JP7079200B2 - Adhesive tape for protecting the surface of semiconductor wafers and processing methods for semiconductor wafers - Google Patents
Adhesive tape for protecting the surface of semiconductor wafers and processing methods for semiconductor wafers Download PDFInfo
- Publication number
- JP7079200B2 JP7079200B2 JP2018538670A JP2018538670A JP7079200B2 JP 7079200 B2 JP7079200 B2 JP 7079200B2 JP 2018538670 A JP2018538670 A JP 2018538670A JP 2018538670 A JP2018538670 A JP 2018538670A JP 7079200 B2 JP7079200 B2 JP 7079200B2
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor wafer
- resin layer
- protecting
- adhesive
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 235000012431 wafers Nutrition 0.000 title claims description 257
- 239000004065 semiconductor Substances 0.000 title claims description 204
- 239000002390 adhesive tape Substances 0.000 title claims description 69
- 238000003672 processing method Methods 0.000 title claims description 5
- 229920005989 resin Polymers 0.000 claims description 211
- 239000011347 resin Substances 0.000 claims description 211
- 239000010410 layer Substances 0.000 claims description 156
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 78
- 239000000853 adhesive Substances 0.000 claims description 49
- 230000001070 adhesive effect Effects 0.000 claims description 48
- 238000000227 grinding Methods 0.000 claims description 32
- 238000002844 melting Methods 0.000 claims description 30
- 230000008018 melting Effects 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 239000012790 adhesive layer Substances 0.000 claims description 22
- 238000012545 processing Methods 0.000 claims description 21
- 239000000155 melt Substances 0.000 claims description 10
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- 229920000034 Plastomer Polymers 0.000 claims description 3
- 239000010408 film Substances 0.000 description 110
- 230000001681 protective effect Effects 0.000 description 60
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- 125000000524 functional group Chemical group 0.000 description 36
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
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- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
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- ROVZEASPTJLFRF-UHFFFAOYSA-N 2,2-dimethoxy-1-(2-phenylphenyl)ethanone Chemical compound COC(OC)C(=O)C1=CC=CC=C1C1=CC=CC=C1 ROVZEASPTJLFRF-UHFFFAOYSA-N 0.000 description 2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本発明は、半導体ウェハ表面保護用粘着テープ及び半導体ウェハの加工方法に関する。 The present invention relates to an adhesive tape for protecting the surface of a semiconductor wafer and a method for processing a semiconductor wafer.
半導体パッケージは、高純度シリコン単結晶等をスライスして半導体ウェハとした後、イオン注入、エッチング等により当該ウェハ表面に集積回路を形成して製造される。集積回路が形成された半導体ウェハの裏面を研削、研磨等することにより、半導体ウェハは所望の厚みに加工される。この際、半導体ウェハ表面に形成された集積回路を保護するために、半導体ウェハ表面保護用粘着テープ（以下、単に「表面保護テープ」ともいう。）が用いられる。
裏面研削された半導体ウェハは、裏面研削が終了した後にウェハカセットに収納され、ダイシング工程へ運搬され、半導体チップに加工される。A semiconductor package is manufactured by slicing a high-purity silicon single crystal or the like into a semiconductor wafer and then forming an integrated circuit on the wafer surface by ion implantation, etching, or the like. By grinding, polishing, or the like on the back surface of the semiconductor wafer on which the integrated circuit is formed, the semiconductor wafer is processed to a desired thickness. At this time, in order to protect the integrated circuit formed on the surface of the semiconductor wafer, an adhesive tape for protecting the surface of the semiconductor wafer (hereinafter, also simply referred to as “surface protection tape”) is used.
After the backside grinding is completed, the backside ground semiconductor wafer is stored in a wafer cassette, transported to a dicing process, and processed into a semiconductor chip.
従来は、裏面研削等により半導体ウェハの厚みを２００～４００μｍ程度とすることが求められていた。しかし、近年の高密度実装技術の進歩に伴い、半導体チップを小型化する必要が生じ、それに伴い、半導体ウェハの薄膜化も進んでいる。半導体チップの種類によっては、半導体ウェハを１００μｍ程度まで薄くすることが必要となっている。一方で、一度の加工によって製造できる半導体チップの数を多くするために、もとの半導体ウェハを大径化する傾向にある。これまでは直径が５インチや６インチの半導体ウェハが主流だったのに対し、近年では直径８～１２インチの半導体ウェハを半導体チップ化する加工が主流となっている。
半導体ウェハを薄膜化と同時に大径化する流れは、特に、ＮＡＮＤ型やＮＯＲ型が存在するフラッシュメモリの分野や、揮発性メモリであるＤＲＡＭなどの分野で顕著である。例えば、直径１２インチの半導体ウェハを１５０μｍ以下の厚みまで研削することも珍しくない。Conventionally, it has been required to increase the thickness of a semiconductor wafer to about 200 to 400 μm by backside grinding or the like. However, with the progress of high-density mounting technology in recent years, it has become necessary to reduce the size of semiconductor chips, and along with this, the thinning of semiconductor wafers is also progressing. Depending on the type of semiconductor chip, it is necessary to make the semiconductor wafer as thin as about 100 μm. On the other hand, in order to increase the number of semiconductor chips that can be manufactured by one processing, the diameter of the original semiconductor wafer tends to be increased. Until now, semiconductor wafers with a diameter of 5 inches or 6 inches have been the mainstream, but in recent years, processing to convert semiconductor wafers with a diameter of 8 to 12 inches into semiconductor chips has become the mainstream.
The trend of increasing the diameter of semiconductor wafers at the same time as thinning them is particularly remarkable in the field of flash memory in which NAND type and NOR type exist, and in the field of DRAM which is volatile memory. For example, it is not uncommon to grind a semiconductor wafer with a diameter of 12 inches to a thickness of 150 μm or less.
これに加え、特に近年、スマートフォンの普及や携帯電話の性能向上および音楽プレーヤの小型化、かつ性能向上などに伴い、耐衝撃性などを考慮した電極付半導体ウェハを用いたフリップチップ実装に用いるウェハについても薄膜化の要求が増えてきている。またバンプ付半導体ウェハについても半導体ウェハ部分を１００μｍ以下の薄膜研削をする必要が出てきている。フリップチップ接続されるためのバンプは、転送速度向上のため高密度化されてきており、バンプの高さ（半導体ウェハ表面からの突出高さ）が低くなってきており、それに伴ってバンプ間距離が短くなってきている。また近年ではＤＲＡＭにもフリップチップ接続が実施されてきているためウェハの薄膜化も加速している。 In addition to this, especially in recent years, with the spread of smartphones, the improvement of mobile phone performance, the miniaturization of music players, and the improvement of performance, wafers used for flip chip mounting using semiconductor wafers with electrodes in consideration of impact resistance, etc. There is an increasing demand for thin film. Further, with respect to a semiconductor wafer with bumps, it is becoming necessary to grind the semiconductor wafer portion with a thin film of 100 μm or less. The bumps for flip-chip connection have been densified to improve the transfer speed, and the bump height (protruding height from the semiconductor wafer surface) has become lower, and the distance between the bumps has been increased accordingly. Is getting shorter. In recent years, flip-chip connections have also been implemented in DRAMs, so the thinning of wafers is accelerating.
フリップチップ実装は、近年の電子機器の小型化、高密度化に対して半導体素子を最小の面積で実装できる方法として注目されてきた。このフリップチップ実装に使用される半導体素子の電極上にはバンプが形成されており、バンプと回路基板上の配線とを電気的に接合する。これらのバンプの組成としては、主に半田や金が使用されている。この半田バンプや金バンプは、蒸着やメッキで、チップの内部配線につながる露出したアルミ端子上などに形成する。 Flip-chip mounting has attracted attention as a method for mounting semiconductor elements in a minimum area in order to reduce the size and density of electronic devices in recent years. A bump is formed on the electrode of the semiconductor element used for mounting the flip chip, and the bump and the wiring on the circuit board are electrically bonded. As the composition of these bumps, solder and gold are mainly used. These solder bumps and gold bumps are formed on exposed aluminum terminals connected to the internal wiring of the chip by vapor deposition or plating.
しかし、バンプ付半導体ウェハは、その表面に大きな凹凸を有しているため薄膜加工が難しく、通常の表面保護テープを用いて裏面研削を行うと半導体ウェハに割れが生じたり、半導体ウェハの厚み精度が悪化したりする。そのため、バンプ付半導体ウェハの研削は、特別に設計された表面保護テープを用いて行われている（例えば、特許文献１参照）。 However, the bumped semiconductor wafer has large irregularities on its surface, so it is difficult to process a thin film. Will get worse. Therefore, the bumped semiconductor wafer is ground using a specially designed surface protective tape (see, for example, Patent Document 1).
しかしながら、これらの表面保護テープではバンプを十分に吸収して研削性を確保しているため剥離性との両立が非常に難しい。これまでのフリップチップ実装されてきたチップの仕上げ厚みは２００μｍ厚以上とある程度の厚みがあり、剛性を保てたため何とか剥離できてきた。しかし、最近、半導体ウェハ仕上げ厚みが、よりいっそう薄膜となり、バンプ密度も高くなってきているため、表面保護テープは、剥離が容易にできない、糊残りするといった問題を引き起こしてしまっている。また逆に、剥離性を確保すると密着が不十分となり、裏面研削時にシーページ（例えば、ダストや研削水の浸入）を引き起こしてしまっている。 However, since these surface protective tapes sufficiently absorb bumps to ensure grindability, it is very difficult to achieve both peelability and peelability. The finished thickness of the chips mounted on the flip chips so far is 200 μm or more, which is a certain thickness, and the rigidity is maintained, so that the chips can be peeled off somehow. However, recently, the finishing thickness of the semiconductor wafer has become even thinner and the bump density has also increased, so that the surface protective tape has caused problems such as not being easily peeled off and residual adhesive. On the contrary, if the peelability is ensured, the adhesion becomes insufficient, causing seapage (for example, infiltration of dust and grinding water) during backside grinding.
一方、ウェハレベルパッケージに使用されるバンプ付半導体ウェハのバンプ高さは依然高いままであり、高さ２５０μｍ以上のバンプも搭載されている。ウェハレベルパッケージではチップをスタックする必要がないためメモリ系半導体ウェハのように５０μｍ以下といった極薄研削されることがないが、高いバンプがついているため厚膜研削でも非常に割れやすく、１５０μｍ厚以下の研削厚で容易に半導体ウェハ割れの問題が発生する。 On the other hand, the bump height of the bumped semiconductor wafer used for the wafer level package is still high, and bumps having a height of 250 μm or more are also mounted. Wafer level packages do not require stacking of chips, so they are not ground as thin as 50 μm or less like memory semiconductor wafers, but because they have high bumps, they are very fragile even in thick film grinding and have a thickness of 150 μm or less. The problem of semiconductor wafer cracking easily occurs due to the grinding thickness of.
このような半導体ウェハに対して専用の表面保護テープが提案されている（特許文献２～４参照）。特許文献２には、半導体ウェハ加工時には半導体ウェハに強固に密着するとともに、剥離時に、半導体ウェハの破損や糊残りすることなく剥離することができる半導体ウェハ表面保護用粘着テープが記載されている。この表面保護テープは、基材フィルム上に、層厚及び収縮値を特定の範囲内にした放射線硬化型粘着剤層を有する。また、特許文献３には、バンプ高さの高いバンプウェハの裏面研削に用いる表面保護用粘着テープで、ウェハを研削してもウェハの破損防止やシーページが生じないで、剥離力の軽減と糊残りの抑制された半導体ウェハ表面保護用粘着テープが開示されている。この表面保護テープは、特定のタック力と層厚を有する。また、特許文献４には、ウェハ表面に形成された凸凹の高低差以下までウエハの裏面を研削する際に、ウェハ表面の凸凹の保護と、ウェハ表面への研削屑や研削水などの浸入防止、及び研削後のウェハの破損防止を図ることのできる半導体ウエハ保護用粘着シートの貼り合わせ方法が開示されている。この方法に用いられる表面保護シートは、５０℃～１００℃における損失正接を特定の範囲内にした中間層と粘着剤層とを有する。
Dedicated surface protection tapes for such semiconductor wafers have been proposed (see
特許文献２記載の表面保護テープは、半導体ウェハの破損や糊残りは一定程度抑制することができる。また、特許文献３記載の表面保護テープは、剥離性は良好である。しかし、より高いバンプを、より狭いピッチで有する半導体ウェハに適用するには、特許文献２記載の表面保護テープは、剥離性ないし糊残りをさらに改善する余地がある。また、特許文献３記載の表面保護テープは、密着性をさらに向上させ、シーページを抑制し、糊残りを改善する余地がある。
The surface protective tape described in
特許文献４記載の方法に用いられる表面保護テープは、追従性が極めて良好であるために、高さ２５０μｍ以上のバンプに追従した際に、テープが凹凸状に変形してしまい、吸引搬送している加工装置内で搬送中の半導体ウェハが落下し、破損してしまうこともある。 Since the surface protective tape used in the method described in Patent Document 4 has extremely good followability, the tape is deformed into an uneven shape when following a bump having a height of 250 μm or more, and is sucked and conveyed. The semiconductor wafer being transported may fall and be damaged in the processing equipment.
本発明は、上記問題に鑑み、半導体ウェハ加工時には半導体ウェハに強固に密着し、シーページ、加工装置内での搬送エラー、半導体ウェハ破損を抑制し、剥離時には糊残りすることなく剥離することができる半導体ウェハ表面保護用粘着テープおよびそれを用いた半導体ウェハの加工方法を提供することを課題とする。 In view of the above problems, the present invention can firmly adhere to the semiconductor wafer during processing of the semiconductor wafer, suppress seapage, transfer error in the processing apparatus, and damage to the semiconductor wafer, and can be peeled without adhesive residue during peeling. An object of the present invention is to provide an adhesive tape for protecting the surface of a semiconductor wafer and a method for processing a semiconductor wafer using the adhesive tape.
本発明者らは、上記課題を解決するため、鋭意検討を行った結果、基材フィルム、中間樹脂層及び粘着剤層を有する半導体ウェハ表面保護用粘着テープにおいて、前記中間樹脂層を構成する樹脂の融点若しくはビカット軟化点及びメルトマスフローレート（ＭＦＲ）を、それぞれ、特定の範囲内とし、この表面保護テープを特定の凹凸差を有する半導体ウェハ表面に特定温度で加熱貼合することにより、表面保護テープを半導体ウェハの回路面に強固に密着させることができ、半導体ウェハ加工時にはシーページ、加工装置内での搬送エラー、半導体ウェハ破損を抑制でき、剥離した際には、糊残りすることなく剥離でき、さらには半導体ウェハ表面に貼合した状態での反りを抑制できることを見出した。本発明はこの知見に基づきなされるに至ったものである。 As a result of diligent studies to solve the above problems, the present inventors have made a resin constituting the intermediate resin layer in the adhesive tape for protecting the surface of a semiconductor wafer having a base film, an intermediate resin layer and an adhesive layer. The melting point or the Vicat softening point and the melt mass flow rate (MFR) are each within a specific range, and the surface protection tape is heat-bonded to the surface of a semiconductor wafer having a specific unevenness difference at a specific temperature to protect the surface. The tape can be firmly adhered to the circuit surface of the semiconductor wafer, and seapage, transfer error in the processing equipment, and damage to the semiconductor wafer can be suppressed during semiconductor wafer processing, and when peeled, it is peeled without adhesive residue. Furthermore, it was found that the warp in the state of being bonded to the surface of the semiconductor wafer can be suppressed. The present invention has been made based on this finding.
すなわち、上記課題は以下の手段により解決された。
＜１＞
２０μｍ以上の凹凸差を有する半導体ウェハの表面に、４０℃～９０℃の条件で加熱貼合して用いる半導体ウェハ表面保護用粘着テープであって、
前記半導体ウェハ表面保護用粘着テープは、基材フィルムと、粘着剤層と、該基材フィルムと該粘着剤層との間に中間樹脂層とを有し、
前記中間樹脂層の厚みが、前記凹凸差以上であり、該中間樹脂層を構成する樹脂の融点若しくはビカット軟化点が４０℃～９０℃であり、該中間樹脂層を構成する樹脂のメルトマスフローレートが、１０ｇ／１０ｍｉｎ～１００ｇ／１０ｍｉｎである、半導体ウェハ表面保護用粘着テープ。
＜２＞
紫外線照射後の前記粘着剤層の、２３℃のＳＵＳ２８０研磨面に対する粘着力が０．５Ｎ／２５ｍｍ以上５．０Ｎ／２５ｍｍ以下であり、かつ５０℃のＳＵＳ２８０研磨面に対する粘着力が、０．３Ｎ／２５ｍｍ以上７．０Ｎ／２５ｍｍ以下である、＜１＞に記載の半導体ウェハ表面保護用粘着テープ。
That is, the above problem was solved by the following means.
<1>
An adhesive tape for protecting the surface of a semiconductor wafer, which is used by heating and bonding to the surface of a semiconductor wafer having an unevenness difference of 20 μm or more under the conditions of 40 ° C to 90 ° C.
The adhesive tape for protecting the surface of a semiconductor wafer has a base film, an adhesive layer, and an intermediate resin layer between the base film and the adhesive layer.
The thickness of the intermediate resin layer is equal to or greater than the unevenness difference, the melting point or vicut softening point of the resin constituting the intermediate resin layer is 40 ° C to 90 ° C, and the melt mass flow rate of the resin constituting the intermediate resin layer. Is an adhesive tape for protecting the surface of a semiconductor wafer, which is 10 g / 10 min to 100 g / 10 min.
<2>
The adhesive force of the adhesive layer after irradiation with ultraviolet rays on the SUS280 polished surface at 23 ° C. is 0.5 N / 25 mm or more and 5.0 N / 25 mm or less, and the adhesive force on the SUS280 polished surface at 50 ° C. is 0.3 N. The adhesive tape for protecting the surface of a semiconductor wafer according to <1>, which is 25 mm or more and 7.0 N / 25 mm or less.
＜３＞
前記基材フィルムの厚みと前記中間樹脂層の厚みの比が、基材フィルムの厚み：中間樹脂層の厚み＝０．５：９．５～７：３である、＜１＞または＜２＞に記載の半導体ウェハ表面保護用粘着テープ。
＜４＞
前記中間樹脂層を構成する樹脂が、エチレン－アクリル酸メチルコポリマー樹脂、エチレン－アクリル酸エチルコポリマー樹脂およびエチレン－アクリル酸ブチルコポリマー樹脂の少なくとも１種である、＜１＞～＜３＞のいずれか１項に記載の半導体ウェハ表面保護用粘着テープ。
＜５＞
前記基材フィルムの構成材料の融点が９０℃～１５０℃である、＜１＞～＜４＞のいずれか１項に記載の半導体ウェハ表面保護用粘着テープ。
＜６＞
前記中間樹脂層の厚みが、１００μｍ～４００μｍである、＜１＞～＜５＞のいずれか１項に記載の半導体ウェハ表面保護用粘着テープ。
＜７＞
前記粘着剤層の厚みが、５μｍ～４０μｍである、＜１＞～＜６＞のいずれか１項に記載の半導体ウェハ表面保護用粘着テープ。
＜８＞
前記基材フィルムの厚みが２５μｍ～１００μｍである、＜１＞～＜７＞のいずれか１項に記載の半導体ウェハ表面保護用粘着テープ。<3>
The ratio of the thickness of the base film to the thickness of the intermediate resin layer is <1> or <2>, in which the thickness of the base film: the thickness of the intermediate resin layer = 0.5: 9.5 to 7: 3. Adhesive tape for surface protection of semiconductor wafers described in.
<4>
Any one of <1> to <3>, wherein the resin constituting the intermediate resin layer is at least one of an ethylene-methyl acrylate copolymer resin, an ethylene-ethyl acrylate copolymer resin, and an ethylene-butyl acrylate copolymer resin. The adhesive tape for protecting the surface of the semiconductor wafer according to item 1.
<5>
The adhesive tape for protecting the surface of a semiconductor wafer according to any one of <1> to <4>, wherein the constituent material of the base film has a melting point of 90 ° C. to 150 ° C.
<6>
The adhesive tape for protecting the surface of a semiconductor wafer according to any one of <1> to <5>, wherein the thickness of the intermediate resin layer is 100 μm to 400 μm.
<7>
The pressure-sensitive adhesive tape for protecting the surface of a semiconductor wafer according to any one of <1> to <6>, wherein the pressure-sensitive adhesive layer has a thickness of 5 μm to 40 μm.
<8>
The adhesive tape for protecting the surface of a semiconductor wafer according to any one of <1> to <7>, wherein the base film has a thickness of 25 μm to 100 μm.
＜９＞
２０μｍ以上の凹凸差を有する半導体ウェハの表面に、半導体ウェハ表面保護用粘着テープを、４０℃～９０℃の条件で加熱貼合し、半導体ウェハ裏面を研削することを含む半導体ウェハの加工方法であって、
前記半導体ウェハ表面保護用粘着テープは、基材フィルムと、粘着剤層と、該基材フィルムと該粘着剤層との間に中間樹脂層とを有し、
該中間樹脂層の厚みが、前記凹凸差以上であり、該中間樹脂層を構成する樹脂の融点若しくはビカット軟化点が４０℃～９０℃であり、該中間樹脂層を構成する樹脂のメルトマスフローレートが、１０ｇ／１０ｍｉｎ～１００ｇ／１０ｍｉｎである、半導体ウェハの加工方法。
<9>
A semiconductor wafer processing method that includes grinding the back surface of a semiconductor wafer by heating and adhering an adhesive tape for protecting the surface of the semiconductor wafer to the surface of a semiconductor wafer having an unevenness difference of 20 μm or more under the conditions of 40 ° C to 90 ° C. There,
The adhesive tape for protecting the surface of a semiconductor wafer has a base film, an adhesive layer, and an intermediate resin layer between the base film and the adhesive layer.
The thickness of the intermediate resin layer is equal to or greater than the unevenness difference, the melting point or the Vicat softening point of the resin constituting the intermediate resin layer is 40 ° C to 90 ° C, and the melt mass flow rate of the resin constituting the intermediate resin layer. Is a method for processing a semiconductor wafer, which is 10 g / 10 min to 100 g / 10 min.
本発明の説明において、半導体ウェハの表面とは、半導体ウェハの凹凸を有する面、すなわち、集積回路が形成された面を意味する。また、この表面の反対側の面を裏面と称する。
本発明の説明において、凹凸差とは、凸部のうちの最高部からウェハ表面までの距離または凹部のうちの最深部から半導体ウェハ表面までの距離を意味する。例えば、半導体ウェハ上に金属電極（バンプ）が形成されている場合において、最高部とは最も高いバンプの頂上部であり、そこから半導体ウェハ表面までの距離、すなわち、バンプの高さが凹凸差である。あるいは、半導体ウェハにスクライブライン（ダイシングライン）が形成されている場合において、最深部とはスクライブラインのうち最も深い位置であり、そこから半導体ウェハ表面までの距離を凹凸差という。
本発明の説明において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。In the description of the present invention, the surface of the semiconductor wafer means a surface having irregularities of the semiconductor wafer, that is, a surface on which an integrated circuit is formed. Further, the surface opposite to this front surface is referred to as a back surface.
In the description of the present invention, the unevenness difference means the distance from the highest portion of the convex portion to the wafer surface or the distance from the deepest portion of the concave portion to the semiconductor wafer surface. For example, when a metal electrode (bump) is formed on a semiconductor wafer, the highest part is the top of the highest bump, and the distance from there to the surface of the semiconductor wafer, that is, the height of the bump is the difference in unevenness. Is. Alternatively, when a scribe line (dicing line) is formed on the semiconductor wafer, the deepest portion is the deepest position of the scribe line, and the distance from the scribe line to the surface of the semiconductor wafer is referred to as an unevenness difference.
In the description of the present invention, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
本発明の半導体ウェハ表面保護用粘着テープは、半導体ウェハ加工時には半導体ウェハに強固に密着することでシーページの発生を低減し、また加工装置内での搬送エラーないし半導体ウェハ破損を抑制することができ、剥離した際には糊残りを生じにくい。さらに、本発明の半導体ウェハ表面保護用粘着テープは、半導体ウェハ表面に貼合した状態での反りを抑制できる。また、本発明の半導体ウェハの加工方法によれば、上記半導体ウェハ表面保護用粘着テープを用いて、高いバンプを狭いピッチで有する薄膜状の半導体ウェハを得ることが可能になる。 The adhesive tape for protecting the surface of a semiconductor wafer of the present invention can reduce the occurrence of sea pages by firmly adhering to the semiconductor wafer during semiconductor wafer processing, and can suppress transfer errors or semiconductor wafer damage in the processing equipment. It can be peeled off, and it is difficult for adhesive residue to occur. Further, the adhesive tape for protecting the surface of the semiconductor wafer of the present invention can suppress warpage in a state of being bonded to the surface of the semiconductor wafer. Further, according to the method for processing a semiconductor wafer of the present invention, it is possible to obtain a thin film semiconductor wafer having high bumps at a narrow pitch by using the adhesive tape for protecting the surface of the semiconductor wafer.
以下に、本発明の好ましい実施の形態について詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in detail.
［半導体ウェハ表面保護用粘着テープ］
本発明の半導体ウェハ表面保護用粘着テープは、２０μｍ以上の凹凸差を有する半導体ウェハの表面に、４０℃～９０℃の条件で加熱貼合する半導体ウェハ表面保護用粘着テープであって、該半導体ウェハ表面保護用粘着テープは、基材フィルムと、粘着剤層とを有し、さらに、該基材フィルムと該粘着剤層との間に中間樹脂層を少なくとも有する。前記中間樹脂層の厚みは、前記凹凸差以上である。また、前記中間樹脂層を構成する樹脂の融点若しくはビカット軟化点が４０℃～９０℃であり、該中間樹脂層のメルトマスフローレートが、１０ｇ／１０ｍｉｎ～１００ｇ／１０ｍｉｎである。
前記粘着剤層は、特に制限されないが、放射線硬化型粘着剤層が好ましく、「放射線硬化型粘着剤層」とは、放射線〔例えば、紫外線のような光線（レーザー光線を含む）、電子線などの電離性放射線〕の照射で硬化する粘着剤層をいう。照射する放射線は紫外線が好ましい。
[Adhesive tape for protecting the surface of semiconductor wafers]
The adhesive tape for protecting the surface of a semiconductor wafer of the present invention is an adhesive tape for protecting the surface of a semiconductor wafer, which is heat-bonded to the surface of a semiconductor wafer having an unevenness difference of 20 μm or more under the conditions of 40 ° C to 90 ° C. The adhesive tape for protecting the surface of the wafer has a base film and a pressure-sensitive adhesive layer, and further has at least an intermediate resin layer between the base film and the pressure-sensitive adhesive layer. The thickness of the intermediate resin layer is greater than or equal to the unevenness difference. Further, the melting point or the Vicat softening point of the resin constituting the intermediate resin layer is 40 ° C. to 90 ° C., and the melt mass flow rate of the intermediate resin layer is 10 g / 10 min to 100 g / 10 min.
The pressure-sensitive adhesive layer is not particularly limited, but a radiation-curable pressure-sensitive adhesive layer is preferable. Ionizing radiation] refers to an adhesive layer that cures when irradiated. Ultraviolet rays are preferable as the radiation to be irradiated.
＜基材フィルム＞
本発明の半導体ウェハ表面保護用粘着テープに用いられる基材フィルムは、特に制限されない。本発明の半導体ウェハ表面保護用粘着テープにおいて、基材フィルムを構成する材料の融点は９０℃～１５０℃の範囲が好ましく、１００℃～１４０℃の範囲がより好ましく、１１０℃～１３０℃の範囲が更に好ましい。基材フィルムの融点が前記範囲であることにより、表面保護テープを貼合する工程で貼合ローラーやチャックテーブルへの融着を防いで、２０μｍ以上の凹凸を有する半導体ウェハへの十分な貼合ができる。また、ダイシングダイボンディング一体型フィルム（ＤＤＦ）を貼合する場合も、チャックテーブルへの融着を防いでＤＤＦの貼合が可能となる。本発明の半導体ウェハ表面保護用粘着テープは、中間樹脂層に熱をかけることで中間樹脂層の流動性が向上し、２０μｍ以上の凹凸差を有する半導体ウェハに対して十分な密着性を確保するため、十分高い温度である４０℃～９０℃の条件で加熱貼合される。従って、基材フィルムを構成する材料の融点が低すぎると基材フィルムの背面が溶けてしまい貼合ローラーやチャックテーブルと融着してしまうおそれがある。基材フィルムが、例えばスチレンのように非結晶性の樹脂で構成される場合は、融点が存在しないためビカット軟化点が指標となる。すなわち、ビカット軟化点が上記融点の範囲にあることが好ましい。ビカット軟化点が高すぎると基材背面（中間樹脂層と接する面の反対側の面）に流動性が出るため、チャックテーブルのポーラス部に入り込むおそれがある。<Base film>
The base film used for the adhesive tape for protecting the surface of the semiconductor wafer of the present invention is not particularly limited. In the adhesive tape for protecting the surface of the semiconductor wafer of the present invention, the melting point of the material constituting the base film is preferably in the range of 90 ° C to 150 ° C, more preferably in the range of 100 ° C to 140 ° C, and in the range of 110 ° C to 130 ° C. Is more preferable. When the melting point of the base film is within the above range, fusion to the bonding roller and the chuck table is prevented in the process of bonding the surface protective tape, and sufficient bonding to a semiconductor wafer having an unevenness of 20 μm or more is sufficient. Can be done. Further, when the dicing die bonding integrated film (DDF) is bonded, the DDF can be bonded by preventing fusion to the chuck table. The adhesive tape for protecting the surface of a semiconductor wafer of the present invention improves the fluidity of the intermediate resin layer by applying heat to the intermediate resin layer, and secures sufficient adhesion to a semiconductor wafer having an unevenness difference of 20 μm or more. Therefore, they are heat-bonded under the condition of a sufficiently high temperature of 40 ° C to 90 ° C. Therefore, if the melting point of the material constituting the base film is too low, the back surface of the base film may be melted and fused with the bonding roller or the chuck table. When the base film is composed of an amorphous resin such as styrene, the Vicat softening point is an index because there is no melting point. That is, it is preferable that the Vicat softening point is in the range of the above melting point. If the vicut softening point is too high, fluidity will appear on the back surface of the base material (the surface opposite to the surface in contact with the intermediate resin layer), which may enter the porous portion of the chuck table.
本発明の半導体ウェハ表面保護用粘着テープに用いられる基材フィルムは、樹脂からなるものが好ましく、このような樹脂として、本発明の属する技術分野で通常用いられるプラスチック、ゴム等を用いることができる。例えば、ポリオレフィン系樹脂（例えば、ポリエチレン、ポリプロピレン、エチレン－プロピレン共重合体、ポリブテン－１、ポリ－４－メチルペンテン－１、エチレン－酢酸ビニル共重合体、エチレン－アクリル酸エチル共重合体、エチレン－アクリル酸メチル共重合体、エチレン－アクリル酸共重合体又はアイオノマー等のエチレン性不飽和基を含むモノマーの単独重合体もしくは共重合体からなる樹脂）、ポリエステル樹脂（例えば、ポリエチレンテレフタレート又はポリエチレンナフタレートからなる樹脂）、ポリカーボネート樹脂、ポリウレタン樹脂、エンジニアリングプラスチック（例えば、ポリメチルメタクリレート）、合成ゴム類（例えば、スチレン－エチレン－ブテンもしくはペンテン系共重合体）、熱可塑性エラストマー（例えば、ポリアミド－ポリオール共重合体）が挙げられる。本発明の表面保護テープに用いられる基材フィルムは、上記樹脂１種単独からなるフィルムでもよく、２種以上を組み合わせたフィルムでもよい。また、本発明の表面保護テープに用いられる基材フィルムは、単層でもよく、複層にしたものを使用してもよい。なお、複層の基材フィルムは、中間樹脂層と反対側の最外層を構成する材料の融点が上記範囲にあることが好ましい。
本発明の表面保護テープにおいて、基材フィルムは、ポリエステル樹脂またはポリオレフィン系樹脂からなるフィルムが好ましい。The base film used for the adhesive tape for protecting the surface of the semiconductor wafer of the present invention is preferably made of a resin, and as such a resin, plastic, rubber or the like usually used in the technical field to which the present invention belongs can be used. .. For example, polyolefin resins (eg polyethylene, polypropylene, ethylene-propylene copolymer, polybutene-1, poly-4-methylpentene-1, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene. -Methyl acrylate copolymer, ethylene-acrylic acid copolymer or a resin composed of a homopolymer or copolymer of a monomer containing an ethylenically unsaturated group such as ionomer), a polyester resin (for example, polyethylene terephthalate or polyethylene na). Phtalate resin), polycarbonate resin, polyurethane resin, engineering plastic (eg polymethylmethacrylate), synthetic rubbers (eg styrene-ethylene-butene or penten copolymers), thermoplastic elastomers (eg polyamide-polypolymer) Copolymer). The base film used for the surface protective tape of the present invention may be a film made of the above-mentioned resin type 1 alone, or a film in which two or more types are combined. Further, the base film used for the surface protective tape of the present invention may be a single layer or a multi-layered film. In the multi-layer base film, it is preferable that the melting point of the material constituting the outermost layer on the opposite side of the intermediate resin layer is in the above range.
In the surface protective tape of the present invention, the base film is preferably a film made of a polyester resin or a polyolefin resin.
基材フィルムの厚みは、半導体ウェハの反りの矯正力と表面保護テープの剥離性のバランス、コストや製造適性などの面を考慮すると、２５μｍ以上が好ましく、５０μｍ以上が更に好ましい。上限は、２００μｍ以下が好ましく、１５０μｍ以下がより好ましく、１００μｍ以下が特に好ましい。基材フィルムの厚みが前記範囲にあることで、半導体ウェハを５０μｍ以下に薄膜研削した場合においても搬送エラーを抑制しつつ研削可能であり、表面保護テープの剥離性を向上させることができる。なお、「半導体ウェハを５０μｍ以下に薄膜研削した場合」とは、バンプを有する半導体ウェハにおいては、バンプを除く、半導体ウエハ自体の厚みを５０μｍ以下になるまで裏面研削することを意味する。また、スクライブラインが形成された半導体ウェハにおいては、上述の最深部から、裏面までの距離を意味する。 The thickness of the base film is preferably 25 μm or more, more preferably 50 μm or more, in consideration of the balance between the warp straightening force of the semiconductor wafer and the peelability of the surface protective tape, cost and manufacturing aptitude. The upper limit is preferably 200 μm or less, more preferably 150 μm or less, and particularly preferably 100 μm or less. When the thickness of the base film is within the above range, even when the semiconductor wafer is thin-film ground to 50 μm or less, it can be ground while suppressing the transfer error, and the peelability of the surface protective tape can be improved. In addition, "when the semiconductor wafer is thin-film ground to 50 μm or less" means that in the semiconductor wafer having bumps, the back surface is ground until the thickness of the semiconductor wafer itself excluding the bumps is 50 μm or less. Further, in the semiconductor wafer on which the scribe line is formed, it means the distance from the deepest part described above to the back surface.
＜中間樹脂層＞
本発明の半導体ウェハ表面保護用粘着テープは、中間樹脂層を必須とする。表面保護テープを、半導体ウェハ表面に４０～９０℃の温度条件で加熱貼合することにより中間樹脂層が溶融し、２０μｍ以上の凹凸差を有する半導体ウェハの表面の形状に対して粘着剤層及び中間樹脂層の形状が追従する。さらに貼合後は冷却されるため、粘着剤層が半導体ウェハの表面に密着した状態で表面保護テープが固定されることでダスト侵入等を抑制することができる。本発明の表面保護テープに用いられる中間樹脂層を構成する樹脂の融点若しくはビカット軟化点は、４０℃～９０℃の範囲であって、より好ましくは６０℃～８０℃の範囲である。表面保護テープを４０℃～９０℃の範囲で加熱貼合し、粘着剤層を半導体ウェハの表面に密着させる必要があるため、この温度範囲で中間樹脂層の引張り弾性率が大きく変化する必要がある。すなわち、半導体ウェハ研削時は通常の温度であり、この温度において樹脂が流動してしまうと研削の際の厚み精度が極端に悪化するため高弾性であることが好ましい。一方、加熱貼合する際に半導体ウェハの表面に十分に追従させるためには低弾性である必要があることから、中間樹脂層には相反する性能が求められる。この相反する性能を実現するため、引張り弾性率及び流動性に大きく影響する融点若しくはビカット軟化点が４０～９０℃である必要がある。融点及びビカット軟化点は、実施例に記載の方法で測定される。本発明において中間樹脂層は、融点若しくはビカット軟化点の両方が４０～９０℃であることも好ましい。
中間樹脂層を構成する樹脂の融点及びビカット軟化点が４０℃未満である場合、成形することが困難であり、また厚み精度も悪化してしまう。すなわち、中間樹脂層の厚みが不均一になってしまう。一方、中間樹脂層を構成する樹脂の融点及びビカット軟化点が９０℃を超える場合、４０～９０℃の条件で加熱貼合しても半導体ウェハの表面の形状に対して十分に追従しないため、ダスト侵入やウェハ割れが生じやすくなる。<Intermediate resin layer>
The adhesive tape for protecting the surface of the semiconductor wafer of the present invention requires an intermediate resin layer. The intermediate resin layer is melted by heat-bonding the surface protective tape to the surface of the semiconductor wafer under a temperature condition of 40 to 90 ° C. The shape of the intermediate resin layer follows. Further, since it is cooled after bonding, the surface protective tape is fixed in a state where the adhesive layer is in close contact with the surface of the semiconductor wafer, so that dust intrusion and the like can be suppressed. The melting point or the Vicat softening point of the resin constituting the intermediate resin layer used in the surface protective tape of the present invention is in the range of 40 ° C. to 90 ° C., more preferably in the range of 60 ° C. to 80 ° C. Since it is necessary to heat and bond the surface protective tape in the range of 40 ° C to 90 ° C to bring the pressure-sensitive adhesive layer into close contact with the surface of the semiconductor wafer, the tensile elastic modulus of the intermediate resin layer needs to change significantly in this temperature range. be. That is, it is a normal temperature when grinding a semiconductor wafer, and if the resin flows at this temperature, the thickness accuracy at the time of grinding is extremely deteriorated, so that it is preferable to have high elasticity. On the other hand, since it is necessary to have low elasticity in order to sufficiently follow the surface of the semiconductor wafer during heat bonding, the intermediate resin layer is required to have contradictory performance. In order to realize this contradictory performance, it is necessary that the melting point or the Vicat softening point, which greatly affects the tensile elastic modulus and the fluidity, is 40 to 90 ° C. The melting point and the Vicat softening point are measured by the methods described in the Examples. In the present invention, it is also preferable that the intermediate resin layer has both a melting point and a Vicat softening point of 40 to 90 ° C.
When the melting point and the bicut softening point of the resin constituting the intermediate resin layer are less than 40 ° C., molding is difficult and the thickness accuracy is deteriorated. That is, the thickness of the intermediate resin layer becomes non-uniform. On the other hand, when the melting point and the bicut softening point of the resin constituting the intermediate resin layer exceed 90 ° C., even if they are heat-bonded under the condition of 40 to 90 ° C., they do not sufficiently follow the shape of the surface of the semiconductor wafer. Dust intrusion and wafer cracking are likely to occur.
本発明の表面保護テープに用いられる中間樹脂層を構成する樹脂は、融点若しくはビカット軟化点が４０～９０℃であり、さらに、メルトマスフローレート（ＭＦＲ）が１０ｇ／１０ｍｉｎ～１００ｇ／１０ｍｉｎである。融点又はビカット軟化点が上記範囲内にある中間樹脂層は、前述の通り、表面保護テープを４０～９０℃の条件で半導体ウェハに貼合すると、半導体ウェハの表面の形状に対して中間樹脂層及び粘着剤層の形状が追従する。その結果、粘着剤層が半導体ウェハ表面に十分に密着する。しかし、中間樹脂層を構成する樹脂の融点又はビカット軟化点が上記範囲内にあるだけでは、半導体ウェハの凹凸差が２５０μｍ以上となると表面保護テープ自体が凹凸状に変形し、搬送エラーを誘発する。ＭＦＲを１０ｇ／１０ｍｉｎ～１００ｇ／１０ｍｉｎの範囲とすることにより加熱貼合時の中間樹脂層に適度な流動性が生まれ、凹凸に追従し変形した表面保護テープを平らな状態へ戻すことができる。これにより、搬送エラー及び半導体ウェハの落下による破損を防ぐことができる。中間樹脂層のメルトマスフローレート（ＭＦＲ）が１０ｇ／１０ｍｉｎ未満であると、流動性が不足し、表面保護テープ自体が変形したままの状態で加工されるため、搬送エラーや半導体ウェハの破損が発生してしまう。一方、中間樹脂層を構成する樹脂のメルトマスフローレート（ＭＦＲ）が１００ｇ／１０ｍｉｎを超えると、基材としての厚み精度（厚みの均一性）を維持したままの製膜が困難となってしまう。また、研削後の半導体ウェハの厚み精度も悪化する。本発明の表面保護テープは、中間樹脂層を構成する樹脂の融点又はビカット軟化点が上記範囲内にあり、さらに、ＭＦＲが１０ｇ／１０ｍｉｎ～１００ｇ／１０ｍｉｎの範囲にあることにより、半導体ウェハの凹凸差が２５０μｍ以上の半導体ウェハの加工にも適用することができる。本発明の表面保護テープを適用することができる半導体ウェハの凹凸差の上限は、３００μｍ以下であることが実際的である。
なお、ＭＦＲは、実施例に記載の方法で測定される。
The resin constituting the intermediate resin layer used in the surface protective tape of the present invention has a melting point or a Vicat softening point of 40 to 90 ° C., and has a melt mass flow rate (MFR) of 10 g / 10 min to 100 g / 10 min. be. As described above, the intermediate resin layer having the melting point or the Vicat softening point within the above range is an intermediate resin layer with respect to the shape of the surface of the semiconductor wafer when the surface protective tape is attached to the semiconductor wafer under the condition of 40 to 90 ° C. And the shape of the pressure-sensitive adhesive layer follows. As a result, the pressure-sensitive adhesive layer is sufficiently adhered to the surface of the semiconductor wafer. However, if the melting point or the Vicat softening point of the resin constituting the intermediate resin layer is only within the above range, the surface protective tape itself is deformed into an uneven shape when the unevenness difference of the semiconductor wafer is 250 μm or more, which induces a transfer error. .. By setting the MFR in the range of 10 g / 10 min to 100 g / 10 min, appropriate fluidity is created in the intermediate resin layer during heat bonding, and it is possible to return the deformed surface protective tape to a flat state by following the unevenness. can. This makes it possible to prevent damage due to transfer errors and dropping of the semiconductor wafer. If the melt mass flow rate (MFR) of the intermediate resin layer is less than 10 g / 10 min, the fluidity will be insufficient and the surface protection tape itself will be processed in a deformed state, resulting in transfer errors and damage to the semiconductor wafer. It will occur. On the other hand, if the melt mass flow rate (MFR) of the resin constituting the intermediate resin layer exceeds 100 g / 10 min, it becomes difficult to form a film while maintaining the thickness accuracy (thickness uniformity) of the base material. .. In addition, the thickness accuracy of the semiconductor wafer after grinding also deteriorates. The surface protective tape of the present invention has a melting point or a Vicat softening point of the resin constituting the intermediate resin layer within the above range, and further, the MFR is in the range of 10 g / 10 min to 100 g / 10 min, so that the semiconductor wafer It can also be applied to the processing of semiconductor wafers having an unevenness difference of 250 μm or more. It is practical that the upper limit of the unevenness difference of the semiconductor wafer to which the surface protective tape of the present invention can be applied is 300 μm or less.
The MFR is measured by the method described in Examples.
中間樹脂層は粘着することを目的とするものでないため、非粘着性が好ましい。非粘着性とは常温においてべたつきが無い状態をいう。
このような樹脂層もしくは樹脂フィルムを構成する樹脂として、例えば、ラジカル重合性酸コモノマー、アクリル酸エステルコモノマー、メタクリル酸エステルコモノマー及びカルボン酸ビニルエステルコモノマーから選択される少なくとも１種のコモノマーと、エチレンとの共重合体であるエチレン系共重合体からなる樹脂、アイオノマー等のエチレン性不飽和基を含むモノマーの単独重合体または共重合体からなる樹脂、ポリエチレン（例えば、低密度ポリエチレン）からなる樹脂が挙げられる。本発明の表面保護テープに用いられる中間樹脂層には、これらの樹脂を１種単独で用いてもよく、２種以上組み合わせて用いてもよい。また、上記中間樹脂層は２層以上有してもよい。Since the intermediate resin layer is not intended to be adhesive, non-adhesive is preferable. Non-adhesive refers to a state in which there is no stickiness at room temperature.
Examples of the resin constituting such a resin layer or resin film include at least one comonomer selected from a radically polymerizable acid comonomer, an acrylic acid ester comonomer, a methacrylic acid ester comonomer, and a carboxylic acid vinyl ester comonomer, and ethylene. A resin made of an ethylene-based copolymer which is a copolymer of the above, a homopolymer of a monomer containing an ethylenically unsaturated group such as ionomer, a resin made of a copolymer, and a resin made of polyethylene (for example, low-density polyethylene). Can be mentioned. In the intermediate resin layer used for the surface protective tape of the present invention, these resins may be used alone or in combination of two or more. Further, the intermediate resin layer may have two or more layers.
上記ラジカル重合性酸コモノマーとしては、具体的には、マレイン酸、フマル酸、シトラコン酸、イタコン酸等のα，β－不飽和ジカルボン酸またはこれらの無水物、アクリル酸、メタクリル酸、クロトン酸、ビニル酢酸、ペンテン酸等の不飽和モノカルボン酸等が挙げられ、中でも無水マレイン酸、アクリル酸、メタクリル酸が好ましい。
上記アクリル酸エステルコモノマーとしては、具体的には、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル等が挙げられ、中でもアクリル酸メチル、アクリル酸エチル、アクリル酸ブチルが好ましい。Specific examples of the radically polymerizable acid comonomer include α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid, or anhydrides thereof, acrylic acid, methacrylic acid, and crotonic acid. Examples thereof include unsaturated monocarboxylic acids such as vinylacetic acid and pentenic acid, and among them, maleic anhydride, acrylic acid and methacrylic acid are preferable.
Specific examples of the acrylate comonomer include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, with methyl acrylate, ethyl acrylate, and butyl acrylate being preferred.
上記メタクリル酸エステルコモノマーとしては、具体的には、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル等が挙げられ、中でもメタクリル酸メチル、メタクリル酸エチルが好ましい。
上記カルボン酸ビニルエステルコモノマーとしては、具体的には、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル等が挙げられ、中でも酢酸ビニルが好ましい。Specific examples of the methacrylic acid ester comonomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like, with methyl methacrylate and ethyl methacrylate being preferred.
Specific examples of the carboxylic acid vinyl ester comonomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and the like, with vinyl acetate being preferred.
エチレン系共重合体の具体例としては、二元系共重合体として、例えば、エチレン－アクリル酸共重合体、エチレン－メタクリル酸共重合体、エチレン－無水マレイン酸共重合体、エチレン－アクリル酸メチル共重合体、エチレン－アクリル酸エチル共重合体、エチレン－メタクリル酸メチル共重合体、エチレン－メタクリル酸エチル共重合体、エチレン－酢酸ビニル共重合体が挙げられる。
三元系共重合体として、例えば、エチレン－アクリル酸－アクリル酸メチル共重合体、エチレン－アクリル酸－アクリル酸エチル共重合体、エチレン－アクリル酸－酢酸ビニル共重合体、エチレン－メタクリル酸－メタクリル酸メチル共重合体、エチレン－メタクリル酸－メタクリル酸エチル共重合体、エチレン－メタクリル酸－酢酸ビニル共重合体、エチレン－無水マレイン酸－アクリル酸メチル共重合体、エチレン－無水マレイン酸－アクリル酸エチル共重合体、エチレン－無水マレイン酸－メタクリル酸メチル共重合体、エチレン－無水マレイン酸－メタクリル酸エチル共重合体、エチレン－無水マレイン酸－酢酸ビニル共重合体が挙げられる。
さらに、上記のコモノマーを組み合わせた多元系の共重合体も挙げられる。
上記共重合体の中でも、特に、エチレン－アクリル酸共重合体、エチレン－メタクリル酸共重合体、エチレン－アクリル酸メチル共重合体、エチレン－アクリル酸エチル共重合体、エチレン－アクリル酸ブチル共重合体、エチレン－無水マレイン酸－アクリル酸メチル共重合体、エチレン－無水マレイン酸－アクリル酸エチル共重合体、エチレン－無水マレイン酸－メタクリル酸メチル共重合体及びエチレン－無水マレイン酸－メタクリル酸エチル共重合体が好ましく、エチレン－アクリル酸メチル共重合体、エチレン－アクリル酸エチル共重合体及びエチレン－アクリル酸ブチル共重合体が好ましい。Specific examples of the ethylene-based copolymer include, as binary copolymers, for example, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-maleic anhydride copolymer, and an ethylene-acrylic acid. Examples thereof include a methyl copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-ethyl methacrylate copolymer, and an ethylene-vinyl acetate copolymer.
Examples of the ternary copolymer include ethylene-acrylic acid-methyl acrylate copolymer, ethylene-acrylic acid-ethyl acrylate copolymer, ethylene-acrylic acid-vinyl acetate copolymer, and ethylene-methacrylic acid-. Methyl methacrylate copolymer, ethylene-methacrylic acid-ethyl methacrylate copolymer, ethylene-methacrylic acid-vinyl acetate copolymer, ethylene-maleic anhydride-methyl acrylate copolymer, ethylene-maleic anhydride-acrylic anhydride Examples thereof include ethyl acid copolymer, ethylene-maleic anhydride-methyl methacrylate copolymer, ethylene-maleic anhydride-ethyl methacrylate copolymer, and ethylene-maleic anhydride-vinyl acetate copolymer.
Further, a multidimensional copolymer in which the above comonomer is combined can also be mentioned.
Among the above copolymers, in particular, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-butyl acrylate copolymer. Combined, ethylene-maleic anhydride-methyl acrylate copolymer, ethylene-maleic anhydride-ethyl acrylate copolymer, ethylene-maleic anhydride-methyl methacrylate copolymer and ethylene-maleic anhydride-ethyl methacrylate Copolymers are preferred, and ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers and ethylene-butyl acrylate copolymers are preferred.
エチレン系共重合体の合成に用いられるエチレンとコモノマ―との合計質量中、コモノマーの割合は１０質量％～５０質量％が好ましく、１５質量％～４０質量％が更に好ましい。
中間樹脂層は、上述のように単層でもよく、複層であっても良い。製造性の点から、複層の方が単層に比べてフィルム化が容易である。複層にした場合、基材フィルム側の層は低密度ポリエチレン若しくはエチレン－酢酸ビニル共重合体からなる樹脂層ないし樹脂フィルムであることが好ましく、押し出しにより複層の中間樹脂層の製膜の際に不良率を低下させることができ且つ安価に製造することができる。中間樹脂層が複層である場合の融点ないしビカット軟化点は、粘着剤層と接している層またはフィルムを構成する樹脂の融点ないしビカット軟化点を示す。
樹脂層もしくは樹脂フィルムの積層方法は、樹脂層もしくは樹脂フィルムの厚みの精度や、該樹脂層もしくは樹脂フィルムに欠陥に影響を及ぼさない範囲であれば、特に制限されるものではない。例えば、共押出による製膜や接着剤による貼り合わせなどが挙げられる。The proportion of the comonomer in the total mass of ethylene and comomomer used for synthesizing the ethylene-based copolymer is preferably 10% by mass to 50% by mass, more preferably 15% by mass to 40% by mass.
The intermediate resin layer may be a single layer or a plurality of layers as described above. From the viewpoint of manufacturability, the multi-layer is easier to form into a film than the single layer. In the case of a multi-layer, the layer on the base film side is preferably a resin layer or a resin film made of low-density polyethylene or an ethylene-vinyl acetate copolymer, and when the intermediate resin layer of the multi-layer is formed by extrusion. The defect rate can be reduced and the product can be manufactured at low cost. The melting point or Vicat softening point when the intermediate resin layer is a plurality of layers indicates the melting point or Vicat softening point of the resin constituting the layer or film in contact with the pressure-sensitive adhesive layer.
The method for laminating the resin layer or the resin film is not particularly limited as long as it does not affect the accuracy of the thickness of the resin layer or the resin film and the defects in the resin layer or the resin film. For example, film formation by coextrusion and bonding with an adhesive can be mentioned.
基材フィルムの厚みと中間樹脂層の厚みとの比は、基材フィルムの厚み：中間樹脂層の厚み＝０．５：９．５～３：７の範囲であることが、粘着剤層及び中間樹脂層の半導体ウェハの表面形状に対する追従性の点から好ましい。基材フィルムと中間樹脂層の積層方法は、一体となったフィルムの欠陥に影響を及ぼさなければ特に制限されるものではなく、共押出しによる製膜や接着剤による貼り合わせが可能である。 The ratio of the thickness of the base film to the thickness of the intermediate resin layer should be in the range of the thickness of the base film: the thickness of the intermediate resin layer = 0.5: 9.5 to 3: 7. It is preferable from the viewpoint of followability to the surface shape of the semiconductor wafer of the intermediate resin layer. The method of laminating the base film and the intermediate resin layer is not particularly limited as long as it does not affect the defects of the integrated film, and film formation by coextrusion or bonding by an adhesive is possible.
本発明の表面保護テープに用いられる中間樹脂層の厚みは半導体ウェハの凹凸差以上が必要であるが、製造性や厚み精度の点から１００μｍ～４００μｍであることが好ましい。半導体ウェハの凹凸差よりも薄いと、粘着剤層が半導体ウェハに十分に密着しないためダスト侵入やウェハ割れが発生する。本発明の表面保護テープに用いられる中間樹脂層の厚みは、半導体ウェハの凹凸差よりも１０μｍ～３０μｍ厚いことが好ましい。中間樹脂層が厚すぎると、半導体ウェハの厚み精度が悪化する恐れがあり、また製造コストも増加する。また、バンプ付き半導体ウェハのバンプ部分を製造する際、１０μｍ程度の誤差が生じるため、平均バンプ高さに加えて１０μｍの厚みがあると余裕をもって追従することが可能となる。 The thickness of the intermediate resin layer used for the surface protective tape of the present invention needs to be greater than or equal to the unevenness difference of the semiconductor wafer, but is preferably 100 μm to 400 μm from the viewpoint of manufacturability and thickness accuracy. If it is thinner than the unevenness difference of the semiconductor wafer, the adhesive layer does not sufficiently adhere to the semiconductor wafer, so that dust intrusion and wafer cracking occur. The thickness of the intermediate resin layer used for the surface protective tape of the present invention is preferably 10 μm to 30 μm thicker than the unevenness difference of the semiconductor wafer. If the intermediate resin layer is too thick, the thickness accuracy of the semiconductor wafer may deteriorate, and the manufacturing cost also increases. Further, when manufacturing the bump portion of the semiconductor wafer with bumps, an error of about 10 μm occurs, so that if there is a thickness of 10 μm in addition to the average bump height, it is possible to follow with a margin.
＜粘着剤層＞
本発明の表面保護テープが有する粘着剤層に用いられる粘着剤は、特に制限されないが、放射線硬化型粘着剤が好ましい。
放射線硬化型粘着剤は、放射線により硬化し三次元網状化する性質を有すればよく、大きく分けて、１）側鎖にエチレン性不飽和基（放射線重合性炭素－炭素二重結合でエチレン性二重結合とも称す）を有するベース樹脂（重合体）からなる粘着剤と、２）通常のゴム系あるいは（メタ）アクリル系のベース樹脂（ポリマー）に対して、分子中に少なくとも２個のエチレン性不飽和基を有する低分子量化合物（以下、放射線重合性低分子量化合物という）および光重合開始剤を配合する粘着剤に分類される。
本発明の表面保護テープでは、上記の２）が好ましい。<Adhesive layer>
The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer of the surface protective tape of the present invention is not particularly limited, but a radiation-curable pressure-sensitive adhesive is preferable.
The radiation-curable pressure-sensitive adhesive may have the property of being cured by radiation to form a three-dimensional network. A pressure-sensitive adhesive made of a base resin (polymer) having a double bond) and 2) at least two ethylenes in the molecule with respect to a normal rubber-based or (meth) acrylic-based base resin (polymer). It is classified into a pressure-sensitive adhesive containing a low molecular weight compound having a sex unsaturated group (hereinafter referred to as a radiopolymerizable low molecular weight compound) and a photopolymerization initiator.
In the surface protection tape of the present invention, the above 2) is preferable.
１）側鎖にエチレン性不飽和基を有するベース樹脂からなる粘着剤
側鎖にエチレン性不飽和基を有する粘着剤は、（メタ）アクリル系粘着剤が好ましく、ベース樹脂が（メタ）アクリル重合体もしくは（メタ）アクリル重合体を主成分として含むものがより好ましい。
ここで、「（メタ）アクリル重合体を主成分として含む」とは、ベース樹脂を構成する重合体ないし樹脂のうち、（メタ）アクリル系重合体の含有量が少なくとも５０質量％以上であり、好ましくは８０質量％以上（１００質量％以下）であることを意味する。1) Adhesive made of a base resin having an ethylenically unsaturated group in the side chain The pressure-sensitive adhesive having an ethylenically unsaturated group in the side chain is preferably a (meth) acrylic pressure-sensitive adhesive, and the base resin is a (meth) acrylic weight. It is more preferable to use a combined or (meth) acrylic polymer as a main component.
Here, "containing a (meth) acrylic polymer as a main component" means that the content of the (meth) acrylic polymer among the polymers or resins constituting the base resin is at least 50% by mass or more. It means that it is preferably 80% by mass or more (100% by mass or less).
（メタ）アクリル重合体は、少なくとも側鎖にエチレン性不飽和基を有することで放射線照射による硬化が可能となる。（メタ）アクリル重合体は、さらにエポキシ基やカルボキシ基などの官能基を有してもよい。 The (meth) acrylic polymer has an ethylenically unsaturated group at least in the side chain, so that it can be cured by irradiation. The (meth) acrylic polymer may further have a functional group such as an epoxy group or a carboxy group.
側鎖にエチレン性不飽和基を有する（メタ）アクリル重合体は、どのようにして製造されたものでもよいが、例えば、側鎖に官能基（α）を有する（メタ）アクリル重合体と、（メタ）アクリルロイル基、（メタ）アクリルロイルオキシ基などのエチレン性不飽和基を有する基を有し、かつ、この（メタ）アクリル重合体の側鎖の官能基（α）と反応し得る官能基（β）をもつ化合物とを反応させて得たものが好ましい。
エチレン性不飽和基を有する基は、非芳香族性のエチレン性二重結合を有すればどのような基でも構わないが、（メタ）アクリロイル基、（メタ）アクリロイルオキシ基、（メタ）アクリロイルアミノ基、アリル基、１－プロペニル基、ビニル基（スチレンもしくは置換スチレンを含む）が好ましく、（メタ）アクリロイル基、（メタ）アクリロイルオキシ基がより好ましい。
官能基（α）、（β）としては、カルボキシ基、水酸基、アミノ基、スルファニル基、環状酸無水物基、エポキシ基、イソシアネート基（－Ｎ＝Ｃ＝Ｏ）等が挙げられる。The (meth) acrylic polymer having an ethylenically unsaturated group in the side chain may be produced in any way, and for example, a (meth) acrylic polymer having a functional group (α) in the side chain may be used. It has a group having an ethylenically unsaturated group such as a (meth) acrylic loyl group and a (meth) acrylic loyloxy group, and can react with the functional group (α) of the side chain of this (meth) acrylic polymer. Those obtained by reacting with a compound having a functional group (β) are preferable.
The group having an ethylenically unsaturated group may be any group as long as it has a non-aromatic ethylenic double bond, but it may be a (meth) acryloyl group, a (meth) acryloyloxy group, or a (meth) acryloyl. Amino group, allyl group, 1-propenyl group and vinyl group (including styrene or substituted styrene) are preferable, and (meth) acryloyl group and (meth) acryloyloxy group are more preferable.
Examples of the functional group (α) and (β) include a carboxy group, a hydroxyl group, an amino group, a sulfanyl group, a cyclic acid anhydride group, an epoxy group, an isocyanate group (—N = C = O) and the like.
ここで、官能基（α）と官能基（β）のうちの一方の官能基が、カルボキシ基、水酸基、アミノ基、スルファニル基、または環状酸無水物基である場合には、他方の官能基は、エポキシ基、イソシアネート基が挙げられる。一方の官能基が環状酸無水物基の場合、他方の官能基はカルボキシ基、水酸基、アミノ基、スルファニル基が挙げられる。なお、一方の官能基が、エポキシ基である場合は、他方の官能基はエポキシ基であってもよい。 Here, when one of the functional group (α) and the functional group (β) is a carboxy group, a hydroxyl group, an amino group, a sulfanyl group, or a cyclic acid anhydride group, the other functional group is used. Examples include an epoxy group and an isocyanate group. When one functional group is a cyclic acid anhydride group, the other functional group may be a carboxy group, a hydroxyl group, an amino group or a sulfanyl group. When one functional group is an epoxy group, the other functional group may be an epoxy group.
官能基（α）としては、カルボキシ基、水酸基が好ましく、水酸基が特に好ましい。
側鎖に官能基（α）を有する（メタ）アクリル系重合体は、官能基（α）を有する（メタ）アクリル系モノマー、好ましくは（メタ）アクリル酸エステル〔特に、アルコール部に官能基（α）を有するもの〕をモノマー成分に使用することで得ることができる。
側鎖に官能基（α）を有する（メタ）アクリル系重合体は、共重合体である場合が好ましく、この共重合成分は、（メタ）アクリル酸アルキルエステル、なかでもアルコール部に官能基（α）やエチレン性不飽和基を有する基が置換していない（メタ）アクリル酸アルキルエステルが好ましい。As the functional group (α), a carboxy group and a hydroxyl group are preferable, and a hydroxyl group is particularly preferable.
The (meth) acrylic polymer having a functional group (α) in the side chain is a (meth) acrylic monomer having a functional group (α), preferably a (meth) acrylic acid ester [particularly, a functional group (particularly, a functional group in the alcohol portion). Those having α)] can be obtained by using the monomer component.
The (meth) acrylic polymer having a functional group (α) in the side chain is preferably a copolymer, and this copolymer component is a (meth) acrylic acid alkyl ester, particularly a functional group (in particular, the alcohol portion). A (meth) acrylic acid alkyl ester in which α) or a group having an ethylenically unsaturated group is not substituted is preferable.
（メタ）アクリル酸エステルとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート及びドデシル（メタ）アクリレート、デシル（メタ）アクリレートヘキシルアクリレートが挙げられる。
（メタ）アクリル酸エステルは１種単独で用いてもよく２種以上を組み合わせて用いてもよく、アルコール部の炭素数が５以下のものと炭素数が６～１２のものを併用することが好ましい。Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth). ) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and dodecyl (meth) acrylate, decyl (meth) acrylate hexyl acrylate.
The (meth) acrylic acid ester may be used alone or in combination of two or more, and the alcohol portion having 5 or less carbon atoms and 6 to 12 carbon atoms may be used in combination. preferable.
なお、アルコール部の炭素数の大きなモノマーを使用するほどガラス転移点（Ｔｇ）は低くなるので、所望のガラス転移点のものを得ることができる。また、ガラス転移点の他、相溶性と各種性能を上げる目的で酢酸ビニル、スチレン、アクリロニトリルなどの炭素－炭素二重結合をもつ低分子化合物を配合することも好ましく、この場合、これらのモノマー成分の含有量は５質量％以下の範囲内が好ましい。 Since the glass transition point (Tg) becomes lower as the monomer having a larger carbon number in the alcohol portion is used, a desired glass transition point can be obtained. In addition to the glass transition point, it is also preferable to blend a low molecular weight compound having a carbon-carbon double bond such as vinyl acetate, styrene, and acrylonitrile for the purpose of improving compatibility and various performances. In this case, these monomer components are also preferable. The content of the above is preferably in the range of 5% by mass or less.
官能基（α）を有する（メタ）アクリル系モノマーとしては、アクリル酸、メタクリル酸、けい皮酸、イタコン酸、フマル酸、フタル酸、２－ヒドロキシアルキルアクリレート類、２－ヒドロキシアルキルメタクリレート類、グリコールモノアクリレート類、グリコールモノメタクリレート類、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド、アリルアルコール、Ｎ－アルキルアミノエチルアクリレート類、Ｎ－アルキルアミノエチルメタクリレート類、アクリルアミド類、メタクリルアミド類、無水マレイン酸、無水イタコン酸、無水フマル酸、無水フタル酸、グリシジルアクリレート、グリシジルメタクリレート、アリルグリシジルエーテル、ポリイソシアネート化合物のイソシアネート基の一部を水酸基またはカルボキシ基およびエチレン性不飽和基を有する単量体でウレタン化したものなどが挙げられる。 Examples of the (meth) acrylic monomer having a functional group (α) include acrylic acid, methacrylic acid, carcinous acid, itaconic acid, fumaric acid, phthalic acid, 2-hydroxyalkyl acrylates, 2-hydroxyalkyl methacrylates, and glycol. Monoacrylates, glycol monomethacrylates, N-methylolacrylamides, N-methylolmethacrylicamides, allyl alcohols, N-alkylaminoethylacrylates, N-alkylaminoethylmethacrylates, acrylamides, methacrylates, maleic anhydride, Urethane of some of the isocyanate groups of itaconic anhydride, fumaric anhydride, phthalic anhydride, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and polyisocyanate compound with a hydroxyl group or a monomer having a carboxy group and an ethylenically unsaturated group. And so on.
これらの中でも、アクリル酸、メタクリル酸、２－ヒドロキシアルキルアクリレート類、２－ヒドロキシアルキルメタクリレート類、グリシジルアクリレート、グリシジルメタクリレートが好ましく、アクリル酸、メタクリル酸、２－ヒドロキシアルキルアクリレート類、２－ヒドロキシアルキルメタクリレート類がより好ましく、メタクリル酸、２－ヒドロキシアルキルアクリレート類、２－ヒドロキシアルキルメタクリレート類がさらに好ましい。 Among these, acrylic acid, methacrylic acid, 2-hydroxyalkyl acrylates, 2-hydroxyalkyl methacrylates, glycidyl acrylates and glycidyl methacrylates are preferable, and acrylic acid, methacrylic acid, 2-hydroxyalkyl acrylates and 2-hydroxyalkyl methacrylates are preferable. Classes are more preferable, and methacrylic acid, 2-hydroxyalkyl acrylates, and 2-hydroxyalkyl methacrylates are even more preferable.
エチレン性不飽和基と官能基（β）を有する化合物における官能基（β）としては、イソシアネート基が好ましく、例えば、アルコール部にイソシアネート（－Ｎ＝Ｃ＝Ｏ）基を有する（メタ）アクリル酸エステルが挙げられ、なかでもイソシアネート（－Ｎ＝Ｃ＝Ｏ）基で置換された（メタ）アクリル酸アルキルエステルが好ましい。このようなモノマーとしては、例えば、２－イソシアナトエチルメタクリレート、２－イソシアナトエチルアクリレート等が挙げられる。
また、官能基（β）がイソシアネート基以外の場合の好ましい化合物は、官能基（α）を有する（メタ）アクリル系モノマーで例示した化合物が挙げられる。As the functional group (β) in the compound having an ethylenically unsaturated group and a functional group (β), an isocyanate group is preferable, and for example, a (meth) acrylic acid having an isocyanate (-N = C = O) group in the alcohol portion. Examples thereof include ester, and among them, (meth) acrylic acid alkyl ester substituted with an isocyanate (-N = C = O) group is preferable. Examples of such a monomer include 2-isocyanatoethyl methacrylate and 2-isocyanatoethyl acrylate.
Moreover, the preferable compound when the functional group (β) is other than the isocyanate group includes the compound exemplified by the (meth) acrylic monomer having a functional group (α).
エチレン性不飽和基と官能基（β）を有する化合物は、側鎖に官能基（α）を有する（メタ）アクリル系重合体に加えて重合体の側鎖の官能基（α）、好ましくは水酸基と反応することで共重合体に重合性基を組み込むことができ、放射線照射後の粘着力を低下させることができる。 The compound having an ethylenically unsaturated group and a functional group (β) is a functional group (α) on the side chain of the polymer in addition to the (meth) acrylic polymer having a functional group (α) on the side chain, preferably. By reacting with the hydroxyl group, a polymerizable group can be incorporated into the copolymer, and the adhesive strength after irradiation can be reduced.
（メタ）アクリル系共重合体の合成において、反応を溶液重合で行う場合の有機溶剤としては、ケトン系、エステル系、アルコール系、芳香族系のものを使用することができるが、中でもトルエン、酢酸エチル、イソプロピルアルコール、ベンゼンメチルセロソルブ、エチルセロソルブ、アセトン、メチルエチルケトンなどの、一般に（メタ）アクリル系ポリマーの良溶媒で、沸点６０～１２０℃の溶剤が好ましい。重合開始剤としては、α，α’－アゾビスイソブチロニトリルなどのアゾビス系、ベンゾイルペルオキシドなどの有機過酸化物系などのラジカル発生剤を通常用いる。この際、必要に応じて触媒、重合禁止剤を併用することができ、重合温度および重合時間を調節することにより、所望の分子量の（メタ）アクリル系共重合体を得ることができる。また、分子量を調節することに関しては、メルカプタン、四塩化炭素等の溶剤を用いることが好ましい。なお、この反応は溶液重合に限定されるものではなく、塊状重合、懸濁重合など別の方法でもさしつかえない。 In the synthesis of the (meth) acrylic copolymer, a ketone-based, ester-based, alcohol-based, or aromatic-based solvent can be used as the organic solvent when the reaction is carried out by solution polymerization. Among them, toluene and Generally, it is a good solvent for (meth) acrylic polymers such as ethyl acetate, isopropyl alcohol, benzenemethyl cellosolve, ethyl cellosolve, acetone and methyl ethyl ketone, and a solvent having a boiling point of 60 to 120 ° C. is preferable. As the polymerization initiator, radical generators such as azobis-based agents such as α, α'-azobisisobutyronitrile and organic peroxide-based agents such as benzoyl peroxide are usually used. At this time, a catalyst and a polymerization inhibitor can be used in combination as needed, and a (meth) acrylic copolymer having a desired molecular weight can be obtained by adjusting the polymerization temperature and the polymerization time. Further, regarding the adjustment of the molecular weight, it is preferable to use a solvent such as mercaptan or carbon tetrachloride. Note that this reaction is not limited to solution polymerization, and other methods such as bulk polymerization and suspension polymerization may be used.
側鎖にエチレン性不飽和基を有するベース樹脂〔好ましくは（メタ）アクリル系共重合体〕の質量平均分子量は、２０万～１００万程度が好ましい。
質量平均分子量が大きすぎると、放射線照射した場合に、放射線照射後の粘着剤の可撓性がなく、脆くなっているため、剥離時に半導体チップ面に糊残りを生じる。質量平均分子量が小さすぎると、放射線照射前の凝集力が小さく、粘着力が弱いため、ダイシング時に十分に半導体チップを保持することができず、チップ飛びが生じるおそれがある。また、放射線照射後も硬化が不十分で、剥離時に半導体チップ面に糊残りを生じる。これらを極力防止するためには、質量平均分子量が２０万以上であることが好ましい。
なお、本発明の説明において、質量平均分子量は、常法によるポリスチレン換算の質量平均分子量である。The mass average molecular weight of the base resin [preferably (meth) acrylic copolymer] having an ethylenically unsaturated group in the side chain is preferably about 200,000 to 1,000,000.
If the mass average molecular weight is too large, the pressure-sensitive adhesive after irradiation is not flexible and becomes brittle when irradiated, so that adhesive residue is generated on the surface of the semiconductor chip during peeling. If the mass average molecular weight is too small, the cohesive force before irradiation is small and the adhesive force is weak, so that the semiconductor chip cannot be sufficiently held during dicing, and chip skipping may occur. In addition, curing is insufficient even after irradiation, and adhesive residue is generated on the surface of the semiconductor chip during peeling. In order to prevent these as much as possible, it is preferable that the mass average molecular weight is 200,000 or more.
In the description of the present invention, the mass average molecular weight is the polystyrene-equivalent mass average molecular weight according to a conventional method.
側鎖にエチレン性不飽和基を有するベース樹脂のガラス転移点は、－７０～－１０℃が好ましく、－５０～－１０℃がより好ましい。ガラス転移点が低すぎると、粘着剤の流動性が高く糊残りの原因となってしまい、高すぎると流動性が不十分で半導体ウェハの裏面になじみにくく、半導体ウェハの研削加工時に研削水がウェハ表面に浸入する原因となってしまう。 The glass transition point of the base resin having an ethylenically unsaturated group in the side chain is preferably −70 to −10 ° C., more preferably −50 to −10 ° C. If the glass transition point is too low, the fluidity of the adhesive will be high and it will cause adhesive residue. It causes penetration into the wafer surface.
側鎖にエチレン性不飽和基を有するベース樹脂の酸価〔ベース樹脂１ｇ中に存在する遊離脂肪酸を中和するのに必要な水酸化カリウムのｍｇ数〕は、０．５～３０が好ましく、１～２０がより好ましい。
側鎖にエチレン性不飽和基を有するベース樹脂の水酸基価〔ベース樹脂１ｇをアセチル化させたとき、水酸基と結合した酢酸を中和するのに必要とする水酸化カリウムのｍｇ数〕は、５～１００が好ましく、１０～８０がより好ましい。
このようにすることで、さらに半導体ウェハ表面保護用粘着テープ剥離時の糊残り防止効果に優れる。The acid value of the base resin having an ethylenically unsaturated group in the side chain [the number of mg of potassium hydroxide required to neutralize the free fatty acid present in 1 g of the base resin] is preferably 0.5 to 30. 1 to 20 are more preferable.
The hydroxyl value of the base resin having an ethylenically unsaturated group in the side chain [the number of mg of potassium hydroxide required to neutralize acetic acid bonded to the hydroxyl group when 1 g of the base resin is acetylated] is 5. ~ 100 is preferable, and 10-80 is more preferable.
By doing so, the effect of preventing adhesive residue when the adhesive tape for protecting the surface of the semiconductor wafer is peeled off is further excellent.
なお、酸価や水酸基価の調製は、側鎖に官能基（α）を有する（メタ）アクリル系重合体と、エチレン性不飽和基を有し、かつ、この（メタ）アクリル系重合体の側鎖の官能基（α）と反応し得る官能基（β）をもつ化合物とを反応させる段階で、未反応の官能基を残すことにより所望のものに調製することができる。 The acid value and hydroxyl value are prepared for the (meth) acrylic polymer having a functional group (α) in the side chain and the (meth) acrylic polymer having an ethylenically unsaturated group. At the stage of reacting the functional group (α) of the side chain with the compound having a functional group (β) capable of reacting, the desired product can be prepared by leaving an unreacted functional group.
側鎖にエチレン性不飽和基を有するベース樹脂を放射線照射によって硬化させる場合には、必要に応じて、光重合開始剤、例えばイソプロピルベンゾインエーテル、イソブチルベンゾインエーテル、ベンゾフェノン、フェニルジメトキシアセチルベンゼン、ミヒラーズケトン、クロロチオキサントン、ドデシルチオキサントン、ジメチルチオキサントン、ジエチルチオキサントン、ベンジルジメチルケタール、α－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシメチルフェニルプロパン等を使用することができる。
これら光重合開始剤の配合量は、ベース樹脂１００質量部に対して０．０１～１０質量部が好ましく、０．０１～５質量部がより好ましい。配合量が少なすぎると反応が不十分であり、配合量が多すぎると低分子成分が増加することで汚染性に影響を与えることになる。When the base resin having an ethylenically unsaturated group in the side chain is cured by irradiation, a photopolymerization initiator such as isopropylbenzoin ether, isobutylbenzoin ether, benzophenone, phenyldimethoxyacetylbenzene, Michler's ketone, etc. Chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, benzyldimethylketal, α-hydroxycyclohexylphenylketone, 2-hydroxymethylphenylpropane and the like can be used.
The blending amount of these photopolymerization initiators is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the base resin. If the blending amount is too small, the reaction will be insufficient, and if the blending amount is too large, the amount of small molecule components will increase, which will affect the pollutability.
側鎖にエチレン性不飽和基を有するベース樹脂からなる粘着剤は、架橋剤を含有することが好ましい。
このような架橋剤は、どのようなものでも構わないが、ポリイソシアネート類、メラミン・ホルムアルデヒド樹脂およびエポキシ樹脂の群から選択される架橋剤が好ましい。
このなかでも、本発明の表面保護テープでは、ポリイソシアネート類が好ましい。The pressure-sensitive adhesive made of a base resin having an ethylenically unsaturated group in the side chain preferably contains a cross-linking agent.
Any such cross-linking agent may be used, but a cross-linking agent selected from the group of polyisocyanates, melamine / formaldehyde resins and epoxy resins is preferable.
Among these, polyisocyanates are preferable in the surface protective tape of the present invention.
ポリイソシアネート類としては、特に制限がなく、例えば、４，４’－ジフェニルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、４，４’－ジフェニルエーテルジイソシアネート、４，４’－〔２，２－ビス（４－フェノキシフェニル）プロパン〕ジイソシアネート等の芳香族イソシアネート、ヘキサメチレンジイソシアネート、２，２，４－トリメチル－ヘキサメチレンジイソシアネート、イソフォロンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、２，４’－ジシクロヘキシルメタンジイソシアネート、リジンジイソシアネート、リジントリイソシアネート等が挙げられる。具体的には、コロネートＬ（日本ポリウレタン株式会社製、商品名）等を用いることができる。 The polyisocyanates are not particularly limited, and are, for example, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-[2,2-bis (4). -Phenoxyphenyl) propane] Aromatic isocyanates such as diisocyanates, hexamethylene diisocyanates, 2,2,4-trimethyl-hexamethylene diisocyanates, isophorone diisocyanates, 4,4'-dicyclohexylmethane diisocyanates, 2,4'-dicyclohexylmethane diisocyanates , Lysine diisocyanate, lysine triisocyanate and the like. Specifically, Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name) and the like can be used.
メラミン・ホルムアルデヒド樹脂としては、具体的には、ニカラックＭＸ－４５（三和ケミカル社製、商品名）、メラン（日立化成工業社製、商品名）等を用いることができる。 As the melamine / formaldehyde resin, specifically, Nicarac MX-45 (manufactured by Sanwa Chemical Co., Ltd., trade name), Melan (manufactured by Hitachi Kasei Kogyo Co., Ltd., trade name) and the like can be used.
エポキシ樹脂としては、ＴＥＴＲＡＤ－Ｘ（三菱化学社製、商品名）等を用いることができる。 As the epoxy resin, TETRAD-X (manufactured by Mitsubishi Chemical Corporation, trade name) or the like can be used.
架橋剤の配合量は、ベース樹脂１００質量部に対して０．１～１０質量部が好ましく、１～１０質量部がより好ましい。
粘着剤塗布後に、架橋剤により、ベース樹脂が架橋構造を形成し、粘着剤の凝集力を向上させることができる。The blending amount of the cross-linking agent is preferably 0.1 to 10 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the base resin.
After the pressure-sensitive adhesive is applied, the cross-linking agent allows the base resin to form a cross-linked structure, and the cohesive force of the pressure-sensitive adhesive can be improved.
架橋剤の配合量が少なすぎると凝集力向上効果が十分でないため、粘着剤の流動性が高く糊残りの原因となってしまう。架橋剤の配合量が多すぎると粘着剤弾性率が高くなりすぎてしまい、半導体ウェハ表面を保護できなくなってしまう。 If the amount of the cross-linking agent is too small, the effect of improving the cohesive force is not sufficient, so that the fluidity of the pressure-sensitive adhesive is high and it causes adhesive residue. If the amount of the cross-linking agent is too large, the elastic modulus of the pressure-sensitive adhesive becomes too high, and the surface of the semiconductor wafer cannot be protected.
２）放射線重合性低分子量化合物を含む粘着剤
放射線重合性低分子量化合物を含む粘着剤の主成分としては、特に限定されるものではなく、粘着剤に使用される通常の塩素化ポリプロピレン樹脂、アクリル樹脂〔（メタ）アクリル樹脂〕、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂等を使用することができる。2) Adhesive containing a radiation-polymerizable low molecular weight compound The main component of the pressure-sensitive adhesive containing a radiation-polymerizable low molecular weight compound is not particularly limited, and is an ordinary chlorinated polypropylene resin or acrylic used for the pressure-sensitive adhesive. Resin [(meth) acrylic resin], polyester resin, polyurethane resin, epoxy resin and the like can be used.
本発明の表面保護テープでは、粘着剤のベース樹脂としては、アクリル樹脂〔（メタ）アクリル樹脂〕が好ましく、前述の側鎖にエチレン性不飽和基を有するベース樹脂を合成する際の原料である側鎖に官能基（α）を有する（メタ）アクリル系重合体が特に好ましい。
この場合の粘着剤としては、ベース樹脂としてのアクリル樹脂および放射線重合性低分子量化合物に加え、光重合開始剤、硬化剤ないし架橋剤等を適宜配合して粘着剤を調製するのが好ましい。In the surface protective tape of the present invention, an acrylic resin [(meth) acrylic resin] is preferable as the base resin for the pressure-sensitive adhesive, and it is a raw material for synthesizing the base resin having an ethylenically unsaturated group in the side chain described above. A (meth) acrylic polymer having a functional group (α) in the side chain is particularly preferable.
In this case, the pressure-sensitive adhesive is preferably prepared by appropriately blending an acrylic resin as a base resin, a radiation-polymerizable low molecular weight compound, a photopolymerization initiator, a curing agent, a cross-linking agent, and the like.
粘着剤のベース樹脂の質量平均分子量は、２０万～２００万程度が好ましい。
粘着剤は、ベース樹脂に加え、質量平均分子量が、１，０００～２０，０００のオリゴマーを少なくとも１種含むことが好ましい。オリゴマーの質量平均分子量は、１，１００～２０，０００がより好ましく、１，３００～２０，０００がさらに好ましく、１，５００～１０，０００が特に好ましい。The mass average molecular weight of the base resin of the pressure-sensitive adhesive is preferably about 200,000 to 2,000,000.
The pressure-sensitive adhesive preferably contains at least one oligomer having a mass average molecular weight of 1,000 to 20,000 in addition to the base resin. The mass average molecular weight of the oligomer is more preferably 1,100 to 20,000, further preferably 1,300 to 20,000, and particularly preferably 1,500 to 10,000.
放射線重合性低分子量化合物としては、放射線照射によって三次元網状化しうる、分子内にエチレン性不飽和基（放射線重合性炭素－炭素二重結合）を少なくとも２個以上有し、官能基（β）のうちの少なくとも１種（好ましくはヒドロキシ基）を有する低分子量化合物が用いられる。
特に、本発明の表面保護テープでは、上記のオリゴマーが、エチレン性不飽和基を有する放射線重合性低分子量化合物である場合が好ましい。The radiopolymerizable low molecular weight compound has at least two ethylenically unsaturated groups (radiopolymerizable carbon-carbon double bonds) in the molecule, which can be three-dimensionally networked by irradiation, and is a functional group (β). A low molecular weight compound having at least one of them (preferably a hydroxy group) is used.
In particular, in the surface protective tape of the present invention, it is preferable that the above oligomer is a radiation-polymerizable low molecular weight compound having an ethylenically unsaturated group.
放射線重合性低分子量化合物としては、具体的には、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールモノヒドロキシペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、１，４－ブチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレートや、オリゴエステル（メタ）アクリレート等の（メタ）アクリレート系化合物が適用可能である。 Specific examples of the radiopolymerizable low molecular weight compound include trimethylolpropanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol monohydroxypenta (meth) acrylate. Dipentaerythritol hexa (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoester (meth) acrylate, etc. A (meth) acrylate compound can be applied.
また、上記のような（メタ）アクリレート系化合物のほかに、放射線重合性低分子量化合物として、ウレタン（メタ）アクリレート系オリゴマーを用いることもできる。ウレタン（メタ）アクリレート系オリゴマーは、ポリエステル型またはポリエーテル型などのポリオール化合物と、多価イソシアナート化合物（例えば、２，４－トリレンジイソシアナート、２，６－トリレンジイソシアナート、１，３－キシリレンジイソシアナート、１，４－キシリレンジイソシアナート、ジフェニルメタン－４，４－ジイソシアナートなど）を反応させて得られる末端イソシアナートウレタンプレポリマーに、ヒドロキシ基を有する（メタ）アクリレート（例えば、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルアクリレート、２－ヒドロキシプロピルメタクリレート、ポリエチレングリコールアクリレート、ポリエチレングリコールメタクリレートなど）を反応させて得られる。
放射線重合性低分子量化合物は１種でも２種以上併用してもよい。Further, in addition to the (meth) acrylate-based compound as described above, a urethane (meth) acrylate-based oligomer can also be used as the radiation-polymerizable low molecular weight compound. Urethane (meth) acrylate-based oligomers include polyol compounds such as polyester type or polyether type and polyvalent isocyanate compounds (for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3). -A (meth) acrylate having a hydroxy group (for example,) is added to a terminal isocyanate urethane prepolymer obtained by reacting with xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4-diisocyanate, etc.). , 2-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, etc.).
The radiation-polymerizable low molecular weight compound may be used alone or in combination of two or more.
放射線硬化型粘着剤には、必要に応じて光重合開始剤を含むことができる。光重合開始剤には基材を透過する放射線により反応するものであれば、特に制限はなく、通常のものを用いることができる。例えば、ベンゾフェノン、４，４’－ジメチルアミノベンゾフェノン、４，４’－ジエチルアミノベンゾフェノン、４，４’－ジクロロベンゾフェノン等のベンゾフェノン類、アセトフェノン、ジエトキシアセトフェノン、フェニルジメトキシアセチルベンゼン等のアセトフェノン類、２－エチルアントラキノン、ｔ－ブチルアントラキノン等のアントラキノン類、２－クロロチオキサントン、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンジル、２，４，５－トリアリ－ルイミダゾール二量体（ロフィン二量体）、アクリジン系化合物、アシルフォスフィンオキサイド類、等を挙げることができ、これらは単独で、または２種以上を組み合わせて用いることができる。 The radiation-curable pressure-sensitive adhesive may contain a photopolymerization initiator, if necessary. The photopolymerization initiator is not particularly limited as long as it reacts with radiation transmitted through the substrate, and ordinary ones can be used. For example, benzophenones such as benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 4,4'-dichlorobenzophenone, acetophenone, diethoxyacetophenone, acetophenone such as phenyldimethoxyacetylbenzene, 2- Anthraquinones such as ethyl anthraquinone and t-butyl anthraquinone, 2-chlorothioxanthone, benzoin ethyl ether, benzoin isopropyl ether, benzyl, 2,4,5-triary-luimidazole dimer (lofin dimer), aclysine compound , Acylphosphinoxides, etc., which can be used alone or in combination of two or more.
光重合開始剤の添加量は、ベース樹脂１００質量部に対して０．１～１０質量部が好ましく、０．３～７．５質量部がより好ましく、０．５～５質量部がさらに好ましい。光重合開始剤の添加量が多すぎると放射線硬化が多地点で、かつ、急激に発生するため、放射線硬化収縮が大きくなってしまうため、従来の放射線硬化型の表面保護用粘着テープに比べ光重合開始剤の量を少なくすることも放射線硬化収縮の抑制の点から有用である。 The amount of the photopolymerization initiator added is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7.5 parts by mass, still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the base resin. .. If the amount of the photopolymerization initiator added is too large, radiation curing will occur at multiple points and rapidly, resulting in a large radiation curing shrinkage. Reducing the amount of the polymerization initiator is also useful from the viewpoint of suppressing radiation curing shrinkage.
粘着剤には硬化剤ないし架橋剤を含有することが好ましい。
硬化剤もしくは架橋剤としては、多価イソシアネート化合物、多価エポキシ化合物、多価アジリジン化合物、キレート化合物等を挙げることができる。The pressure-sensitive adhesive preferably contains a curing agent or a cross-linking agent.
Examples of the curing agent or cross-linking agent include a polyvalent isocyanate compound, a polyvalent epoxy compound, a polyvalent aziridine compound, and a chelate compound.
多価イソシアネート化合物としては、特に制限がなく、例えば、４，４’－ジフェニルメタンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、４，４’－ジフェニルエーテルジイソシアネート、４，４’－〔２，２－ビス（４－フェノキシフェニル）プロパン〕ジイソシアネート等の芳香族イソシアネート、ヘキサメチレンジイソシアネート、２，２，４－トリメチル－ヘキサメチレンジイソシアネート、イソフォロンジイソシアネート、４，４’－ジシクロヘキシルメタンジイソシアネート、２，４’－ジシクロヘキシルメタンジイソシアネート、リジンジイソシアネート、リジントリイソシアネート等が挙げられる。具体的には、コロネートＬ〔日本ポリウレタン工業（株）製、商品名〕等を用いることができる。 The polyvalent isocyanate compound is not particularly limited, and is, for example, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-[2,2-bis (2,2-bis). 4-Phenoxyphenyl) Propane] Aromatic isocyanate such as diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane Examples thereof include diisocyanate, lysine diisocyanate, and lysine triisocyanate. Specifically, Coronate L [manufactured by Nippon Polyurethane Industry Co., Ltd., trade name] and the like can be used.
多価エポキシ化合物としては、エポキシ樹脂が挙げられ、例えば、エチレングリコールジグリシジルエーテル、テレフタル酸ジグリシジルエステルアクリレート、Ｎ原子に２つのグリジジル基が置換したアニリン類等を挙げることができる。また、上述のＴＥＴＲＡＤ－Ｘも用いることができる。
なお、アニリン類としては、Ｎ，Ｎ’－テトラグリシジル－ｍ－フェニレンジアミンが挙げられる。Examples of the polyvalent epoxy compound include epoxy resins, and examples thereof include ethylene glycol diglycidyl ether, terephthalic acid diglycidyl ester acrylate, and anilines in which N atoms are substituted with two glycidyl groups. Further, the above-mentioned TETRAD-X can also be used.
Examples of anilines include N, N'-tetraglycidyl-m-phenylenediamine.
多価アジリジン化合物は、トリス－２，４，６－（１－アジリジニル）－１，３，５－トリアジン、トリス〔１－（２－メチル）－アジリジニル〕ホスフィンオキシド、ヘキサ〔１－（２－メチル）－アジリジニル〕トリホスファトリアジン等を挙げることができる。またキレート化合物としては、エチルアセトアセテートアルミニウムジイソプロピレート、アルミニウムトリス（エチルアセトアセテート）等を挙げることができる。 Polyvalent aziridine compounds include tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, tris [1- (2-methyl) -aziridinyl] phosphine oxide, hexa [1- (2- (2-) Methyl) -aziridinyl] triphosphatriazine and the like can be mentioned. Examples of the chelate compound include ethyl acetoacetate aluminum diisopropyrate and aluminum tris (ethyl acetoacetate).
硬化剤もしくは架橋剤の配合量は、ベース樹脂１００質量部に対して０．１～１０質量部が好ましく、０．１～５．０質量部がより好ましく、０．５～４．０質量部がさらに好ましい。 The blending amount of the curing agent or the cross-linking agent is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5.0 parts by mass, and 0.5 to 4.0 parts by mass with respect to 100 parts by mass of the base resin. Is even more preferable.
（粘着剤層の厚み）
粘着剤層の厚みは、製造性の点から５μｍ以上が好ましく、１０μｍ以上がより好ましく、２０μｍ以上が更に好ましい。上限は、７５μｍ以下が好ましく、５０μｍ以下がより好ましく、４０μｍ以下が特に好ましい。粘着剤層は複層であってもよく、その場合は、少なくとも、半導体ウェハ表面と接する最外層の粘着剤が、放射線硬化型粘着剤であることが好ましい。(Thickness of adhesive layer)
The thickness of the pressure-sensitive adhesive layer is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 20 μm or more from the viewpoint of manufacturability. The upper limit is preferably 75 μm or less, more preferably 50 μm or less, and particularly preferably 40 μm or less. The pressure-sensitive adhesive layer may be a plurality of layers, and in that case, at least the pressure-sensitive adhesive of the outermost layer in contact with the surface of the semiconductor wafer is preferably a radiation-curable pressure-sensitive adhesive.
（粘着剤層もしくは粘着剤の特性）
〔放射線硬化型粘着剤層中に有するエチレン性不飽和基の含有量〕
本発明の表面保護テープにおいて、粘着剤層を構成する放射線硬化型粘着剤が有するエチレン性不飽和基（放射線重合性炭素－炭素二重結合）の含有量は、０．２～２．０ｍｍｏｌ／ｇが好ましい。
放射線硬化型粘着剤が有するエチレン性不飽和基の含有量は、放射線硬化型粘着剤が含有するエチレン性不飽和基を有する化合物が有する全てのエチレン性不飽和基の総和であり、放射線硬化型粘着剤の単位ｇ当たりのエチレン性不飽和基の総和のモル数である。なお、エチレン性不飽和基を有する化合物とは、例えば、側鎖にエチレン性不飽和基を有するベース樹脂のような重合体、放射線重合性低分子量化合物である。(Characteristics of adhesive layer or adhesive)
[Contents of ethylenically unsaturated groups in the radiation-curable pressure-sensitive adhesive layer]
In the surface protective tape of the present invention, the content of ethylenically unsaturated groups (radiopolymerizable carbon-carbon double bonds) contained in the radiation-curable pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is 0.2 to 2.0 mmol /. g is preferable.
The content of the ethylenically unsaturated group contained in the radiation-curable pressure-sensitive adhesive is the sum of all the ethylenically unsaturated groups contained in the compound having the ethylenically unsaturated group contained in the radiation-curable pressure-sensitive adhesive. It is the total number of moles of ethylenically unsaturated groups per unit g of the pressure-sensitive adhesive. The compound having an ethylenically unsaturated group is, for example, a polymer such as a base resin having an ethylenically unsaturated group in the side chain, or a radiation-polymerizable low molecular weight compound.
放射線硬化型粘着剤が有するエチレン性不飽和基の含有量は、０．２～１．８ｍｍｏｌ／ｇが好ましく、０．２～１．５ｍｍｏｌ／ｇがより好ましく、０．５～１．５ｍｍｏｌ／ｇがより好ましい。
粘着剤層が複層の場合には、全ての粘着剤層を１層と見做したときに、粘着剤層を構成する放射線硬化型粘着剤が有するエチレン性不飽和基の含有量が上記範囲を満たすことが好ましく、それぞれの層が上記範囲を満たすことがより好ましい。The content of the ethylenically unsaturated group contained in the radiation-curable pressure-sensitive adhesive is preferably 0.2 to 1.8 mmol / g, more preferably 0.2 to 1.5 mmol / g, and 0.5 to 1.5 mmol / g. g is more preferable.
When the pressure-sensitive adhesive layer is a multi-layer, the content of ethylenically unsaturated groups contained in the radiation-curable pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is within the above range when all the pressure-sensitive adhesive layers are regarded as one layer. It is preferable that the above range is satisfied, and it is more preferable that each layer satisfies the above range.
放射線硬化型粘着剤が有するエチレン性不飽和基の含有量は、上記官能基（β）をもつ化合物及び放射線重合性低分子量化合物が有するエチレン性不飽和基の数やこれらの化合物の配合量で調節できる。 The content of ethylenically unsaturated groups contained in the radiation-curable pressure-sensitive adhesive depends on the number of ethylenically unsaturated groups contained in the above-mentioned compound having a functional group (β) and the radiation-polymerizable low molecular weight compound and the blending amount of these compounds. Can be adjusted.
放射線硬化型粘着剤が有するエチレン性不飽和基の含有量は、上記のように使用する化合物の量ないしこれらの化合物が有するエチレン性不飽和基の数から求めることができる。また、放射線硬化型粘着剤のヨウ素価〔ベース樹脂及び放射線重合性低分子量化合物の合計１００ｇに付加するヨウ素（Ｉ２）のｇ数〕を求め、Ｉ２の分子量が２５３．８であることから、この値をｍｍｏｌ／ｇに単位変換することで求められる。The content of the ethylenically unsaturated group contained in the radiation-curable pressure-sensitive adhesive can be determined from the amount of the compound used as described above or the number of ethylenically unsaturated groups contained in these compounds. Further, the iodine value of the radiation-curable pressure-sensitive adhesive [the number of g of iodine (I 2 ) added to a total of 100 g of the base resin and the radiation-polymerizable low molecular weight compound] was obtained, and the molecular weight of I 2 was 253.8. , This value can be obtained by converting the unit to mmol / g.
〔ＳＵＳ板に対する紫外線硬化後の粘着力〕
本発明の表面保護テープにおける粘着剤層の紫外線照射後の粘着力は、２３℃のＳＵＳ研磨面に対して０．５Ｎ／２５ｍｍ以上が好ましく、０．７Ｎ／２５ｍｍ以上がより好ましい。上限は、５．０Ｎ／２５ｍｍ以下が好ましく、３．０Ｎ／２５ｍｍ以下がより好ましく、１．５Ｎ／２５ｍｍ以下がさらに好ましい。また、上記粘着剤層の紫外線照射後の粘着力は、５０℃のＳＵＳ研磨面に対して０．３Ｎ／２５ｍｍ以上が好ましく、０．５Ｎ／２５ｍｍ以上がより好ましい。上限は、７．０Ｎ／２５ｍｍ以下が好ましく、４．０Ｎ／２５ｍｍ以下がより好ましく、２．５Ｎ／２５ｍｍ以下がさらに好ましい。この粘着力は、表面保護テープ自体の特性である。
なお、紫外線照射後とは、紫外線を積算照射量５００ｍＪ／ｃｍ２となるように粘着剤層全体を照射して硬化させた後を意味する。[Adhesive strength to SUS plate after UV curing]
The adhesive strength of the pressure-sensitive adhesive layer of the surface protective tape of the present invention after irradiation with ultraviolet rays is preferably 0.5 N / 25 mm or more, more preferably 0.7 N / 25 mm or more with respect to the SUS polished surface at 23 ° C. The upper limit is preferably 5.0 N / 25 mm or less, more preferably 3.0 N / 25 mm or less, still more preferably 1.5 N / 25 mm or less. The adhesive strength of the pressure-sensitive adhesive layer after irradiation with ultraviolet rays is preferably 0.3 N / 25 mm or more, more preferably 0.5 N / 25 mm or more with respect to the SUS polished surface at 50 ° C. The upper limit is preferably 7.0 N / 25 mm or less, more preferably 4.0 N / 25 mm or less, and even more preferably 2.5 N / 25 mm or less. This adhesive strength is a characteristic of the surface protective tape itself.
The term "after irradiation with ultraviolet rays" means after the entire pressure-sensitive adhesive layer is irradiated and cured so that the cumulative irradiation amount of ultraviolet rays is 500 mJ / cm 2 .
具体的には、以下のようにして求めることができる。
放射線照射前の表面保護テープから幅２５ｍｍ×長さ１５０ｍｍの試験片をそれぞれ３点採取する。その試験片をＪＩＳ Ｒ ６２５３に規定する２８０番の耐水研磨紙で仕上げたＪＩＳ Ｇ ４３０５に規定する厚さ１．５ｍｍ～２．０ｍｍのＳＵＳ鋼板上に２ｋｇのゴムローラを３往復かけ圧着する。常温（２５℃）で１時間放置後、積算照射量５００ｍＪ／ｃｍ２の紫外線を照射して粘着剤層を硬化させる。粘着剤層を硬化後、測定値がその容量の１５～８５％の範囲に入るＪＩＳ Ｂ ７７２１に適合する引張試験機を用いて、３点の粘着力の平均値を求める。粘着力の測定は、引張速度５０ｍｍ／ｍｉｎで９０°引きはがし法により常温、湿度５０％で行う。この試験において、試験片をＳＵＳ鋼板に圧着する前に、ホットプレート等を用いて、ＳＵＳ鋼板を所定の温度（２３℃、５０℃）に調整しておく。なお、上記引張試験機として、例えば、インストロン社製の引張試験機：ツインコラム卓上モデル５５６７（商品名）を用いることができる。Specifically, it can be obtained as follows.
Three test pieces each having a width of 25 mm and a length of 150 mm are collected from the surface protective tape before irradiation. The test piece is finished with No. 280 water-resistant abrasive paper specified in JIS R 6253, and a 2 kg rubber roller is crimped on a SUS steel plate having a thickness of 1.5 mm to 2.0 mm specified in JIS G 4305 over three reciprocations. After leaving it at room temperature (25 ° C.) for 1 hour, the pressure-sensitive adhesive layer is cured by irradiating it with ultraviolet rays having a cumulative irradiation amount of 500 mJ / cm 2 . After the pressure-sensitive adhesive layer is cured, the average value of the pressure-sensitive adhesive strength at three points is obtained using a tensile tester conforming to JIS B 7721 whose measured value is in the range of 15 to 85% of its capacity. The adhesive strength is measured at a tensile speed of 50 mm / min at room temperature and humidity of 50% by a 90 ° peeling method. In this test, before crimping the test piece to the SUS steel sheet, the SUS steel sheet is adjusted to a predetermined temperature (23 ° C., 50 ° C.) using a hot plate or the like. As the tensile tester, for example, a tensile tester manufactured by Instron: Twin Column Desktop Model 5567 (trade name) can be used.
ＳＵＳ研磨面に対する紫外線硬化後の粘着力は、粘着剤に用いられる化合物の種類や量、架橋剤等の添加剤の種類や量、粘着剤層の厚み等を適宜調節することで本発明の好ましい範囲にできる。
ＳＵＳ研磨面に対する上記粘着力を小さくしすぎると、架橋反応による硬化収縮が大きくなるため、バンプウェハなど表面凹凸が大きい被着体からの剥離力は逆に大きくなってしまう。ＳＵＳ研磨面に対する見かけの粘着力が大きすぎると放射線硬化が不十分で剥離不良や糊残りが発生してしまう。The adhesive strength of the SUS polished surface after UV curing is preferably adjusted by appropriately adjusting the type and amount of the compound used for the pressure-sensitive adhesive, the type and amount of additives such as a cross-linking agent, the thickness of the pressure-sensitive adhesive layer, and the like. Can be in the range.
If the adhesive force to the SUS polished surface is made too small, the curing shrinkage due to the cross-linking reaction becomes large, so that the peeling force from an adherend having a large surface unevenness such as a bump wafer becomes large. If the apparent adhesive force to the SUS polished surface is too large, radiation curing will be insufficient, resulting in poor peeling and adhesive residue.
＜剥離ライナー＞
半導体ウェハ表面保護用粘着テープは、粘着剤層上に剥離ライナーを有してもよい。剥離ライナーとしては、シリコーン離型処理したポリエチレンテレフタレートフィルムなどが用いられる。また必要に応じて、シリコーン離型処理をしないポリプロピレンフィルムなども用いられる。<Peeling liner>
The adhesive tape for protecting the surface of the semiconductor wafer may have a release liner on the adhesive layer. As the release liner, a polyethylene terephthalate film or the like that has been subjected to a silicone mold release treatment is used. Further, if necessary, a polypropylene film or the like that is not subjected to a silicone mold release treatment is also used.
＜＜半導体ウェハの加工方法＞＞
本発明の半導体ウェハの加工方法は、本発明の半導体ウェハ表面保護用粘着テープを使用する半導体ウェハの加工方法である。
本発明の半導体ウェハ表面保護用粘着テープは、半導体ウェハの加工工程ならどの工程で使用してもよい。例えば、半導体ウェハ裏面研削工程、ダイシング工程、ダイシングダイボンディング工程などが好ましく挙げられる。<< Semiconductor wafer processing method >>
The method for processing a semiconductor wafer of the present invention is a method for processing a semiconductor wafer using the adhesive tape for protecting the surface of the semiconductor wafer of the present invention.
The adhesive tape for protecting the surface of a semiconductor wafer of the present invention may be used in any process of processing a semiconductor wafer. For example, a semiconductor wafer back surface grinding step, a dicing step, a dicing die bonding step and the like are preferably mentioned.
本発明の半導体ウェハ表面保護用粘着テープは、２０μｍ以上の凹凸差を有する半導体ウェハの表面に貼合して使用される。
凹凸差〔バンプ（電極）の高さないしスクライブラインの深さ〕が、２０～４００μｍの半導体ウェハに適用するのがより好ましく、５０～２５０μｍの半導体ウェハに適用するのがさらに好ましい。The adhesive tape for protecting the surface of a semiconductor wafer of the present invention is used by being bonded to the surface of a semiconductor wafer having an unevenness difference of 20 μm or more.
It is more preferable to apply it to a semiconductor wafer having a difference in unevenness [the height of the bump (electrode) and the depth of the scribe line] of 20 to 400 μm, and even more preferably to apply it to a semiconductor wafer having a thickness of 50 to 250 μm.
半導体ウェハ表面のバンプの配設密度（高密度）は、特に限定されるものではないが、バンプの高さの０．５～３倍以下、好ましくは１～２倍以下のピッチ（バンプの高さ方向の頂点から、次に配置されたバンプの高さ方向の頂点までの距離）のものに対して適用できる。また、全面に均一にバンプが配置された半導体ウェハにも用いられる。 The arrangement density (high density) of the bumps on the surface of the semiconductor wafer is not particularly limited, but the pitch is 0.5 to 3 times or less, preferably 1 to 2 times or less the height of the bumps (the height of the bumps). It can be applied to the one (distance from the vertex in the vertical direction to the vertex in the height direction of the next placed bump). It is also used for semiconductor wafers in which bumps are uniformly arranged on the entire surface.
半導体ウェハの厚みは、半導体ウェハ表面保護用粘着テープを用いる加工方法により裏面研削された半導体ウェハの厚みにおいて、２０～５００μｍが好ましく、５０～２００μｍがより好ましく、８０～２００μｍがさらに好ましい。
本発明の半導体ウェハ表面保護用粘着テープを用いることで、薄膜半導体ウェハを高い歩留まりで得ることができる。この半導体ウェハの加工方法は、５０μｍ以下に薄膜研削された電極付半導体ウェハの製造方法として好適である。The thickness of the semiconductor wafer is preferably 20 to 500 μm, more preferably 50 to 200 μm, still more preferably 80 to 200 μm, in terms of the thickness of the semiconductor wafer grounded on the back surface by a processing method using an adhesive tape for protecting the surface of the semiconductor wafer.
By using the adhesive tape for protecting the surface of the semiconductor wafer of the present invention, a thin film semiconductor wafer can be obtained with a high yield. This method for processing a semiconductor wafer is suitable as a method for manufacturing a semiconductor wafer with electrodes which is thin-film ground to a size of 50 μm or less.
本発明の半導体ウェハの加工方法は、本発明の半導体ウェハ表面保護用粘着テープを半導体ウェハ表面に貼合した後、放射線、特に、紫外線照射して、半導体ウェハ表面保護用粘着テープを剥離する工程を含むことが好ましい。 The method for processing a semiconductor wafer of the present invention is a step of attaching the semiconductor wafer surface protection adhesive tape of the present invention to the semiconductor wafer surface and then irradiating with radiation, particularly ultraviolet rays, to peel off the semiconductor wafer surface protection adhesive tape. It is preferable to include.
具体的には、まず、半導体ウェハの回路パターン面（表面）に、本発明の半導体ウェハ表面保護用粘着テープを粘着剤層が貼合面となるように貼合する。次に、半導体ウェハの回路パターンのない面側を半導体ウェハの厚みが所定の厚み、例えば１０～２００μｍになるまで研削する。その後、この半導体ウェハ表面保護用粘着テープの貼合された面を下側にして加熱吸着台に載せ、その状態で、半導体ウェハの回路パターンのない研削した面側に、ダイシング・ダイボンディングフィルムを貼合してもよい。
ダイシング工程を行い、その後、半導体ウェハ表面保護用粘着テープの基材フィルムの背面に、ヒートシールタイプ（熱融着タイプ）もしくは粘着タイプの剥離テープを接着して半導体ウェハから半導体ウェハ表面保護用粘着テープを剥離する。Specifically, first, the adhesive tape for protecting the surface of the semiconductor wafer of the present invention is attached to the circuit pattern surface (surface) of the semiconductor wafer so that the adhesive layer serves as the bonding surface. Next, the surface side of the semiconductor wafer without the circuit pattern is ground until the thickness of the semiconductor wafer becomes a predetermined thickness, for example, 10 to 200 μm. After that, the semiconductor wafer surface protection adhesive tape is placed on the heating adsorption table with the bonded surface facing down, and in that state, a dicing die bonding film is placed on the ground side of the semiconductor wafer without a circuit pattern. You may stick them together.
A dicing step is performed, and then a heat seal type (heat fusion type) or adhesive type release tape is adhered to the back surface of the base film of the adhesive tape for protecting the surface of the semiconductor wafer, and the adhesive for protecting the surface of the semiconductor wafer is adhered from the semiconductor wafer. Peel off the tape.
以下に、本発明を実施例に基づいて、さらに詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
（粘着剤組成物の調製）
以下のようにして、粘着剤組成物１Ａ～１Ｃを調製した。(Preparation of adhesive composition)
The pressure-sensitive adhesive compositions 1A to 1C were prepared as follows.
１）粘着剤組成物１Ａの調製
２－エチルヘキシルアクリレート７８質量部、２－ヒドロキシエチルアクリレート１７質量部、メタクリル酸５質量部から、質量平均分子量５５万からなる共重合体を得た。この共重合体１００質量部に対して、アクリレート５官能で、官能基（β）としてヒドロキシ基を有する質量平均分子量３，０００のウレタンアクリレートオリゴマー１００質量部およびポリイソシアネートのコロネートＬ〔商品名、日本ポリウレタン工業社製〕５．０質量部、光重合開始剤としてＳＰＥＥＤＣＵＲＥ ＢＫＬ〔商品名、ＤＫＳＨジャパン社製〕５．０質量部を加えて、混合して、粘着剤組成物１Ａを得た。1) Preparation of Adhesive Composition 1A A copolymer having a mass average molecular weight of 550,000 was obtained from 78 parts by mass of 2-ethylhexyl acrylate, 17 parts by mass of 2-hydroxyethyl acrylate, and 5 parts by mass of methacrylic acid. With respect to 100 parts by mass of this copolymer, 100 parts by mass of a urethane acrylate oligomer having a mass average molecular weight of 3,000 and having a hydroxy group as a functional group (β) and coronate L of polyisocyanate [trade name, Japan]. Polyurethane Industry Co., Ltd.] 5.0 parts by mass and SPEEDCURE BKL [trade name, manufactured by DKSH Japan Co., Ltd.] 5.0 parts by mass as a photopolymerization initiator were added and mixed to obtain a pressure-sensitive adhesive composition 1A.
２）粘着剤組成物１Ｂの調製
２－エチルヘキシルアクリレート７０質量部、２－ヒドロキシエチルアクリレート７質量部、メタクリル酸２３質量部を、酢酸エチル中で重合させ、得られた質量平均分子量１００万のメタアクリル系ポリマーを得た。このメタアクリル系ポリマー１００質量部に対して、エポキシ系硬化剤２．０質量部を混合して、粘着剤組成物Ｂを得た。2) Preparation of Adhesive Composition 1B 70 parts by mass of 2-ethylhexyl acrylate, 7 parts by mass of 2-hydroxyethyl acrylate, and 23 parts by mass of methacrylic acid were polymerized in ethyl acetate to obtain a meta having a mass average molecular weight of 1 million. An acrylic polymer was obtained. 2.0 parts by mass of an epoxy-based curing agent was mixed with 100 parts by mass of this methacrylic polymer to obtain a pressure-sensitive adhesive composition B.
３）粘着剤組成物１Ｃの調製
２－エチルヘキシルアクリレート７８質量部、２－ヒドロキシエチルアクリレート１３質量部、メタクリル酸９質量部から質量平均分子量６０万からなる共重合体を得た。この共重合体１００質量部に対して、アクリレート３官能で、官能基（β）としてヒドロキシ基を有する質量平均分子量１，５００のウレタンアクリレートオリゴマー１００質量部およびポリイソシアネートのコロネートＬ ３．０質量部、エポキシ樹脂のＴＥＴＲＡＤ－Ｘ〔三菱ガス化学社製〕０．５質量部、光重合開始剤としてＳＰＥＥＤＣＵＲＥ ＢＫＬ５．０質量部を加えて混合して、粘着剤組成物１Ｃを得た。3) Preparation of Adhesive Composition 1C A copolymer having a mass average molecular weight of 600,000 was obtained from 78 parts by mass of 2-ethylhexyl acrylate, 13 parts by mass of 2-hydroxyethyl acrylate, and 9 parts by mass of methacrylic acid. With respect to 100 parts by mass of this copolymer, 100 parts by mass of a urethane acrylate oligomer having a acrylate trifunctionality and having a hydroxy group as a functional group (β) and having a mass average molecular weight of 1,500 and 3.0 parts by mass of coronate L of polyisocyanate. , 0.5 part by mass of TETRAD-X [manufactured by Mitsubishi Gas Chemicals Co., Ltd.] of epoxy resin and 5.0 parts by mass of SPEEDCURE BKL as a photopolymerization initiator were added and mixed to obtain a pressure-sensitive adhesive composition 1C.
（基材フィルムおよび中間樹脂層の製膜）
以下のようにして、中間樹脂層および基材フィルム２Ａ～２Ｇを製膜した。(Film formation of base film and intermediate resin layer)
The intermediate resin layer and the base film 2A to 2G were formed as follows.
１）フィルム２Ａの作製
中間樹脂層を構成する樹脂としてエチレン－アクリル酸エチルコポリマー（ＥＥＡ）樹脂（日本ポリエチレン社製、商品名：レクスパールＥＥＡ Ａ６２００）を用い、基材フィルムを構成する樹脂として低密度ポリエチエレン（ＬＤＰＥ）樹脂（東ソー社製、商品名：ペトロセン２１２）を用いた。押し出し機により、これらの樹脂を押し出し成形することで、中間樹脂層を有する基材フィルム（フィルム２Ａ）を作製した。ＬＤＰＥ層の厚みは１２．５μｍ、ＥＥＡの厚みは２３７．５μｍであった。
1) Preparation of film 2A A resin constituting a base film using an ethylene- ethyl acrylate copolymer (EEA) resin (manufactured by Nippon Polyethylene Co., Ltd., trade name: Lexpearl EEA A 6200) as a resin constituting the intermediate resin layer. A low-density polyethylene (LDPE) resin (manufactured by Toso Co., Ltd., trade name: Petrosen 212) was used as the resin. By extruding these resins with an extruder, a base film (film 2A) having an intermediate resin layer was produced. The thickness of the LDPE layer was 12.5 μm, and the thickness of the EEA was 237.5 μm.
２）フィルム２Ｂの作製
中間樹脂層を構成する樹脂としてエチレン－アクリル酸メチルコポリマー（ＥＭＡ）樹脂（日本ポリエチレン社製、商品名：レクスパールＥＢ３３０Ｈ）を用い、基材フィルムを構成する樹脂として低密度ポリエチエレン（ＬＤＰＥ）樹脂（東ソー社製、商品名：ペトロセン２１２）を用いた。押し出し機により、これらの樹脂を押し出し成形することで、中間樹脂層を有する基材フィルム（フィルム２Ｂ）を作製した。ＬＤＰＥ層の厚みは１４０．０μｍ、ＥＥＡの厚みは２１０．０μｍであった。2) Preparation of film 2B Ethethylene-methyl acrylate copolymer (EMA) resin (manufactured by Nippon Polyethylene, trade name: Lexpearl EB330H) is used as the resin constituting the intermediate resin layer, and the resin having a low density is used as the resin constituting the base film. Polyethylene (LDPE) resin (manufactured by Toso Co., Ltd., trade name: Petrosen 212) was used. By extruding these resins with an extruder, a base film (film 2B) having an intermediate resin layer was produced. The thickness of the LDPE layer was 140.0 μm, and the thickness of the EEA was 210.0 μm.
３）フィルム２Ｃの作製
中間樹脂層を構成する樹脂としてエチレン系特殊コポリマー樹脂（日本ポリエチレン社製、商品名：レクスパールＥＴ７２０Ｘ）を用い、基材フィルムを構成する樹脂として低密度ポリエチエレン（ＬＤＰＥ）樹脂（東ソー社製、商品名：ペトロセン２１２）を用いた。押し出し機により、これらの樹脂を押し出し成形することで、中間樹脂層を有する基材フィルム（フィルム２Ｃ）を作製した。ＬＤＰＥ層の厚みは５０．０μｍ、エチレン系特殊コポリマー樹脂層の厚みは２００．０μｍであった。3) Preparation of film 2C An ethylene-based special copolymer resin (manufactured by Nippon Polyethylene, trade name: Lexpearl ET720X) is used as the resin constituting the intermediate resin layer, and low-density polyethylene (LDPE) is used as the resin constituting the base film. A resin (manufactured by Toso Co., Ltd., trade name: Petrosen 212) was used. By extruding these resins with an extruder, a base film (film 2C) having an intermediate resin layer was produced. The thickness of the LDPE layer was 50.0 μm, and the thickness of the ethylene-based special copolymer resin layer was 200.0 μm.
４）フィルム２Ｄの作製
中間樹脂層を構成する樹脂としてメタロセンプラストマー樹脂（日本ポリエチレン社製、商品名：カーネルＫＪ６４０Ｔ）を用い、基材フィルムを構成する樹脂として低密度ポリエチエレン（ＬＤＰＥ）樹脂（日本ポリエチレン社製、商品名：ノバテックＬＬ ＵＪ５８０）を用いた。押し出し機により、これらの樹脂を押し出し成形することで、中間樹脂層を有する基材フィルム（フィルム２Ｄ）を作製した。ＬＤＰＥ層の厚みは９０μ．０ｍ、エチレン系特殊コポリマー樹脂層の厚みは２１０．０μｍであった。4) Preparation of film 2D Metallocene plastomer resin (manufactured by Nippon Polyethylene Co., Ltd., trade name: Kernel KJ640T) is used as the resin constituting the intermediate resin layer, and low-density polyethylene (LDPE) resin (LDPE) resin is used as the resin constituting the base film. A product name: Novatec LL UJ580) manufactured by Nippon Polyethylene Co., Ltd. was used. By extruding these resins with an extruder, a base film (film 2D) having an intermediate resin layer was produced. The thickness of the LDPE layer is 90 μ. At 0 m, the thickness of the ethylene-based special copolymer resin layer was 210.0 μm.
５）フィルム２Ｅの作製
中間樹脂層を構成する樹脂としてエチレン系特殊ポリマー樹脂（日本ポリエチレン社製、商品名：レクスパールＥＴ２２０Ｘ）を用い、基材フィルムを構成する樹脂として低密度ポリエチエレン（ＬＤＰＥ）樹脂（東ソー社製、商品名：ペトロセン２１２）を用いた。押し出し機により、これらの樹脂を押し出し成形することで、中間樹脂層を有する基材フィルム（フィルム２Ｅ）を作製した。ＬＤＰＥ層の厚みは１５０．０μｍ、エチレン系特殊コポリマー樹脂層の厚みは１５０．０μｍであった。5) Preparation of film 2E An ethylene-based special polymer resin (manufactured by Nippon Polyethylene, trade name: Lexpearl ET220X) is used as the resin constituting the intermediate resin layer, and low-density polyethylene (LDPE) is used as the resin constituting the base film. A resin (manufactured by Toso Co., Ltd., trade name: Petrosen 212) was used. By extruding these resins with an extruder, a base film (film 2E) having an intermediate resin layer was produced. The thickness of the LDPE layer was 150.0 μm, and the thickness of the ethylene-based special copolymer resin layer was 150.0 μm.
６）フィルム２Ｆの作製
中間樹脂層を構成する樹脂としてエチレン－ブチルアクリレートコポリマー樹脂（アルケマ社製、商品名：ロトリル２８ＢＡ１７５）と、基材フィルムを構成する樹脂として低密度ポリエチエレン（ＬＤＰＥ）樹脂（日本ポリエチレン社製、商品名：ノバテックＬＬ ＵＪ５８０）を用いた。押し出し機により、これらの樹脂を押し出し成形することで、中間樹脂層を有する基材フィルム（フィルム２Ｆ）を作製した。ＬＤＰＥ層の厚みは９０．０μｍ、エチレン－ブチルアクリレートコポリマー樹脂層の厚みは２１０．０μｍであった。6) Preparation of film 2F Ethylene-butyl acrylate copolymer resin (manufactured by Alchema, trade name: Rotril 28BA175) as the resin constituting the intermediate resin layer, and low-density polyethylene (LDPE) resin (LDPE) resin as the resin constituting the base film. A product name: Novatec LL UJ580) manufactured by Nippon Polyethylene Co., Ltd. was used. By extruding these resins with an extruder, a base film (film 2F) having an intermediate resin layer was produced. The thickness of the LDPE layer was 90.0 μm, and the thickness of the ethylene-butyl acrylate copolymer resin layer was 210.0 μm.
７）フィルム２Ｇの製膜
中間樹脂層を構成する樹脂としてエチレン－アクリル酸メチルコポリマー樹脂（日本ポリエチレン社製、商品名：ＥＢ２４０Ｈ）と、基材フィルムを構成する樹脂として低密度ポリエチエレン（ＬＤＰＥ）樹脂（東ソー社製、商品名：ペトロセン２１２）を用いた。押し出し機により、これらの樹脂を押し出し成形することで、中間樹脂層を有する基材フィルム（フィルム２Ｇ）を作製した。ＬＤＰＥ層の厚みは９０．０μｍ、エチレン－アクリル酸メチルコポリマー樹脂層の厚みは２１０．０μｍであった。7) Film formation of film 2G Ethethylene-methyl acrylate copolymer resin (manufactured by Nippon Polyethylene, trade name: EB240H) as the resin constituting the intermediate resin layer, and low-density polyethylene (LDPE) as the resin constituting the base film. A resin (manufactured by Toso Co., Ltd., trade name: Petrosen 212) was used. By extruding these resins with an extruder, a base film (film 2G) having an intermediate resin layer was produced. The thickness of the LDPE layer was 90.0 μm, and the thickness of the ethylene-methyl acrylate copolymer resin layer was 210.0 μm.
８）フィルム２Ｈの製膜
中間樹脂層を構成する樹脂として低密度ポリエチレン（ＬＤＰＥ）樹脂（東ソー社製、商品名：ペトロセン１８０）と、基材フィルムを構成する樹脂として低密度ポリエチエレン（ＬＤＰＥ）樹脂（東ソー社製、商品名：ペトロセン２１２）を用いた。押し出し機により、これらの樹脂を押し出し成形することで、中間樹脂層を有する基材フィルム（フィルム２Ｈ）を作製した。中間樹脂層として用いたＬＤＰＥ層の厚みは９０．０μｍ、基材フィルムとして用いたＬＤＰＥ層の厚みは２１０．０μｍであった。8) Film formation of film 2H Low-density polyethylene (LDPE) resin (manufactured by Toso Co., Ltd., trade name: Petrosen 180) as the resin constituting the intermediate resin layer, and low-density polyethylene (LDPE) as the resin constituting the base film. A resin (manufactured by Toso Co., Ltd., trade name: Petrosen 212) was used. By extruding these resins with an extruder, a base film (film 2H) having an intermediate resin layer was produced. The thickness of the LDPE layer used as the intermediate resin layer was 90.0 μm, and the thickness of the LDPE layer used as the base film was 210.0 μm.
（実施例１）
乾燥後の厚みが３０μｍになるように、粘着剤組成物１Ａを透明な剥離ライナー上に塗工し、乾燥させた。剥離ライナー上の粘着剤層と、フィルム２Ａの中間樹脂層とが接するように張り合わせ、剥離ライナーを除いて、図１に示す構成の半導体ウェハ表面保護用粘着テープを得た。(Example 1)
The pressure-sensitive adhesive composition 1A was applied onto a transparent release liner and dried so that the thickness after drying was 30 μm. The pressure-sensitive adhesive layer on the release liner and the intermediate resin layer of the film 2A were bonded to each other so as to be in contact with each other, and the release liner was removed to obtain an adhesive tape for protecting the surface of the semiconductor wafer having the configuration shown in FIG.
（参考例２）
実施例１において、粘着剤組成物１Ａを粘着剤組成物１Ｂに、フィルム２Ａをフィルム２Ｂに変えた以外は、実施例１と同様にして、図１に示す構成の半導体ウェハ表面保護用粘着テープを得た。
( Reference example 2)
In the first embodiment, the adhesive tape for protecting the surface of the semiconductor wafer having the configuration shown in FIG. 1 is the same as that of the first embodiment except that the pressure-sensitive adhesive composition 1A is changed to the pressure-sensitive adhesive composition 1B and the film 2A is changed to the film 2B. Got
（参考例３）
実施例１において、粘着剤組成物１Ａを粘着剤組成物１Ｃに、フィルム２Ａをフィルム２Ｃに変えた以外は、実施例１と同様にして、図１に示す構成の半導体ウェハ表面保護用粘着テープを得た。
( Reference example 3)
In the first embodiment, the adhesive tape for protecting the surface of the semiconductor wafer having the configuration shown in FIG. 1 is the same as that of the first embodiment except that the pressure-sensitive adhesive composition 1A is changed to the pressure-sensitive adhesive composition 1C and the film 2A is changed to the film 2C. Got
（実施例４）
実施例１において、粘着剤組成物１Ａを粘着剤組成物１Ｂに、フィルム２Ａをフィルム２Ｄに変えた以外は、実施例１と同様にして、図１に示す構成の半導体ウェハ表面保護用粘着テープを得た。(Example 4)
In the first embodiment, the adhesive tape for protecting the surface of the semiconductor wafer having the configuration shown in FIG. 1 is the same as that of the first embodiment except that the pressure-sensitive adhesive composition 1A is changed to the pressure-sensitive adhesive composition 1B and the film 2A is changed to the film 2D. Got
（比較例１）
実施例１において、粘着剤組成物１Ａを粘着剤組成物１Ｃに、フィルム２Ａをフィルム２Ｅに変えた以外は、実施例１と同様にして、半導体ウェハ表面保護用粘着テープを得た。(Comparative Example 1)
An adhesive tape for protecting the surface of a semiconductor wafer was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition 1A was changed to the pressure-sensitive adhesive composition 1C and the film 2A was changed to the film 2E.
（比較例２）
実施例１において、粘着剤組成物１Ａを粘着剤組成物１Ｂに、フィルム２Ａをフィルム２Ｆに変えた以外は、実施例１と同様にして、半導体ウェハ表面保護用粘着テープを得た。(Comparative Example 2)
An adhesive tape for protecting the surface of a semiconductor wafer was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition 1A was changed to the pressure-sensitive adhesive composition 1B and the film 2A was changed to the film 2F.
（比較例３）
実施例１において、フィルム２Ａをフィルム２Ｇに変えた以外は、実施例１と同様にして、半導体ウェハ表面保護用粘着テープを得た。(Comparative Example 3)
An adhesive tape for protecting the surface of a semiconductor wafer was obtained in the same manner as in Example 1 except that the film 2A was changed to the film 2G in Example 1.
（比較例４）
実施例１において、フィルム２Ａをフィルム２Ｈに変えた以外は、実施例１と同様にして、半導体ウェハ表面保護用粘着テープを得た。(Comparative Example 4)
An adhesive tape for protecting the surface of a semiconductor wafer was obtained in the same manner as in Example 1 except that the film 2A was changed to the film 2H in Example 1.
上記の実施例、参考例及び比較例で作製した半導体ウェハ表面保護用粘着テープについて、以下の試験を行い、その性能を評価した。評価結果を下記表１に記載した。なお、参考例２、３、実施例４及び比較例１～３で作製した表面保護テープについても、実施例１と同様にして試験を行った。
The following tests were performed on the adhesive tapes for protecting the surface of the semiconductor wafer produced in the above Examples , Reference Examples and Comparative Examples, and their performances were evaluated. The evaluation results are shown in Table 1 below. The surface protective tapes produced in Reference Examples 2 and 3, Example 4 and Comparative Examples 1 to 3 were also tested in the same manner as in Example 1.
＜試験例１＞密着性試験
（１）高さ５０μｍのバンプに対する密着性
高さ５０μｍ、バンプピッチ１００μｍのＣｕピラーバンプを有する直径８インチのバンプ付シリコンウェハ（シリコンウェハ自体の厚み７２５μｍ）の表面に、日東精機社製ＤＲ８５００ＩＩＩ（商品名）を用いて、テーブル温度８０℃及びローラー温度６０℃、貼合圧０．３５ＭＰａ、貼合速度低速（９ｍｍ／ｓｅｃ）の条件で、上記実施例１で作製した表面保護テープを上記ウェハに貼合した。このようにして、表面保護テープ付ウェハ（バンプ高さ：５０μｍ）を２５枚作製した。この貼合条件で、融点８０℃以下の樹脂からなる中間樹脂層を構成層とする表面保護テープの中間樹脂層は溶融した（以下の試験例２の場合も同様であった）。その時の密着性を目視にて確認を行い、表面保護テープと上記ウェハとの間へのエアー混入の有無を調べた。
（２）高さ２００μｍのバンプに対する密着性
高さ２００μｍ、バンプピッチ４００μｍのソルダーバンプを有する直径８インチのバンプ付シリコンウェハ（バンプを除いた部分の厚み７２５μｍ）の表面に、日東精機社製ＤＲ８５００ＩＩＩ（商品名）を用いて、テーブル温度８０℃及びローラー温度６０℃、貼合圧０．３５ＭＰａ、貼合速度低速（９ｍｍ／ｓｅｃ）の条件で、上記実施例１で作製した表面保護テープを上記ウェハに貼合した。このようにして、表面保護テープ付ウェハ（バンプ高さ：２００μｍ）を５枚作製した。その時の密着性を目視にて確認を行い、表面保護テープと上記ウェハとの間へのエアー混入の有無を調べた。評価基準を以下に示す。Ａ及びＢが合格である。<Test Example 1> Adhesion test (1) Adhesion to a bump with a height of 50 μm On the surface of a silicon wafer with a bump (thickness 725 μm of the silicon wafer itself) having a Cu pillar bump with a height of 50 μm and a bump pitch of 100 μm and having a diameter of 8 inches. Made in Example 1 above using DR8500III (trade name) manufactured by Nitto Seiki Co., Ltd. under the conditions of a table temperature of 80 ° C., a roller temperature of 60 ° C., a bonding pressure of 0.35 MPa, and a bonding speed of low speed (9 mm / sec). The surface protection tape was attached to the wafer. In this way, 25 wafers with surface protective tape (bump height: 50 μm) were produced. Under these bonding conditions, the intermediate resin layer of the surface protective tape having an intermediate resin layer made of a resin having a melting point of 80 ° C. or lower as a constituent layer was melted (the same was true for Test Example 2 below). The adhesion at that time was visually confirmed, and the presence or absence of air contamination between the surface protective tape and the wafer was examined.
(2) Adhesion to bumps with a height of 200 μm DR8500III manufactured by Nitto Seiki Co., Ltd. on the surface of an 8-inch diameter bumped silicon wafer (thickness 725 μm excluding bumps) having solder bumps with a height of 200 μm and a bump pitch of 400 μm. Using (trade name), the surface protective tape produced in Example 1 above was used under the conditions of a table temperature of 80 ° C., a roller temperature of 60 ° C., a bonding pressure of 0.35 MPa, and a bonding speed of low speed (9 mm / sec). It was bonded to the wafer. In this way, five wafers with surface protective tape (bump height: 200 μm) were produced. The adhesion at that time was visually confirmed, and the presence or absence of air contamination between the surface protective tape and the wafer was examined. The evaluation criteria are shown below. A and B pass.
（評価基準）
Ａ：貼合後、室温（２５℃）で静置し、７２時間を超えても、全ての表面保護テープ付ウェハにエアー混入が観察されなかった。
Ｂ：貼合後、室温で静置し、４８時間を超え７２時間以内に、全ての表面保護テープ付ウェハにエアー混入が観察されなかった。
Ｃ：貼合後、室温で静置し、少なくとも１枚の表面保護テープ付ウェハに、貼合後４８時間以内にエアーが観察された。(Evaluation criteria)
A: After bonding, the wafer was allowed to stand at room temperature (25 ° C.), and even after 72 hours, no air contamination was observed in all the wafers with surface protective tape.
B: After bonding, the wafer was allowed to stand at room temperature, and no air contamination was observed in all the wafers with surface protective tape within more than 48 hours and within 72 hours.
C: After bonding, the mixture was allowed to stand at room temperature, and air was observed on at least one wafer with surface protective tape within 48 hours after bonding.
＜試験例２＞研削試験
（１）ダスト侵入
上記と同様にして、表面保護テープを上記ウェハに貼合し、実施例１の表面保護テープ付ウェハ（バンプ高さ：５０μｍ）５枚と、実施例１の表面保護テープ付ウェハ（バンプ高さ：２００μｍ）５枚を作製した。表面保護テープを上記ウェハに貼合後４８時間静置した後、裏面研削を行った。この裏面研削には、インライン機構を持つグラインダー〔株式会社ディスコ製ＤＦＧ８７６０（商品名）〕を使用した。その後、研削後の表面保護テープ付ウェハについて、ウェハと表面保護テープ間にシリコンダストの侵入の有無の確認を目視で行った。尚、実施例１の表面保護テープ付ウェハ（バンプ高さ：５０μｍ）についてはウェハの最終研削厚みが５０μｍになるまで裏面研削を行った。一方、実施例１の表面保護テープ付ウェハ（バンプ高さ：２００μｍ）についてはシリコンの最終研削厚みが２００μｍになるまで裏面研削を行い、以下の評価基準に従って評価した。<Test Example 2> Grinding test (1) Dust intrusion In the same manner as above, the surface protection tape was attached to the wafer, and the wafer was carried out with 5 wafers with surface protection tape (bump height: 50 μm) of Example 1. Five wafers with surface protection tape (bump height: 200 μm) of Example 1 were produced. After the surface protective tape was attached to the wafer and allowed to stand for 48 hours, the back surface was ground. For this back surface grinding, a grinder having an in-line mechanism [DFG8760 (trade name) manufactured by Disco Corporation] was used. Then, with respect to the wafer with the surface protection tape after grinding, the presence or absence of silicon dust intrusion between the wafer and the surface protection tape was visually confirmed. For the wafer with surface protection tape (bump height: 50 μm) of Example 1, backside grinding was performed until the final grinding thickness of the wafer reached 50 μm. On the other hand, the wafer with the surface protective tape (bump height: 200 μm) of Example 1 was subjected to backside grinding until the final grinding thickness of silicon reached 200 μm, and evaluated according to the following evaluation criteria.
（評価基準）
合格：表面保護テープ付ウェハ（バンプ高さ：５０μｍ）及び表面保護テープ付ウェハ（バンプ高さ：２００μｍ）のいずれについてもダスト侵入が見られなかった。
不合格：表面保護テープ付ウェハ（バンプ高さ：５０μｍ）及び表面保護テープ付ウェハ（バンプ高さ：２００μｍ）のいずれか少なくとも１枚にダスト侵入が見られた。(Evaluation criteria)
Pass: No dust intrusion was observed on either the wafer with surface protection tape (bump height: 50 μm) or the wafer with surface protection tape (bump height: 200 μm).
Fail: Dust intrusion was observed in at least one of the wafer with surface protection tape (bump height: 50 μm) and the wafer with surface protection tape (bump height: 200 μm).
（２）搬送エラー
評価基準を以下に示す。Ａ及びＢが合格である。
Ａ：研削試験において、全てのウェハで研削装置内での搬送エラーが発生しなかった。
Ｂ：研削試験において、研削装置内での搬送エラーが１枚発生した。
Ｃ：研削試験において、研削装置内での搬送エラーが２枚以上発生した。
「搬送エラー」とは、基材フィルムが変形し、真空吸着して表面保護テープ付ウェハを搬送できなかったことを意味する。(2) Transport error evaluation criteria are shown below. A and B pass.
A: In the grinding test, no transfer error occurred in the grinding device on all wafers.
B: In the grinding test, one transfer error occurred in the grinding device.
C: In the grinding test, two or more transfer errors occurred in the grinding device.
The “transfer error” means that the base film was deformed and was vacuum-adsorbed so that the wafer with the surface protective tape could not be transferred.
（３）ウェハ破損の評価
研削した各表面保護テープ付ウェハ全体を目視で確認し、光学顕微鏡にてウェハ端部の観察を行いウェハ破損の有無を調べた。評価基準を以下に示す。「無し（Ａ）」が合格である。(3) Evaluation of Wafer Damage The entire ground wafer with surface protective tape was visually confirmed, and the edge of the wafer was observed with an optical microscope to check for wafer damage. The evaluation criteria are shown below. "None (A)" is a pass.
（評価基準）
無し（Ａ）：目視および顕微鏡観察で破損がなかった。
Ｂ：目視では破損はなかったが、顕微鏡によって破損が確認された。
Ｃ：目視で破損が確認された。(Evaluation criteria)
None (A): There was no damage by visual inspection and microscopic observation.
B: There was no visual damage, but damage was confirmed by a microscope.
C: Damage was visually confirmed.
（４）反り評価
ダスト侵入の評価で用いた、実施例１の表面保護テープ付ウェハ（バンプ高さ：５０μｍ）５枚について、反り高さ（表面保護テープ付ウェハを平板の上に置き、平板表面から反ったウェハの最も高い点の下面までの高さ）を測定した。評価基準を以下に示す。Ａが合格である。
（評価基準）
Ａ：反り高さの平均値が５ｍｍ未満
Ｂ：反り高さの平均値が５ｍｍ以上、１０ｍｍ未満
Ｃ：反り高さの平均値が１０ｍｍ以上(4) Warpage evaluation For the five wafers with surface protection tape (bump height: 50 μm) of Example 1 used in the evaluation of dust intrusion, the warp height (wafer with surface protection tape is placed on a flat plate and the flat plate is placed. The height from the surface to the bottom surface of the highest point of the warped wafer) was measured. The evaluation criteria are shown below. A is a pass.
(Evaluation criteria)
A: The average value of the warp height is less than 5 mm B: The average value of the warp height is 5 mm or more and less than 10 mm C: The average value of the warp height is 10 mm or more
（５）剥離性評価
表面に高さ７５μｍのバンプ（バンプピッチ１５０μｍ）を有する８インチ径の半導体ウェハ表面に、上記で製造した各半導体ウェハ表面保護用粘着テープを、貼合温度９０℃で貼合した。その後、株式会社ディスコ製ＤＦＧ８７６０（商品名）を用いて、上記の半導体ウェハ表面保護用粘着テープで貼合されたバンプ付半導体ウェハの裏面を２枚ずつ、２００μｍの厚さまで研削加工した。研削後の半導体ウェハ表面保護用粘着テープ付き半導体ウェハに５００ｍＪ／ｃｍ２の紫外線を照射し、インストロン社製の引張試験機（ツインコラム卓上モデル５５６７（商品名））を用いて半導体ウェハ表面保護用粘着テープを剥離し、剥離時の幅が最大（２００ｍｍ）となったときの剥離力において、以下の基準で評価した。Ａ及びＢが合格である。
なお、表１では「剥離性」として示した。(5) Detachability evaluation Adhesive tape for protecting the surface of each semiconductor wafer manufactured above is attached to the surface of an 8-inch diameter semiconductor wafer having bumps (bump pitch 150 μm) with a height of 75 μm at a bonding temperature of 90 ° C. It fits. Then, using DFG8760 (trade name) manufactured by DISCO Co., Ltd., the back surfaces of the bumped semiconductor wafers bonded with the above-mentioned adhesive tape for protecting the surface of the semiconductor wafer were ground two by two to a thickness of 200 μm. The semiconductor wafer with adhesive tape for protecting the surface of the semiconductor wafer after grinding is irradiated with ultraviolet rays of 500 mJ / cm 2 , and the surface of the semiconductor wafer is protected using a tensile tester manufactured by Instron (twin column desktop model 5567 (trade name)). The adhesive tape was peeled off, and the peeling force when the width at the time of peeling became the maximum (200 mm) was evaluated according to the following criteria. A and B pass.
In Table 1, it is shown as "peeling property".
（評価基準）
Ａ：２０Ｎ／２００ｍｍ以下
Ｂ：２０Ｎ／２００ｍｍ越５０Ｎ／２００ｍｍ以下
Ｃ：５０Ｎ／２００ｍｍ越(Evaluation criteria)
A: 20N / 200mm or less B: 20N / 200mm over 50N / 200mm or less C: 50N / 200mm over
（６）糊残り評価
剥離性評価で用いた、実施例１の表面保護テープ付ウェハ（バンプ高さ：５０μｍ）５枚について、光学顕微鏡（オリンパス）を用いて糊残り観察を行った。評価基準を以下に示す。
（評価基準）
合格：全ての表面保護テープ付ウェハに糊残りが発生しなかった。
不合格：少なくとも１枚の表面保護テープ付ウェハに糊残りが発生した。(6) Evaluation of glue residue The five wafers with surface protective tape (bump height: 50 μm) of Example 1 used in the peelability evaluation were observed with an optical microscope (Olympus). The evaluation criteria are shown below.
(Evaluation criteria)
Pass: No adhesive residue was generated on all wafers with surface protection tape.
Fail: Adhesive residue was generated on at least one wafer with surface protection tape.
＜試験例３＞耐熱性試験
ミラーウェハに実施例１の表面保護テープの貼合を行った。貼合条件は試験例２でシリコンウェハに表面保護テープを貼合した条件と同一である。その後、９０℃に加熱したホットプレート上にテープ面を下向きにして、表面保護テープの基材フィルムがホットプレートと接するようにして、３分間静置した後、テープ表面を目視にて観察を行った。
（評価基準）
合格：基材フィルムが溶けなかった。
不合格：基材フィルムが溶けた。<Test Example 3> Heat resistance test The surface protective tape of Example 1 was attached to the mirror wafer. The bonding conditions are the same as the conditions for bonding the surface protective tape to the silicon wafer in Test Example 2. Then, the tape surface was turned downward on the hot plate heated to 90 ° C., the base film of the surface protective tape was in contact with the hot plate, and the mixture was allowed to stand for 3 minutes, and then the tape surface was visually observed. rice field.
(Evaluation criteria)
Pass: The base film did not melt.
Fail: The base film has melted.
＜物性の測定＞
（融点、ビカット軟化点、ＭＦＲ）
中間樹脂層を構成する樹脂の融点及びビカット軟化点については、ＪＩＳ Ｋ ７２０６に基づいて測定を行った。中間樹脂層を構成する樹脂のメルトマスフローレート（ＭＦＲ）については、ＪＩＳ Ｋ ７２１０に基づいて測定を行った。基材フィルムの構成材料の融点は、ＪＩＳ Ｋ ６９７７－２に基づいて測定を行った。
（粘着力）
上述した方法により測定した。<Measurement of physical properties>
(Melting point, Vicat softening point, MFR)
The melting point and the Vicat softening point of the resin constituting the intermediate resin layer were measured based on JIS K 7206. The melt mass flow rate (MFR) of the resin constituting the intermediate resin layer was measured based on JIS K 7210. The melting point of the constituent material of the base film was measured based on JIS K 6977-2.
(Adhesive force)
It was measured by the method described above.
＜表の注＞
粘着力の行の括弧書きは、粘着剤層の形成に使用した粘着剤組成物の種類を示す。<Note to the table>
The brackets in the adhesive strength line indicate the type of adhesive composition used to form the adhesive layer.
表１から明らかなように、実施例１、参考例２、３及び実施例４の表面保護テープは、密着性にすぐれ、ダスト侵入、搬送エラー、ウェハ破損を抑制することができた。さらに、実施例１、参考例２、３及び実施例４の表面保護テープは、半導体ウェハ表面に貼合した状態での反りを抑制でき、剥離性、糊残り及び耐熱性に優れた。
これに対し、比較例１～３の表面保護テープは少なくとも２つの評価項目が不合格であった。
As is clear from Table 1 , the surface protective tapes of Examples 1, Reference Examples 2, 3 and 4 have excellent adhesion and can suppress dust intrusion, transfer error, and wafer breakage. Further, the surface protective tapes of Examples 1, Reference Examples 2, 3 and 4 can suppress warpage in a state of being bonded to the surface of the semiconductor wafer, and are excellent in peelability, adhesive residue and heat resistance.
On the other hand, the surface protective tapes of Comparative Examples 1 to 3 failed at least two evaluation items.
本発明をその実施態様とともに説明したが、我々は特に指定しない限り我々の発明を説明のどの細部においても限定しようとするものではなく、添付の請求の範囲に示した発明の精神と範囲に反することなく幅広く解釈されるべきであると考える。 Although the present invention has been described with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified, and it is contrary to the spirit and scope of the invention shown in the appended claims. I think it should be broadly interpreted without any.
本願は、２０１７年３月３１日に日本国で特許出願された特願２０１７－７１３４６に基づく優先権を主張するものであり、これはいずれもここに参照してその内容を本明細書の記載の一部として取り込む。 The present application claims priority based on Japanese Patent Application No. 2017-71346 filed in Japan on March 31, 2017, both of which are described herein with reference to this. Incorporate as part of.
１０ 半導体ウェハ表面保護用粘着テープ
１ 粘着剤層
２ 中間樹脂層
３ 基材フィルム10 Adhesive tape for surface protection of semiconductor wafer 1
Claims (8)
前記半導体ウェハ表面保護用粘着テープは、基材フィルムと、粘着剤層と、該基材フィルムと該粘着剤層との間に中間樹脂層とを有し、
前記中間樹脂層の厚みが、前記凹凸差以上であり、該中間樹脂層を構成する樹脂がメタロセンプラストマー樹脂であり、該中間樹脂層を構成する樹脂の融点若しくはビカット軟化点が４０℃～９０℃であり、該中間樹脂層を構成する樹脂のメルトマスフローレートが、１０ｇ／１０ｍｉｎ～１００ｇ／１０ｍｉｎである、半導体ウェハ表面保護用粘着テープ。 An adhesive tape for protecting the surface of a semiconductor wafer, which is used by heating and bonding to the surface of a semiconductor wafer having an unevenness difference of 20 μm or more under the conditions of 40 ° C to 90 ° C.
The adhesive tape for protecting the surface of a semiconductor wafer has a base film, an adhesive layer, and an intermediate resin layer between the base film and the adhesive layer.
The thickness of the intermediate resin layer is equal to or greater than the unevenness difference, the resin constituting the intermediate resin layer is a metallocene plastomer resin, and the melting point or the Vicat softening point of the resin constituting the intermediate resin layer is 40 ° C. to 90 ° C. An adhesive tape for protecting the surface of a semiconductor wafer, which is at ° C. and has a melt mass flow rate of 10 g / 10 min to 100 g / 10 min of the resin constituting the intermediate resin layer.
前記半導体ウェハ表面保護用粘着テープは、基材フィルムと、粘着剤層と、該基材フィルムと該粘着剤層との間に中間樹脂層とを有し、
該中間樹脂層の厚みが、前記凹凸差以上であり、該中間樹脂層を構成する樹脂がメタロセンプラストマー樹脂であり、該中間樹脂層を構成する樹脂の融点若しくはビカット軟化点が４０℃～９０℃であり、該中間樹脂層を構成する樹脂のメルトマスフローレートが、１０ｇ／１０ｍｉｎ～１００ｇ／１０ｍｉｎである、半導体ウェハの加工方法。
A semiconductor wafer processing method that includes grinding the back surface of a semiconductor wafer by heating and adhering an adhesive tape for protecting the surface of the semiconductor wafer to the surface of a semiconductor wafer having an unevenness difference of 20 μm or more under the conditions of 40 ° C to 90 ° C. There,
The adhesive tape for protecting the surface of a semiconductor wafer has a base film, an adhesive layer, and an intermediate resin layer between the base film and the adhesive layer.
The thickness of the intermediate resin layer is equal to or greater than the unevenness difference, the resin constituting the intermediate resin layer is a metallocene plastomer resin, and the melting point or the Vicat softening point of the resin constituting the intermediate resin layer is 40 ° C. to 90 ° C. A method for processing a semiconductor wafer, wherein the temperature is 1 ° C. and the melt mass flow rate of the resin constituting the intermediate resin layer is 10 g / 10 min to 100 g / 10 min.
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| JP2017071346 | 2017-03-31 | ||
| PCT/JP2018/012284 WO2018181240A1 (en) | 2017-03-31 | 2018-03-27 | Adhesive tape for semiconductor wafer surface protection, and semiconductor wafer processing method |
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| WO2020175363A1 (en) * | 2019-02-26 | 2020-09-03 | 株式会社ディスコ | Adhesive sheet for backgrinding and production method for semiconductor wafer |
| KR20210128382A (en) * | 2019-02-26 | 2021-10-26 | 가부시기가이샤 디스코 | Adhesive sheet for backside grinding and manufacturing method of semiconductor wafer |
| JP7289688B2 (en) * | 2019-03-26 | 2023-06-12 | 日東電工株式会社 | Dicing tape with adhesive film |
| JP6678796B1 (en) * | 2019-04-08 | 2020-04-08 | 古河電気工業株式会社 | Electronic component tape and electronic component processing method |
| JP6678795B1 (en) * | 2019-04-08 | 2020-04-08 | 古河電気工業株式会社 | Electronic component tape and electronic component processing method |
| KR102411362B1 (en) * | 2021-07-09 | 2022-06-22 | 구동필 | Adhesion film for wafer back grinding and its manufacturing method |
| CN118077037A (en) * | 2021-10-20 | 2024-05-24 | 电化株式会社 | Substrate for adhesive sheet for processing semiconductor wafer having convex portion |
| WO2023083248A1 (en) * | 2021-11-11 | 2023-05-19 | Ddp Specialty Electronic Materials Us, Llc | Adhesive system |
| JP7173392B1 (en) | 2022-05-12 | 2022-11-16 | 大日本印刷株式会社 | Adhesive tape for semiconductor processing |
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