後述する２次含浸工程後の研磨パッドの密度と、をそれぞれ測定し、密度差から算出することもできる。なお、密度の測定は上記と同様にして測定できる。 In the polishing pad of the present embodiment, the content of the non-woven fabric is 10 to 50 mass% with respect to the total amount of the non-woven fabric, the first resin, and the second resin, from the viewpoint of retaining the tensile strength during polishing, and It is preferable that the content of the first resin is 10 to 60% by mass, and the content of the second resin is 10 to 70% by mass. From the same viewpoint, the content of the nonwoven fabric is 20 to 40% by mass, the content of the first resin is 20 to 60% by mass, and the content of the second resin is 20 to 50% by mass. % Is more preferable. The content of the non-woven fabric, the first resin, and the second resin in the polishing pad is the mass or residue of the component to be eluted by utilizing the difference in solubility (polarity) in polar solvents and the difference in amine decomposability. It can be obtained from the mass of. Further, the density of the polishing pad after the primary impregnation step described below, the density of the polishing pad after the immersion step described below, and the density of the polishing pad after the secondary impregnation step described below were measured, respectively, from the density difference. It can also be calculated. The density can be measured in the same manner as above.
本実施形態の研磨パッドは、上述の不織布及び樹脂の他、本実施形態の所望の効果を阻害しない範囲において、通常の研磨パッドに含まれ得る各種添加剤を含んでもよい。そのような添加剤としては、以下に限定されないが、例えば、カーボンブラック等の顔料、親水性活性剤及び疎水性活性剤が挙げられる。 The polishing pad of the present embodiment may include various additives that can be contained in a normal polishing pad, in addition to the above-mentioned nonwoven fabric and resin, as long as the desired effects of the present embodiment are not impaired. Such additives include, but are not limited to, pigments such as carbon black, hydrophilic activators and hydrophobic activators.
本実施形態において、研磨パッドの引張強度に対する、３質量％の過マンガン酸カリウム水溶液に硝酸を加えてｐＨ２に調整した溶液（以下、単に「試験液」ともいう。）に当該研磨パッドを２５℃で４８時間浸漬した後の当該研磨パッドの引張強度の比（以下、単に「引張強度保持率」ともいう。）が、４５％以上であることが好ましい。このような引張強度保持率を満足する場合、本実施形態の研磨パッドは、より耐薬品性に優れる傾向にあり、強酸化剤を用いた研磨に供した場合でも十分に長い寿命が確保される傾向にある。 In the present embodiment, the polishing pad is placed at 25° C. in a solution prepared by adding nitric acid to 3% by mass potassium permanganate aqueous solution with respect to the tensile strength of the polishing pad to adjust the pH to 2 (hereinafter, simply referred to as “test solution”). It is preferable that the ratio of the tensile strength of the polishing pad after soaking for 48 hours (hereinafter, also simply referred to as “tensile strength retention rate”) is 45% or more. When satisfying such a tensile strength retention rate, the polishing pad of the present embodiment tends to be more excellent in chemical resistance, and a sufficiently long life is ensured even when subjected to polishing using a strong oxidant. There is a tendency.
本実施形態における引張強度保持率の測定方法について説明する。まず、試験液に浸漬する前の研磨パッドの引張強度（ａ）を測定する。上記引張強度は、引張万能試験機（「テンシロン」、Ａ＆Ｄ社製、ＲＴＣ−１２１０Ａ）を用い、日本工業規格（ＪＩＳ Ｋ ６５５０）に準拠して測定することができる。次いで、３質量％の過マンガン酸カリウム水溶液に硝酸を加えてｐＨ２に調整し、試験液とする。このように調製された試験液に、研磨パッドを２５℃で４８時間浸漬する。なお、浸漬の開始から２４時間経過後に試験液及び研磨パッドを収容した容器を数分間振とうする。浸漬の開始から４８時間経過後、研磨パッドを試験液から取り出し、流水洗浄し、５分間の超音波洗浄を行い、さらに流水洗浄し、キッチンペーパーで加圧しながら残留した液を拭き取り、上記と同様にして研磨パッドの引張強度（ｂ）を測定する。引張強度保持率は、引張強度（ａ）と引張強度（ｂ）の値から、以下の式で算出する。
引張強度保持率＝引張強度（ｂ）／引張強度（ａ）×１００ ％
A method for measuring the tensile strength retention rate in this embodiment will be described. First, the tensile strength (a) of the polishing pad before being immersed in the test liquid is measured. The tensile strength can be measured using a universal tensile tester (“Tensilon”, manufactured by A&D, RTC-1210A) in accordance with Japanese Industrial Standards (JIS K 6550). Then, nitric acid is added to a 3 mass% potassium permanganate aqueous solution to adjust the pH to 2 to prepare a test solution. The polishing pad is immersed in the test liquid thus prepared at 25° C. for 48 hours. Note that the container containing the test liquid and the polishing pad is shaken for several minutes after the lapse of 24 hours from the start of the immersion. After 48 hours from the start of immersion, remove the polishing pad from the test solution, wash with running water, ultrasonically clean for 5 minutes, wash with running water, wipe off the remaining solution while pressing with kitchen paper, and repeat as above. Then, the tensile strength (b) of the polishing pad is measured. The tensile strength retention rate is calculated by the following formula from the values of tensile strength (a) and tensile strength (b).
Tensile strength retention = Tensile strength (b)/Tensile strength (a) x 100%
本実施形態において、耐薬品性の観点から、引張強度保持率は、好ましくは４５％以上であり、より好ましくは５０％以上である。引張強度保持率を上記の範囲に調整するには、例えば、後述の好ましい製造方法を採用すればよい。後述の好ましい製造方法において、例えば、第２の樹脂のＮＣＯ当量を下げることにより、引張強度保持率は高くなる傾向にある。 In this embodiment, from the viewpoint of chemical resistance, the tensile strength retention rate is preferably 45% or more, more preferably 50% or more. In order to adjust the tensile strength retention rate within the above range, for example, a preferable manufacturing method described later may be adopted. In the preferred manufacturing method described below, for example, the tensile strength retention rate tends to increase by decreasing the NCO equivalent of the second resin.
研磨パッドの通気度は、研磨液の保持性の観点から、６ｃｃ／ｃｍ2／秒以上であると好ましく、７〜３０ｃｃ／ｃｍ2／秒であるとより好ましい。通気度は、フラジール形試験機（例えば、安田精機社製の織布通気度試験機）を用いて、日本工業規格（ＪＩＳ Ｌ １０９６）に準拠して測定され、５枚の試料片の相加平均により求められる。通気度は、例えば、後述の好ましい製造方法において、１次含浸工程と２次含浸工程の間に第１の樹脂が可溶な溶媒に浸漬する浸漬工程を採用することにより、高くなる傾向にある。 Air permeability of the polishing pad, from the viewpoint of retention of the polishing liquid, preferable to be 6 cc / cm 2 / sec or more, and more preferably 7~30cc / cm 2 / sec. The air permeability is measured using a Frazier type tester (for example, a woven fabric air permeability tester manufactured by Yasuda Seiki Co., Ltd.) in accordance with Japanese Industrial Standards (JIS L 1096), and the addition of 5 sample pieces is performed. Calculated by the average. The air permeability tends to be increased, for example, by adopting a dipping step of immersing the first resin in a solvent in which the first resin is soluble between the primary impregnating step and the secondary impregnating step in the preferred manufacturing method described later. ..
研磨パッドの圧縮率は、被研磨物（以下、単に「ワーク」ともいう。）との良好な密着性を確保する観点及び研磨パッドの変形防止の観点から、０．５〜２０％であると好ましく、２〜８％であるとより好ましい。圧縮率は日本工業規格（ＪＩＳ Ｌ １０２１）に準拠して、ショッパー型厚さ測定器（加圧面：直径１ｃｍの円形）を用いて求められる。具体的には、初荷重で３０秒間加圧した後の厚さｔ0を測定し、次に最終圧力の下で５分間放置後の厚さｔ1を測定する。これらから、圧縮率を下記式により算出する。このとき、初荷重は１００ｇ／ｃｍ2、最終荷重は１１２０ｇ／ｃｍ2とする。
圧縮率（％）＝（ｔ0−ｔ1）／ｔ0×１００
圧縮率は、例えば、後述の好ましい製造方法において、得られる研磨パッドの密度が低くなるように調整することにより、高くなる傾向にある。
The compressibility of the polishing pad is 0.5 to 20% from the viewpoint of ensuring good adhesion to the object to be polished (hereinafter, also simply referred to as "workpiece") and preventing deformation of the polishing pad. It is more preferably 2 to 8%. The compressibility is determined using a Shopper type thickness measuring device (pressurized surface: circular shape having a diameter of 1 cm) in accordance with Japanese Industrial Standards (JIS L 1021). Specifically, the thickness t 0 after pressing with the initial load for 30 seconds is measured, and then the thickness t 1 after standing for 5 minutes under the final pressure is measured. From these, the compression rate is calculated by the following formula. At this time, the initial load is 100 g/cm 2 and the final load is 1120 g/cm 2 .
Compression rate (%)=(t 0 −t 1 )/t 0 ×100
The compressibility tends to increase, for example, by adjusting the density of the obtained polishing pad to be low in the preferred manufacturing method described later.
研磨パッドの圧縮弾性率は、ワークとの良好な密着性を確保する観点及び研磨パッドの変形防止の観点から、５０〜９８％であると好ましく、６０〜９５％であるとより好ましい。圧縮弾性率は、日本工業規格（ＪＩＳ Ｌ １０２１）に準拠し、ショッパー型厚さ測定器（加圧面：直径１ｃｍの円形）を使用して求めることができる。具体的には、無荷重状態から初荷重を３０秒間かけた後の厚さｔ0を測定し、次に、厚さｔ0の状態から最終荷重を３０秒間かけた後の厚さｔ1を測定する。次に、厚さｔ1の状態から全ての荷重を除き、５分間放置（無荷重状態とした）後、再び初荷重を３０秒間かけた後の厚さｔ0’を測定する。これらから、圧縮弾性率を下記式により算出する。このとき、初荷重は１００ｇ／ｃｍ2、最終荷重は１１２０ｇ／ｃｍ2とする。
圧縮弾性率（％）＝１００×（ｔ0’−ｔ1）／（ｔ0−ｔ1）
圧縮弾性率は、例えば、後述の好ましい製造方法において、第２の樹脂の含有率を高くすることにより、高くなる傾向にある。
The compression elastic modulus of the polishing pad is preferably 50 to 98%, and more preferably 60 to 95% from the viewpoint of ensuring good adhesion to the work and preventing deformation of the polishing pad. The compressive elastic modulus can be determined by using a Shopper type thickness meter (pressurized surface: circular shape having a diameter of 1 cm) in accordance with Japanese Industrial Standards (JIS L 1021). Specifically, the thickness t 0 after over 30 seconds initial load from a no-load state is measured, then the thickness t 1 after applying a final load 30 seconds from the state of the thickness t 0 taking measurement. Next, all the loads are removed from the state of the thickness t 1 and after leaving for 5 minutes (no load), the initial load is again applied for 30 seconds and the thickness t 0 ′ is measured. From these, the compressive elastic modulus is calculated by the following formula. At this time, the initial load is 100 g/cm 2 and the final load is 1120 g/cm 2 .
Compression modulus (%) = 100 × (t 0 '-t 1) / (t 0 -t 1)
The compressive elastic modulus tends to increase, for example, by increasing the content of the second resin in the preferred manufacturing method described later.
研磨パッドのＡ硬度は、特に限定されないが、ワークとの良好な密着性を確保する観点及び研磨パッドの変形防止の観点から、５０〜９０°であると好ましく、６０〜８５°であるとより好ましい。Ａ硬度は、バネを介して厚さ４．５ｍｍ以上の試験片（研磨パッドが４．５ｍｍ未満の厚さである場合は、厚さが４．５ｍｍ以上になるまで研磨パッドを重ねて試験片を得る。）表面に押針（測定子）を押し付け３０秒後の押針の押し込み深さから求められる。これを３回行って相加平均からＡ硬度が求められる。Ａ硬度は、例えば、後述の好ましい製造方法において、第２の樹脂の含有率を高くすることにより、高くなる傾向にある。 The A hardness of the polishing pad is not particularly limited, but is preferably 50 to 90°, and more preferably 60 to 85° from the viewpoint of ensuring good adhesion with the work and the viewpoint of preventing deformation of the polishing pad. preferable. A hardness is a test piece having a thickness of 4.5 mm or more via a spring (when the polishing pad has a thickness of less than 4.5 mm, the polishing pad is stacked until the thickness becomes 4.5 mm or more. It is determined from the depth of pushing of the push needle 30 seconds after the push needle (measuring element) is pressed on the surface. This is repeated three times to obtain the A hardness from the arithmetic mean. The A hardness tends to increase, for example, by increasing the content rate of the second resin in the preferred manufacturing method described later.
研磨パッドの密度は、研磨パッドの永久歪みを抑制する観点、ワークとの接触面積の増大による作用点の圧力低下を抑制する観点、及び研磨液の保持性を高める観点から、０．３５〜０．６０であると好ましく、０．３５〜０．５０であるとより好ましい。密度は、日本工業規格（ＪＩＳ Ｋ ６５０５）に準拠して測定される。具体的には、厚さの測定で用いたのと同様の試料片の質量を自動天秤で測定後、下記式により密度を算出し、３枚の試料片の相加平均を求める。
密度（ｇ／ｃｍ3）＝質量（ｇ）／（１０（ｃｍ）×１０（ｃｍ）×試料片の厚さ（ｃｍ））
密度は、例えば、後述の好ましい製造方法において、不織布に対する第１の樹脂及び第２の樹脂の含有率を高くすることにより、高くなる傾向にある。
The density of the polishing pad is 0.35 to 0 from the viewpoint of suppressing the permanent set of the polishing pad, suppressing the pressure drop at the action point due to an increase in the contact area with the work, and improving the retention of the polishing liquid. It is preferably 0.60 and more preferably 0.35 to 0.50. The density is measured according to Japanese Industrial Standards (JIS K 6505). Specifically, after measuring the mass of the sample piece similar to that used in the thickness measurement with an automatic balance, the density is calculated by the following formula, and the arithmetic mean of the three sample pieces is obtained.
Density (g/cm 3 )=mass (g)/(10 (cm)×10 (cm)×thickness of sample piece (cm))
The density tends to increase, for example, by increasing the content of the first resin and the second resin in the nonwoven fabric in the preferred manufacturing method described later.
本実施形態の研磨パッドの厚さは、特に限定されないが、ワークとの平坦な接触面を十分に確保する観点、平坦性を確保する観点及び研磨液を貯留する観点から、０．８〜３．０ｍｍであると好ましく、１．０〜１．８ｍｍであるとより好ましい。厚さは、日本工業規格（ＪＩＳ Ｋ ６５０５）に準拠して測定される。具体的には、研磨パッドを１０ｃｍ×１０ｃｍ角に切り抜いて得た試料片３枚を用意し、各試料片毎に、厚さ測定器の所定位置にセットした後、４８０ｇ／ｃｍ2の荷重をかけた加圧面を試料片の表面に載せ、５秒経過後に厚さを測定する。１枚の試料片につき、５箇所の厚さを測定し相加平均を算出し、さらに３枚の試料片の相加平均を求める。 The thickness of the polishing pad of the present embodiment is not particularly limited, but from the viewpoint of sufficiently ensuring a flat contact surface with the work, the viewpoint of ensuring flatness, and the viewpoint of storing the polishing liquid, 0.8 to 3 is used. The thickness is preferably 0.0 mm, and more preferably 1.0 to 1.8 mm. The thickness is measured according to Japanese Industrial Standards (JIS K 6505). Specifically, three polishing pieces obtained by cutting out a polishing pad into 10 cm×10 cm squares were prepared, and a load of 480 g/cm 2 was applied after setting each sample piece at a predetermined position of a thickness measuring instrument. The applied pressure surface is placed on the surface of the sample piece, and the thickness is measured after 5 seconds have elapsed. The thickness of five sample pieces is measured, the arithmetic mean is calculated, and the arithmetic mean of three sample pieces is calculated.
［研磨パッドの製造方法］
本実施形態の研磨パッドの製造方法は、上述した本実施形態の研磨パッドの構成が得られる方法である限り、特に限定されるものではない。以下、本実施形態の研磨パッドの好適な製造方法を例示する。
[Method of manufacturing polishing pad]
The method for manufacturing the polishing pad of this embodiment is not particularly limited as long as it is a method that can obtain the configuration of the polishing pad of this embodiment described above. Hereinafter, a suitable method for manufacturing the polishing pad of this embodiment will be exemplified.
本実施形態の研磨パッドの製造方法は、不織布に第１の樹脂を含む樹脂溶液を含浸させ、湿式凝固を行うことにより、樹脂含浸不織布を得る１次含浸工程と、樹脂含浸不織布を、第１の樹脂が可溶な溶媒に浸漬する浸漬工程と、浸漬工程の後の樹脂含浸不織布を、ＮＣＯ当量５００以下のウレタンプレポリマーと、２官能以上かつＯＨ当量５００〜１００００であるポリアルキレンエーテルグリコールと、硬化剤とを含む溶液に含浸する２次含浸工程と、を有し、ウレタンプレポリマーにおけるＮＣＯ基の量に対するポリアルキレンエーテルグリコールにおけるＯＨ基の量のモル比が０．０１〜０．１５である。本実施形態の研磨パッドの製造方法は、上記のように構成されているため、研磨レートに優れ、研磨時の目詰まり及びスクラッチの発生を防止できる研磨パッドが得られる。さらに、このようにして得られる研磨パッドは、耐薬品性に優れ、強酸化剤を用いた研磨に供した場合でも十分なライフを確保できる。 The polishing pad manufacturing method of the present embodiment includes a primary impregnation step of obtaining a resin-impregnated non-woven fabric by impregnating the non-woven fabric with a resin solution containing a first resin and performing wet coagulation. The resin impregnated non-woven fabric after the dipping step of immersing the resin in a solvent in which the resin is soluble, a urethane prepolymer having an NCO equivalent of 500 or less, and a polyalkylene ether glycol having a functionality of 2 or more and an OH equivalent of 500 to 10,000. A second impregnation step of impregnating with a solution containing a curing agent, wherein the molar ratio of the amount of OH groups in the polyalkylene ether glycol to the amount of NCO groups in the urethane prepolymer is 0.01 to 0.15. is there. Since the polishing pad manufacturing method of the present embodiment is configured as described above, a polishing pad having an excellent polishing rate and capable of preventing clogging and scratching during polishing can be obtained. Further, the polishing pad thus obtained has excellent chemical resistance and can secure a sufficient life even when subjected to polishing using a strong oxidant.
上記１次含浸工程においては、不織布に樹脂溶液を含浸させた上で湿式凝固法により樹脂含浸不織布を得る。湿式凝固法とは、樹脂溶液を、樹脂に対して貧溶媒である凝固液に常温で浸漬することで樹脂を凝固再生させる方法である。本実施形態のように不織布に樹脂溶液を含浸させた上で湿式凝固法を用いる場合、凝固液中では、不織布の繊維に付着している樹脂溶液の表面で樹脂溶液の溶媒と凝固液との置換の進行により樹脂が繊維の表面に凝固再生される。 In the above primary impregnation step, a nonwoven fabric is impregnated with a resin solution, and then a resin-impregnated nonwoven fabric is obtained by a wet coagulation method. The wet coagulation method is a method in which a resin solution is immersed in a coagulation liquid, which is a poor solvent for the resin, at room temperature to coagulate and regenerate the resin. When the wet coagulation method is used after impregnating the non-woven fabric with the resin solution as in the present embodiment, in the coagulation liquid, the solvent of the resin solution and the coagulation liquid are formed on the surface of the resin solution adhering to the fibers of the non-woven fabric. The resin is coagulated and regenerated on the surface of the fiber as the substitution proceeds.
上記１次含浸工程の具体例としては、次のとおりである。まず、上述したような湿式樹脂と、当該湿式樹脂を溶解可能であって、後述の凝固液に混和する溶媒と、必要に応じて研磨パッドに配合するその他の添加剤とを混合し、更に必要に応じて減圧下で脱泡して樹脂溶液を準備する。上記溶媒としては、特に限定されないが、例えば、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）、メチルエチルケトン（ＭＥＫ）及びジメチルスルホキシドが挙げられる。樹脂に対する良溶媒を選択する観点、さらに凝固浴に対して均一に混和させて湿式凝固をより容易にする観点から、第１の樹脂が、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルアセトアミド及びメチルエチルケトンからなる群より選ばれる１種以上の溶媒に可溶であることが好ましい。同様に、上記溶媒が、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルアセトアミド及びメチルエチルケトンからなる群より選ばれる１種以上の溶媒を含むことが好ましい。 The specific example of the primary impregnation step is as follows. First, a wet resin as described above, a solvent capable of dissolving the wet resin and miscible with the coagulating liquid described later, and other additives to be added to the polishing pad as needed are mixed, and further required. Prepare a resin solution by degassing under reduced pressure according to. The solvent is not particularly limited, but examples thereof include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), methyl ethyl ketone (MEK), and dimethyl sulfoxide. From the viewpoint of selecting a good solvent for the resin and further facilitating the wet coagulation by uniformly mixing with the coagulation bath, the first resin is a group consisting of N,N-dimethylformamide, dimethylacetamide and methyl ethyl ketone. It is preferably soluble in one or more solvents selected from the above. Similarly, the solvent preferably contains at least one solvent selected from the group consisting of N,N-dimethylformamide, dimethylacetamide and methylethylketone.
不織布の全体に亘って樹脂を含浸する観点、及び、樹脂の含浸量を十分に確保する観点から、上記樹脂溶液について、Ｂ型回転粘度計を用いて２０℃で測定した粘度が８０００ｃｐ以下であると好ましく、１００ｃｐ〜５０００ｃｐであるとより好ましく、４００ｃｐ〜３０００ｃｐであると更に好ましい。そのような粘度の数値範囲にある樹脂溶液を得る観点から、例えば、ポリウレタン樹脂を、樹脂溶液の全体量に対して５〜２５質量％の範囲、より好ましくは８〜１５質量％の範囲で溶媒に溶解させてもよい。樹脂溶液の粘性は、用いる樹脂の種類及び分子量にも依存するため、これらを総合的に考慮し、樹脂の選定、濃度設定等を行うことが好ましい。 From the viewpoint of impregnating the entire nonwoven fabric with the resin, and from the viewpoint of sufficiently securing the impregnated amount of the resin, the viscosity of the above resin solution measured at 20° C. using a B type rotational viscometer is 8000 cp or less. Is preferable, 100 cp to 5000 cp is more preferable, and 400 cp to 3000 cp is further preferable. From the viewpoint of obtaining a resin solution having such a numerical value range of viscosity, for example, a polyurethane resin is used as a solvent in the range of 5 to 25% by mass, more preferably 8 to 15% by mass with respect to the total amount of the resin solution. May be dissolved in. Since the viscosity of the resin solution depends on the type and molecular weight of the resin used, it is preferable to comprehensively consider these factors when selecting the resin and setting the concentration.
次に、樹脂溶液に不織布を十分に浸漬した後、樹脂溶液が付着した不織布から、１対のローラ間で加圧可能なマングルローラを用いて樹脂溶液を絞り落とすことで、樹脂溶液の不織布への付着量を所望の量に調整し、不織布に樹脂溶液を均一又は略均一に含浸させる。次いで、樹脂溶液を含浸した不織布を、樹脂に対する貧溶媒、例えば水、を主成分とする凝固液中に浸漬することにより、湿式樹脂を凝固再生させる。凝固液には、樹脂の再生速度を調整するために、樹脂溶液中の溶媒以外の極性溶媒等の有機溶媒を添加してもよい。また、凝固液の温度は、樹脂を凝固できる温度であれば特に限定されず、例えば、１５〜６０℃であってもよい。 Next, after the non-woven fabric is sufficiently immersed in the resin solution, the non-woven fabric to which the resin solution has adhered is squeezed from the non-woven fabric by using a mangle roller capable of pressurizing between the pair of rollers to thereby form the non-woven fabric of the resin solution. Is adjusted to a desired amount, and the nonwoven fabric is impregnated with the resin solution uniformly or substantially uniformly. Next, the non-woven fabric impregnated with the resin solution is immersed in a coagulating liquid containing a poor solvent for the resin, for example, water as a main component to coagulate and regenerate the wet resin. An organic solvent such as a polar solvent other than the solvent in the resin solution may be added to the coagulation liquid in order to adjust the regeneration rate of the resin. Further, the temperature of the coagulation liquid is not particularly limited as long as it is a temperature at which the resin can be solidified, and may be, for example, 15 to 60°C.
本実施形態において、上述の湿式凝固を行ったのち、以下のような洗浄・乾燥工程に供することが好ましい。まず、湿式樹脂が凝固再生された不織布を水等の洗浄液中で洗浄し、不織布中に残存するＤＭＦ等の溶媒を除去する。洗浄後、不織布を洗浄液から引き上げ、マングルローラ等を用いて余分な洗浄液を絞り落とす。その後、不織布基材を、１００℃〜１５０℃の乾燥機中で乾燥させてもよい。また、上記乾燥の後、得られる樹脂含浸不織布をさらにスライス、バフ等による加工に供し、表層のスキン層を除去し、所定の厚さにすることが、次工程の浸漬工程の均一性を高める観点から好ましい。 In the present embodiment, it is preferable that after the above-mentioned wet coagulation is performed, it is subjected to the following washing/drying steps. First, the non-woven fabric in which the wet resin is coagulated and regenerated is washed in a washing liquid such as water to remove the solvent such as DMF remaining in the non-woven fabric. After washing, the nonwoven fabric is pulled out of the washing liquid, and the excess washing liquid is squeezed out using a mangle roller or the like. Then, the non-woven fabric substrate may be dried in a dryer at 100°C to 150°C. Further, after the drying, the obtained resin-impregnated non-woven fabric is further subjected to processing by slicing, buffing, etc. to remove the skin layer of the surface layer to a predetermined thickness, which enhances the uniformity of the next dipping step. It is preferable from the viewpoint.
本実施形態における浸漬工程は、上述の樹脂含浸不織布を、上述の湿式樹脂が可溶な溶媒に浸漬させることで、当該湿式樹脂を溶媒に再溶解させる工程である。浸漬工程により、樹脂含浸不織布内部の気泡（例えば閉気孔及び開口部の小さい開気孔）が減少し、不織布と湿式樹脂との密着性が向上すると考えられる。浸漬工程に用いる溶媒としては、特に限定されないが、例えば、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）、メチルエチルケトン（ＭＥＫ）、及びジメチルスルホキシドが挙げられる。また、浸漬させる際の温度条件としては、第１の樹脂の気泡を減少させ、かつ、溶媒への樹脂の溶出を防止する観点から、１５．０〜２５．０℃であることが好ましく、浸漬時間としては、同様の観点から、５〜３０秒であることが好ましい。なお、上述の浸漬工程の後に、乾燥工程を設けることが好ましい。 The immersion step in the present embodiment is a step of re-dissolving the wet resin in the solvent by immersing the resin-impregnated nonwoven fabric in the solvent in which the wet resin is soluble. It is considered that the dipping step reduces air bubbles (for example, closed pores and open pores with small openings) inside the resin-impregnated nonwoven fabric, and improves the adhesion between the nonwoven fabric and the wet resin. The solvent used in the dipping step is not particularly limited, but examples thereof include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), methyl ethyl ketone (MEK), and dimethyl sulfoxide. The temperature condition for the immersion is preferably 15.0 to 25.0° C. from the viewpoint of reducing bubbles of the first resin and preventing the resin from eluting into the solvent. From the same viewpoint, the time is preferably 5 to 30 seconds. A drying step is preferably provided after the above-mentioned dipping step.
本実施形態における２次含浸工程は、浸漬工程の後の樹脂含浸不織布を、ＮＣＯ当量５００以下のウレタンプレポリマーと、２官能以上かつＯＨ当量５００〜１００００であるポリアルキレンエーテルグリコールと、硬化剤とを含む溶液に含浸する工程である。２次含浸工程により、上述した湿式樹脂の表面に乾式樹脂が形成されるものと推測される。 In the secondary impregnation step in the present embodiment, the resin-impregnated non-woven fabric after the immersion step is treated with a urethane prepolymer having an NCO equivalent of 500 or less, a polyalkylene ether glycol having a functionality of 2 or more and an OH equivalent of 500 to 10,000, and a curing agent. Is a step of impregnating a solution containing It is speculated that the dry resin is formed on the surface of the above-mentioned wet resin by the secondary impregnation step.
２次含浸工程の具体例としては、まず、末端にイソシアネート基を有するウレタンプレポリマーであって、ＮＣＯ当量５００以下であるものと、２官能以上かつＯＨ当量５００〜１００００であるポリアルキレンエーテルグリコールと、硬化剤（例えば、多官能ポリアミン化合物及び／又は多価アルコール化合物）と、それらを溶解可能な溶媒とを含む溶液を準備する。ここで、前述した観点から、ウレタンプレポリマーにおけるＮＣＯ基の量に対するポリアルキレンエーテルグリコールにおけるＯＨ基の量のモル比が、０．０１〜０．１５となるように調整する。なお、ウレタンプレポリマー、ポリアルキレンエーテルグリコール、硬化剤（例えば、多官能ポリアミン化合物及び／又は多価アルコール化合物）及び溶媒は、上記で例示したものと同様のものを用いることができる。また、これらのウレタンプレポリマー及び硬化剤は、それぞれ、１種を単独で又は２種以上を組み合わせて用いられる。 As a specific example of the secondary impregnation step, first, a urethane prepolymer having an isocyanate group at a terminal and having an NCO equivalent of 500 or less and a polyalkylene ether glycol having a functionality of 2 or more and an OH equivalent of 500 to 10,000. A solution containing a curing agent (for example, a polyfunctional polyamine compound and/or a polyhydric alcohol compound) and a solvent capable of dissolving them is prepared. From the above-mentioned viewpoint, the molar ratio of the amount of OH groups in the polyalkylene ether glycol to the amount of NCO groups in the urethane prepolymer is adjusted to 0.01 to 0.15. The urethane prepolymer, polyalkylene ether glycol, curing agent (for example, polyfunctional polyamine compound and/or polyhydric alcohol compound) and solvent may be the same as those exemplified above. In addition, these urethane prepolymers and curing agents may be used alone or in combination of two or more.
次に、上記溶液に浸漬工程の後の樹脂含浸不織布を浸漬した後、溶液が付着した樹脂含浸不織布から、１対のローラ間で加圧可能なマングルローラを用いて溶液を絞り落とすことで、溶液の樹脂含浸不織布への付着量を所望の量に調整し、樹脂含浸不織布に溶液を均一又は略均一に含浸させる。次いで、溶液を含浸させた樹脂含浸不織布を乾燥機内で乾燥させる。これにより、ウレタンプレポリマーと硬化剤により重合して、樹脂含浸不織布に乾式樹脂を含浸させた本実施形態の研磨パッドが得られる。乾燥温度としては、例えば、１００℃〜１４０℃であってもよい。 Next, after immersing the resin-impregnated non-woven fabric after the dipping step in the above-mentioned solution, by squeezing the solution from the resin-impregnated non-woven fabric to which the solution is attached by using a mangle roller which can be pressed between a pair of rollers, The amount of the solution deposited on the resin-impregnated nonwoven fabric is adjusted to a desired amount, and the resin-impregnated nonwoven fabric is impregnated with the solution uniformly or substantially uniformly. Then, the resin-impregnated nonwoven fabric impregnated with the solution is dried in a dryer. Thus, the polishing pad of the present embodiment obtained by polymerizing the urethane prepolymer and the curing agent to impregnate the resin-impregnated nonwoven fabric with the dry resin is obtained. The drying temperature may be, for example, 100°C to 140°C.
上述した１次含浸工程、浸漬工程及び２次含浸工程を経ることで、本実施形態の所望の構成を有する研磨パッドが得られる。この研磨パッドは、以下に説明する内容に限定する趣旨ではないが、次のような構成を有しているものと推察される。すなわち、１次含浸工程を経ることで、不織布の表面に湿式樹脂が形成される。特に、１次含浸工程では湿式凝固を採用することにより、湿式樹脂が不織布内で均一に付着する。ただし、この段階では、得られる樹脂含浸不織布の樹脂内部において、湿式凝固法に由来する微細な気泡が多く、不織布と湿式樹脂との密着性及び強度は十分とはいえない。次いで、浸漬工程を経ることで、湿式樹脂の微細な気泡に浸漬溶液が充填され、好ましくは乾燥時の加温により湿式樹脂が再溶解し、樹脂含浸不織布内部の微細な気泡（例えば閉気孔及び開口部の小さい開気孔）が減少すると共に、不織布に含浸している樹脂（湿式樹脂）が繊維周辺で高密度化するので、不織布の繊維と湿式樹脂との密着性が向上するとともに強度が向上する。また、微細気泡が減少することで、２次含浸工程における乾式樹脂の含浸の均一化や強度向上につながる。さらに、２次含浸工程を経ることで、不織布繊維上の湿式樹脂の層の表面に、さらに乾式樹脂の層が形成される。浸漬工程を経ずに２次含浸工程に移ると、樹脂含浸不織布内部の気泡内の空間への乾式樹脂の侵入が困難になり、乾式樹脂の付着が不均一になる。この場合、湿式樹脂と乾式樹脂が不均一に付着した状態となり、部分的に弾性特性や剛性特性が不均一になるため、研磨の際に研磨パッド内の樹脂が剥離し、寿命が短くなってしまう。また、強酸化剤への耐性に優れた乾式樹脂の存在しない気泡内に強酸化剤が侵入しやすくなるため、耐薬品性に劣ると共に、寿命が短くなってしまう。一方、本実施形態によると、浸漬工程において、気泡が減少するため、２次含浸工程において含浸可能な空隙が確保されるとともに通気性が改善され、乾式樹脂が侵入し難い箇所が少なくなり、乾式樹脂の存在する領域が増加する。そのため、乾式樹脂の存在しない領域への強酸化剤の侵入が抑制され、耐薬品性が向上し、寿命を長くすることができる。また、不織布に直接付着していない部分の湿式樹脂が減少するため、研磨の際に研磨パッド内の樹脂の剥離が抑制され、寿命を長くすることができる。さらに、乾式樹脂の層は、特定のＮＣＯ当量を有するウレタンプレポリマーを用いて形成されるため、良好な耐薬品性が付与される。ここで、乾式樹脂は湿式樹脂に比べ水分の保持性が良好でないため、従来の乾式樹脂のみでは研磨液の十分な保持が困難であるが、本実施形態における乾式樹脂の層は、上記ウレタンプレポリマーに加えてポリアルキレンエーテルグリコールを用いて形成されるため、その表面におけるＯＨ基の量が所望の範囲に調整されており、研磨パッドの接着性を保持しつつも研磨液との親和性を向上させることができる。研磨パッドと研磨液との親和性が向上する結果、研磨液の循環が良くなり、立ち上がり時間（研磨液の供給から研磨を開始するまでの時間）が短縮されると共に研磨レートが向上する。さらに、研磨時における研磨液中のシリカによる目詰まりや、被研磨物におけるスクラッチの発生を防止できる。
上記のように、本実施形態の研磨パッドにおいては、不織布を基材とし、当該不織布上に湿式樹脂の層が形成され、当該湿式樹脂の層上に乾式樹脂の層が形成されるものと推察され、また、研磨パッドの全体としては、不織布と湿式樹脂の層との間の密着性及び湿式樹脂の層と乾式樹脂の層との密着性は、いずれも良好であるものと推察される。上記の観点から、本実施形態の研磨パッドは、耐薬品性に優れ、強酸化剤を用いた研磨に供した場合でも十分なライフを確保することができるものと考えられる。
なお、１次含浸工程と浸漬工程を省略し、２次含浸工程により不織布に乾式樹脂を含浸させた場合、不織布と乾式樹脂の馴染みが悪く、繊維と樹脂の密着性に問題が生じ、構造上の安定性を損ねることとなる。また、不織布に乾式樹脂のみを付着させ、湿式樹脂を付着させない場合、研磨パッドとして高硬度、低弾性となり、研磨中の被研磨物に対する追従性が悪く、研磨に支障をきたす。
A polishing pad having a desired configuration of the present embodiment can be obtained through the above-mentioned primary impregnation step, dipping step and secondary impregnation step. This polishing pad is not limited to the contents described below, but is presumed to have the following configuration. That is, the wet resin is formed on the surface of the non-woven fabric through the primary impregnation step. In particular, by adopting wet coagulation in the primary impregnation step, the wet resin is evenly attached in the nonwoven fabric. However, at this stage, in the resin of the obtained resin-impregnated nonwoven fabric, there are many fine bubbles derived from the wet coagulation method, and the adhesiveness and strength between the nonwoven fabric and the wet resin are not sufficient. Then, by going through the dipping step, the dipping solution is filled in the fine bubbles of the wet resin, preferably the wet resin is redissolved by heating during drying, and the fine bubbles inside the resin-impregnated nonwoven fabric (for example, closed pores and Since the number of small open pores in the openings is reduced and the resin (wet resin) impregnating the non-woven fabric is densified around the fibers, the adhesion between the non-woven fabric fibers and the wet resin is improved and the strength is improved. To do. Further, the reduction of fine bubbles leads to uniform impregnation of the dry resin in the secondary impregnation step and improvement in strength. Further, a dry resin layer is further formed on the surface of the wet resin layer on the non-woven fabric fiber by passing through the secondary impregnation step. If the process proceeds to the secondary impregnation process without passing through the dipping process, it becomes difficult for the dry resin to enter the space inside the bubbles inside the resin-impregnated nonwoven fabric, and the adhesion of the dry resin becomes uneven. In this case, the wet resin and the dry resin are non-uniformly adhered, and the elastic properties and the rigidity properties are partially non-uniform, so that the resin in the polishing pad peels off during polishing and the life is shortened. I will end up. In addition, since the strong oxidant easily penetrates into the bubbles in which the dry resin having excellent resistance to the strong oxidant does not exist, the chemical resistance is poor and the life is shortened. On the other hand, according to the present embodiment, since air bubbles are reduced in the dipping step, voids that can be impregnated are secured in the secondary impregnating step, the air permeability is improved, and there are few places where the dry resin is unlikely to enter. The area where the resin is present increases. Therefore, the invasion of the strong oxidant into the region where the dry resin does not exist is suppressed, the chemical resistance is improved, and the life can be extended. Further, since the amount of the wet resin that does not directly adhere to the non-woven fabric is reduced, peeling of the resin in the polishing pad is suppressed during polishing, and the life can be extended. Further, since the dry resin layer is formed by using the urethane prepolymer having a specific NCO equivalent, good chemical resistance is imparted. Here, since the dry resin does not have a good water retention property as compared with the wet resin, it is difficult to sufficiently retain the polishing liquid only with the conventional dry resin, but the layer of the dry resin in the present embodiment has Since it is formed by using polyalkylene ether glycol in addition to the polymer, the amount of OH groups on the surface is adjusted to the desired range, and while maintaining the adhesiveness of the polishing pad, it has an affinity with the polishing liquid. Can be improved. As a result of the improved affinity between the polishing pad and the polishing liquid, the circulation of the polishing liquid is improved, the rise time (the time from the supply of the polishing liquid to the start of polishing) is shortened, and the polishing rate is improved. Further, it is possible to prevent the clogging of the polishing liquid with silica during polishing and the occurrence of scratches on the object to be polished.
As described above, in the polishing pad of the present embodiment, it is assumed that a nonwoven fabric is used as a base material, a wet resin layer is formed on the nonwoven fabric, and a dry resin layer is formed on the wet resin layer. It is assumed that the polishing pad as a whole has good adhesion between the non-woven fabric and the wet resin layer and adhesion between the wet resin layer and the dry resin layer. From the above viewpoint, it is considered that the polishing pad of the present embodiment has excellent chemical resistance and can secure a sufficient life even when subjected to polishing using a strong oxidant.
If the non-woven fabric is impregnated with the dry resin by the secondary impregnation process by omitting the primary impregnation process and the dipping process, the non-woven fabric and the dry resin are not well-adapted to each other and a problem occurs in the adhesion between the fiber and the resin. Will impair the stability of. Further, when only the dry resin is adhered to the non-woven fabric and the wet resin is not adhered, the polishing pad has high hardness and low elasticity, and the followability to the object to be polished during polishing is poor, which hinders polishing.
本実施形態の研磨パッドが上記のとおりに推察される構成を有していることは、以下に限定されないが、例えば、当該研磨パッドの引張強度保持率の値だけでなく、上述した通気度の値や、研磨パッドにおける不織布、第１の樹脂及び第２の樹脂の各含有量の値等から確認することができる。 That the polishing pad of the present embodiment has a configuration conjectured as described above is not limited to the following, for example, not only the value of the tensile strength retention rate of the polishing pad, but also the above-mentioned air permeability. It can be confirmed from the value, the value of each content of the nonwoven fabric, the first resin and the second resin in the polishing pad, and the like.
上述のようにして得られた研磨パッドは、その後、必要に応じて、円形等の所望の形状、寸法に裁断されてもよく、汚れや異物等の付着がないことを確認する等の検査を施されてもよい。 The polishing pad obtained as described above may then be cut into a desired shape and size such as a circle, if necessary, and an inspection such as confirming that there is no dirt or foreign matter attached. May be given.
得られた研磨パッドは、その表面が研磨面となるが、その研磨パッドを用いてワークを研磨する場合、予め、研磨パッドの研磨面とは反対側の面に、研磨機の研磨定盤に研磨パッドを貼着するための両面テープ（粘着層及び剥離紙を備えるもの）を貼り合わせてもよい。 The obtained polishing pad has a surface serving as a polishing surface, but when polishing a workpiece using the polishing pad, the surface opposite to the polishing surface of the polishing pad is previously attached to the polishing surface plate of the polishing machine. A double-sided tape (having an adhesive layer and release paper) for attaching the polishing pad may be attached.
［研磨方法］
本実施形態の研磨方法は、本実施形態の研磨パッドを用いて研磨を行う限り特に限定されるものではないが、化合物半導体ウェハを、過マンガン酸カリウムを含む溶液に接触させながら本実施形態の研磨パッドにより研磨する工程を有するものとすることができる。その具体的な一例を説明する。まず、片面研磨機の保持定盤にワークを保持させる。次いで、保持定盤と対向するように配置された研磨定盤に研磨パッドを装着する。研磨定盤に研磨パッドを装着する際、両面テープから剥離紙を剥離して粘着層を露出させた後、露出した粘着層を研磨定盤に接触させ押圧する。そして、ワークと研磨パッドとの間に過マンガン酸カリウム及び必要に応じて砥粒を含む溶液（研磨液）を循環供給すると共に、ワークを研磨パッドの方に所定の研磨圧にて押圧しながら研磨定盤ないし保持定盤を回転させることで、ワークを化学機械研磨により研磨する。この際、本実施形態の研磨パッドを用いることにより、高い研磨レート、長い研磨パッドの寿命と共に、十分に高い被研磨物の平坦性を確保することが可能となる。なお、本実施形態の研磨方法において、過マンガン酸カリウムに加えて又は代えて、過マンガン酸ナトリウムなどの強酸化剤を用いてもよい。
[Polishing method]
The polishing method of the present embodiment is not particularly limited as long as polishing is performed using the polishing pad of the present embodiment, but the compound semiconductor wafer is contacted with a solution containing potassium permanganate while the polishing method of the present embodiment is being performed. It may have a step of polishing with a polishing pad. A specific example will be described. First, the work is held on the holding platen of the single-side polishing machine. Then, the polishing pad is attached to the polishing platen which is arranged so as to face the holding platen. When the polishing pad is attached to the polishing platen, the release paper is peeled off from the double-sided tape to expose the adhesive layer, and then the exposed adhesive layer is brought into contact with the polishing platen and pressed. Then, while supplying a solution (polishing liquid) containing potassium permanganate and, if necessary, abrasive grains between the work and the polishing pad, while pressing the work against the polishing pad at a predetermined polishing pressure. The work is polished by chemical mechanical polishing by rotating the polishing platen or the holding platen. At this time, by using the polishing pad of the present embodiment, it is possible to secure a sufficiently high flatness of the object to be polished as well as a high polishing rate and a long life of the polishing pad. In the polishing method of the present embodiment, a strong oxidizer such as sodium permanganate may be used in addition to or instead of potassium permanganate.
［研磨パッドの用途］
本実施形態の研磨パッドは、レンズ、平行平面板、反射ミラー等の光学材料、ハードディスク用基板、半導体用シリコンウェハ、液晶ディスプレイ用ガラス基板、サファイヤや窒化ガリウムを始めとする難削材等の研磨に特に好適に用いられる。ただし、本実施形態の研磨パッドの用途はそれらに限定されない。
[Uses of polishing pad]
The polishing pad of this embodiment is for polishing optical materials such as lenses, plane parallel plates, and reflection mirrors, substrates for hard disks, silicon wafers for semiconductors, glass substrates for liquid crystal displays, difficult-to-cut materials such as sapphire and gallium nitride. It is particularly preferably used for. However, the use of the polishing pad of this embodiment is not limited to them.
以下、実施例によって本実施形態を更に詳細に説明するが、本実施形態はこれらの実施例に限定されるものではない。 Hereinafter, the present embodiment will be described in more detail with reference to examples, but the present embodiment is not limited to these examples.
［使用原料］
実施例及び比較例で用いる１次含浸用の樹脂（１次含浸樹脂）、１次含浸用の架橋剤（１次架橋剤）、１次含浸用の溶媒（１次含浸溶媒）、浸漬工程用の溶媒（浸漬溶媒）、２次含浸用の樹脂（２次含浸樹脂）、ポリアルキレンエーテルグリコール、２次含浸用の硬化剤（２次硬化剤）としては、下記のものを用いた。これらをまとめて表１に示す。なお、２次含浸樹脂、ポリアルキレンエーテルグリコール及び２次硬化剤の詳細については表２に示す。
[Raw materials used]
Resin for primary impregnation (primary impregnating resin) used in Examples and Comparative Examples, crosslinking agent for primary impregnation (primary crosslinking agent), solvent for primary impregnation (primary impregnation solvent), for dipping step The following were used as the solvent (immersion solvent), the resin for secondary impregnation (secondary impregnation resin), the polyalkylene ether glycol, and the curing agent for secondary impregnation (secondary curing agent). These are summarized in Table 1. Details of the secondary impregnating resin, polyalkylene ether glycol and secondary curing agent are shown in Table 2.
（１次含浸樹脂）
ＵＷ−１：エステル系ウレタン樹脂（ＤＩＣ社製、商品名「クリスボンＵＷ−１」）
（１次架橋剤）
ＤＮ−９５０：ウレタンプレポリマー（ＤＩＣ社製、商品名「バーノックＤＮ９５０」）
（１次含浸溶媒）
Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）
（浸漬溶媒）
ＤＭＦ／水 （質量比６５／３５）
（２次含浸樹脂）
ＵＰ１２１：ウレタンプレポリマー（三菱樹脂社製、商品名「ノバレタン ＵＰ１２１」、ＮＣＯ当量４４０）
ＤＣ６９１２：ウレタンプレポリマー（東ソー社製、商品名「ＤＣ６９１２」、ＮＣＯ当量５４０）
なお、上記のＮＣＯ当量は、ＪＩＳ Ｋ ７３０１に準拠して測定した。
（ポリアルキレンエーテルグリコール）
ＴＧ−３０００：ポリオキシプロピレングリコール（ＤＩＣ社製、商品名「ハイプロックスＴＧ−３０００」、ＯＨ当量１００７）
なお、上記のＯＨ当量はＪＩＳ Ｋ００７０に準拠し測定した。
（２次硬化剤）
Ｅ（ＭＯＣＡ）：硬化剤（ＤＩＣ社製、商品名「パンデックスＥ」、ＮＨ2当量１３３．５８）
なお、上記のＮＨ2当量は、ＪＩＳ Ｋ７２３７に準拠し測定した。
(Primary impregnation resin)
UW-1: Ester-based urethane resin (manufactured by DIC, product name "Chrisbon UW-1")
(Primary cross-linking agent)
DN-950: Urethane prepolymer (manufactured by DIC, trade name "Bernock DN950")
(Primary impregnation solvent)
N,N-dimethylformamide (DMF)
(Immersion solvent)
DMF/water (mass ratio 65/35)
(Secondary impregnation resin)
UP121: Urethane prepolymer (manufactured by Mitsubishi Plastics Co., Ltd., trade name "Novaretan UP121", NCO equivalent 440)
DC6912: Urethane prepolymer (manufactured by Tosoh Corporation, trade name "DC6912", NCO equivalent 540)
The NCO equivalent was measured according to JIS K7301.
(Polyalkylene ether glycol)
TG-3000: Polyoxypropylene glycol (manufactured by DIC, trade name "HYPROX TG-3000", OH equivalent 1007)
The above OH equivalent was measured according to JIS K0070.
(Secondary curing agent)
E (MOCA): Hardener (manufactured by DIC, trade name "Pandex E", NH 2 equivalent 133.58)
The above NH 2 equivalent was measured according to JIS K7237.
［実施例１〜４、比較例１〜３］
（１次含浸工程）
上述の１次含浸樹脂、１次架橋剤、及び１次含浸溶媒を、表１に示す配合で混合し調製した樹脂溶液に、繊維材料がＰＥＴで、厚さが３．５ｍｍで、目付が６２０ｇ／ｍ2である不織布（繊度３ｄ）を浸漬した。浸漬後、１対のローラ間を加圧可能なマングルローラを用いて樹脂溶液を絞り落として、不織布に樹脂溶液を略均一に含浸させた。次いで、室温の水からなる凝固液中に浸漬することにより、１次含浸樹脂を凝固再生させて樹脂含浸不織布を得た。その後、樹脂含浸不織布を凝固液から取り出し、更に水からなる洗浄液に浸漬して、ＤＭＦを除去した後、乾燥させた。乾燥後、バフィングにより表面のスキン層が除去された樹脂含浸不織布を得た。
（浸漬工程）
次いで、ＤＭＦと純水とを６５対３５で混合した浸漬溶媒に、上記で得られた樹脂含浸不織布を浸漬した。その後、洗浄・乾燥を行い、浸漬工程後の樹脂含浸不織布を得た。
（２次含浸工程）
さらに、２次含浸樹脂、ポリアルキレンエーテルグリコール及び２次硬化剤を表２に示す配合で調製した溶液に、浸漬工程後の樹脂含浸不織布を浸漬した。その後、洗浄・乾燥を行い、実施例１〜４及び比較例１〜３の研磨パッドを得た。
[Examples 1 to 4, Comparative Examples 1 to 3]
(Primary impregnation process)
A resin solution prepared by mixing the above-mentioned primary impregnating resin, primary cross-linking agent, and primary impregnating solvent with the composition shown in Table 1 was PET as the fiber material, had a thickness of 3.5 mm, and had a basis weight of 620 g. A non-woven fabric (fineness 3d) having a density of /m 2 was immersed. After the immersion, the resin solution was squeezed using a mangle roller capable of pressing between the pair of rollers to impregnate the nonwoven fabric with the resin solution substantially uniformly. Then, the primary impregnated resin was coagulated and regenerated by immersing it in a coagulating liquid consisting of water at room temperature to obtain a resin-impregnated non-woven fabric. Then, the resin-impregnated non-woven fabric was taken out from the coagulation liquid, further immersed in a cleaning liquid containing water to remove DMF, and then dried. After drying, a resin-impregnated non-woven fabric having a surface skin layer removed by buffing was obtained.
(Immersion process)
Next, the resin-impregnated non-woven fabric obtained above was immersed in an immersion solvent in which DMF and pure water were mixed in a ratio of 65:35. Then, washing and drying were performed to obtain a resin-impregnated non-woven fabric after the dipping process.
(Secondary impregnation process)
Further, the resin-impregnated non-woven fabric after the dipping step was dipped in a solution prepared by mixing the secondary impregnated resin, the polyalkylene ether glycol, and the secondary curing agent with each other as shown in Table 2. Then, washing and drying were performed to obtain polishing pads of Examples 1 to 4 and Comparative Examples 1 to 3.
［物性評価］
上述のようにして得られた各実施例及び比較例の研磨パッドについて、下記のとおりに物性を測定し、品質を評価した。それらの結果を表２に示す。
[Evaluation of the physical properties]
With respect to the polishing pads of the respective Examples and Comparative Examples obtained as described above, the physical properties were measured as follows and the quality was evaluated. The results are shown in Table 2.
（厚さ）
日本工業規格（ＪＩＳ Ｋ ６５０５）に準拠して、次のとおりに研磨パッドの厚さを測定した。まず、研磨パッドを１０ｃｍ×１０ｃｍ角に切り抜いて得た試料片３枚を用意し、各試料片毎に、厚さ測定器の所定位置にセットした。その後、４８０ｇ／ｃｍ2の荷重をかけた加圧面を試料片の表面に載せ、５秒経過後に厚さを測定した。その際、１枚の試料片につき、５箇所の厚さを測定し、相加平均を算出し、さらに３枚の試料片の相加平均を求めて研磨パッドの厚さとした。
(thickness)
The thickness of the polishing pad was measured as follows in accordance with Japanese Industrial Standards (JIS K 6505). First, three polishing pieces obtained by cutting out a polishing pad into 10 cm×10 cm squares were prepared, and each polishing piece was set at a predetermined position of a thickness measuring instrument. Then, a pressure surface to which a load of 480 g/cm 2 was applied was placed on the surface of the sample piece, and the thickness was measured after 5 seconds had elapsed. At that time, the thickness of each sample piece was measured at five locations, the arithmetic average was calculated, and the arithmetic average of the three sample pieces was calculated as the polishing pad thickness.
（密度）
日本工業規格（ＪＩＳ Ｋ ６５０５）に準拠して、次のとおりに研磨パッドの密度を測定した。すなわち、厚さの測定で用いたものと同様の試料片を用意し、その質量を自動天秤で測定後、下記式により密度を算出し、３枚の試料片の相加平均を求めて研磨パッドの密度とした。
密度（ｇ／ｃｍ3）＝質量（ｇ）／（１０（ｃｍ）×１０（ｃｍ）×試料片の厚さ（ｃｍ））
(density)
The density of the polishing pad was measured as follows according to Japanese Industrial Standards (JIS K 6505). That is, a sample piece similar to the one used in the thickness measurement is prepared, the mass is measured by an automatic balance, the density is calculated by the following formula, and the arithmetic average of three sample pieces is calculated to obtain a polishing pad. And the density.
Density (g/cm 3 )=mass (g)/(10 (cm)×10 (cm)×thickness of sample piece (cm))
（不織布、湿式樹脂及び乾式樹脂の各含有量）
研磨パッドにおける不織布、湿式樹脂及び乾式樹脂の各含有量は、上述した１次含浸工程後の研磨パッドの密度と、浸漬工程後の研磨パッドの密度と、２次含浸工程後の研磨パッドの密度と、をそれぞれ測定し、密度差から算出した。なお、密度の測定は上記（密度）と同様にして測定した。
(Contents of non-woven fabric, wet resin and dry resin)
The content of the non-woven fabric, the wet resin, and the dry resin in the polishing pad is the density of the polishing pad after the above-mentioned primary impregnation step, the density of the polishing pad after the dipping step, and the density of the polishing pad after the secondary impregnation step. And were respectively measured and calculated from the density difference. The density was measured in the same manner as the above (density).
（通気度）
フラジール形試験機（安田精機社製の織布通気度試験機）を用い、日本工業規格（ＪＩＳ Ｌ １０９６）に準拠して、研磨パッドの通気度を測定した。なお、５枚の試料片の相加平均を研磨パッドの通気度とした。
(Air permeability)
Using a Frazier type tester (woven fabric air permeability tester manufactured by Yasuda Seiki Co., Ltd.), the air permeability of the polishing pad was measured according to Japanese Industrial Standards (JIS L 1096). The arithmetic mean of the five sample pieces was used as the air permeability of the polishing pad.
（圧縮率）
ショッパー型厚さ測定器（加圧面：直径１ｃｍの円形）を用い、日本工業規格（ＪＩＳ Ｌ １０２１）に準拠して、次のとおりに研磨パッドの圧縮率を測定した。すなわち、初荷重で３０秒間加圧した後の厚さｔ0を測定し、次に最終圧力の下で５分間放置後の厚さｔ1を測定した。これらから、圧縮率を下記式により算出した。このとき、初荷重は１００ｇ／ｃｍ2、最終荷重は１１２０ｇ／ｃｍ2とした。
圧縮率（％）＝（ｔ0−ｔ1）／ｔ0×１００
(Compression rate)
The compressibility of the polishing pad was measured as follows according to Japanese Industrial Standards (JIS L 1021) using a Shopper type thickness meter (pressurized surface: circular shape with a diameter of 1 cm). That is, the thickness t 0 after pressing for 30 seconds with the initial load was measured, and then the thickness t 1 after standing for 5 minutes under the final pressure was measured. From these, the compression ratio was calculated by the following formula. At this time, the initial load was 100 g/cm 2 and the final load was 1120 g/cm 2 .
Compression rate (%)=(t 0 −t 1 )/t 0 ×100
（圧縮弾性率）
ショッパー型厚さ測定器（加圧面：直径１ｃｍの円形）を用い、日本工業規格（ＪＩＳ Ｌ １０２１）に準拠して、次のとおりに研磨パッドの圧縮弾性率を測定した。すなわち、無荷重状態から初荷重を３０秒間かけた後の厚さｔ0を測定し、次に、厚さｔ0の状態から最終荷重を３０秒間かけた後の厚さｔ1を測定した。次に、厚さｔ1の状態から全ての荷重を除き、５分間放置（無荷重状態とした）後、再び初荷重を３０秒間かけた後の厚さｔ0’を測定した。これらから、圧縮弾性率を下記式により算出した。このとき、初荷重は１００ｇ／ｃｍ2、最終荷重は１１２０ｇ／ｃｍ2とした。
圧縮弾性率（％）＝１００×（ｔ0’−ｔ1）／（ｔ0−ｔ1）
(Compression modulus)
The compressive elastic modulus of the polishing pad was measured as follows in accordance with Japanese Industrial Standards (JIS L 1021) using a Shopper type thickness meter (pressurized surface: a circle having a diameter of 1 cm). That is, the thickness t 0 after the initial load was applied for 30 seconds from the unloaded state was measured, and then the thickness t 1 after the final load was applied for 30 seconds from the state of the thickness t 0 was measured. Next, all the loads were removed from the state of the thickness t 1 , left for 5 minutes (no load), and the initial load was applied again for 30 seconds, and the thickness t 0 ′ was measured. From these, the compressive elastic modulus was calculated by the following formula. At this time, the initial load was 100 g/cm 2 and the final load was 1120 g/cm 2 .
Compression modulus (%) = 100 × (t 0 '-t 1) / (t 0 -t 1)
（Ａ硬度）
研磨パッドのＡ硬度は、次のようにして測定した。すなわち、厚さ４．５ｍｍ以上の試験片（１０ｃｍ×１０ｃｍ）の表面にバネを介して押針（測定子）を押し付け、３０秒後の押針の押し込み深さをＡ型硬度計（日本工業規格、ＪＩＳ Ｋ ７３１１）により測定した。なお、研磨パッドが４．５ｍｍ未満の厚さである場合は、厚さが４．５ｍｍ以上になるまで研磨パッドを重ね、試験片とした。これを３回行って相加平均から研磨パッドのＡ硬度を求めた。
(A hardness)
The A hardness of the polishing pad was measured as follows. That is, a push needle (measuring element) is pressed against the surface of a test piece (10 cm×10 cm) having a thickness of 4.5 mm or more via a spring, and the pushing depth of the push needle after 30 seconds is measured by an A-type hardness tester (Japan Industrial It was measured according to the standard, JIS K 7311). When the polishing pad had a thickness of less than 4.5 mm, the polishing pad was piled up to a thickness of 4.5 mm or more to obtain a test piece. This was repeated three times to determine the A hardness of the polishing pad from the arithmetic mean.
（引張強度保持率）
引張万能試験機（「テンシロン」、Ａ＆Ｄ社製、ＲＴＣ−１２１０Ａ）を用い、日本工業規格（ＪＩＳ Ｋ ６５５０）に準拠して、試験液に浸漬する前の研磨パッドの引張強度（ａ）を測定した。次いで、３質量％の過マンガン酸カリウム水溶液に硝酸を加えてｐＨ２に調整し、試験液を調製した。この試験液に、研磨パッドを２５℃で４８時間浸漬した。なお、浸漬の開始から２４時間経過後に試験液と研磨パッドを収容した容器を数分間振とうした。浸漬の開始から４８時間経過後、研磨パッドを試験液から取り出し、流水洗浄し、５分間の超音波洗浄を行った。次いで、流水洗浄し、キッチンペーパーで加圧しながら残留した試験液を拭き取り上記と同様に研磨パッドの引張強度（ｂ）を測定した。このようにして測定された引張強度（ａ）と引張強度（ｂ）の値から、引張強度保持率を以下の式で算出した。
引張強度保持率＝引張強度（ｂ）／引張強度（ａ）×１００ （％）
(Tensile strength retention rate)
Using a tensile universal testing machine ("Tensilon", A&D Co., RTC-1210A), in accordance with Japanese Industrial Standards (JIS K 6550), the tensile strength (a) of the polishing pad before being immersed in the test solution is measured. did. Next, nitric acid was added to a 3% by mass potassium permanganate aqueous solution to adjust the pH to 2 to prepare a test solution. The polishing pad was immersed in this test solution at 25° C. for 48 hours. Note that, 24 hours after the start of the immersion, the container containing the test liquid and the polishing pad was shaken for several minutes. After 48 hours from the start of the immersion, the polishing pad was taken out from the test solution, washed with running water, and ultrasonically cleaned for 5 minutes. Then, the sample was washed with running water and the residual test liquid was wiped off with pressure with kitchen paper, and the tensile strength (b) of the polishing pad was measured in the same manner as above. From the values of the tensile strength (a) and the tensile strength (b) thus measured, the tensile strength retention rate was calculated by the following formula.
Tensile strength retention rate = Tensile strength (b)/Tensile strength (a) x 100 (%)
＜研磨試験＞
各実施例及び比較例の研磨パッドについて、以下に示すとおりに研磨加工を行い、研磨レート、スクラッチ発生、ブラウンシリカの堆積を評価した。
まず、各例で得られた研磨パッドを研磨機（不二越株式会社製、商品名「ＭＣＰ−１５０Ｘ」）の定盤に貼り付け、９００ｍＬ／ｍｉｎで水を供給しながら研磨パッドの研磨面をドレス加工した（加圧１．３ｋＰａ、時間：１０ｍｉｎ）。その際、ダイヤモンドドレッサーとして、旭ダイヤモンド工業株式会社製「ダイヤモンドドレッサー（＃１００）」を使用した。次いで、被研磨物をシリコンウェハ（直径８インチ×厚さ７００μｍ）とし、下記に示す研磨条件にて研磨を行った。
（研磨条件）
研磨液：コロイダルシリカを含有する研磨液として、（株）フジミインコーポレーテッド製の「ＧＬＡＮＺＯＸ ＨＰ−２０」を用い、ＧＬＡＮＺＯＸ ＨＰ−２０：水＝１：１９の比率で調製したものを使用した。
研磨液流量：６００ｍＬ／ｍｉｎ（温度調節せず）
Ｔｏｐ回転数：６０ｒｐｍ
プラテン回転数：６０ｒｐｍ
研磨時間：６０ｍｉｎ／ＢＴ
研磨圧：２００ｇｆ／ｃｍ2（１３．５ｋｐａ）
<Polishing test>
The polishing pads of Examples and Comparative Examples were polished as shown below, and the polishing rate, scratch generation, and brown silica deposition were evaluated.
First, the polishing pad obtained in each example was attached to a surface plate of a polishing machine (manufactured by Fujikoshi Co., Ltd., product name "MCP-150X"), and the polishing surface of the polishing pad was dressed while supplying water at 900 mL/min. Processed (pressure 1.3 kPa, time: 10 min). At that time, "Diamond Dresser (#100)" manufactured by Asahi Diamond Industry Co., Ltd. was used as a diamond dresser. Next, a silicon wafer (diameter 8 inches×thickness 700 μm) was used as the object to be polished, and polishing was performed under the polishing conditions shown below.
(Polishing conditions)
Polishing liquid: As a polishing liquid containing colloidal silica, "GLANZOX HP-20" manufactured by Fujimi Incorporated Co., Ltd. was used, which was prepared at a ratio of GLANZOX HP-20:water=1:19.
Polishing liquid flow rate: 600 mL/min (without temperature adjustment)
Top rotation speed: 60 rpm
Platen rotation speed: 60 rpm
Polishing time: 60min/BT
Polishing pressure: 200 gf/cm 2 (13.5 kpa)
（研磨レート）
研磨レートは、研磨加工の前後のシリコンウェハ厚の差である研磨量を研磨時間で除して表したものであり、シリコンウェハの比重、面積および研磨前後の重量差を測定し算出した。
(Polishing rate)
The polishing rate is represented by dividing the amount of polishing, which is the difference in the thickness of the silicon wafer before and after polishing, by the polishing time, and was calculated by measuring the specific gravity, area and weight difference before and after polishing of the silicon wafer.
（スクラッチ発生の有無）
上記研磨加工後の被研磨物の表面を対象とし、ハロゲンランプの強光下にてスクラッチ発生の有無を目視により下記基準で評価した。
○：殆ど確認できない。
△：やや確認できる。
×：明確に確認できる。
(Presence or absence of scratches)
For the surface of the object to be polished after the above polishing, the presence or absence of scratches under the strong light of a halogen lamp was visually evaluated according to the following criteria.
◯: Almost no confirmation is possible.
Δ: A little can be confirmed.
X: Can be clearly confirmed.
（ブラウンシリカ発生の有無）
ここでいう「ブラウンシリカ」とは研磨液の砥粒に由来するシリカが研磨パッド表面に体積したものを意味し、目詰まりの指標となる。上記研磨加工後の研磨パッドの表面を対象とし、ブラウンシリカ発生の有無を目視により下記基準で評価した。
○：殆ど褐色を呈していない。
△：やや褐色を呈している。
×：褐色を呈している。
(Presence or absence of brown silica)
The term "brown silica" as used herein means that silica derived from the abrasive grains of the polishing liquid is accumulated on the surface of the polishing pad and serves as an index of clogging. For the surface of the polishing pad after the polishing process, the presence or absence of brown silica was visually evaluated according to the following criteria.
◯: Almost no brown color is exhibited.
Δ: It is slightly brown.
X: It has a brown color.
Claims (8)
前記第２の樹脂が、ＮＣＯ当量５００以下のウレタンプレポリマーと、２官能以上かつＯＨ当量５００〜１００００であるポリアルキレンエーテルグリコールと、硬化剤との反応物であり、
前記第１の樹脂が、湿式含浸により前記不織布に含浸できる樹脂であり（ただし、前記第２の樹脂に該当するものを除く。）、
前記ウレタンプレポリマーにおけるＮＣＯ基の量に対する前記ポリアルキレンエーテルグリコールにおけるＯＨ基の量のモル比が、０．０１〜０．１５である、研磨パッド。 A polishing pad having a non-woven fabric, a first resin, and a second resin different from the first resin,
The second resin is a reaction product of a urethane prepolymer having an NCO equivalent of 500 or less, a polyalkylene ether glycol having a functionality of 2 or more and an OH equivalent of 500 to 10,000, and a curing agent,
The first resin is a resin capable of impregnating the non-woven fabric by wet impregnation (however, excluding those corresponding to the second resin).
The polishing pad, wherein the molar ratio of the amount of OH groups in the polyalkylene ether glycol to the amount of NCO groups in the urethane prepolymer is 0.01 to 0.15.
不織布に前記第１の樹脂を含む樹脂溶液を含浸させ、湿式凝固を行うことにより、樹脂含浸不織布を得る１次含浸工程と、
前記樹脂含浸不織布を、前記第１の樹脂が可溶な溶媒に浸漬する浸漬工程と、
前記浸漬工程の後の前記樹脂含浸不織布を、前記ウレタンプレポリマーと、前記ポリアルキレンエーテルグリコールと、前記硬化剤とを含む溶液に含浸する２次含浸工程と、
を有し、
前記ウレタンプレポリマーにおけるＮＣＯ基の量に対する前記ポリアルキレンエーテルグリコールにおけるＯＨ基の量のモル比が、０．０１〜０．１５である、研磨パッドの製造方法。 A method for manufacturing the polishing pad according to any one of claims 1 to 4, comprising:
Nonwoven fabric impregnated with a resin solution containing the first resin, by performing wet coagulation, a primary impregnation step of obtaining a resin-impregnated nonwoven fabric,
A dipping step of dipping the resin-impregnated nonwoven fabric in a solvent in which the first resin is soluble;
The resin-impregnated nonwoven fabric after the immersion step, and the urethane prepolymer, and the polyalkylene ether glycol, a secondary impregnation step of impregnating a solution containing said curing agent,
Have
The method for producing a polishing pad, wherein the molar ratio of the amount of OH groups in the polyalkylene ether glycol to the amount of NCO groups in the urethane prepolymer is 0.01 to 0.15.
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| JP2002283221A (en) * | 2001-03-21 | 2002-10-03 | Rodel Nitta Co | Abrasive cloth |
| JP2005212055A (en) * | 2004-01-30 | 2005-08-11 | Kanebo Ltd | Polishing cloth for nonwoven fabric base, and its fablication method |
| JP4754921B2 (en) * | 2005-09-30 | 2011-08-24 | 富士紡ホールディングス株式会社 | Polishing cloth |
| JP5358996B2 (en) * | 2008-03-26 | 2013-12-04 | 日立金属株式会社 | Method for manufacturing SiC single crystal substrate |
| TWI410299B (en) * | 2009-08-24 | 2013-10-01 | Bestac Advanced Material Co Ltd | Polishing pad, use thereof and method for making the same |
| JP6068025B2 (en) * | 2012-07-05 | 2017-01-25 | 富士紡ホールディングス株式会社 | Polishing cloth |
| US8980749B1 (en) * | 2013-10-24 | 2015-03-17 | Rohm And Haas Electronic Materials Cmp Holdings, Inc. | Method for chemical mechanical polishing silicon wafers |
| JP5871978B2 (en) * | 2014-03-14 | 2016-03-01 | 東洋ゴム工業株式会社 | Polishing pad and manufacturing method thereof |
| JP6654357B2 (en) * | 2015-04-02 | 2020-02-26 | 富士紡ホールディングス株式会社 | Polishing pad, method for manufacturing polishing pad and polishing method |
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