TW201630734A - Surface protective sheet - Google Patents
Surface protective sheet Download PDFInfo
- Publication number
- TW201630734A TW201630734A TW104134629A TW104134629A TW201630734A TW 201630734 A TW201630734 A TW 201630734A TW 104134629 A TW104134629 A TW 104134629A TW 104134629 A TW104134629 A TW 104134629A TW 201630734 A TW201630734 A TW 201630734A
- Authority
- TW
- Taiwan
- Prior art keywords
- film
- surface protection
- adhesive
- wafer
- adhesive portion
- Prior art date
Links
- 230000001681 protective effect Effects 0.000 title abstract description 39
- 239000000853 adhesive Substances 0.000 claims abstract description 110
- 230000001070 adhesive effect Effects 0.000 claims abstract description 110
- 239000011347 resin Substances 0.000 claims abstract description 70
- 229920005989 resin Polymers 0.000 claims abstract description 70
- 239000004065 semiconductor Substances 0.000 claims abstract description 30
- 239000011247 coating layer Substances 0.000 claims abstract description 29
- 239000011231 conductive filler Substances 0.000 claims abstract description 24
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000000758 substrate Substances 0.000 claims description 52
- 239000011248 coating agent Substances 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 31
- 239000012790 adhesive layer Substances 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 20
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- 238000005498 polishing Methods 0.000 claims description 14
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- 238000000227 grinding Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 58
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- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本發明係關於表面保護用膜片，更詳言之，係在表面形成電路的半導體晶圓的背面研磨時，可用於保護電路面的表面保護用膜片。 The present invention relates to a film for surface protection, and more particularly to a film for surface protection for protecting a circuit surface when the back surface of a semiconductor wafer on which a circuit is formed is polished.
隨著半導體裝置的高密度構裝化，半導體晶片與基板的接合，大多使用由焊料所組成的球狀、柱狀或圓錐台狀的電極(以下，「凸塊」)。將在電路面形成如此的凸塊的晶圓背面研磨，則因凸塊的落差所造成的壓力差會直接影響背面，以使用於保護表面的黏著膜片的緩衝性無法抑制，而使凸塊及晶圓在研磨步驟中破損，或生成凹陷(在背面生成凹坑)，而成為損及完成的裝置的可靠度的主要原因。如此的情形，在先前為避免晶圓破損而以完成厚度較厚，或採取凸塊的排列密度較疏的設計來迴避。 In order to achieve high-density mounting of a semiconductor device, a spherical, columnar, or truncated-cone electrode (hereinafter, "bump") composed of solder is often used for bonding a semiconductor wafer to a substrate. When the back surface of the wafer on which the bumps are formed on the circuit surface is ground, the pressure difference caused by the drop of the bump directly affects the back surface, so that the cushioning property of the adhesive film used for the protective surface cannot be suppressed, and the bump is not formed. And the wafer is broken in the polishing step, or a depression is formed (a pit is formed on the back surface), which is a factor that degrades the reliability of the completed device. In such a case, in the past, in order to avoid wafer breakage, it is necessary to avoid thickening of the thickness, or to adopt a design with a dense arrangement of bumps.
但是，近年要求將凸塊高密度排列的裝置變多。對如此的裝置使用通常的表面保護用的黏著膜片A，則如第6圖所示，凸塊阻礙使黏著劑層無法黏貼到晶圓的端部。結果，背面研磨時以去除熱或切削屑為目的所噴霧的洗淨水的一部分，滲入電路面側，而污損電路面。 However, in recent years, there has been a demand for a device having a high density of bumps. When the conventional adhesive film A for surface protection is used for such a device, as shown in Fig. 6, the bumps prevent the adhesive layer from adhering to the end of the wafer. As a result, a part of the washing water sprayed for the purpose of removing heat or cutting chips during back grinding penetrates into the circuit surface side and stains the circuit surface.
因此，藉由將黏著劑層的厚度加厚，進一步提升 黏著劑的流動性，使黏著劑層與晶圓的端部貼緊來對應。但是，當黏著劑流動化，則黏著劑變得容易繞入凸塊的根部，而在黏著膜片的剝離操作附著在凸塊的根部的黏著劑會引起層內破損，而其中的一部分殘著在電路面。此在使用能量線硬化型黏著劑的黏著膜片時，亦係可能發生的問題。殘著在電路面的黏著劑，若沒有以溶劑洗淨等去除，則殘留成裝置的異物而損及完成的裝置的可靠度。 Therefore, it is further enhanced by thickening the thickness of the adhesive layer. The fluidity of the adhesive corresponds to the adhesion of the adhesive layer to the ends of the wafer. However, when the adhesive fluidizes, the adhesive becomes easy to wrap around the root of the bump, and the adhesive adhered to the root of the bump at the peeling operation of the adhesive film causes breakage in the layer, and a part of it remains. On the circuit side. This is also a problem that may occur when an adhesive film of an energy ray-curable adhesive is used. If the adhesive remaining on the circuit surface is removed by washing with a solvent or the like, the foreign matter of the device remains, and the reliability of the completed device is impaired.
專利文獻1，揭示一種對半導體晶圓黏貼保護膠帶的方法，其特徵在於：使用藉由適宜處理可控制黏著力的保護膠帶，僅對半導體晶圓的周邊部，將保護膠帶以強黏著狀態黏貼。該方法，主要是使用紫外線硬化型黏著膠帶作為保護膠帶，在黏貼半導體晶圓之前，將抵接晶圓的元件形成區域的黏著劑層硬化，僅以晶圓的周邊部進行晶圓的固定。 Patent Document 1 discloses a method of attaching a protective tape to a semiconductor wafer, characterized in that a protective tape which can be controlled by an appropriate treatment is used, and the protective tape is adhered to the peripheral portion of the semiconductor wafer only in a strong adhesive state. . In this method, an ultraviolet-curable adhesive tape is mainly used as a protective tape, and the adhesive layer abutting on the element formation region of the wafer is hardened before the semiconductor wafer is pasted, and the wafer is fixed only at the peripheral portion of the wafer.
但是，以專利文獻1的方法，硬化黏著劑層與未硬化的黏著劑層在同一平面上。因此，當凸塊的高度變高，則凸塊會阻礙使黏著劑層無法黏貼在晶圓的端部。因此，如第6圖所示，洗淨水滲入電路面的問題，並沒有被充分解決。特別是為提升晶片產率，將電路形成到晶圓的端部，則黏貼黏著膜片的餘白部分變窄，而變得難以黏貼黏著膜片，或黏著膜片容易剝離。 However, in the method of Patent Document 1, the hardened adhesive layer is on the same plane as the uncured adhesive layer. Therefore, when the height of the bump becomes high, the bump prevents the adhesive layer from sticking to the end of the wafer. Therefore, as shown in Fig. 6, the problem that the washing water penetrates into the circuit surface is not sufficiently solved. In particular, in order to increase the yield of the wafer and form the circuit to the end of the wafer, the remaining white portion of the adhesive film is narrowed, and it becomes difficult to adhere to the adhesive film, or the adhesive film is easily peeled off.
專利文獻2，作為對高凸塊晶圓的對策，提案在硬質基材的外周部設環狀的接著部的保護膠帶。環狀的接著部，係與沒有形成凸塊的晶圓的端部相對，密著於晶圓端部，保護電路面。如此的保護膠帶，外周接著部的厚度，係按照晶圓凸 塊的高度設定，先前為100~200μm左右。 Patent Document 2 proposes a protective tape for a ring-shaped adhesive portion on the outer peripheral portion of the hard substrate as a measure against the high bump wafer. The annular contact portion is opposed to the end portion of the wafer on which the bump is not formed, and is adhered to the end portion of the wafer to protect the circuit surface. Such a protective tape, the thickness of the outer peripheral portion is in accordance with the wafer bump The height setting of the block was previously about 100~200μm.
專利文獻1：日本特開平5-62950號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 5-62950
專利文獻2：日本特開2001-196404號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2001-196404
但是，使用專利文獻2的保護膠帶進行晶圓的背面研磨，則在將保護膠帶由晶圓剝離時，會因剝離帶電而產生靜電，而有損及形成在晶圓表面的電路之情形。近年，形成在晶圓表面的電路，由於線路微細化而高密度化，因剝離帶電所產生的靜電特別成問題。 However, when the back surface of the wafer is polished by the protective tape of Patent Document 2, when the protective tape is peeled off from the wafer, static electricity is generated by peeling and charging, and the circuit formed on the surface of the wafer is damaged. In recent years, the circuit formed on the surface of the wafer has been densified due to the miniaturization of the wiring, and static electricity generated by stripping electrification is particularly problematic.
本發明係以提供具有充分的帶電防止性能的表面保護用膜片為目標。 The present invention is directed to providing a film for surface protection having sufficient charging prevention performance.
用於解決上述課題的本發明，包含以下的要點。 The present invention for solving the above problems includes the following points.
[1]一種表面保護用膜片，係使用在電路形成在表面的半導體晶圓的背面研磨時的表面保護用膜片，其特徵在於：具有：非黏著部，其係在由含有無機導電性填充劑與硬化性樹脂(A)的硬化物的帶電防止塗層及由支持薄膜所構成的基材的一面，直徑較黏貼的半導體晶圓的外徑小；及黏著部，其係圍繞該非黏著部， 基材的楊氏模量為100~2000MPa。 [1] A film for surface protection, which is a film for surface protection when a back surface of a semiconductor wafer having a circuit formed on a surface is polished, and has a non-adhesive portion containing inorganic conductivity. The charging prevention coating of the cured material of the hardener (A) and the surface of the substrate composed of the supporting film, the outer diameter of the semiconductor wafer having a smaller diameter; and the adhesive portion surrounding the non-adhesive unit, The Young's modulus of the substrate is 100 to 2000 MPa.
[2]如[1]所述的表面保護用膜片，其中在擴張10%時經過1分鐘後的基材的應力緩和率為60%以上。 [2] The surface protective film according to [1], wherein the stress relaxation rate of the substrate after one minute of expansion at 10% is 60% or more.
[3]如[1]或[2]所述的表面保護用膜片，其中帶電防止塗層，對硬化性樹脂(A)的硬化物100質量部，含有100~600質量部無機導電性填充劑。 [3] The surface protection film according to the above [1], wherein the charge-preventing coating layer contains 100 to 600 parts by mass of the inorganic conductive filler to the cured portion of the curable resin (A). Agent.
[4]如[1]至[3]中任一項所述的表面保護用膜片，其中支持薄膜包含硬化性樹脂(B)的硬化物。 [4] The surface protection film according to any one of [1] to [3] wherein the support film contains a cured product of the curable resin (B).
[5]如[4]所述的表面保護用膜片，其中硬化性樹脂(B)係能量線硬化型含尿烷樹脂。 [5] The surface protective film according to [4], wherein the curable resin (B) is an energy ray-curable urethane-containing resin.
[6]如[1]至[5]中任一項所述的表面保護用膜片，其中帶電防止塗層的厚度為0.2~5μm。 [6] The surface protection film according to any one of [1] to [5] wherein the thickness of the electrification preventing coating layer is 0.2 to 5 μm.
[7]如[1]至[6]中任一項所述的表面保護用膜片，其中黏著部的厚度為30μm以下。 [7] The surface protection film according to any one of [1] to [6] wherein the thickness of the adhesive portion is 30 μm or less.
[8]如[7]所述的表面保護用膜片，其中黏著部係以單層的黏著劑層構成。 [8] The film for surface protection according to [7], wherein the adhesive portion is composed of a single layer of an adhesive layer.
[9]一種表面保護用膜片的製造方法，製造[1]至[8]中任一項所述的表面保護用膜片的方法，其特徵在於依序具有：將包含硬化性樹脂(B)的調合物塗佈於工程膜片預備硬化，形成預備硬化層的步驟；將由包含無機導電性填充劑與硬化性樹脂(A)之調合物所形成之塗膜或樹脂層，設於預備硬化層上的步驟；及使預備硬化層硬化，形成基材的步驟。 [9] A method for producing a film for surface protection according to any one of [1] to [8], wherein the method further comprises: comprising a curable resin (B) The coating composition is applied to the engineered film to be pre-hardened to form a preliminary hardened layer; and the coating film or resin layer formed of the blend comprising the inorganic conductive filler and the curable resin (A) is provided in the preliminary hardening layer. a step on the layer; and a step of hardening the preliminary hardened layer to form a substrate.
根據本發明的表面保護用膜片，可抑制因剝離帶電所產生的靜電，可防止靜電損傷晶圓電路。 According to the surface protection film of the present invention, it is possible to suppress static electricity generated by peeling and charging, and it is possible to prevent electrostatic damage to the wafer circuit.
1‧‧‧帶電防止塗層 1‧‧‧Electrified anti-coating
2‧‧‧支持薄膜 2‧‧‧Support film
3‧‧‧非黏著劑層 3‧‧‧ Non-adhesive layer
4‧‧‧黏著部 4‧‧‧Adhesive
5‧‧‧基材 5‧‧‧Substrate
10‧‧‧表面保護用膜片 10‧‧‧Surface protection diaphragm
第1圖係表示本發明的表面保護用膜片的立體圖。 Fig. 1 is a perspective view showing a film for surface protection of the present invention.
第2圖係第1圖的A-A線剖面圖。 Fig. 2 is a cross-sectional view taken along line A-A of Fig. 1.
第3圖係關於本發明的其他態樣的表面保護用膜片的立體圖。 Fig. 3 is a perspective view of a film for surface protection according to another aspect of the present invention.
第4圖係第3圖的B-B線剖面圖。 Fig. 4 is a cross-sectional view taken along line B-B of Fig. 3.
第5圖係表示將本發明的表面保護用膜片黏貼在晶圓的凸塊面進行晶圓背面研磨的狀態。 Fig. 5 is a view showing a state in which the surface protective film of the present invention is adhered to the bump surface of the wafer to perform backside polishing of the wafer.
第6圖係表示先前的表面保護用膜片的使用態樣之一例。 Fig. 6 is a view showing an example of the use of the conventional film for surface protection.
以下，參照圖面更具體說明本發明。關於本發明的表面保護用膜片10，係使用於進行半導體晶圓的背面研磨時。關於表面保護用膜片10的一態樣，於第1圖表示立體圖示，於第2圖表示第1圖的剖面圖。如圖示，本發明的表面保護用膜片10，係由無機導電性填充劑與硬化性樹脂(A)的硬化物所構成的帶電防止塗層1及由支持薄膜2所構成的基材5的一面，具有直徑較黏貼的半導體晶圓的外徑小的非黏著部3，及圍繞該非黏著部3的黏著部4。 Hereinafter, the present invention will be more specifically described with reference to the drawings. The surface protection film 10 of the present invention is used for performing back surface polishing of a semiconductor wafer. One aspect of the surface protective film 10 is a perspective view in the first drawing, and a cross-sectional view in the first drawing in the second drawing. As shown in the figure, the surface protection film 10 of the present invention is a charging prevention coating layer 1 composed of a cured product of an inorganic conductive filler and a curable resin (A), and a substrate 5 composed of a support film 2 One side has a non-adhesive portion 3 having a small outer diameter of the semiconductor wafer having a relatively small diameter, and an adhesive portion 4 surrounding the non-adhesive portion 3.
再者，在本發明的其他的態樣，如第3圖的立體圖，第4圖所示剖面圖，亦可為非黏著部3的表面與黏著部4 的表面，連續在同一平面上的形態。 Furthermore, in another aspect of the present invention, as shown in the perspective view of FIG. 3, the cross-sectional view shown in FIG. 4 may also be the surface of the non-adhesive portion 3 and the adhesive portion 4. The surface, continuous in the same plane.
使用於本發明的表面保護用膜片的基材，係由帶電防止塗層與支持薄膜所構成。以下，依序說明帶電防止塗層、支持薄膜。 The substrate used for the surface protection film of the present invention is composed of a charging prevention coating layer and a supporting film. Hereinafter, the electrification preventing coating and the supporting film will be described in order.
(帶電防止塗層) (charged anti-coating)
帶電防止塗層，係披覆後述的支持薄膜的單面或雙面而形成。藉由設置帶電防止塗層，在將關於本發明的表面保護用膜片由被著體(例如半導體晶圓等)剝離時可有效地使剝離帶電所產生的靜電擴散，提升帶電防止性能。帶電防止塗層，係由無機導電性填充劑與硬化性樹脂(A)的硬化物構成，可由使包含無機導電性填充劑與硬化性樹脂(A)之調合物硬化的方法而得。 The charge preventing coating layer is formed by coating one or both sides of a support film to be described later. When the surface protective film of the present invention is peeled off from a substrate (for example, a semiconductor wafer or the like) by the provision of the electrification preventing coating, the static electricity generated by the peeling electrification can be effectively diffused, and the charging prevention performance can be improved. The charge-preventing coating layer is composed of an inorganic conductive filler and a cured product of the curable resin (A), and can be obtained by a method of curing a mixture containing an inorganic conductive filler and a curable resin (A).
無機導電性填充劑，並無特別限定，可舉例如Cu、Al、Ni、Sn、Zn等的金屬粉末等的金屬填充劑；或氧化鋅系、氧化鈦系、氧化錫系、氧化銦系、氧化銻系等的金屬氧化物填充劑。該等之中，相對較廉價，且有通用性，以氧化錫系的金屬氧化物填充劑為佳。氧化錫系的金屬氧化物填充劑，具體可使用銻摻雜氧化錫(ATO)，磷摻雜氧化錫(PTO)等。 The inorganic conductive filler is not particularly limited, and examples thereof include metal fillers such as metal powders such as Cu, Al, Ni, Sn, and Zn; and zinc oxide, titanium oxide, tin oxide, and indium oxide. A metal oxide filler such as lanthanum oxide. Among these, it is relatively inexpensive and versatile, and a tin oxide-based metal oxide filler is preferred. As the tin oxide-based metal oxide filler, specifically, antimony-doped tin oxide (ATO), phosphorus-doped tin oxide (PTO), or the like can be used.
無機導電性填充劑的平均粒徑，並無特別限定，以0.01~1μm為佳，以0.02~0.5μm更佳。平均粒徑，係以粒度分佈測定裝置(日機裝公司製的Microtrack UPA-150)測定之值。 The average particle diameter of the inorganic conductive filler is not particularly limited, and is preferably 0.01 to 1 μm, more preferably 0.02 to 0.5 μm. The average particle diameter is a value measured by a particle size distribution measuring apparatus (Microtrack UPA-150, manufactured by Nikkiso Co., Ltd.).
帶電防止塗層，對硬化性樹脂(A)的硬化物100質量部，含有無機導電性填充劑100~600質量部為佳，以150~600 質量部更佳，以200~600質量部特別佳。再者，通常硬化前的硬化性樹脂(A)及與無機導電性填充劑的調合量比，與硬化性樹脂(A)的硬化物及無機導電性填充劑的調合量比，大體上沒有差。因此，在本發明，將硬化前的硬化性樹脂(A)及無機導電性填充劑的調合量比，視為硬化性樹脂(A)的硬化物及無機導電性填充劑的調合量比。藉由使無機導電性填充劑在於帶電防止塗層的含量在上述範圍，可顯現優良的帶電防止性能。在帶電防止塗層的無機導電性填充劑的含量未滿100質量部時，有降低帶電防止性能的情形。又，在帶電防止塗層的無機導電性填充劑的含量超過600質量部時，在加工半導體晶圓的步驟，帶電防止塗層有發生龜裂的情形，結果降低帶電防止性能。 The charge-preventing coating layer is preferably 100 parts by mass of the cured product of the curable resin (A), and contains 100 to 600 parts of the inorganic conductive filler, preferably 150 to 600. The quality department is better, especially in the 200~600 quality department. Further, in general, the ratio of the amount of the curable resin (A) before curing and the amount of the inorganic conductive filler to the amount of the cured product of the curable resin (A) and the inorganic conductive filler is substantially the same. . Therefore, in the present invention, the blending ratio of the curable resin (A) and the inorganic conductive filler before curing is regarded as the blending ratio of the cured product of the curable resin (A) and the inorganic conductive filler. By making the content of the inorganic conductive filler in the charge prevention coating layer in the above range, excellent charge prevention performance can be exhibited. When the content of the inorganic conductive filler of the charge preventing coating layer is less than 100 parts by mass, the charging prevention performance may be lowered. In addition, when the content of the inorganic conductive filler of the charge preventing coating layer exceeds 600 parts by mass, the step of processing the semiconductor wafer causes cracking of the charging preventing coating layer, and as a result, the charging prevention performance is lowered.
硬化性樹脂(A)，並無特別限定，可使用能量線硬化型樹脂、熱硬化型樹脂等，而使用能量線硬化型樹脂為佳。 The curable resin (A) is not particularly limited, and an energy ray-curable resin or a thermosetting resin can be used, and an energy ray-curable resin is preferably used.
能量線硬化型樹脂，並無特別限定，可良好地使用例如，以能量線聚合性的尿烷(甲基)丙烯酸酯寡聚物、環氧(甲基)丙烯酸酯寡聚物等的寡聚物系能量線硬化型樹脂作為主劑的樹脂組成物。尿烷(甲基)丙烯酸酯寡聚物或環氧(甲基)丙烯酸酯寡聚物的重量平均分子量Mw(指以凝膠滲透層析之聚苯乙烯換算值。)，通常為1000~70000左右，以1500~60000的範圍為佳。上述尿烷(甲基)丙烯酸酯寡聚物或環氧(甲基)丙烯酸酯寡聚物，可以一種單獨或組合二種以上使用。 The energy ray-curable resin is not particularly limited, and for example, an oligomer of an energy ray-polymerizable urethane (meth) acrylate oligomer or an epoxy (meth) acrylate oligomer can be preferably used. A resin composition of an energy ray-curable resin as a main component. The weight average molecular weight Mw of the urethane (meth) acrylate oligomer or the epoxy (meth) acrylate oligomer (referred to as a polystyrene equivalent value by gel permeation chromatography), usually 1000 to 70,000 Left and right, it is better to range from 1500 to 60,000. The urethane (meth) acrylate oligomer or the epoxy (meth) acrylate oligomer may be used alone or in combination of two or more.
使寡聚物系能量線硬化型樹脂在能量線硬化型樹脂的含量變大，則有降低與後述的支持薄膜的密著性之情形。為提升與支持薄膜的密著性，亦可在硬化性樹脂(A)的成分中 添加膠合劑成分。如此的膠合劑成分，可舉丙烯酸樹脂、聚酯樹脂、尿烷樹脂、聚醯胺樹脂等。 When the content of the energy ray-curable resin in the oligomer-based energy ray-curable resin is increased, the adhesion to the support film to be described later may be lowered. In order to improve the adhesion of the supporting film, it may also be in the composition of the curable resin (A). Add a binder component. Examples of such a binder component include an acrylic resin, a polyester resin, a urethane resin, and a polyamide resin.
又，能量線硬化型樹脂，亦可係於側鏈具有能量線硬化性官能基的聚合物。使用如此的聚合物作為能量線硬化型樹脂，則可不降低架橋密度而提升與支持薄膜的密著性。如此的聚合物，可使用例如，主鏈為丙烯酸聚合物，於側鏈具有能量線硬化性雙鍵鍵結或環氧基作為官能基者。 Further, the energy ray-curable resin may be a polymer having an energy ray-curable functional group in a side chain. When such a polymer is used as the energy ray-curable resin, the adhesion to the support film can be improved without lowering the bridging density. As such a polymer, for example, an acrylic polymer having a main chain and an energy ray hardening double bond or an epoxy group as a functional group in a side chain can be used.
藉由在能量線硬化型樹脂，混入光聚合起始劑，可減少藉由能量線照射的聚合硬化時間及照射量。光聚合起始劑，可舉安息香化合物、苯乙酮化合物、醯基氧化膦化合物、二茂鈦化合物、噻噸酮化合物、過氧化物等的光聚合起始劑；胺或醌等的光增感劑等，具體可舉1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基-丙1-烷、安息香、安息香甲醚、安息香***、安息香異丙醚等。 By mixing the photopolymerization initiator in the energy ray-curable resin, the polymerization hardening time and the irradiation amount by the energy ray irradiation can be reduced. The photopolymerization initiator may, for example, be a photopolymerization initiator of a benzoin compound, an acetophenone compound, a mercaptophosphine oxide compound, a titanocene compound, a thioxanthone compound, a peroxide, or the like; Specific examples of the sensitizer include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-al, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
又，為提升無機導電性填充劑的樹脂中的分散性，亦可在硬化性樹脂(A)調合分散劑。又，亦可含有顏料或染料等的著色劑等的添加劑。 Moreover, in order to improve the dispersibility in the resin of the inorganic conductive filler, the dispersing agent may be blended in the curable resin (A). Further, an additive such as a coloring agent such as a pigment or a dye may be contained.
帶電防止塗層，可將含有無機導電性填充劑與硬化性樹脂(A)的調合物直接在後述的支持薄膜上製膜、硬化而形成。又，可將含有無機導電性填充劑與硬化性樹脂(A)的調合物以液體的狀態，以薄膜狀澆鑄在工程薄膜上，進一步在其上，將後述的含有硬化性樹脂(B)的調合物澆鑄，得到由帶電防止塗層與支持薄膜所構成的基材。此時，進行硬化的程序，可在各個製膜之後，亦可在製膜基材之後，一口氣進行。 The charge-preventing coating layer can be formed by directly forming and curing a blend containing an inorganic conductive filler and a curable resin (A) on a support film to be described later. In addition, the blend containing the inorganic conductive filler and the curable resin (A) can be cast on the engineering film in a liquid state in a liquid state, and further, a curable resin (B) to be described later can be further added thereto. The blend is cast to obtain a substrate composed of a charge preventing coating and a supporting film. At this time, the process of hardening may be performed after each film formation or after the film formation substrate.
帶電防止塗層的厚度，以0.2~5μm，以0.5~5μm為佳，以1~4μm更佳。藉由使帶電防止塗層的厚度在上述範圍，有可維持較高的帶電防止性能的傾向。 The thickness of the electrification preventing coating is preferably 0.2 to 5 μm, preferably 0.5 to 5 μm, more preferably 1 to 4 μm. When the thickness of the electrification preventing coating layer is in the above range, there is a tendency that the high charging prevention performance can be maintained.
又，帶電防止塗層的表面電阻率，以1×1012Ω/□以下為佳，以1×1011Ω/□以下更佳，以1×1010Ω/□以下特別佳。帶電防止塗層的表面電阻率超過1×1012Ω/□，則在將本發明的表面保護用膜片由被著體剝離時，有難以穩定地抑制產生靜電之情形。藉由使帶電防止塗層的表面電阻率在上述範圍，可提升表面保護用膜片的帶電防止性能。帶電防止塗層的表面電阻率，係將帶電防止塗層裁切成100mm×100mm而得的樣品，在23℃、平均濕度50%RH的條件下調濕24小時之後，將其表面的阻抗值，遵照JIS K6911；1995測定。 Further, the surface resistivity of the electrification preventing coating layer is preferably 1 × 10 12 Ω / □ or less, more preferably 1 × 10 11 Ω / □ or less, and particularly preferably 1 × 10 10 Ω / □ or less. When the surface resistivity of the surface protective film of the present invention is more than 1 × 10 12 Ω/□, it is difficult to stably suppress the generation of static electricity when the film for surface protection of the present invention is peeled off from the object. By setting the surface resistivity of the electrification preventing coating layer to the above range, the charging prevention performance of the surface protective film can be improved. The surface resistivity of the electrification preventing coating is a sample obtained by cutting the charging preventing coating into 100 mm × 100 mm, and after adjusting the humidity for 24 hours under the condition of 23 ° C and an average humidity of 50% RH, the impedance value of the surface is Determined in accordance with JIS K6911; 1995.
(支持薄膜) (support film)
使用於本發明的表面保護用膜片的支持薄膜，只要是樹脂膜片，並無特別限定，可使用各種樹脂膜片。如此的樹脂膜片，可舉例如聚烯烴、聚氯乙烯、丙烯酸橡膠、尿烷等的樹脂薄膜。支持薄膜，可為該等的單層，亦可由層積體構成。又，亦可為施以架橋等的處理的薄膜。 The support film used for the surface protection film of the present invention is not particularly limited as long as it is a resin film, and various resin films can be used. Such a resin film may, for example, be a resin film such as polyolefin, polyvinyl chloride, acrylic rubber or urethane. The support film may be such a single layer or may be composed of a laminate. Further, it may be a film subjected to treatment such as bridging.
如此的支持薄膜，可使用將熱可塑性樹脂藉由擠出成形膜片化者，亦可使用將硬化性樹脂(B)以既定手段薄膜化、硬化的硬化物所構成的薄膜。支持薄膜，使用硬化性樹脂(B)的硬化物所構成的薄膜，則基材的應力緩和率及楊氏模量的控制變得容易的同時，可提升帶電防止塗層的密著性。 As such a support film, a film formed by extrusion molding a thermoplastic resin or a cured product obtained by thinning and hardening a curable resin (B) by a predetermined means may be used. In the support film, a film made of a cured product of the curable resin (B) can easily control the stress relaxation rate and the Young's modulus of the substrate, and can improve the adhesion of the charge prevention coating.
硬化性樹脂(B)，並無特別限定，可與使用於帶電 防止塗層的硬化性樹脂(A)同樣，使用能量線硬化型樹脂、熱硬化型樹脂等，而使用能量線硬化型樹脂為佳。能量線硬化型樹脂，並無特別限定，可使用例如能量線硬化型含尿烷樹脂。含有能量線硬化型含尿烷樹脂的硬化物的支持薄膜，由於應力緩和性優良，容易將基材的應力緩合率調整在後述的範圍而佳。 The curable resin (B) is not particularly limited and can be used for charging In the same manner as the curable resin (A) for preventing coating, an energy ray-curable resin, a thermosetting resin, or the like is used, and an energy ray-curable resin is preferably used. The energy ray-curable resin is not particularly limited, and for example, an energy ray-curable urethane-containing resin can be used. The support film containing the cured product of the energy ray-curable urethane-containing resin is excellent in stress relaxation property, and it is easy to adjust the stress relaxation ratio of the substrate to a range described later.
能量線硬化型含尿烷樹脂，可舉以尿烷(甲基)丙烯酸酯樹脂或尿烷聚合物、與能量線聚合性單體為主要成分的能量線硬化型樹脂。 The energy ray-curable urethane-containing resin may, for example, be a urethane (meth) acrylate resin or a urethane polymer or an energy ray-curable resin containing an energy ray polymerizable monomer as a main component.
尿烷(甲基)丙烯酸酯樹脂，係包含尿烷(甲基)丙烯酸酯寡聚物的調合物，按照必要亦可包含在分子內含有硫醇基的化合物、或N-亞硝胺系聚合禁止劑及/或N-氧基系聚合禁止劑。 A urethane (meth) acrylate resin comprising a urethane (meth) acrylate oligomer, and if necessary, a thiol group-containing compound or an N-nitrosamine-based polymer. Prohibition agent and / or N-oxyl polymerization inhibitor.
尿烷(甲基)丙烯酸酯寡聚物，係具有(甲基)丙烯醯基，且具有尿烷鍵結的化合物。如此的尿烷(甲基)丙烯酸酯寡聚物，係多元醇化合物與多價異氰酸酯化合物反應而得的末端異氰酸酯尿烷預聚合物，與具有羥基的(甲基)丙烯酸酯反應而得。再者，在本說明書，(甲基)丙烯酸係以包含丙烯酸及甲基丙烯酸二者的意思使用。 A urethane (meth) acrylate oligomer is a compound having a (meth) acrylonitrile group and having a urethane bond. Such a urethane (meth) acrylate oligomer is obtained by reacting a terminal isocyanate urethane prepolymer obtained by reacting a polyol compound with a polyvalent isocyanate compound with a (meth) acrylate having a hydroxyl group. Further, in the present specification, the (meth)acrylic acid is used in the sense of containing both acrylic acid and methacrylic acid.
多元醇化合物，只要是具有兩個羥基以上的化合物，並無特別限定，可使用習知者。具體可為例如，亞烷二醇、聚醚型多元醇、聚酯型多元醇、聚碳酸酯型多元醇的任一，藉由使用聚醚型多元醇，可得更佳的效果。又，只要是多元醇，並無特別限定，可為2官能的二醇、3官能的三醇、再者亦可 為4官能以上的多元醇，由取得的容易性、通用性、反應性等的觀點，使用二醇特別佳。該等之中，可良好地使用聚醚型二醇。 The polyol compound is not particularly limited as long as it has two or more hydroxyl groups, and a conventional one can be used. Specifically, for example, any of an alkylene glycol, a polyether polyol, a polyester polyol, and a polycarbonate polyol can be used, and a polyether polyol can be used to obtain a more excellent effect. Further, the polyhydric alcohol is not particularly limited, and may be a bifunctional diol or a trifunctional triol, or may be a polyhydric alcohol. The diol is particularly preferably used from the viewpoint of availability, versatility, reactivity, and the like of the tetrafunctional or higher polyhydric alcohol. Among these, a polyether diol can be used favorably.
聚醚型多元醇的代表例之聚醚型二醇，一般係以HO-(-R-O-)n-H表示。在此，R係2價的碳化氫基、以亞烷基為佳，以碳數1~6的亞烷基更佳，以碳數2或3的亞烷基特別佳。又，碳數1~6的亞烷基之中，以乙烯、丙烯或四亞甲基更佳，以乙烯或丙烯特別佳。因此特別佳的聚醚型二醇，可舉聚乙二醇、聚丙二醇、聚四亞甲基二醇，再者特別佳的聚醚型二醇，可舉聚乙二醇、聚丙二醇。n係R的反覆數，以10~250左右為佳，以25~205左右更好，以40~185左右特別佳。n小於10，則尿烷(甲基)丙烯酸酯寡聚物的尿烷鍵結濃度變高，而支持薄膜的彈性躍昇，而使本發明的基材的楊氏模量變得過高。n大於250，則起因於聚醚鏈的相互作用變強，有使楊氏模量超過後述範圍的上限之虞。 A polyether diol which is a representative example of the polyether polyol is generally represented by HO-(-RO-) n -H. Here, the R-based divalent hydrocarbon group is preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 2 or 3 carbon atoms. Further, among the alkylene groups having 1 to 6 carbon atoms, ethylene, propylene or tetramethylene is more preferable, and ethylene or propylene is particularly preferable. Therefore, a particularly preferable polyether diol is polyethylene glycol, polypropylene glycol, or polytetramethylene glycol, and particularly preferred polyether diol, and polyethylene glycol or polypropylene glycol is exemplified. The number of repetitions of the n-series R is preferably about 10 to 250, more preferably about 25 to 205, and particularly preferably about 40 to 185. When n is less than 10, the urethane bond concentration of the urethane (meth) acrylate oligomer becomes high, and the elastic jump of the support film is caused, and the Young's modulus of the substrate of the present invention is excessively high. When n is more than 250, the interaction of the polyether chain becomes strong, and the Young's modulus exceeds the upper limit of the range described later.
藉由聚醚型二醇與多價異氰酸酯化合物的反應，生成導入醚鍵結部(-(-R-O-)n-)的末端異氰酸酯尿烷預聚合物。藉由使用如此的聚醚型二醇，尿烷(甲基)丙烯酸酯寡聚物，含有由聚醚型二醇衍生的構成單位。 By reacting a polyether diol with a polyvalent isocyanate compound, a terminal isocyanate urethane prepolymer which is introduced into an ether bond (-(-RO-) n- ) is formed. By using such a polyether diol, the urethane (meth) acrylate oligomer contains a constituent unit derived from a polyether diol.
聚酯型多元醇，可藉由多元醇化合物與多元酸成分聚縮合而得。多元醇化合物，可舉乙二醇、二甘醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、戊二醇、3-甲基-1,5-戊二醇、2,2,4-三甲基-1,3-戊二醇、己二醇、辛二醇、2,2-二乙基-1,3-丙二醇、2-乙基-2-丁基-1,3- 丙二醇、14-環己烷二甲醇、雙酚A的乙二醇或丙二醇加成物等的習知的各種二醇類等。用於製造聚酯型多元醇的多元酸成分，可使用一般已知作為聚酯的多元酸成分的各種習知者。具體可舉例如己二酸、馬來酸、琥珀酸、草酸、富馬酸、丙二酸、戊二酸、庚二酸、壬二酸、癸二酸、辛二酸等的二元酸；芳香族多元酸；對應該等的酸酐；其衍生物及二聚物酸；加氫二聚物酸等。再者為對塗膜賦予適度的硬度，使用芳香族多元酸為佳。該芳香族多元酸，可舉例如無水鄰苯二甲酸、間苯二甲酸、對苯二甲酸、2,6-二羧酸等的二元酸；或偏苯三酸、均苯四甲酸等的多元酸及對應該等的酸酐或其衍生物。再者該酯化反應，亦可按照需要使用各種習知的觸媒。觸媒，可舉例如二丁基氧化錫、辛酸亞錫等的錫化合物或鈦酸四丁酯、鈦酸四丙酯等的烷氧基鈦。 The polyester polyol can be obtained by polycondensation of a polyol compound and a polybasic acid component. The polyol compound may, for example, be ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl Alcohol, pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, hexanediol, octanediol, 2,2-di Ethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3- Various conventional glycols such as propylene glycol, 14-cyclohexanedimethanol, ethylene glycol or propylene glycol adduct of bisphenol A, and the like. As the polybasic acid component for producing the polyester polyol, various conventionally known as a polybasic acid component of a polyester can be used. Specific examples thereof include dibasic acids such as adipic acid, maleic acid, succinic acid, oxalic acid, fumaric acid, malonic acid, glutaric acid, pimelic acid, sebacic acid, sebacic acid, and suberic acid; An aromatic polybasic acid; an acid anhydride corresponding thereto; a derivative thereof and a dimer acid; a hydrogenated dimer acid. Further, in order to impart a moderate hardness to the coating film, it is preferred to use an aromatic polybasic acid. The aromatic polybasic acid may, for example, be a dibasic acid such as anhydrous phthalic acid, isophthalic acid, terephthalic acid or 2,6-dicarboxylic acid; or trimellitic acid or pyromellitic acid. A polybasic acid and an acid anhydride or a derivative thereof. Further, in the esterification reaction, various conventional catalysts may be used as needed. The catalyst may, for example, be a tin compound such as dibutyltin oxide or stannous octoate or a titanium alkoxide such as tetrabutyl titanate or tetrapropyl titanate.
聚碳酸酯型多元醇，並無特別限定，可使用習知者。具體可舉例如，上述乙二醇類與亞烷基碳酸酯的反應物等。 The polycarbonate polyol is not particularly limited, and a conventional one can be used. Specific examples thereof include a reaction product of the above ethylene glycols and an alkylene carbonate.
多元醇化合物的分子量，以500~10000左右為佳，以800~9000左右更佳。分子量較1000低，則尿烷(甲基)丙烯酸酯寡聚物的尿烷鍵結濃度變高，會使本發明的基材的楊氏模量變高。分子量過高，則起因於聚醚鏈的相互作用變強，有使楊氏模量超過後述範圍的上限之虞。 The molecular weight of the polyol compound is preferably from about 500 to 10,000, more preferably from about 800 to 9000. When the molecular weight is lower than 1,000, the urethane bond concentration of the urethane (meth) acrylate oligomer becomes high, and the Young's modulus of the substrate of the present invention becomes high. When the molecular weight is too high, the interaction due to the polyether chain becomes strong, and the Young's modulus exceeds the upper limit of the range described later.
又，多元醇化合物的分子量，係多元醇官能基數×56.11×1000/羥基價[mgKOH/g]，由多元醇化合物的羥基價計算出。 Further, the molecular weight of the polyol compound is the number of polyol functional groups × 56.11 × 1000 / hydroxyl group [mgKOH / g], and is calculated from the hydroxyl value of the polyol compound.
多價異氰酸酯化合物，可舉四亞甲基二異氰酸 酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯等的脂肪族系聚異氰酸酯類；異佛爾酮二異氰酸酯、降冰片烷二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、二環己基甲烷-2,4'-二異氰酸酯、ω,ω’-二異氰酸酯二甲基環己烷等的脂環族系二異氰酸酯類；4,4'-二苯基甲烷二異氰酸酯、甲苯二異氰酸酯、二甲苯二異氰酸酯、二異氰酸聯甲苯胺、四亞甲基二甲苯二異氰酸酯、萘-1,5-二異氰酸酯等的芳香族系二異氰酸酯類等。該等之中，使用異佛爾酮二異氰酸酯或六亞甲基二異氰酸酯、二甲苯二異氰酸酯，可維持尿烷(甲基)丙烯酸酯寡聚物的低黏度，使操作性良好而佳。 a polyvalent isocyanate compound, which may be tetramethylene diisocyanate Aliphatic polyisocyanates such as esters, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate; isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane-4, 4'- Alicyclic diisocyanates such as diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, ω,ω'-diisocyanate dimethylcyclohexane; 4,4'-diphenylmethane diisocyanate An aromatic diisocyanate such as toluene diisocyanate, xylene diisocyanate, diisocyanate diisocyanate, tetramethylene xylene diisocyanate or naphthalene-1,5-diisocyanate. Among these, isophorone diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate are used, and the low viscosity of the urethane (meth) acrylate oligomer can be maintained, and the workability is good.
對如上所述的多元醇化合物，與多價異氰酸酯化合物反應而得的末端異氰酸酯尿烷預聚合物，使具有羥基的(甲基)丙烯酸酯反應可得尿烷(甲基)丙烯酸酯寡聚物。 For the polyol compound as described above, a terminal isocyanate urethane prepolymer obtained by reacting a polyvalent isocyanate compound, and reacting a (meth) acrylate having a hydroxyl group to obtain a urethane (meth) acrylate oligomer .
具有羥基的(甲基)丙烯酸酯，只要是在1分子中具有羥基及(甲基)丙烯醯基的化合物，並無特別限定，可使用習知者。具體可舉例如2-羥基乙基(甲基)丙烯酸酯、2-羥基(甲基)丙基丙烯酸酯、4-羥基丁基(甲基)丙烯酸酯、4-羥環己基(甲基)丙烯酸酯、5-羥基環辛基(甲基)丙烯酸酯、2-羥基-3-苯基氧丙基(甲基)丙烯酸酯、異戊四醇三(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、丙二醇單(甲基)丙烯酸酯等的羥基烷基(甲基)丙烯酸酯、N-羥甲基(甲基)丙烯醯胺等的含有羥基的(甲基)丙烯醯胺、使(甲基)丙烯酸與雙酚A的二縮水甘油基反應而得的反應物等。 The (meth) acrylate having a hydroxyl group is not particularly limited as long as it has a hydroxyl group and a (meth)acryl fluorenyl group in one molecule, and a conventional one can be used. Specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) propyl acrylate, 4-hydroxybutyl (meth) acrylate, and 4-hydroxycyclohexyl (meth) acrylate. Ester, 5-hydroxycyclooctyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol single Hydroxyalkyl (meth) acrylate such as hydroxyalkyl (meth) acrylate or propylene glycol mono (meth) acrylate or hydroxyl group such as N-methylol (meth) acrylamide An amine or a reaction product obtained by reacting (meth)acrylic acid with a diglycidyl group of bisphenol A.
使具有末端異氰酸酯尿烷預聚合物及羥基的(甲基) 丙烯酸酯反應的條件，係將末端異氰酸酯尿烷預聚合物與具有羥基之(甲基)丙烯酸酯，按照需要在溶劑、觸媒的存在下，以60~100℃左右反應1~4小時左右即可。 (methyl) having a terminal isocyanate urethane prepolymer and a hydroxyl group The acrylate reaction is carried out by reacting a terminal isocyanate urethane prepolymer with a hydroxyl group-containing (meth) acrylate, and if necessary, in the presence of a solvent or a catalyst at about 60 to 100 ° C for about 1 to 4 hours. can.
所得尿烷(甲基)丙烯酸酯寡聚物，係在分子內具有光聚合性的雙鍵鍵結，可藉由能量線的照射而聚合硬化，形成皮膜的性質。上述尿烷(甲基)丙烯酸酯寡聚物，可以一種單獨或組合二種以上使用。尿烷(甲基)丙烯酸酯寡聚物，可為分子中僅具有1個(甲基)丙烯醯基的單官能尿烷(甲基)丙烯酸酯寡聚物，亦可為分子中具有2個以上的(甲基)丙烯醯基的多官能尿烷(甲基)丙烯酸酯寡聚物，以多官能尿烷(甲基)丙烯酸酯寡聚物為佳。尿烷(甲基)丙烯酸酯寡聚物為多官能尿烷(甲基)丙烯酸酯寡聚物，則如後所述，有藉由調整尿烷(甲基)丙烯酸酯寡聚物的重量平均分子量，可容易控制所得基材的楊氏模量優點。具有多官能尿烷(甲基)丙烯酸酯寡聚物的(甲基)丙烯醯基的數量，以2~3個為佳，以2個(尿烷(甲基)丙烯酸酯寡聚物為二官能尿烷(甲基)丙烯酸酯寡聚物)更佳。 The obtained urethane (meth) acrylate oligomer is a photopolymerizable double bond bond in the molecule, and can be polymerized and hardened by irradiation with an energy ray to form a film. The urethane (meth) acrylate oligomer may be used alone or in combination of two or more. The urethane (meth) acrylate oligomer may be a monofunctional urethane (meth) acrylate oligomer having only one (meth) acryl oxime group in the molecule, or may have two in the molecule The above (meth)acrylonitrile-based polyfunctional urethane (meth) acrylate oligomer is preferably a polyfunctional urethane (meth) acrylate oligomer. The urethane (meth) acrylate oligomer is a polyfunctional urethane (meth) acrylate oligomer, as described later, by adjusting the weight average of the urethane (meth) acrylate oligomer The molecular weight can easily control the Young's modulus advantage of the resulting substrate. The number of (meth)acryl fluorenyl groups having a polyfunctional urethane (meth) acrylate oligomer is preferably 2 to 3, and 2 (urethane (meth) acrylate oligomer is 2 A functional urethane (meth) acrylate oligomer is more preferred.
如此所得的尿烷(甲基)丙烯酸酯寡聚物的重量平均分子量(指以凝膠滲透層析之聚苯乙烯換算值，以下相同。)，並無特別限定，尿烷(甲基)丙烯酸酯寡聚物為多官能尿烷(甲基)丙烯酸酯寡聚物時，重量平均分子量以1500~10000左右為佳，以4000~9000左右更佳。藉由使重量平均分子量為1500以上，可抑制尿烷(甲基)丙烯酸酯寡聚物的聚合物的架橋密度的上升，而容易將基材的楊氏模量調整在不超過後述的範圍的上限的程度。又，藉由使之在10000以下，抑制尿烷(甲基)丙 烯酸酯寡聚物在聚合物的架橋密度的降低，可容易調整基材的楊氏模量不低過後述的範圍的下限。又，可使尿烷(甲基)丙烯酸酯寡聚物的黏度較低，提升製膜用塗佈液的操作性。 The weight average molecular weight of the urethane (meth) acrylate oligomer thus obtained (referred to as a polystyrene equivalent value by gel permeation chromatography, the same applies hereinafter), and is not particularly limited, and urethane (meth)acrylic acid When the ester oligomer is a polyfunctional urethane (meth) acrylate oligomer, the weight average molecular weight is preferably about 1,500 to 10,000, more preferably about 4,000 to 9000. When the weight average molecular weight is 1,500 or more, the bridging density of the polymer of the urethane (meth) acrylate oligomer can be suppressed, and the Young's modulus of the substrate can be easily adjusted to not exceed the range described later. The extent of the upper limit. Also, by making it below 10,000, urethane (methyl) propyl is inhibited. The reduction in the bridging density of the polymer of the enoate oligomer can easily adjust the Young's modulus of the substrate to be lower than the lower limit of the range described later. Further, the viscosity of the urethane (meth) acrylate oligomer can be made low, and the workability of the coating liquid for film formation can be improved.
使用如上所述的尿烷(甲基)丙烯酸酯時，由於難以成膜支持薄膜的情形較多，通常係以能量線聚合性單體稀釋成膜之後，將此硬化得到支持薄膜。能量線聚合性單體，係於分子內具有能量線聚合性的雙鍵鍵結，特別是在本發明，使用異冰片基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、苯基羥基丙基(甲基)丙烯酸酯等的具有體積較大的基的(甲基)丙烯酸酯系化合物為佳。 When the urethane (meth) acrylate as described above is used, since it is difficult to form a film-supporting film, it is usually diluted with a power ray-polymerizable monomer to form a film, and then cured to obtain a support film. The energy ray polymerizable monomer is a double bond bond having energy ray polymerization in a molecule, and particularly in the present invention, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate is used. A (meth) acrylate-based compound having a relatively large group such as phenylhydroxypropyl (meth) acrylate is preferred.
上述能量線聚合性單體，對尿烷(甲基)丙烯酸酯系寡聚物100質量部，以5~900質量部為佳，以10~500質量部更佳，以30~200質量部的比例使用特別佳。藉由使能量線聚合性單體的調合量在如此的範圍，在尿烷(甲基)丙烯酸酯寡聚物與能量線聚合性單體的共聚物，來自尿烷(甲基)丙烯酸酯寡聚物的(甲基)丙烯醯基的部分的間隔成為適當的程度，可容易將基材的楊氏模量控制在後述的範圍。 The energy ray polymerizable monomer is preferably 5 to 900 parts by mass, more preferably 10 to 500 parts by mass, and 30 to 200 parts by mass for the urethane (meth) acrylate type oligomer 100. The ratio is particularly good. By blending the energy ray polymerizable monomer in such a range, a copolymer of a urethane (meth) acrylate oligomer and an energy ray polymerizable monomer is derived from a urethane (meth) acrylate oligo. The interval between the portions of the (meth)acrylonitrile group of the polymer is appropriately adjusted, and the Young's modulus of the substrate can be easily controlled to the range described later.
由能量線硬化型樹脂的硬化物所構成的薄膜，亦可使用使尿烷聚合物與能量線聚合性單體為主要成分的能量線硬化型含尿烷樹脂硬化而得的支持薄膜。 A film composed of a cured product of the energy ray-curable resin may be a support film obtained by curing an energy ray-curable urethane resin containing a urethane polymer and an energy ray polymerizable monomer as a main component.
尿烷聚合物，係與尿烷(甲基)丙烯酸酯寡聚物不同，係在分子中沒有(甲基)丙烯醯基等的聚合性官能基的尿烷系聚合體，例如可使上述的多元醇化合物與多價異氰酸酯化合物反應而得。 The urethane polymer is a urethane-based polymer having no polymerizable functional group such as a (meth) acrylonitrile group in the molecule, unlike a urethane (meth) acrylate oligomer. The polyol compound is obtained by reacting a polyvalent isocyanate compound.
能量線聚合性單體，可使用與上述相同將尿烷(甲基)丙烯酸酯樹脂稀釋者之外，亦可使用N,N-二甲基胺基乙基丙烯酸酯、N,N-二甲基胺基丙基甲基丙烯醯胺、丙烯醯基嗎啉、N,N-二甲基丙烯醯胺、N,N-二乙基丙烯醯胺、醯亞胺丙烯酸酯、N-乙烯基咯烷酮等的含氮單體。 The energy ray polymerizable monomer may be used in the same manner as described above, in which the urethane (meth) acrylate resin is diluted, and N,N-dimethylaminoethyl acrylate or N,N-dimethyl hydride may be used. Aminopropyl methacrylamide, acryloyl morpholine, N,N-dimethyl decylamine, N,N-diethyl acrylamide, quinone acrylate, N-vinyl A nitrogen-containing monomer such as an alkyl ketone.
上述能量線聚合性單體，對尿烷聚合物100質量部，以5~900質量部為佳，以10~500質量部更佳，以30~200質量部的比例使用特別佳。 The energy ray polymerizable monomer is preferably from 5 to 900 parts by mass, more preferably from 10 to 500 parts by mass, and particularly preferably from 30 to 200 parts by mass, based on 100 parts by mass of the urethane polymer.
將支持薄膜，由上述能量線硬化型樹脂形成時，藉由在該樹脂混入光聚合起始劑，可減少藉由能量線照射的聚合硬化時間及照射量。光聚合起始劑，可混入與混入硬化性樹脂(A)之相同者。 When the support film is formed of the energy ray-curable resin, the polymerization hardening time and the irradiation amount by the energy ray irradiation can be reduced by mixing the photopolymerization initiator in the resin. The photopolymerization initiator can be mixed in the same manner as the curable resin (A).
光聚合起始劑的使用量，對能量線硬化型樹脂100質量部，以0.05~15質量部為佳，以0.1~10質量部更佳，以0.5~5質量部特別佳。光聚合起始劑，可混入與混入硬化性樹脂(A)之相同者。 The amount of the photopolymerization initiator to be used is preferably 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass. The photopolymerization initiator can be mixed in the same manner as the curable resin (A).
又，亦可在上述硬化性樹脂(B)中，含有碳酸鈣、二氧化矽、雲母等的無機填充劑；鐵、鉛等的金屬填充劑；顏料或染料等的著色劑等的添加劑。 In addition, the curable resin (B) may contain an inorganic filler such as calcium carbonate, ceria or mica; a metal filler such as iron or lead; or an additive such as a pigment or a dye.
支持薄膜的製膜方法，可藉由將包含硬化性樹脂(B)的調合物以液狀的狀態薄膜狀澆鑄在工程薄膜上之後，將此以既定的手段薄膜化，藉由去除工程薄膜而製造支持薄膜。根據如此的製法，樹脂在製膜時所受到應力較小，不容易發生因經時或加熱的尺寸變化。又，由於容易去除固體雜質，故所 製膜的薄膜較少形成魚眼，藉此可提升膜厚的均勻性，而厚度精度，通常在2%以內。 The film forming method for supporting the film can be formed by film-forming a composition containing the curable resin (B) in a liquid state on the engineering film, and then thinning the film by a predetermined means, thereby removing the engineering film. A support film is produced. According to such a production method, the resin receives less stress at the time of film formation, and it is less likely to undergo dimensional change due to passage or heating. Moreover, since it is easy to remove solid impurities, The film-forming film is less likely to form fish eyes, thereby increasing the uniformity of the film thickness, and the thickness accuracy is usually within 2%.
支持薄膜的厚度，以40~300μm為佳，以60~250μm更佳，以80~200μm特別佳。 The thickness of the supporting film is preferably 40 to 300 μm, more preferably 60 to 250 μm, and particularly preferably 80 to 200 μm.
再者，支持薄膜的形成帶電防止塗層的面或設置黏著劑層的面，為提升與該等層的密著性，亦可施以電暈處理，或施以底層處理等設置其他的層。 Further, the surface of the support film for forming the charge-preventing coating layer or the surface on which the adhesive layer is provided may be corona-treated or may be provided with an underlayer treatment to enhance the adhesion to the layers. .
藉由如上所述的原材料及方法所製膜的支持薄膜，顯示優良的應力緩和性。例如，藉由採用該應力緩和性優良的支持薄膜等，使用於本發明的基材顯示優良的應力緩和性。在擴張10%時經過1分鐘後的基材的應力緩和率為60%以上，以65%以上為佳，以75~90%更佳。藉由使基材的應力緩和率在上述範圍，使用該基材的本發明的表面保護用膜片，可迅速的消除在黏貼於被著體時所產生的殘留應力，在研磨半導體晶圓的背面的步驟(加工半導體晶圓的步驟)，將半導體晶圓研磨的極薄時，亦可抑制半導體晶圓的彎曲。若基材的應力緩和率未滿60%以下，則半導體晶圓會因在加工半導體晶圓的步驟所產生的應力而發生彎曲。 The support film formed by the raw materials and methods as described above exhibits excellent stress relaxation properties. For example, by using a support film excellent in stress relaxation property or the like, the substrate used in the present invention exhibits excellent stress relaxation properties. The stress relaxation rate of the substrate after one minute of expansion at 10% is 60% or more, preferably 65% or more, more preferably 75 to 90%. When the stress relaxation rate of the substrate is within the above range, the surface protection film of the present invention using the substrate can quickly eliminate residual stress generated when adhering to the object, and polishing the semiconductor wafer. The step on the back side (the step of processing the semiconductor wafer) can suppress the bending of the semiconductor wafer when the semiconductor wafer is extremely thin. When the stress relaxation rate of the substrate is less than 60%, the semiconductor wafer is bent by the stress generated in the step of processing the semiconductor wafer.
又，基材的楊氏模量為100~2000MPa，以125~1500MPa為佳，以125~1000MPa更佳。在表面保護用膜片設置帶電防止塗層，則有在晶圓的背面研磨步驟，帶電防止塗層發生龜裂(斷裂)之情形。因出現該龜裂，切斷帶電防止塗層的面方向的導電性，而有降低將剝離帶電擴散的效果。根據本發明的表面保護用膜片，藉由使基材的楊氏模量在上述範 圍，對表面保護用膜片的拉伸賦予適當的耐性，防止帶電防止塗層的龜裂，可抑制帶電防止性能的下降。基材的楊氏模量未滿100MPa，則帶電防止塗層會發生龜裂，而降低帶電防止性能。又，基材的楊氏模量超過2000MPa，則降低基材的應力緩和率，難以得到具有所期望範圍的應力緩和率的基材，降低防止晶圓彎曲的效果。 Further, the Young's modulus of the substrate is from 100 to 2,000 MPa, preferably from 125 to 1,500 MPa, more preferably from 125 to 1,000 MPa. When the surface protection film is provided with a charging prevention coating, there is a case where the coating is subjected to a back surface polishing step to prevent the coating from being cracked (broken). When the crack occurs, the electrical conductivity of the surface of the coating is prevented from being cut off, and the effect of diffusing the stripping is reduced. The film for surface protection according to the present invention, wherein the Young's modulus of the substrate is in the above-mentioned range In addition, it is possible to impart appropriate resistance to the stretching of the surface protection film, prevent cracking of the charging prevention coating layer, and suppress deterioration of the charging prevention performance. When the Young's modulus of the substrate is less than 100 MPa, the coating is prevented from being cracked by the charging, and the charging prevention performance is lowered. Further, when the Young's modulus of the substrate exceeds 2000 MPa, the stress relaxation rate of the substrate is lowered, and it is difficult to obtain a substrate having a stress relaxation ratio in a desired range, and the effect of preventing warpage of the wafer is reduced.
[黏著部] [adhesive part]
於基材的一面，形成有直徑較黏貼之半導體晶圓的外徑小的非黏著部，及圍繞該非黏著部的黏著部。 On one side of the substrate, a non-adhesive portion having a smaller outer diameter of the semiconductor wafer having a larger diameter and an adhesive portion surrounding the non-adhesive portion are formed.
黏著部，可以雙面膠帶構成，又，亦可以單層的黏著劑層構成。雙面膠帶，係於芯材薄膜的雙面形成黏著劑層而得。 The adhesive portion may be formed of double-sided tape or a single layer of adhesive layer. The double-sided tape is obtained by forming an adhesive layer on both sides of the core film.
將黏著部以單層的黏著劑層形成時，黏著部的厚度，只要根據設於黏貼表面保護用膜片的半導體晶圓上的凸塊等的凹凸的高度適宜調整即可，惟以3~100μm為佳，以5~50μm更佳，以7~30μm程度特別佳。黏著部的厚度過薄時，無法得到充分的黏著力，而降低保護功能。另一方面，黏著部的厚度變厚時，可藉由雙面膠帶形成黏著部，無需使用單層黏著薄膜。又，將黏著部4以雙面膠帶形成時，黏著部的厚度，以5~300μm為佳，以10~200μm程度更佳。 When the adhesive portion is formed of a single-layer adhesive layer, the thickness of the adhesive portion may be appropriately adjusted according to the height of the unevenness of the bump or the like provided on the semiconductor wafer of the adhesive surface protective film, but only 3~ 100 μm is preferred, preferably 5 to 50 μm, and particularly preferably 7 to 30 μm. When the thickness of the adhesive portion is too thin, sufficient adhesion cannot be obtained, and the protective function is lowered. On the other hand, when the thickness of the adhesive portion is increased, the adhesive portion can be formed by a double-sided tape, and it is not necessary to use a single-layer adhesive film. Further, when the adhesive portion 4 is formed of a double-sided tape, the thickness of the adhesive portion is preferably 5 to 300 μm, more preferably 10 to 200 μm.
又，黏著部的厚度為30μm以下時，將表面保護用膜片黏貼在半導體晶圓時，表面保護用膜片，與沒有設置凸塊的區域的半導體晶圓表面接近。因此，有較黏著部的厚度較30μm厚時，表面保護用膜片有增加發生剝離帶電的傾向。本 發明的表面保護用膜片，即使如此地使黏著部的厚度變小，亦可抑制剝離帶電發生。 When the thickness of the adhesive portion is 30 μm or less, when the surface protective film is adhered to the semiconductor wafer, the surface protective film is close to the surface of the semiconductor wafer in the region where the bump is not provided. Therefore, when the thickness of the adhesive portion is thicker than 30 μm, the surface protective film tends to increase in peeling electrification. this In the diaphragm for surface protection of the invention, even if the thickness of the adhesive portion is made small, the occurrence of peeling electrification can be suppressed.
在此情形，使用單層黏著薄膜作為黏著部為佳。雙面膠帶的芯材薄膜的厚度雖可各式各樣，一般為10μm左右。因此，黏著部較薄時，將黏著部以雙面膠帶構成，則黏著劑層的厚度會變薄，而無法得到充分的黏著力。 In this case, it is preferred to use a single-layer adhesive film as the adhesive portion. The thickness of the core material film of the double-sided tape can be various, and is generally about 10 μm. Therefore, when the adhesive portion is thin, when the adhesive portion is formed of a double-sided tape, the thickness of the adhesive layer is reduced, and sufficient adhesive force cannot be obtained.
再者，黏著部的高度亦可為0(零)。此時，如第3圖的立體圖、第4圖所示剖面圖，呈非黏著部的表面與黏著部的表面連續在同一平面上的形態。如此的表面保護用膜片，於基材的全面形成如後所述的能量線硬化型黏著劑層，僅將晶圓的電路面與接觸的內周面以能量線硬化，使黏著力降低，僅於外周部保持黏著力而得。 Furthermore, the height of the adhesive portion can also be 0 (zero). At this time, as shown in the perspective view of Fig. 3 and the cross-sectional view shown in Fig. 4, the surface of the non-adhesive portion and the surface of the adhesive portion are continuous on the same plane. In such a surface protection film, an energy ray-curable pressure-sensitive adhesive layer as described later is formed on the entire surface of the substrate, and only the circuit surface of the wafer and the inner circumferential surface of the contact are hardened by energy rays to lower the adhesion. It only retains adhesion at the outer periphery.
又，黏著部的寬度，會影響黏著力，黏著部的寬度越寬黏著力越高。在本發明黏著部的寬度，以0.1~30mm為佳，以1~20mm更佳，以2~10mm程度特別佳。黏著部的寬度過窄時，表面保護用膜片的黏著力會變得不充分。另一方面黏著部的寬度過寬，則黏著部擴及晶圓的電路形成區域，而有黏著劑污染電路之情形。 Moreover, the width of the adhesive portion affects the adhesive force, and the wider the width of the adhesive portion, the higher the adhesive force. The width of the adhesive portion of the present invention is preferably 0.1 to 30 mm, more preferably 1 to 20 mm, and particularly preferably 2 to 10 mm. When the width of the adhesive portion is too narrow, the adhesion of the surface protection film is insufficient. On the other hand, if the width of the adhesive portion is too wide, the adhesive portion spreads over the circuit formation region of the wafer, and the adhesive contaminates the circuit.
黏著部，只要對晶圓有適當的再剝離性，其種類並無特定，可由先前已知的各種黏著劑形成。如此的黏著劑，並無任何限定，可使用例如，橡膠系、丙烯酸系、矽酮系、尿烷系、聚乙烯基醚等的黏著劑。又，亦可使用藉由能量線的照射而硬化成為再剝離性的能量線硬化型黏著劑、或加熱發泡型、水膨潤型的黏著劑。 The adhesive portion is not particularly specific as long as it has appropriate re-peelability to the wafer, and can be formed of various adhesives known in the prior art. Such an adhesive is not limited, and for example, an adhesive such as a rubber-based, acrylic-based, anthrone-based, urethane-based or polyvinyl ether can be used. Further, an energy ray-curable adhesive which is cured by re-peelability by irradiation with an energy ray, or a heat-foaming type or water-swellable type of adhesive may be used.
能量線硬化(紫外線硬化、電子線硬化)型黏著劑，特別是使用紫外線硬化型黏著劑。如此的能量線硬化型黏著劑的具體例，可舉例如日本特開昭60-196956號公報及日本特開昭60-223139號公報所記載。又，作為水膨潤型黏著劑，可良好地使用例如日本特公平5-77284號公報、日本特公平6-101455號公報等所記載者。 Energy line hardening (ultraviolet curing, electron beam hardening) type adhesive, especially ultraviolet curing type adhesive. Specific examples of such an energy ray-curable adhesive include those described in JP-A-60-196956 and JP-A-60-223139. In addition, as the water-swelling type adhesive, those described in, for example, Japanese Patent Publication No. Hei 5-77284 and Japanese Patent Publication No. Hei 6-110455 can be used.
[非黏著部] [non-adhesive part]
非黏著部，係以上述黏著部圍饒，通常，設計成直徑較黏貼的半導體晶圓的外徑稍小。非黏著部，可為完全不顯示黏著性的表面狀態，為只要是顯示600mN/25mm以下的適度的再剝離性的黏著力，則可無問題地使用。如此的非黏著部，具體可為上述基材的表面(第1圖、第2圖)，又，亦可以能量線硬化型黏著劑層的硬化物形成(第3圖、第4圖)。 The non-adhesive portion is surrounded by the above-mentioned adhesive portion, and generally, the outer diameter of the semiconductor wafer having a relatively small diameter is designed to be slightly smaller. The non-adhesive portion may be a surface state in which adhesion is not exhibited at all, and may be used without any problem as long as it exhibits an appropriate removability of 600 mN/25 mm or less. Specifically, the non-adhesive portion may be a surface of the base material (Fig. 1 and Fig. 2), or may be formed of a cured product of the energy ray-curable adhesive layer (Fig. 3 and Fig. 4).
(表面保護用膜片10的製作) (Production of the surface protection film 10)
關於本發明的表面保護用膜片10，如第1圖所示，在由上述帶電防止塗層1與支持薄膜2所構成的基材5的一面，具有直徑較黏貼於半導體晶圓的外徑小的非黏著部3，及圍繞該非黏著部3的黏著部4。以下，說明其製作方法之一例。非黏著部3及黏著部4，可設於帶電防止塗層1上或支持薄膜2上。再者，在第1圖，於支持薄膜2上形成非黏著部3及黏著部4。 As shown in FIG. 1, the surface protection film 10 of the present invention has a diameter which is adhered to the outer diameter of the semiconductor wafer on one surface of the substrate 5 composed of the above-described charging prevention coating 1 and the supporting film 2. A small non-adhesive portion 3, and an adhesive portion 4 surrounding the non-adhesive portion 3. Hereinafter, an example of a method of manufacturing the same will be described. The non-adhesive portion 3 and the adhesive portion 4 may be provided on the electrification preventing coating 1 or on the support film 2. Further, in Fig. 1, the non-adhesive portion 3 and the adhesive portion 4 are formed on the support film 2.
表面保護用膜片10，在其使用時，係如第5圖所示，在被黏貼的晶圓7的設有凸塊8的電路形成部分，與非黏著部3相對，而沒有形成電路的晶圓4的外圍部分與黏著部4相對的構成。以下，以黏著部4係以單層的黏著劑層形成時(第 1圖、第2圖所示構成)為例說明表面保護用膜片10的製作例。 The surface protective film 10 is used as shown in Fig. 5, and the circuit forming portion of the wafer 7 to which the bumps 8 are attached is provided opposite to the non-adhesive portion 3 without forming a circuit. The peripheral portion of the wafer 4 is opposed to the adhesive portion 4. Hereinafter, when the adhesive portion 4 is formed as a single layer of an adhesive layer (the first The example shown in Fig. 1 and Fig. 2 is an example of the production of the surface protective film 10.
黏著部4，係由單層的黏著劑層(黏著薄膜)組成，將黏著薄膜層積於基材5之前，以沖出等的手段裁切去除呈略圓形，形成沒有形成黏著部的開口部。此時，將黏著薄膜以2片剝離薄膜包夾，將一方的剝離薄膜與黏著薄膜沖出，而不將另一方的剝離薄膜完全沖出，則殘留的剝離薄膜成為黏著薄膜的載體，之後的加工亦可使用捲對捲(roll-to-roll)連續進行而佳。 The adhesive portion 4 is composed of a single layer of adhesive layer (adhesive film). Before the adhesive film is laminated on the substrate 5, the adhesive film is cut and removed to form a circular shape to form an opening without forming an adhesive portion. unit. At this time, the adhesive film is sandwiched between two release films, and one of the release film and the adhesive film is punched out, and the other release film is completely washed out, and the remaining release film becomes a carrier of the adhesive film. Processing can also be carried out continuously using roll-to-roll.
形成基材5的方法，並無特別限定，將帶電防止塗層1與支持薄膜2分別製膜，層積得到基材5的方法(製法(I))，或將包含硬化性樹脂(B)的調合物塗佈在工程膜片上，使之預備硬化，形成預備硬化層的步驟；將包含無機導電性填充劑與硬化性樹脂(A)的調合物塗布在預備硬化層上，形成塗膜層的步驟；及使預備硬化層及塗膜層硬化，形成基材的步驟的方法(製法(II))。具有以製法(II)所得的基材5的表面保護用膜片10，係在預備硬化層狀態的支持薄膜的表面，形成成為帶電防止塗層的塗佈層，為將帶電防止塗層1與支持薄膜2一口氣完全硬化，故帶電防止塗層1與支持薄膜2的密著性優良，又，可提升帶電防止性能。又，亦可採用將包含無機導電性填充劑與硬化性樹脂(A)的調合物塗布在其他的工程薄膜上，使之硬化得到樹脂膜之後，與預備硬化層層積的方法(製法(III))。即使在此情形，帶電防止塗層1與支持薄膜2的密著性有較製法(I)之情形有變高的傾向。 The method of forming the substrate 5 is not particularly limited, and a method of forming the film by the charge preventing coating layer 1 and the support film 2, laminating the substrate 5 (method (I)), or containing a curable resin (B) The composition is coated on the engineered film to prepare a hardened layer to form a preliminary hardened layer; and a blend containing the inorganic conductive filler and the curable resin (A) is coated on the preliminary hardened layer to form a coating film. a step of forming a layer; and a method of forming a substrate by hardening the preliminary hardened layer and the coating film layer (Process (II)). The surface protective film 10 having the substrate 5 obtained by the method (II) is formed on the surface of the support film in the state of the preliminary hardened layer, and a coating layer serving as a charging prevention coating layer is formed, and the charging prevention coating layer 1 is formed. The support film 2 is completely hardened in one breath, so that the charging prevention coating 1 and the support film 2 are excellent in adhesion, and the charge prevention performance can be improved. Further, a method in which a blend containing an inorganic conductive filler and a curable resin (A) is applied to another engineering film and cured to obtain a resin film, and then laminated with a preliminary hardened layer (Method (III) )). Even in this case, the adhesion of the charging prevention coating 1 and the support film 2 tends to be higher than in the case of the production method (I).
接著，將沖出的黏著薄膜層積於基材5，得到表面 保護用膜片10。由於在上述開口部不存在黏著劑層，故成為非黏著部3。 Next, the punched adhesive film is laminated on the substrate 5 to obtain a surface. Protective film 10. Since the adhesive layer is not present in the opening portion, the non-adhesive portion 3 is formed.
亦可以此階段的構成(以下亦稱為「未成形構成」)使用於作為本發明的表面保護用膜片10。在此構成使用時，邊將表面保護用膜片10的非黏著部3與晶圓的電路面的位置對位，將黏著部4黏貼在晶圓的外廓。然後，將由晶圓溢出的表面保護用膜片沿著晶圓7的外周切斷分離供於背面研磨。 The composition for this stage (hereinafter also referred to as "unformed structure") can be used for the surface protective film 10 of the present invention. In this configuration, the non-adhesive portion 3 of the surface protective film 10 is aligned with the position of the circuit surface of the wafer, and the adhesive portion 4 is adhered to the outer periphery of the wafer. Then, the surface protection film overflowing from the wafer is cut and separated along the outer periphery of the wafer 7 for back grinding.
本發明的表面保護用膜片以外的態樣，係接著未成形構成的製作，與非黏著部3略同心圓狀，且配合黏貼的晶圓的外徑，沖出黏著部4的外周等而成形的構成。即，預先將基材5及黏著部4配合晶圓4的外徑進行裁切去除，暫黏在剝離薄膜上。藉由預先切割成與晶圓相同形狀，在將表面保護用膜片黏貼在晶圓上時，無須以刀具切除表面保護用膜片的步驟。如此，不會以刀刃傷到晶圓的端部，在之後的加工導致晶圓損傷。 The aspect other than the film for surface protection of the present invention is formed by the unformed structure, and is slightly concentric with the non-adhesive portion 3, and the outer diameter of the adhered wafer is punched out, and the outer periphery of the adhesive portion 4 is punched out. Forming composition. That is, the base material 5 and the adhesive portion 4 are previously cut and removed in accordance with the outer diameter of the wafer 4, and temporarily adhered to the release film. When the surface protection film is adhered to the wafer by cutting into the same shape as the wafer in advance, there is no need to remove the surface protection film by the cutter. In this way, the end of the wafer is not damaged by the blade, and the subsequent processing causes wafer damage.
又，第3圖、第4圖所示表面保護用膜片，係在基材5上形成能量線硬化型黏著劑層，將能量線硬化型黏著劑層，配合晶圓的電路形成區域的大小、形狀照射能量線，形成對應電路形成區域的非黏著部3而得。 Further, in the surface protection film shown in Figs. 3 and 4, an energy ray-curable adhesive layer is formed on the substrate 5, and the energy ray-curable adhesive layer is bonded to the size of the circuit formation region of the wafer. The shape is irradiated with an energy ray to form a non-adhesive portion 3 corresponding to the circuit formation region.
(晶圓的背面研磨) (back grinding of wafer)
接著，將本膜片使用於作為晶圓的背面研磨時的表面保護用膜片之情形為例說明本發明的表面保護用膜片的使用態樣的一例。 Next, an example of the use of the surface protection film of the present invention will be described by taking a case where the film is used as a film for surface protection during back surface polishing of a wafer.
在晶圓的背面研磨時，如第5圖所示，不使表面 保護用膜片10的黏著部4，與晶圓7的凸塊8相對地精度優良地對位之後，使黏著部4與晶圓7的外周端部密著，作成用於研磨半導體晶圓的表面保護形態。 When grinding on the back side of the wafer, as shown in Figure 5, the surface is not made. After the adhesion portion 4 of the protective film 10 is aligned with the bump 8 of the wafer 7 with high precision, the adhesive portion 4 is adhered to the outer peripheral end portion of the wafer 7 to be used for polishing the semiconductor wafer. Surface protection form.
又，基材5，黏著部4沒有預先裁切成與晶圓同形狀時，再將表面保護用膜片10黏貼在晶圓之後，以刀具將表面保護用膜片的不需要的部分(由晶圓溢出的部分)切除。 Further, when the substrate 5 and the adhesive portion 4 are not previously cut into the same shape as the wafer, the surface protective film 10 is adhered to the wafer, and the unnecessary portion of the surface protective film is cut by the cutter. Part of the wafer overflow) is removed.
晶圓，亦可係在電路面不具有凸塊的晶圓，惟本發明的表面保護用膜片，可特別良好地使用在電路面上具有凸塊的晶圓的電路面的保護。凸塊的高度，並無特別限定，將黏著部4以單層黏著劑層構成時，凸塊的高度以5~300μm左右為佳。又，配置在最外側的凸塊的位置，由晶圓的外周，以0.7~30mm內側為佳。如此的凸塊形成到外周部附近的晶圓，雖以先前的表面保護黏著膜片難以保護，但在本發明可良好地使用。 The wafer may be a wafer having no bumps on the circuit surface. However, the surface protection film of the present invention can particularly preferably be used for the protection of the circuit surface of a wafer having bumps on the circuit surface. The height of the bump is not particularly limited. When the adhesive portion 4 is formed of a single adhesive layer, the height of the bump is preferably about 5 to 300 μm. Further, the position of the bump disposed at the outermost side is preferably 0.7 to 30 mm inside from the outer circumference of the wafer. Such a bump is formed in a wafer in the vicinity of the outer peripheral portion, and it is difficult to protect the adhesive film from the prior surface protection, but it can be suitably used in the present invention.
以如上所述表面保護形態的晶圓7，係將表面保護用膜片10側載置於晶圓研磨裝置的晶圓固定台(無圖示)，以使用研磨機6等的通常的研磨手法進行研磨。 In the wafer 7 of the surface protection type as described above, the surface protection film 10 is placed on a wafer fixing station (not shown) of the wafer polishing apparatus, and a general polishing method such as a polishing machine 6 is used. Grinding.
由於黏著部4圍著晶圓7的外廓部全周正確實地黏著，故不會發生研磨加工時的洗淨水等的滲入，而不會污染晶圓的電路面。又，由於對晶圓電路面，凸塊的頂點以適度的壓力與基材5接觸，故研磨加工時不容易發生表面保護用膜片的剝落或偏移等。 Since the adhesive portion 4 is adhered to the entire circumference of the wafer 7 in the entire circumference, the penetration of the washing water or the like during the polishing process does not occur, and the circuit surface of the wafer is not contaminated. Further, since the apex of the bump is in contact with the substrate 5 with an appropriate pressure on the wafer circuit surface, peeling or offset of the surface protective film is less likely to occur during polishing.
之後，若黏著部4係以能量線硬化型黏著劑形成，則對黏著部照射能量線，將晶圓7由表面保護用膜片10分離。 晶圓7，係如圖所示，在環狀的黏著部4固定表面保護用膜片10。環狀的黏著部4的寬度狹窄，因此黏著力亦弱，故晶圓7容易剝離。又，根據本發明的表面保護用膜片10，將表面保護用膜片10由晶圓表面剝離時，晶圓表面的受到來自表面保護用膜片的殘渣物的污染極少，可抑制發生不良品，又所得半導體晶片的品質穩定。再者，根據本發明的表面保護用膜片10，將表面保護用膜片10由晶圓7分離時可有效地將剝離帶電所產生的靜電擴散。 Thereafter, when the adhesive portion 4 is formed of an energy ray-curable adhesive, the adhesive portion is irradiated with an energy ray, and the wafer 7 is separated from the surface protective film 10 . The wafer 7 is fixed to the surface protective film 10 in the annular adhesive portion 4 as shown in the drawing. Since the width of the annular adhesive portion 4 is narrow, the adhesive force is also weak, so that the wafer 7 is easily peeled off. Further, according to the surface protection film 10 of the present invention, when the surface protection film 10 is peeled off from the surface of the wafer, the surface of the wafer is contaminated with the residue from the surface protection film, and the occurrence of defective products can be suppressed. Moreover, the quality of the obtained semiconductor wafer is stable. Further, according to the surface protection film sheet 10 of the present invention, when the surface protection film 10 is separated from the wafer 7, the static electricity generated by the peeling electrification can be effectively diffused.
實施例 Example
以下，以實施例說明本發明，惟本發明不應限定於該等實施例。再者，在以下的實施例及比較例，各種物性係如下進行評估。 Hereinafter, the present invention will be described by way of examples, but the invention should not be construed as limited to the examples. Further, in the following examples and comparative examples, various physical properties were evaluated as follows.
<基材的楊氏模量> <Young's modulus of the substrate>
基材的楊氏模量，係使用萬能拉伸試驗機(ORIENTEC公司製的萬能拉力機RTA-T-2M)，遵照JIS K7161：1994，在於23°C、濕度50%的環境下，以拉伸速度200mm/分測定。 The Young's modulus of the substrate is a universal tensile tester (RTA-T-2M, manufactured by ORIENTEC), in accordance with JIS K7161:1994, in an environment of 23 ° C and a humidity of 50%. The extension speed was measured at 200 mm/min.
<基材的應力緩和率> <Stress relaxation rate of substrate>
將使用於實施例或比較例的基材，切出寬度15mm、長度100mm得到試驗片。將該試驗片，使用ORIENTEC公司製的萬能拉力機RTA-100，在室溫(23℃)，拉伸速度200mm/分拉伸。以擴張10%的狀態停止拉伸，以此時的應力A，及停止擴張1分鐘後的應力B，基於應力緩和率=(A-B)/A×100(%)之式，計算應力緩和率。 The substrate used in the examples or the comparative examples was cut out to have a width of 15 mm and a length of 100 mm to obtain a test piece. The test piece was stretched at room temperature (23 ° C) at a tensile speed of 200 mm/min using a universal tensile machine RTA-100 manufactured by ORIENTEC. The stretching was stopped in a state of 10% expansion, and the stress relaxation rate was calculated based on the stress A at this time and the stress B after the expansion was stopped for 1 minute, based on the stress relaxation ratio = (A - B) / A × 100 (%).
<研磨後的晶圓彎曲> <Fibered wafer bending>
將實施例或比較例所製作的表面保護用膜片，使用膠帶貼合機(LINTEC公司製Adwill RAD-3500)，黏貼於矽晶圓(200mm ψ，厚度750μm)。之後，使用DISCO公司製DFG-840，將矽晶圓研磨成厚度150μm。研磨之後，不去除表面保護用膜片，使表面保護用膜片朝上，將晶圓載置在遵照JIS B 7513；1992的平面度1級的精密檢查用固定盤上。 The film for surface protection produced in the examples or the comparative examples was adhered to a tantalum wafer (200 mm ψ, thickness: 750 μm) using a tape bonding machine (Adwill RAD-3500, manufactured by LINTEC Co., Ltd.). Thereafter, the crucible wafer was ground to a thickness of 150 μm using DFG-840 manufactured by DISCO Corporation. After the polishing, the surface protection film was not removed, and the surface protection film was faced upward, and the wafer was placed on a precision inspection fixed disk of the flatness level 1 according to JIS B 7513;
測定係以固定盤作為零點，測定17處測定點。彎曲量，係最大值與最小值之差。 The measurement was performed with a fixed disk as a zero point, and 17 measurement points were measured. The amount of bending is the difference between the maximum and minimum values.
<剝離帶電> <peeling electrification>
在晶圓電路面，黏貼實施例或比較例的表面保護用膜片，得到晶圓與表面保護用膜片的層積體。將層積體，由製作層積體後，放置在平均溫度約23℃，平均濕度65%RH的環境下，30天。放置後，首先，將層積體裁切成10×10cm的四角形。接著，將表面保護用膜片以500mm/分由晶圓剝離。此時，將在表面保護用膜片所帶電的帶電電位，以集電式電位測定儀(春日電機公司製KSD-6110)，由50mm的距離，以23℃，濕度65%RH的環境下測定(測定下限值0.1kV)。 A film for surface protection of the examples or the comparative examples was adhered to the wafer circuit surface to obtain a laminate of the wafer and the surface protective film. The laminate was placed in an environment having an average temperature of about 23 ° C and an average humidity of 65% RH for 30 days. After standing, first, the laminate was cut into a square shape of 10 × 10 cm. Next, the film for surface protection was peeled off from the wafer at 500 mm/min. At this time, the charged potential charged by the surface protection diaphragm was measured by a collector type potentiometer (KSD-6110 manufactured by Kasuga Electric Co., Ltd.) at a distance of 50 mm at 23 ° C and a humidity of 65% RH. (Measurement lower limit value 0.1 kV).
<晶圓的龜裂> <Chip cracking>
以與評估研磨後的晶圓彎曲的相同方法研磨晶圓之後，將表面保護用膜片由晶圓剝離，將帶電防止塗層面以數位顯微鏡觀察，確認帶電防止塗層有無龜裂。 After the wafer was polished in the same manner as the evaluation of the wafer after the polishing, the surface protection film was peeled off from the wafer, and the surface of the charging prevention coating was observed by a digital microscope to confirm whether or not the coating was prevented from being cracked by the charging.
(實施例1) (Example 1)
將包含以分子量2000的聚酯型多元醇與異佛爾酮二異氰酸酯合成的尿烷寡聚物作為骨架，於其末端加成2-羥基乙基丙 烯酸酯而得之二官能尿烷丙烯酸酯寡聚物(重量平均分子量8000)50質量部，丙烯酸系單體(能量線聚合性單體)之異冰片基丙烯酸酯25質量部及2-羥基-3-苯氧基丙基丙烯酸酯25質量部的混合物，及光聚合起始劑之DAROCURE1173(產品名，BASF公司製)1質量部的調合物，塗佈展延在剝離薄膜上，以紫外線使之硬化得到厚度100μm的支持薄膜。 A urethane oligomer comprising a polyester polyol having a molecular weight of 2000 and isophorone diisocyanate is used as a skeleton, and 2-hydroxyethyl propyl is added to the terminal thereof. a difunctional urethane acrylate oligomer (weight average molecular weight: 8,000) of 50 parts by mass of an acid ester, and an isobornyl acrylate 25 mass part and a 2-hydroxy group of an acrylic monomer (energy ray polymerizable monomer) a mixture of 25 parts by mass of -3-phenoxypropyl acrylate and a blend of 1 part by mass of DAROCURE 1173 (product name, manufactured by BASF Corporation) of a photopolymerization initiator, spread on a release film, and ultraviolet rays It was hardened to obtain a support film having a thickness of 100 μm.
對環氧基丙烯酸酯系樹脂100質量部(質量平均分子量2000)，調合平均粒徑0.1μm的銻摻雜氧化錫(ATO)230質量部、光聚合起始劑(BASF公司製的IRGACURE184)2質量部得到調合物。將該調合物塗佈在支持薄膜的一面，藉由照射紫外線設置厚度2μm的帶電防止塗層。另一方面，預先藉由沖出去除黏著劑，製作不存在圓形的黏著劑的部分的紫外線硬化型黏著劑所構成的單層的20μm厚的黏著劑層(單層黏著薄膜)。將該黏著劑層與支持薄膜設有帶電防止塗層的面的相反面黏合，製作具有非黏著部與黏著部的表面保護用膜片。非黏著部的大小，為直徑190mm。將各評估結果示於第1表。 To 100 parts by mass of the epoxy acrylate-based resin (mass average molecular weight: 2000), 230 parts by mass of yttrium-doped tin oxide (ATO) having an average particle diameter of 0.1 μm, and a photopolymerization initiator (IRGACURE 184 manufactured by BASF Corporation) 2 The mass fraction is obtained. The blend was applied to one side of the support film, and a charge-preventing coating layer having a thickness of 2 μm was provided by irradiation with ultraviolet rays. On the other hand, a single-layer 20 μm thick adhesive layer (single-layer adhesive film) composed of an ultraviolet-curable adhesive in which a portion of a non-circular adhesive is not present is prepared by punching out an adhesive. The adhesive layer was bonded to the opposite surface of the surface on which the support film was provided with the charge preventing coating layer to form a film for surface protection having a non-adhesive portion and an adhesive portion. The size of the non-adhesive portion is 190 mm in diameter. The results of each evaluation are shown in Table 1.
(實施例2) (Example 2)
除在支持薄膜的製造把尿烷(甲基)丙烯酸酯寡聚物的重量平均分子量作為3000之外和實施例1同樣地製作表面保護用膜片。將各評估結果示於第1表。 A film for surface protection was produced in the same manner as in Example 1 except that the weight average molecular weight of the urethane (meth) acrylate oligomer was 3,000. The results of each evaluation are shown in Table 1.
(實施例3) (Example 3)
在支持薄膜的製造，使尿烷(甲基)丙烯酸酯寡聚物的重量平均分子量為6000，ATO的添加量為400質量部，帶電防止塗層的厚度為0.25μm以外，以與實施例1同樣地製作表面保 護用膜片。將各評估結果示於第1表。 In the production of the support film, the weight average molecular weight of the urethane (meth) acrylate oligomer was 6000, the amount of ATO added was 400 parts by mass, and the thickness of the electrification preventing coating layer was 0.25 μm, in the same manner as in Example 1. Same surface protection Protective diaphragm. The results of each evaluation are shown in Table 1.
(實施例4) (Example 4)
使ATO的添加量為150質量部，帶電防止塗層的厚度作為4.8μm以外，以與實施例1同樣地製作表面保護用膜片。將各評估結果示於第1表。 A surface protective film was produced in the same manner as in Example 1 except that the amount of the ATO added was 150 parts by mass, and the thickness of the charging preventing coating layer was 4.8 μm. The results of each evaluation are shown in Table 1.
(比較例1) (Comparative Example 1)
沒有設置帶電防止塗層以外，以與實施例1同樣地製作表面保護用膜片。將各評估結果示於第1表。 A film for surface protection was produced in the same manner as in Example 1 except that the charging prevention coating layer was not provided. The results of each evaluation are shown in Table 1.
(比較例2) (Comparative Example 2)
在支持薄膜的製造，使尿烷(甲基)丙烯酸酯寡聚物的重量平均分子量為12000以外，以與實施例1同樣地製作表面保護用膜片。將各評估結果示於第1表。 In the production of the support film, a film for surface protection was produced in the same manner as in Example 1 except that the weight average molecular weight of the urethane (meth) acrylate oligomer was 12,000. The results of each evaluation are shown in Table 1.
3‧‧‧非黏著劑層 3‧‧‧ Non-adhesive layer
4‧‧‧黏著部 4‧‧‧Adhesive
5‧‧‧基材 5‧‧‧Substrate
10‧‧‧表面保護用膜片 10‧‧‧Surface protection diaphragm
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| CN113165136A (en) * | 2019-02-26 | 2021-07-23 | 株式会社迪思科 | Adhesive sheet for grinding back surface and method for manufacturing semiconductor wafer |
| TWI813791B (en) * | 2018-10-16 | 2023-09-01 | 日商迪思科股份有限公司 | Wafer processing method |
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| WO2017188205A1 (en) * | 2016-04-28 | 2017-11-02 | リンテック株式会社 | Film for forming protective film, and composite sheet for forming protective film |
| JP6729050B2 (en) * | 2016-06-22 | 2020-07-22 | 住友ベークライト株式会社 | Adhesive tape for protecting semiconductor element and method for manufacturing adhesive tape for protecting semiconductor element |
| KR20210008165A (en) | 2016-07-26 | 2021-01-20 | 미쓰이 가가쿠 토세로 가부시키가이샤 | Method for manufacturing semiconductor device |
| JP7055567B2 (en) * | 2018-06-06 | 2022-04-18 | 株式会社ディスコ | Tape sticking device |
| KR102193721B1 (en) * | 2019-01-21 | 2020-12-21 | 주식회사 야스 | Cover Film for protecting adhesive sheet using adhesive chuck |
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| JP3499957B2 (en) * | 1995-03-10 | 2004-02-23 | リンテック株式会社 | Antistatic adhesive sheet |
| JP2001196404A (en) * | 2000-01-11 | 2001-07-19 | Fujitsu Ltd | Semiconductor device and method of manufacturing the same |
| JP4704225B2 (en) * | 2006-01-30 | 2011-06-15 | 富士フイルム株式会社 | Album creating apparatus, album creating method, and album creating program |
| JP2007296751A (en) * | 2006-04-28 | 2007-11-15 | Mitsubishi Plastics Ind Ltd | Resin laminate |
| JP2010177542A (en) * | 2009-01-30 | 2010-08-12 | Lintec Corp | Antistatic adhesive sheet |
| JP5788165B2 (en) * | 2010-11-02 | 2015-09-30 | 三菱樹脂株式会社 | Flame retardant resin film and method for producing the film |
| JP2012216619A (en) * | 2011-03-31 | 2012-11-08 | Lintec Corp | Surface protection sheet |
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| TWI813791B (en) * | 2018-10-16 | 2023-09-01 | 日商迪思科股份有限公司 | Wafer processing method |
| CN113165136A (en) * | 2019-02-26 | 2021-07-23 | 株式会社迪思科 | Adhesive sheet for grinding back surface and method for manufacturing semiconductor wafer |
| CN113165136B (en) * | 2019-02-26 | 2023-06-13 | 株式会社迪思科 | Adhesive sheet for grinding back surface and method for manufacturing semiconductor wafer |
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| WO2016063917A1 (en) | 2016-04-28 |
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