TWI672354B - Sheet for forming protective film and method of manufacturing semiconductor tip having protective film - Google Patents
Sheet for forming protective film and method of manufacturing semiconductor tip having protective film Download PDFInfo
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- TWI672354B TWI672354B TW104127316A TW104127316A TWI672354B TW I672354 B TWI672354 B TW I672354B TW 104127316 A TW104127316 A TW 104127316A TW 104127316 A TW104127316 A TW 104127316A TW I672354 B TWI672354 B TW I672354B
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- Prior art keywords
- protective film
- sheet
- forming
- film
- workpiece
- Prior art date
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- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 150000001993 dienes Chemical class 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 238000005192 partition Methods 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 229920000306 polymethylpentene Polymers 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
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- 229920001451 polypropylene glycol Polymers 0.000 description 1
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- 238000007639 printing Methods 0.000 description 1
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- 238000005488 sandblasting Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- 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
- H01L21/6835—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 using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/50—Working by transmitting the laser beam through or within the workpiece
- B23K26/53—Working by transmitting the laser beam through or within the workpiece for modifying or reforming the material inside the workpiece, e.g. for producing break initiation cracks
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/8319—Arrangement of the layer connectors prior to mounting
- H01L2224/83192—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on another item or body to be connected to the semiconductor or solid-state body
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Dicing (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laser Beam Processing (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Adhesive Tapes (AREA)
- Formation Of Insulating Films (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
本發明係一種保護膜形成用片，其具備第1支撐片及積層於該第1支撐片之第1面側之保護膜形成膜，該保護膜形成膜包含硬化性材料且具有以下之特性：該保護膜形成膜硬化成為保護膜時，該保護膜之50℃之斷裂應變為20%以下，且損耗正切之峰值溫度T1為25℃至60℃。 The present invention is a sheet for forming a protective film, comprising a first supporting sheet and a protective film forming film laminated on the first surface side of the first supporting sheet. The protective film forming film includes a hardening material and has the following characteristics: When the protective film-forming film is hardened into a protective film, the breaking strain at 50 ° C of the protective film is 20% or less, and the peak temperature T1 of the loss tangent is 25 ° C to 60 ° C.
Description
本發明係關於一種可於半導體晶圓等工件或對前述工件加工所得之加工物(例如半導體晶片)形成保護膜之保護膜形成用片。 The present invention relates to a sheet for forming a protective film that can form a protective film on a workpiece such as a semiconductor wafer or a processed object (for example, a semiconductor wafer) obtained by processing the workpiece.
本案係根據2014年8月22日在日本申請之日本專利特願2014-169266號及日本專利特願2014-169267號主張優先權，且將其內容引用於本文中。 This case claims priority from Japanese Patent Application No. 2014-169266 and Japanese Patent Application No. 2014-169267 filed in Japan on August 22, 2014, and the contents are incorporated herein by reference.
近年來係利用稱為面朝下(face-down)方式之安裝法而製造半導體裝置。該方法中，當安裝具有形成有凸塊等電極之電路面之半導體晶片時，將半導體晶片之電路面側接合於引線框架等晶片搭載部。因此，成為未形成電路之半導體晶片之背面側露出之構造。 In recent years, semiconductor devices have been manufactured using a mounting method called a face-down method. In this method, when a semiconductor wafer having a circuit surface on which electrodes such as bumps are formed is mounted, the circuit surface side of the semiconductor wafer is bonded to a wafer mounting portion such as a lead frame. Therefore, it has a structure in which the back side of the semiconductor wafer on which no circuit is formed is exposed.
專利文獻1及2揭示保護膜形成/切割一體型片(即保護 膜形成用片)，係將可形成上述保護膜之保護膜形成層(即保護膜形成膜)形成於黏著片上而成。該保護膜形成/切割一體型片中，上述保護膜形成膜藉由加熱處理進行硬化，而形成上述保護膜。即，藉由上述保護膜形成/切割一體型片，則可進行切割半導體晶圓及對半導體晶片形成保護膜兩者，而可獲得附有保護膜之半導體晶片。 Patent Documents 1 and 2 disclose a protective film forming / cutting integrated sheet (i.e., protection The film-forming sheet) is formed by forming a protective film-forming layer (that is, a protective film-forming film) that can form the protective film on an adhesive sheet. In the protective film forming / cutting integrated sheet, the protective film forming film is cured by heat treatment to form the protective film. That is, by forming and dicing the integrated film with the protective film, both the dicing of the semiconductor wafer and the formation of the protective film on the semiconductor wafer can be performed, and the semiconductor wafer with the protective film can be obtained.
另一方面，當自半導體晶圓等工件製造包含半導體晶片等片狀體之加工物時，以往通常進行刀切割加工，係一面對工件吹送以清洗等為目的之液體，一面利用旋轉刀將工件切割而獲得片狀體。然而，近年來係採用能以乾式分割成片狀體之隱形切割(stealth dicing)(註冊商標；以下相同)加工(專利文獻3)。 On the other hand, when manufacturing a processed object including a wafer such as a semiconductor wafer from a workpiece such as a semiconductor wafer, conventionally, a knife cutting process is generally performed. The workpiece is cut to obtain a sheet. However, in recent years, stealth dicing (registered trademark; the same applies hereinafter) processing that can be dry-divided into sheet-like bodies has been adopted (Patent Document 3).
例如，專利文獻3中揭示一種隱形切割法，係將積層黏著片(即積層兩層包含基材與黏著劑層之黏著片而成者)貼附於極薄之半導體晶圓，自積層黏著片側透過積層黏著片對半導體晶圓照射雷射光，而於半導體晶圓之內部形成改質部之後，使黏著片延伸，藉此而沿著切割線分割半導體晶圓，而生產半導體晶片。 For example, Patent Document 3 discloses a stealth dicing method in which a laminated adhesive sheet (that is, a laminate of two adhesive sheets including a substrate and an adhesive layer) is attached to a very thin semiconductor wafer, and the side of the self-adhesive adhesive sheet is laminated. The semiconductor wafer is irradiated with laser light through the laminated adhesive sheet, and after the modified portion is formed inside the semiconductor wafer, the adhesive sheet is extended to thereby divide the semiconductor wafer along the cutting line to produce a semiconductor wafer.
[先前技術文獻] [Prior technical literature]
[專利文獻] [Patent Literature]
專利文獻1：日本專利特開2012-33637號公報 Patent Document 1: Japanese Patent Laid-Open No. 2012-33637
專利文獻2：日本專利特開2011-151362號公報 Patent Document 2: Japanese Patent Laid-Open No. 2011-151362
專利文獻3：日本專利第3762409號公報 Patent Document 3: Japanese Patent No. 3762409
如上所述，隱形切割係使黏著片延伸而分割半導體晶圓，因此有將位於黏著片與半導體晶圓之間的構件亦與半導體晶圓同樣地分割之較佳情形。於此種構件為保護膜形成膜時，為了實現恰當之分割，亦有對保護膜形成膜進行冷卻之情形。 As described above, the stealth dicing system extends the adhesive sheet to divide the semiconductor wafer. Therefore, it is preferable to divide the member located between the adhesive sheet and the semiconductor wafer in the same manner as the semiconductor wafer. When such a member is a protective film-forming film, in order to achieve proper division, the protective film-forming film may be cooled.
本發明之目的在於提供一種具備保護膜形成膜之保護膜形成用片，係於隱形切割中，當位於黏著片與半導體晶圓等工件之間的構件為由保護膜形成膜所形成之保護膜時，在使黏著片延伸時可恰當地分割保護膜。另外，作為另一形態，本發明之目的在於提供一種使用該保護膜形成用片而製造附有保護膜之半導體晶片等加工物的方法。 An object of the present invention is to provide a protective film forming sheet having a protective film forming film, which is used in stealth dicing. When a member located between an adhesive sheet and a workpiece such as a semiconductor wafer is a protective film formed by the protective film forming film, In this case, the protective film can be appropriately divided when the adhesive sheet is extended. Furthermore, as another aspect, an object of the present invention is to provide a method for manufacturing a processed object such as a semiconductor wafer with a protective film using the protective film-forming sheet.
為了達成上述目的而提供之本發明包含以下之態樣。 The present invention provided to achieve the above object includes the following aspects.
(1)一種保護膜形成用片，係具備第1支撐片及積層於前述第1支撐片之第1面側之保護膜形成膜，前述保護膜形成膜包含硬化性材料，使前述保護膜形成膜硬化而成之保護膜於50℃之斷裂應變為20%以下，且損耗正切之峰值 溫度T1處於25℃至60℃之範圍內。 (1) A sheet for forming a protective film, comprising a first supporting sheet and a protective film forming film laminated on the first surface side of the first supporting sheet, the protective film forming film including a hardening material to form the protective film The protective film formed by film hardening has a breaking strain of less than 20% at 50 ° C, and the peak of the loss tangent The temperature T1 is in a range of 25 ° C to 60 ° C.
(2)如上述(1)所記載之保護膜形成用片，其中前述保護膜於25℃之儲存彈性模數為5.0×109Pa以上。 (2) The sheet for forming a protective film according to the above (1), wherein the storage elastic modulus of the protective film at 25 ° C. is 5.0 × 10 9 Pa or more.
(3)如上述(1)或(2)所記載之保護膜形成用片，其中前述保護膜於25℃之損耗正切為0.4以下。 (3) The sheet for forming a protective film according to the above (1) or (2), wherein a loss tangent of the protective film at 25 ° C. is 0.4 or less.
(4)如上述(1)至(3)中任一項所記載之保護膜形成用片，其中前述保護膜之波長為1064nm之透光率為40%以上。 (4) The sheet for forming a protective film according to any one of the above (1) to (3), wherein a light transmittance of the protective film having a wavelength of 1064 nm is 40% or more.
(5)如上述(1)至(4)中任一項所記載之保護膜形成用片，其中前述保護膜形成用片具備第2支撐片，係積層於前述保護膜形成膜中與面對前述第1支撐片之面相反的面側。 (5) The sheet for forming a protective film according to any one of the above (1) to (4), wherein the sheet for forming a protective film is provided with a second support sheet, and is laminated on and facing the protective film forming film The surface of the first support sheet is opposite to the surface side.
(6)一種附有保護膜之晶片之製造方法，其具備：貼附步驟，係使如上述(1)至(5)中任一項所記載之保護膜形成用片所具備的前述保護膜形成膜中與面對前述第1支撐片之面為相反側之面露出，將前述面貼附於工件之一面上，而獲得具備前述保護膜形成用片與前述工件之第1積層體；第1硬化步驟，係使前述第1積層體之前述保護膜形成用片所具備之前述保護膜形成膜硬化，而獲得前 述保護膜；第1分割步驟，係於將經過前述第1硬化步驟之前述第1積層體之前述保護膜形成用片所具備的前述保護膜之溫度T2保持在40℃至70℃之範圍內之狀態下，使前述保護膜形成用片所具備之前述第1支撐片伸長，將前述保護膜與前述工件一起分割，而獲得第2積層體，該第2積層體係於前述第1支撐片之一面上配置有將前述工件與前述保護膜之積層體分割而成之複數個附有保護膜之晶片；及第1拾取步驟，係將前述第2積層體所具備之前述複數個附有保護膜之晶片分別自前述第1支撐片分離，而獲得前述附有保護膜之晶片作為加工物；且進行改質層形成步驟，係於開始前述第1分割步驟之前，以聚焦於設定在前述工件內部之焦點的方式照射紅外線區域之雷射光，而於前述工件內部形成改質層。 (6) A method for manufacturing a wafer with a protective film, comprising: a step of attaching the protective film provided in the sheet for forming a protective film according to any one of (1) to (5) above; In the formed film, the surface opposite to the surface facing the first support sheet is exposed, and the surface is adhered to one surface of the workpiece to obtain a first laminated body including the sheet for forming a protective film and the workpiece; The 1 curing step is to harden the protective film-forming film included in the protective film-forming sheet of the first laminated body, The protective film; the first dividing step is to maintain the temperature T2 of the protective film included in the protective film forming sheet of the first laminated body that has undergone the first hardening step within a range of 40 ° C to 70 ° C. In this state, the first support sheet provided in the sheet for forming a protective film is extended, and the protective film and the workpiece are divided together to obtain a second laminated body. The second laminated system is formed on the first support sheet. A plurality of wafers with a protective film, which are obtained by dividing the laminated body of the workpiece and the protective film, are arranged on one side; and the first picking step is to separate the plurality of protective films provided in the second laminated body. The wafers are separated from the first support sheet to obtain the wafer with the protective film as a processed object; and a reforming layer forming step is performed before focusing on the inside of the workpiece before starting the first dividing step. The focal point is irradiated with the laser light in the infrared region, and a modified layer is formed inside the workpiece.
(7)如上述(6)所記載之附有保護膜之晶片之製造方法，其中前述溫度T2為前述溫度T1以上。 (7) The method for manufacturing a wafer with a protective film according to the above (6), wherein the temperature T2 is equal to or higher than the temperature T1.
(8)一種附有保護膜之晶片之製造方法，其具備：積層步驟，係使如上述(1)至(5)中任一項所記載之保護膜形成用片所具備的前述保護膜形成膜中與面對前述第1支撐片之面為相反側之面露出，將前述面貼附於工件之一面上，且將前述保護膜形成用片之前述第1支撐片自前述保護膜形成膜剝離，而獲得具備前述工件與前述保護膜形成膜之第3積層體；第2硬化步驟，係使前述第3積層 體所具備之前述保護膜形成膜硬化，而獲得前述保護膜；第2貼附步驟，係將具備第3基材及積層於前述第3基材之一面側之第3黏著劑層的加工用片之前述第3黏著劑層側之面，與經過前述第2硬化步驟之前述第3積層體之前述保護膜側的面貼合，而獲得具備前述加工用片與前述第3積層體之第4積層體；第2分割步驟，係於將前述第4積層體所具備之前述保護膜之溫度T3保持在40℃至70℃之範圍內的狀態下，使前述第4積層體所具備之前述加工用片伸長，將前述保護膜與前述工件一起分割，而獲得第5積層體，該第5積層體係於前述加工用片之一面上配置有將前述工件與前述保護膜之積層體分割而成之複數個附有保護膜之晶片；及第2拾取步驟，係將前述第5積層體所具備之前述複數個附有保護膜之晶片分別自前述加工用片分離，而獲得前述附有保護膜之晶片作為加工物；且進行改質層形成步驟，係於開始前述第2分割步驟之前，以聚焦於設定在前述工件內部之焦點的方式照射紅外線區域之雷射光，而於前述工件內部形成改質層。 (8) A method for manufacturing a wafer with a protective film, comprising: a laminating step of forming the protective film provided in the sheet for forming a protective film according to any one of (1) to (5) above; In the film, the surface opposite to the surface facing the first support sheet is exposed, the surface is adhered to one surface of the workpiece, and the first support sheet of the sheet for forming a protective film is formed into a film from the protective film. Peeling to obtain a third laminated body including the workpiece and the protective film forming film; the second hardening step is to make the third laminated layer The protective film forming film provided in the body is hardened to obtain the protective film; the second attaching step is used for processing a third adhesive layer provided with a third substrate and a third adhesive layer laminated on one side of the third substrate. The surface on the third adhesive layer side of the sheet is bonded to the surface on the protective film side of the third laminated body that has undergone the second hardening step to obtain a second sheet including the processing sheet and the third laminated body. 4 laminated body; the second division step is to maintain the temperature T3 of the protective film provided in the fourth laminated body within a range of 40 ° C to 70 ° C, and to make the foregoing provided in the fourth laminated body The processing sheet is extended, and the protective film and the workpiece are divided together to obtain a fifth laminated body. The fifth laminated system is formed by dividing the laminated body of the workpiece and the protective film on one side of the processing sheet. The plurality of wafers with a protective film; and the second picking step is to separate the plurality of wafers with a protective film provided in the fifth laminated body from the processing sheet to obtain the protective film Wafer as processing And performing a reforming layer forming step, before starting the second dividing step, irradiating laser light in an infrared region in a manner focused on a focus set inside the workpiece, and forming a reforming layer inside the workpiece.
(9)如上述(8)所記載之附有保護膜之晶片之製造方法，其中前述溫度T3為前述溫度T1以上。 (9) The method for manufacturing a wafer with a protective film according to the above (8), wherein the temperature T3 is equal to or higher than the temperature T1.
即，本發明包含以下之態樣。 That is, the present invention includes the following aspects.
[1]一種保護膜形成用片，係具備第1支撐片及積層於前述第1支撐片之第1面側之保護膜形成膜，前述保護膜形 成膜包含硬化性材料且具有以下之特性：前述保護膜形成膜硬化成為保護膜時，50℃之斷裂應變為20%以下，且損耗正切之峰值溫度T1為25℃至60℃。 [1] A sheet for forming a protective film, comprising a first support sheet and a protective film-forming film laminated on the first surface side of the first support sheet, wherein the protective film has a shape The film formation includes a hardening material and has the following characteristics: when the protective film-forming film is hardened into a protective film, the breaking strain at 50 ° C is 20% or less, and the peak temperature T1 of the loss tangent is 25 ° C to 60 ° C.
[2]如[1]所記載之保護膜形成用片，其中前述保護膜形成膜進一步具有以下特性：前述保護膜之25℃之儲存彈性模數為3.0×109Pa以上。 [2] The sheet for forming a protective film according to [1], wherein the protective film-forming film further has the following characteristics: a storage elastic modulus at 25 ° C. of the protective film is 3.0 × 10 9 Pa or more.
[3]如[1]或[2]所記載之保護膜形成用片，其中前述保護膜形成膜進一步具有以下特性：前述保護膜之25℃之損耗正切為0.4以下。 [3] The sheet for forming a protective film according to [1] or [2], wherein the protective film-forming film further has the following characteristics: a loss tangent of the protective film at 25 ° C. is 0.4 or less.
[4]如[1]至[3]中任一項所記載之保護膜形成用片，其中前述保護膜形成膜進一步具有以下特性：前述保護膜之波長為1064nm之透光率為40%以上。 [4] The sheet for forming a protective film according to any one of [1] to [3], wherein the protective film-forming film further has the following characteristics: a light transmittance of the protective film having a wavelength of 1064 nm is 40% or more .
[5]如[1]至[4]中任一項所記載之保護膜形成用片，其中前述保護膜形成用片進一步具備第2支撐片，係積層於前述保護膜形成膜中與面對前述第1支撐片之面相反之面側。 [5] The sheet for forming a protective film according to any one of [1] to [4], wherein the sheet for forming a protective film further includes a second support sheet, which is laminated on and facing the protective film forming film The surface of the first support sheet is opposite to the surface.
[6]一種附有保護膜之晶片之製造方法，包括：貼附步驟，係使如[1]至[5]中任一項所記載之保護膜形成用片所具備的前述保護膜形成膜中與面對前述第1支撐片之面為相反側之面露出，將前述露出之面貼附於工件之一面上，而獲得具備前述保護膜形成用片與前述工件之第1積層體；第1硬化步驟，係藉由使前述第1積層體中之前述保護膜形成膜硬化，而獲得前述保護膜；第1分割步驟，係於將經過前述第1硬化步驟之前述第1積層體中之前述保護膜 之溫度T2保持在40℃至70℃之範圍內的狀態下，使前述第1支撐片伸長，將前述保護膜與前述工件一起分割，藉此獲得第2積層體，該第2積層體係於前述第1支撐片之一面上配置有將前述工件與前述保護膜之積層體以於厚度方向產生切割面之方式分割而成的複數個附有保護膜之晶片；及第1拾取步驟，係將前述第2積層體所具備之前述複數個附有保護膜之晶片分別自前述第1支撐片分離，而獲得前述附有保護膜之晶片作為加工物；進一步包括改質層形成步驟，係於開始前述第1分割步驟之前，以聚焦於設定在前述工件內部之焦點的方式照射紅外線區域之雷射光，而於前述工件內部形成改質層。 [6] A method for manufacturing a wafer with a protective film, including a step of attaching the protective film-forming film included in the protective film-forming sheet according to any one of [1] to [5]. The surface opposite to the surface facing the first support sheet is exposed, and the exposed surface is adhered to one surface of the workpiece to obtain a first laminated body including the sheet for forming a protective film and the workpiece; The first hardening step is to obtain the protective film by hardening the protective film forming film in the first laminated body, and the first dividing step is based on the first laminated body that has undergone the first hardening step. Aforementioned protective film In a state where the temperature T2 is maintained within a range of 40 ° C to 70 ° C, the first support sheet is extended, and the protective film and the workpiece are divided together to obtain a second laminated body. The second laminated system is based on the foregoing. A plurality of wafers with a protective film are formed on one surface of the first supporting sheet, and the laminated body of the workpiece and the protective film is divided to generate a cutting surface in a thickness direction; and the first picking step is to separate the foregoing The plurality of wafers with a protective film provided in the second laminated body are separated from the first support sheet, respectively, and the wafers with a protective film are obtained as a processed product; further, a reforming layer forming step is started at the beginning of the foregoing. Prior to the first dividing step, laser light in the infrared region is irradiated so as to focus on the focus set inside the workpiece, and a modified layer is formed inside the workpiece.
[7]如[6]所記載之附有保護膜之晶片之製造方法，其中前述溫度T2為前述溫度T1以上。 [7] The method for manufacturing a wafer with a protective film according to [6], wherein the temperature T2 is equal to or higher than the temperature T1.
[8]一種附有保護膜之晶片之製造方法，其包括：積層步驟，係使如[1]至[5]中任一項所記載之保護膜形成用片所具備的前述保護膜形成膜中與面對前述第1支撐片之面為相反側之面露出，將前述露出之面貼附於工件之一面上，且將前述保護膜形成用片之前述第1支撐片自前述保護膜形成膜剝離，藉此獲得具備前述工件與前述保護膜形成膜之第3積層體；第2硬化步驟，係藉由使前述第3積層體所具備之前述保護膜形成膜硬化，而獲得前述保護膜；第2貼附步驟，係將具備第3基材及積層於前述第3基材之一面側之第3黏著劑層的加工用片中之積層有前述第3黏著劑層之側之面，與經過前述第2硬化步驟之前述第3積層體 中之前述保護膜側之面貼合，而獲得具備前述加工用片與前述第3積層體之第4積層體；第2分割步驟，係於將前述第4積層體所具備之前述保護膜之溫度T3保持在40℃至70℃之範圍內的狀態下，使前述第4積層體所具備之前述加工用片伸長，將前述保護膜與前述工件一起分割，藉此獲得第5積層體，該第5積層體係於前述加工用片之一面上配置有將前述工件與前述保護膜之積層體以於厚度方向產生切割面之方式分割而成的複數個附有保護膜之晶片；及第2拾取步驟，係將前述第5積層體所具備之前述複數個附有保護膜之晶片分別自前述加工用片分離，而獲得前述附有保護膜之晶片作為加工物；進一步包括改質層形成步驟，係於開始前述第2分割步驟之前，以聚焦於設定在前述工件內部之焦點的方式照射紅外線區域之雷射光，而於前述工件內部形成改質層。 [8] A method for manufacturing a wafer with a protective film, comprising: a laminating step of using the protective film-forming film included in the protective film-forming sheet according to any one of [1] to [5] The surface opposite to the surface facing the first supporting sheet is exposed, the exposed surface is adhered to one surface of the workpiece, and the first supporting sheet of the protective film forming sheet is formed from the protective film. The film is peeled to obtain a third laminated body including the workpiece and the protective film-forming film; and the second curing step is to obtain the protective film by hardening the protective film-forming film included in the third laminated body. ; The second attaching step is to laminate a processing sheet including a third substrate and a third adhesive layer laminated on one side of the third substrate with the side of the third adhesive layer, And the third laminated body that has undergone the second hardening step The surface on the protective film side is bonded to obtain a fourth laminated body including the processing sheet and the third laminated body; the second division step is to combine the protective film provided in the fourth laminated body While maintaining the temperature T3 within a range of 40 ° C to 70 ° C, the processing sheet provided in the fourth laminated body is extended, and the protective film is divided with the workpiece to obtain a fifth laminated body. The fifth layered system includes a plurality of wafers with a protective film, which are formed on one surface of the processing sheet by dividing a laminated body of the workpiece and the protective film so as to generate a cutting surface in a thickness direction; and a second pickup. The step is to separate the plurality of wafers with a protective film provided in the fifth laminated body from the processing wafers respectively to obtain the wafers with the protective film as a processed product; further comprising a step of forming a modified layer, Before the second division step is started, the laser light in the infrared region is irradiated so as to focus on the focus set inside the workpiece, and a modified layer is formed inside the workpiece.
[9]如[8]所記載之附有保護膜之晶片之製造方法，其中前述溫度T3為前述溫度T1以上。 [9] The method for manufacturing a wafer with a protective film according to [8], wherein the temperature T3 is equal to or higher than the temperature T1.
根據本發明之保護膜形成用片，即便由前述保護膜形成膜形成之保護膜為位於黏著片與半導體晶圓等工件之間的構件，也可於隱形切割中使黏著片延伸時恰當地分割保護膜。因此，可穩定地製造附有保護膜之半導體晶片。 According to the sheet for forming a protective film according to the present invention, even if the protective film formed by the protective film forming film is a member located between an adhesive sheet and a workpiece such as a semiconductor wafer, it can be appropriately divided when the adhesive sheet is extended during stealth dicing. Protective film. Therefore, a semiconductor wafer with a protective film can be manufactured stably.
1‧‧‧保護膜形成膜 1‧‧‧ protective film forming film
3、3A、3B‧‧‧保護膜形成用片 3, 3A, 3B ‧‧‧ Sheet for forming protective film
4‧‧‧支撐片 4‧‧‧ support sheet
41‧‧‧基材 41‧‧‧ Substrate
42‧‧‧黏著劑層 42‧‧‧Adhesive layer
5‧‧‧治具用黏著劑層 5‧‧‧ Adhesive layer for jig
6‧‧‧剝離片 6‧‧‧ peeling sheet
7‧‧‧半導體晶圓 7‧‧‧ semiconductor wafer
8‧‧‧環狀架 8‧‧‧ ring frame
9‧‧‧附有保護膜之晶片 9‧‧‧Chip with protective film
10‧‧‧第1積層體 10‧‧‧The first laminated body
11、20‧‧‧第2積層體 11, 20‧‧‧ 2nd laminated body
12‧‧‧第3積層體 12‧‧‧The third layered body
13‧‧‧加工用片 13‧‧‧ processing tablets
131‧‧‧第3黏著劑層 131‧‧‧3rd adhesive layer
132‧‧‧第3基材 132‧‧‧3rd substrate
14‧‧‧第4積層體 14‧‧‧The fourth laminated body
R‧‧‧環狀構件 R‧‧‧ ring member
P‧‧‧頂起銷 P‧‧‧ jacking pin
C‧‧‧真空吸附筒夾 C‧‧‧Vacuum suction collet
圖1係概念性地表示本發明一實施形態之保護膜形成用片的剖面圖。 FIG. 1 is a cross-sectional view conceptually showing a sheet for forming a protective film according to an embodiment of the present invention.
圖2係概念性地表示自本發明一實施形態之保護膜形成用片使剝離片剝離後之狀態的剖面圖。 2 is a cross-sectional view conceptually showing a state where a release sheet is peeled from a sheet for forming a protective film according to an embodiment of the present invention.
圖3係概念性地表示經過本發明一實施形態之附有保護膜之晶片之製造方法所具備的第1貼附步驟而獲得之第1積層體之剖面圖。 3 is a cross-sectional view conceptually showing a first laminated body obtained through a first attaching step included in a method for manufacturing a wafer with a protective film according to an embodiment of the present invention.
圖4係概念性地表示經過本發明一實施形態之附有保護膜之晶片之製造方法所具備的第1分割步驟而獲得之第2積層體之剖面圖。 FIG. 4 is a cross-sectional view conceptually showing a second laminated body obtained through a first dividing step included in a method for manufacturing a wafer with a protective film according to an embodiment of the present invention.
圖5係概念性地表示正實施本發明一實施形態之附有保護膜之晶片之製造方法所具備的第1拾取步驟之狀態之剖面圖。 5 is a cross-sectional view conceptually showing a state of a first pickup step included in a method for manufacturing a wafer with a protective film according to an embodiment of the present invention.
圖6係概念性地表示本發明之其他實施形態之一的保護膜形成用片之剖面圖。 6 is a cross-sectional view conceptually showing a sheet for forming a protective film according to another embodiment of the present invention.
圖7係概念性地表示經過本發明之另一實施形態之附有保護膜之晶片之製造方法所具備的積層步驟而獲得之第3積層體之剖面圖。 FIG. 7 is a cross-sectional view conceptually showing a third laminated body obtained through a lamination step included in a method for manufacturing a wafer with a protective film according to another embodiment of the present invention.
圖8係概念性地表示經過本發明之另一實施形態之附有保護膜之晶片之製造方法所具備的第2貼附步驟而獲得之第4積層體之剖面圖。 8 is a cross-sectional view conceptually showing a fourth laminated body obtained through a second attaching step included in a method for manufacturing a protective film-attached wafer according to another embodiment of the present invention.
圖9係概念性地表示經過本發明之另一實施形態之附有保護膜之晶片之製造方法所具備的第2分割步驟而獲得之第5積層體之剖面圖。 FIG. 9 is a cross-sectional view conceptually showing a fifth laminated body obtained through a second division step included in a method for manufacturing a wafer with a protective film according to another embodiment of the present invention.
圖10係概念性地表示正實施本發明之另一實施形態之附有保護膜之晶片之製造方法所具備的第2拾取步驟之狀態之剖面圖。 FIG. 10 is a cross-sectional view conceptually showing a state of a second pick-up step included in a method for manufacturing a protective film-attached wafer according to another embodiment of the present invention.
圖11係概念性地表示本發明之其他實施形態之一的保護膜形成用片之剖面圖。 11 is a cross-sectional view conceptually showing a sheet for forming a protective film according to another embodiment of the present invention.
以下說明本發明之實施形態。 Embodiments of the present invention will be described below.
圖1係本發明一實施形態之保護膜形成用片之剖面圖。如圖1所示，本實施形態之保護膜形成用片3構成為具備：第1支撐片4；保護膜形成膜1，係積層於第1支撐片4之一面(後述之「第1面」；圖1中為上表面)側；及治具用黏著劑層5，係積層於保護膜形成膜1中與面對第1支撐片4之面為相反側之面的周緣部。治具用黏著劑層5係用於將保護膜形成用片3接著於環狀架(ring frame)等治具之層。而且，本實施形態之保護膜形成用片3於保護膜形成膜1及治具用黏著劑層5上(即與第1支撐片4為相反側)具備剝離片6。該剝離片6係於保護膜形成用片3使用時要剝離去除之片，於保護膜形成用片3中並非必需之構成要件。 FIG. 1 is a cross-sectional view of a sheet for forming a protective film according to an embodiment of the present invention. As shown in FIG. 1, the protective film-forming sheet 3 of this embodiment is configured to include: a first support sheet 4; and a protective film-forming film 1 laminated on one surface of the first support sheet 4 (the “first surface” described later). (The upper surface in FIG. 1) side; and an adhesive layer 5 for a jig, which is laminated on the peripheral edge portion of the protective film forming film 1 on a surface opposite to the surface facing the first support sheet 4. The adhesive layer 5 for a jig is a layer for bonding the sheet 3 for forming a protective film to a jig such as a ring frame. The protective film-forming sheet 3 of this embodiment includes a release sheet 6 on the protective film-forming film 1 and the adhesive layer 5 for the jig (that is, on the side opposite to the first support sheet 4). This peeling sheet 6 is a sheet to be peeled off when the protective film forming sheet 3 is used, and is not an essential constituent element in the protective film forming sheet 3.
即，本發明一實施形態之保護膜形成用片之一個形態包含：第1支撐片4；保護膜形成膜1，積層於第1支撐片4之一面側；治具用黏著劑層5，積層於保護膜形成膜1中與面對第1支撐片4之面為相反側之面的周緣部；及視需要之剝離片6，係積層於保護膜形成膜1及治具用黏著劑層5上 。 That is, one form of the sheet for forming a protective film according to an embodiment of the present invention includes: a first supporting sheet 4; a protective film forming film 1 laminated on one side of the first supporting sheet 4; an adhesive layer 5 for a jig; In the protective film-forming film 1, the peripheral edge portion of the surface opposite to the surface facing the first support sheet 4; and a release sheet 6 as necessary, laminated on the protective film-forming film 1 and the adhesive layer 5 for jigs on .
本實施形態之保護膜形成用片3用於在對工件進行加工時貼附於前述工件而保持前述工件，並且於前述工件或對前述工件加工所得之加工物上形成保護膜。該保護膜由硬化之保護膜形成膜1構成。 The sheet 3 for forming a protective film according to this embodiment is used to attach the workpiece to hold the workpiece while processing the workpiece, and to form a protective film on the workpiece or a processed product obtained by processing the workpiece. This protective film is composed of a cured protective film forming film 1.
作為一例，本實施形態之保護膜形成用片3用於在作為工件之半導體晶圓之切割加工時，係保持半導體晶圓，並且於藉由切割所得之半導體晶片上形成保護膜，但並不限定於此。 As an example, the protective film-forming sheet 3 of this embodiment is used to hold a semiconductor wafer during dicing of a semiconductor wafer as a workpiece, and to form a protective film on the semiconductor wafer obtained by dicing. Limited to this.
本實施形態之保護膜形成用片3通常形成為長條狀並捲繞成輥狀，且以輥對輥(roll to roll)方式使用。 The sheet 3 for forming a protective film according to this embodiment is generally formed in a long shape and wound into a roll shape, and is used in a roll-to-roll manner.
1.支撐片 Support sheet
與本發明一實施形態之保護膜形成用片3相關之第1支撐片4係具備基材41、及積層於基材41之一面側(即保護膜形成膜1側；圖1中為上側)之黏著劑層42而構成。此處，將第1支撐片4中之要積層保護膜形成膜1側之面稱為「第1面」，將其相反側之面(圖1中為下表面)稱為「第2面」。第1支撐片4中，黏著劑層42積層於第1支撐片4之第1面側，基材41積層於第1支撐片4之第2面側。 The first support sheet 4 related to the protective film-forming sheet 3 according to an embodiment of the present invention includes a base material 41 and a layer on one side of the base material 41 (that is, the protective film-forming film 1 side; the upper side in FIG. 1) The adhesive layer 42 is formed. Here, the surface on the first support sheet 4 where the protective film formation film 1 is to be laminated is referred to as a "first surface", and the surface on the opposite side (the lower surface in Fig. 1) is referred to as a "second surface". . In the first support sheet 4, the adhesive layer 42 is laminated on the first surface side of the first support sheet 4, and the base material 41 is laminated on the second surface side of the first support sheet 4.
1-1.基材 1-1. Substrate
與本發明一實施形態之保護膜形成用片3相關之基材41只要為作為用於隱形切割之黏著片之基材而通常使用的基材，則並無特別限定。基材41可具有單層構造，亦可具有積層構造。於保護膜形成膜1為藉由加熱而形成保護膜之膜，在進行用於形成保護膜之保護膜形成膜1之加熱時，基材41亦被加熱的情形下，要求基材41為於該加熱後亦可恰當地使用(例如可列舉能恰當地延伸等)之基材。 The base material 41 related to the protective film forming sheet 3 according to an embodiment of the present invention is not particularly limited as long as it is a base material generally used as a base material for an adhesive sheet for stealth dicing. The base material 41 may have a single-layer structure or a laminated structure. When the protective film forming film 1 is a film that forms a protective film by heating, and when the protective film forming film 1 for forming a protective film is heated, the substrate 41 is also heated. After the heating, a substrate (for example, which can be appropriately stretched) can be used appropriately.
就該觀點而言，基材41之熔點較佳為90℃~180℃，尤佳為100℃~160℃，進一步較佳為110℃~150℃。 From this viewpoint, the melting point of the substrate 41 is preferably 90 ° C to 180 ° C, particularly preferably 100 ° C to 160 ° C, and still more preferably 110 ° C to 150 ° C.
對基材41之熔點進行調整之方法並無特別限制，通常主要可利用所使用之樹脂材料之熔點進行調整。另外，亦可藉由混合熔點不同之複數種樹脂材料或使複數種單體共聚合而調整成任意之熔點。 The method for adjusting the melting point of the substrate 41 is not particularly limited, and generally, the melting point of the resin material used can be mainly adjusted. In addition, it is also possible to adjust to an arbitrary melting point by mixing a plurality of resin materials having different melting points or copolymerizing a plurality of monomers.
基材41之130℃之儲存彈性模數較佳為1MPa~100MPa。藉由使130℃之儲存彈性模數為上述範圍，可確保基材41之耐熱性，且降低使第1支撐片4延伸時產生不良情形之可能性。就同時實現提高基材41之耐熱性及使第1支撐片4容易地延伸之觀點而言，基材41之130℃之儲存彈性模數更佳為2MPa~80MPa，尤佳為5MPa~50MPa。再者，上述儲存彈性模數之測定方法如後述之試驗例所示。 The storage elastic modulus of the substrate 41 at 130 ° C. is preferably 1 MPa to 100 MPa. By setting the storage elastic modulus at 130 ° C to the above-mentioned range, the heat resistance of the base material 41 can be ensured, and the possibility that a failure occurs when the first support sheet 4 is extended can be reduced. From the viewpoint of simultaneously improving the heat resistance of the base material 41 and easily extending the first support sheet 4, the storage elastic modulus of the base material 41 at 130 ° C is more preferably 2 MPa to 80 MPa, and even more preferably 5 MPa to 50 MPa. The method for measuring the storage elastic modulus is as shown in a test example described later.
對基材41之130℃之儲存彈性模數進行調整之方法並無特別限定，通常主要可利用所使用之樹脂材料之儲存彈性模數進行調整。另外，通常即便為相同化學構造，亦有若分子量高則儲存彈性模數變高之傾向，且有藉由交聯或狹窄之分子量分佈亦使儲存彈性模數變高之傾向。可基於該傾向而調整成任意之儲存彈性模數。 The method for adjusting the storage elastic modulus of the substrate 41 at 130 ° C. is not particularly limited, and usually the storage elastic modulus of the resin material used can be mainly adjusted. In addition, generally, even with the same chemical structure, if the molecular weight is high, the storage elastic modulus tends to be high, and cross-linking or narrow molecular weight distribution also tends to increase the storage elastic modulus. Based on this tendency, it can be adjusted to an arbitrary storage elastic modulus.
於隱形切割等中使用波長為1064nm之雷射光時，基材41之加熱後之波長為1064nm之透光率較佳為40%以上且100%以下，更佳為50%以上且99.9%以下，尤佳為60%以上且99.5%以下。藉由使基材41之加熱後之波長為1064nm之透光率處於上述範圍，利用隱形切割之工件之分割性優異。 When laser light having a wavelength of 1064 nm is used in stealth cutting, the transmittance of the substrate 41 after heating at a wavelength of 1064 nm is preferably 40% or more and 100% or less, more preferably 50% or more and 99.9% or less, Especially preferably, it is 60% or more and 99.5% or less. By making the transmittance of the substrate 41 having a wavelength of 1064 nm after heating within the above range, the workability of the workpiece by stealth cutting is excellent.
另外，於對保護膜進行雷射標記等時，使用波長為532nm之雷射光之情形下，基材41之加熱後之波長為532nm之透光率較佳為0.1%以上且40%以下，更佳為0.3%以上且35%以下，尤佳為0.5%以上且30%以下。藉由使基材41之加熱後之波長為532nm之透光率處於上述範圍，雷射列印性優異。 In addition, when laser-marking the protective film, etc., when using laser light with a wavelength of 532 nm, the transmittance of the substrate 41 after heating at a wavelength of 532 nm is preferably 0.1% or more and 40% or less. It is preferably 0.3% or more and 35% or less, and particularly preferably 0.5% or more and 30% or less. When the light transmittance of the substrate 41 having a wavelength of 532 nm is within the above-mentioned range, the laser printability is excellent.
作為構成基材41之樹脂膜之具體例，可列舉：低密度聚乙烯(Low-Density Polyethylene，LDPE)膜、直鏈低 密度聚乙烯(Linear Low-Density Polyethylene，LLDPE)膜、高密度聚乙烯(High-Density Polyethylene，HDPE)膜等聚乙烯膜、聚丙烯膜、乙烯/丙烯共聚物膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、乙烯/降莰烯共聚物膜、降莰烯樹脂膜等聚烯烴系膜；乙烯/乙酸乙烯酯共聚物膜、乙烯/(甲基)丙烯酸共聚物膜、乙烯/(甲基)丙烯酸酯共聚物膜等乙烯系共聚合膜；聚氯乙烯膜、氯乙烯共聚物膜等聚氯乙烯系膜；聚對苯二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜等聚酯系膜；聚胺基甲酸酯膜；聚醯亞胺膜；聚苯乙烯膜；聚碳酸酯膜；氟樹脂膜等。而且，亦可使用該等之交聯膜、離子聚合物膜之類的改質膜。進一步，亦可為積層複數層上述膜而成之積層膜。另外，本說明書中之「(甲基)丙烯酸」表示丙烯酸及甲基丙烯酸兩者。其他類似用語亦相同。 Specific examples of the resin film constituting the substrate 41 include a low-density polyethylene (LDPE) film and a low-chain straight Polyethylene film such as Linear Low-Density Polyethylene (LLDPE) film, High-Density Polyethylene (HDPE) film, polypropylene film, ethylene / propylene copolymer film, polybutylene film, polybutylene Polyolefin films such as diene film, polymethylpentene film, ethylene / norbornene copolymer film, norbornene resin film; ethylene / vinyl acetate copolymer film, ethylene / (meth) acrylic acid copolymer film , Ethylene / (meth) acrylate copolymer film and other ethylene-based copolymerization films; polyvinyl chloride film, polyvinyl chloride copolymer film and other polyvinyl-based films; polyethylene terephthalate film, polyterephthalate Polyester films such as butyl formate film; polyurethane films; polyimide films; polystyrene films; polycarbonate films; fluororesin films, etc. In addition, modified films such as these crosslinked films and ionic polymer films can also be used. Furthermore, it may be a laminated film in which a plurality of the above-mentioned films are laminated. In addition, "(meth) acrylic acid" in this specification means both acrylic acid and methacrylic acid. The same applies to other similar terms.
上述中較佳為聚烯烴系膜，更佳為聚乙烯膜、聚丙烯膜及乙烯/丙烯共聚物膜，更佳為乙烯/丙烯共聚物膜。藉由該等樹脂膜，則易於滿足前述物性，尤其於乙烯/丙烯共聚物膜時，藉由調整乙烯單體與丙烯單體之共聚合比，而易於滿足前述物性。另外，就工件貼附性或晶片剝離性之觀點而言亦較佳為該等樹脂膜。 Among the above, polyolefin-based films are preferred, polyethylene films, polypropylene films, and ethylene / propylene copolymer films are more preferred, and ethylene / propylene copolymer films are more preferred. With these resin films, it is easy to satisfy the aforementioned physical properties. In particular, when the ethylene / propylene copolymer film is used, it is easy to satisfy the aforementioned physical properties by adjusting the copolymerization ratio of the ethylene monomer and the propylene monomer. Moreover, these resin films are also preferable from a viewpoint of work-piece attachability or wafer peelability.
上述樹脂膜為了使與積層於其表面之黏著劑層42之密接性提高，可視需要對單面或兩面實施利用氧化法或凹 凸化法等之表面處理、或底塗處理。作為上述氧化法，例如可列舉：電暈放電處理、電漿放電處理、鉻氧化處理(濕式)、火焰處理、熱風處理、臭氧、紫外線照射處理等。另外，作為凹凸化法，例如可列舉：噴砂法、熔射處理法等。 In order to improve the adhesiveness with the adhesive layer 42 laminated on the surface of the resin film, one side or both sides may be subjected to an oxidation method or a concave method as required. Surface treatment, such as embossing, or primer treatment. Examples of the oxidation method include a corona discharge treatment, a plasma discharge treatment, a chromium oxidation treatment (wet), a flame treatment, a hot air treatment, ozone, and an ultraviolet irradiation treatment. Examples of the unevenness method include a sandblasting method and a thermal spraying method.
再者，基材41亦可於上述樹脂膜中含有著色劑、阻燃劑、塑化劑、抗靜電劑、潤滑劑、填料等各種添加劑。 The substrate 41 may contain various additives such as a colorant, a flame retardant, a plasticizer, an antistatic agent, a lubricant, and a filler in the resin film.
基材41之厚度只要可於使用保護膜形成用片3之各步驟中恰當地發揮功能，則並無特別限定，較佳為20μm~450μm，更佳為25μm~400μm，尤佳為50μm~350μm。 The thickness of the substrate 41 is not particularly limited as long as it can function properly in each step of using the sheet 3 for forming a protective film, and is preferably 20 μm to 450 μm, more preferably 25 μm to 400 μm, and most preferably 50 μm to 350 μm. .
再者，所謂「厚度」係指於任意5個部位利用接觸式厚度計測定出厚度並以平均表示之值。 In addition, "thickness" means the value which measured the thickness with the contact thickness meter in arbitrary 5 places, and showed it on the average.
1-2.黏著劑層 1-2. Adhesive layer
與本發明一實施形態之保護膜形成用片3相關之第1支撐片4所具備的黏著劑層42可由能量線非硬化性黏著劑構成，亦可由能量線硬化性黏著劑構成。作為能量線非硬化性黏著劑，較佳為具有所需之黏著力及再剝離性，例如可使用丙烯酸系黏著劑、橡膠系黏著劑、聚矽氧系黏著劑、胺基甲酸酯系黏著劑、聚酯系黏著劑、聚乙烯醚系黏著劑等。該等中，較佳為與保護膜形成膜1之密接性高之丙 烯酸系黏著劑。 The adhesive layer 42 included in the first support sheet 4 related to the protective film forming sheet 3 according to an embodiment of the present invention may be composed of an energy ray non-curable adhesive or may be composed of an energy ray curable adhesive. As the energy ray non-hardening adhesive, it is preferable to have the required adhesive force and re-peelability. For example, acrylic adhesive, rubber adhesive, silicone adhesive, and urethane adhesive can be used. Agents, polyester-based adhesives, polyvinyl ether-based adhesives, and the like. Among these, a C which has high adhesion to the protective film-forming film 1 is preferred. An enoic adhesive.
另一方面，能量線硬化性黏著劑藉由能量線照射而黏著力下降。因此，若使用能量線硬化性黏著劑，則當欲使工件或加工物與第1支撐片4分離時，可藉由照射能量線而容易地分離。 On the other hand, the energy ray-curable adhesive is lowered in the adhesive force by irradiation with energy rays. Therefore, if an energy ray-curable adhesive is used, when a workpiece or a processed object is to be separated from the first support sheet 4, it can be easily separated by irradiating the energy rays.
作為能量線，通常使用紫外線、電子束等。能量線之照射量根據能量線之種類而不同，例如於紫外線時，以光量計較佳為50mJ/cm2~1000mJ/cm2，更佳為100mJ/cm2~500mJ/cm2。另外，於電子束時，較佳為10krad~1000krad左右。 As the energy rays, ultraviolet rays, electron beams, and the like are generally used. The irradiation amount of the energy ray varies according to the type of the energy ray. For example, in the case of ultraviolet rays, it is preferably 50 mJ / cm 2 to 1000 mJ / cm 2 in terms of light amount, and more preferably 100 mJ / cm 2 to 500 mJ / cm 2 . In the case of the electron beam, it is preferably about 10 krad to 1000 krad.
於黏著劑層42包含能量線硬化性黏著劑時，保護膜形成用片3中之黏著劑層42較佳為已硬化。使能量線硬化性黏著劑硬化而成之材料通常彈性模數高，且表面之平滑性高，因此，若使與包含該材料之硬化部分接觸之保護膜形成膜1硬化而形成保護膜，則與前述黏著劑層42之硬化部分接觸之前述保護膜表面的平滑性(巨觀)變高，作為晶片之保護膜而言係美觀性優異。另外，若對表面平滑性高之保護膜實施雷射列印，則該列印之視覺辨認性提高。 When the adhesive layer 42 contains an energy-ray-curable adhesive, the adhesive layer 42 in the protective film-forming sheet 3 is preferably cured. A material hardened by an energy ray hardening adhesive generally has a high elastic modulus and high surface smoothness. Therefore, if the protective film-forming film 1 in contact with a hardened portion containing the material is hardened to form a protective film, The surface of the protective film which is in contact with the hardened portion of the adhesive layer 42 has a high smoothness (macro view), and is excellent in appearance as a protective film for a wafer. In addition, when laser printing is performed on a protective film having a high surface smoothness, the visibility of the printing is improved.
構成黏著劑層42之能量線硬化性黏著劑可為以具有能量線硬化性之聚合物為主成分者；亦可為以不具有能量線硬化性之聚合物、與選自能量線硬化性之多官能單體及 低聚物所組成之群中之至少一種成分的混合物為主成分之黏著劑。 The energy ray-curable adhesive constituting the adhesive layer 42 may be a polymer having energy ray-hardenability as a main component; it may also be a polymer having no energy ray-hardenability, and a polymer selected from energy ray-hardenability. Polyfunctional monomer and A mixture of at least one component in the group composed of oligomers is a main component adhesive.
以下說明能量線硬化性黏著劑以具有能量線硬化性之聚合物為主成分之情形。 In the following, a case where the energy ray-curable adhesive contains a polymer having energy ray-curability as a main component will be described.
再者，此處所謂之「主成分」係指相對於能量線硬化性黏著劑之總質量而含有60質量%以上。 In addition, the "main component" here means 60 mass% or more with respect to the total mass of an energy ray hardening adhesive.
具有能量線硬化性之聚合物較佳為於側鏈導入有具有能量線硬化性之官能基(即能量線硬化性基)之(甲基)丙烯酸酯(共)聚合物(A)(以下有時稱為「能量線硬化型聚合物(A)」)。該能量線硬化型聚合物(A)較佳為使具有含官能基之單體單元之(甲基)丙烯酸系共聚物(a1)、與具有會和該官能基鍵結之取代基的含不飽和基之化合物(a2)反應而獲得之聚合物。 The polymer having energy ray-hardening properties is preferably a (meth) acrylate (co) polymer (A) having a functional group having energy ray-hardening properties (i.e., energy ray-curable groups) introduced into the side chain (hereinafter, there are It is called "energy ray hardening polymer (A)". The energy ray-curable polymer (A) is preferably such that a (meth) acrylic copolymer (a1) having a functional unit-containing monomer unit and a functional group containing a substituent A polymer obtained by reacting a saturated compound (a2).
丙烯酸系共聚物(a1)至少包含自含官能基之單體導出之結構單元、與自(甲基)丙烯酸酯單體或其衍生物導出之結構單元。 The acrylic copolymer (a1) includes at least a structural unit derived from a functional group-containing monomer and a structural unit derived from a (meth) acrylate monomer or a derivative thereof.
作為自上述含官能基之單體導出之結構單元中的含官能基之單體，較佳為於分子內具有聚合性之雙鍵，與羥基、胺基、經取代之胺基、環氧基等官能基之單體。 The functional group-containing monomer in the structural unit derived from the functional group-containing monomer is preferably a polymerizable double bond with a hydroxyl group, an amine group, a substituted amine group, and an epoxy group in the molecule. Isofunctional monomers.
作為上述含官能基之單體之更具體之例，可列舉(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯等，該等可單獨使用或組合2種以上而使用。 More specific examples of the functional group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( 4-hydroxybutyl meth), etc., These can be used individually or in combination of 2 or more types.
作為上述(甲基)丙烯酸酯單體，可使用烷基之碳數為1~20之(甲基)丙烯酸烷酯、烷基之碳數為3~11之(甲基)丙烯酸環烷酯、(甲基)丙烯酸苄酯等。該等中，較佳為烷基之碳數為1~18之(甲基)丙烯酸烷酯，例如可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯等。 As the (meth) acrylate monomer, alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group, cycloalkyl (meth) acrylates having 3 to 11 carbon atoms in the alkyl group, Benzyl (meth) acrylate and the like. Among these, alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl group are preferred, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Esters, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
丙烯酸系共聚物(a1)係相對於丙烯酸系共聚物(a1)之總質量，以通常為3質量%~100質量%、較佳為5質量%~40質量%之比率含有自上述含官能基之單體導出之結構單元，且以通常為0質量%~97質量%、較佳為60質量%~95質量%之比率含有自(甲基)丙烯酸酯單體或其衍生物導出之結構單元而成。 The acrylic copolymer (a1) is contained in the above-mentioned functional group at a ratio of usually 3% by mass to 100% by mass, preferably 5% by mass to 40% by mass with respect to the total mass of the acrylic copolymer (a1). Structural unit derived from a monomer, and contains a structural unit derived from a (meth) acrylate monomer or a derivative thereof in a ratio of usually 0% to 97% by mass, preferably 60% to 95% by mass Made.
即，丙烯酸系共聚物(a1)較佳為相對於丙烯酸系共聚物(a1)之總質量，以3質量%~100質量%之比率含有自上述含官能基之單體導出之結構單元，且以通常為0質量%~97質量%之比率含有自(甲基)丙烯酸酯單體或其衍生物導出之結構單元；更佳為以5質量%~40質量%之比 率含有自上述含官能基之單體導出之結構單元，且以通常為60質量%~95質量%之比率含有自(甲基)丙烯酸酯單體或其衍生物導出之結構單元。 That is, the acrylic copolymer (a1) preferably contains a structural unit derived from the functional group-containing monomer at a ratio of 3% by mass to 100% by mass relative to the total mass of the acrylic copolymer (a1), and Contains a structural unit derived from a (meth) acrylate monomer or a derivative thereof in a ratio of usually 0% by mass to 97% by mass; more preferably, a ratio of 5% by mass to 40% by mass The structural unit derived from the functional group-containing monomer is contained, and the structural unit derived from the (meth) acrylate monomer or a derivative thereof is contained at a ratio of usually 60% to 95% by mass.
再者，自上述含官能基之單體導出之結構單元與自(甲基)丙烯酸酯單體或其衍生物導出之結構單元之合計質量不超過100質量%。 In addition, the total mass of the structural unit derived from the functional group-containing monomer and the structural unit derived from the (meth) acrylate monomer or a derivative thereof does not exceed 100% by mass.
丙烯酸系共聚物(a1)可藉由利用常用方法使如上所述之含官能基之單體與(甲基)丙烯酸酯單體或其衍生物共聚合而獲得，除該等單體以外亦可共聚合二甲基丙烯醯胺、甲酸乙烯酯、乙酸乙烯酯、苯乙烯等。 The acrylic copolymer (a1) can be obtained by copolymerizing a functional group-containing monomer as described above with a (meth) acrylate monomer or a derivative thereof by a common method, and other monomers may also be used. Copolymerizes dimethylacrylamide, vinyl formate, vinyl acetate, styrene, etc.
藉由使具有上述含官能基之單體單元(即自含官能基之單體導出之結構單元)之丙烯酸系共聚物(a1)，與具有會和該官能基鍵結之取代基的含不飽和基之化合物(a2)反應，而獲得能量線硬化型聚合物(A)。 The acrylic copolymer (a1) having the above-mentioned functional unit-containing monomer unit (that is, a structural unit derived from the functional group-containing monomer) is allowed to contain the acrylic copolymer (a1) having a substituent which will bond with the functional group. The saturated compound (a2) is reacted to obtain an energy ray-curable polymer (A).
含不飽和基之化合物(a2)所具有之取代基可根據丙烯酸系共聚物(a1)所具有之含官能基之單體單元之官能基的種類而適當選擇。例如，於官能基為羥基、胺基或經取代之胺基時，作為取代基，較佳為異氰酸酯基或環氧基，於官能基為環氧基時，作為取代基，較佳為胺基、羧基或氮丙啶基(aziridinyl)。 The substituent contained in the unsaturated group-containing compound (a2) can be appropriately selected depending on the type of the functional group of the functional group-containing monomer unit in the acrylic copolymer (a1). For example, when the functional group is a hydroxyl group, an amine group, or a substituted amine group, as the substituent, an isocyanate group or an epoxy group is preferred, and when the functional group is an epoxy group, the substituent is preferably an amine group. , Carboxyl or aziridinyl.
另外，含不飽和基之化合物(a2)中每一分子含有1個~5個、較佳為1個~2個能量線聚合性之碳-碳雙鍵。作為此種含不飽和基之化合物(a2)之具體例，例如可列舉：異氰酸2-甲基丙烯醯氧基乙酯、異氰酸間異丙烯基-α,α-二甲基苄酯、甲基丙烯醯基異氰酸酯、異氰酸烯丙酯、異氰酸1,1-(雙丙烯醯氧基甲基)乙酯；藉由二異氰酸酯化合物或多異氰酸酯化合物與(甲基)丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物；藉由二異氰酸酯化合物或多異氰酸酯化合物與多元醇化合物與(甲基)丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物；(甲基)丙烯酸縮水甘油酯；(甲基)丙烯酸、(甲基)丙烯酸2-(1-氮丙啶基)乙酯；或2-乙烯基-2-噁唑啉；2-異丙烯基-2-噁唑啉等烯基噁唑啉化合物等。 In addition, the unsaturated group-containing compound (a2) contains one to five, preferably one to two, energy-polymerizable carbon-carbon double bonds per molecule. Specific examples of such an unsaturated group-containing compound (a2) include, for example, 2-methacryloxyethyl isocyanate and m-isopropenyl-α, α-dimethylbenzyl isocyanate. Esters, methacryl isocyanate, allyl isocyanate, 1,1- (bispropenyloxymethyl) ethyl isocyanate; by means of a diisocyanate compound or a polyisocyanate compound and (meth) acrylic acid Propylene methyl monoisocyanate compound obtained by reaction of hydroxyethyl ester; propylene methyl monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound with polyol compound and hydroxyethyl (meth) acrylate; ( Glycidyl (meth) acrylate; (meth) acrylic acid, 2- (1-aziridinyl) ethyl (meth) acrylate; or 2-vinyl-2-oxazoline; 2-isopropenyl- Alkenyl oxazoline compounds such as 2-oxazoline.
上述中，較佳為異氰酸2-甲基丙烯醯氧基乙酯。 Among the above, 2-methacryloxyethyl isocyanate is preferred.
含不飽和基之化合物(a2)係以相對於上述丙烯酸系共聚物(a1)之含官能基之單體每100當量而通常為10當量~100當量、較佳為20當量~95當量之比率使用。 The unsaturated group-containing compound (a2) is a ratio of usually 10 equivalents to 100 equivalents, preferably 20 equivalents to 95 equivalents per 100 equivalents of the functional group-containing monomer of the acrylic copolymer (a1). use.
丙烯酸系共聚物(a1)與含不飽和基之化合物(a2)之反應中，可根據官能基與取代基之組合而適當選擇反應之溫度、壓力、溶劑、時間、觸媒之有無、觸媒之種類。藉此使丙烯酸系共聚物(a1)中存在之官能基與含不飽和基之化合物(a2)中之取代基反應，將不飽和基導入至丙 烯酸系共聚物(a1)中之側鏈，而獲得能量線硬化型聚合物(A)。 In the reaction between the acrylic copolymer (a1) and the unsaturated group-containing compound (a2), the temperature, pressure, solvent, time, presence or absence of the catalyst, and catalyst can be appropriately selected according to the combination of the functional group and the substituent. Of kind. This allows the functional group present in the acrylic copolymer (a1) to react with the substituent in the unsaturated group-containing compound (a2) to introduce the unsaturated group into the propylene The side chain in the olefinic copolymer (a1) yields an energy ray-curable polymer (A).
如此獲得之能量線硬化型聚合物(A)之重量平均分子量較佳為1萬以上，更佳為15萬~150萬，尤佳為20萬~100萬。再者，本說明書中之重量平均分子量(Mw)係藉由凝膠滲透層析法(GPC法)測定出之聚苯乙烯換算之值。 The weight-average molecular weight of the energy-ray-curable polymer (A) thus obtained is preferably 10,000 or more, more preferably 150,000 to 1.5 million, and even more preferably 200,000 to 1 million. In addition, the weight average molecular weight (Mw) in this specification is a polystyrene conversion value measured by the gel permeation chromatography method (GPC method).
即便於能量線硬化性黏著劑以具有能量線硬化性之聚合物為主成分時，能量線硬化性黏著劑亦可進一步含有選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分(B)。 That is, when the energy-ray-curable adhesive is mainly composed of a polymer having energy-ray-curable properties, the energy-ray-curable adhesive may further contain a group selected from energy-ray-curable monomers and oligomers. At least one ingredient (B).
作為選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分(B)，例如可使用多元醇與(甲基)丙烯酸之酯等。 As at least one component (B) selected from the group consisting of energy ray-curable monomers and oligomers, for example, an ester of a polyhydric alcohol and (meth) acrylic acid can be used.
作為該選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分(B)，例如可列舉：(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯等單官能性丙烯酸酯類；三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6- 己二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、二羥甲基三環癸烷二(甲基)丙烯酸酯等多官能性丙烯酸酯類；聚酯低聚(甲基)丙烯酸酯、聚胺基甲酸酯低聚(甲基)丙烯酸酯等。 Examples of the at least one component (B) selected from the group consisting of energy ray-curable monomers and oligomers include cyclohexyl (meth) acrylate, isofluorenyl (meth) acrylate, and the like. Monofunctional acrylates; trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Polyfunctional acrylates such as hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate; polyester oligomers (Meth) acrylate, polyurethane oligo (meth) acrylate, and the like.
上述中，較佳為多官能性丙烯酸酯類、聚胺基甲酸酯低聚(甲基)丙烯酸酯。 Among the above, polyfunctional acrylates and polyurethane oligo (meth) acrylates are preferred.
於調配選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分(B)時，能量線硬化性黏著劑中的選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分(B)之含量相對於前述能量線硬化性黏著劑之總質量，較佳為5質量%~80質量%，更佳為20質量%~60質量%。 When blending at least one component (B) selected from the group consisting of energy-ray-curable monomers and oligomers, the energy-ray-curable monomer and oligomers selected from energy-ray-curable adhesives The content of the at least one component (B) in the composed group is preferably 5 mass% to 80 mass%, and more preferably 20 mass% to 60 mass% relative to the total mass of the energy ray-curable adhesive.
此處，於使用紫外線作為用於使能量線硬化性樹脂組成物硬化之能量線時，較佳為進一步添加光聚合起始劑(C)，藉由使用該光聚合起始劑(C)，可減少聚合硬化時間及光線照射量。 Here, when ultraviolet rays are used as the energy rays for curing the energy ray-curable resin composition, it is preferable to further add a photopolymerization initiator (C), and by using the photopolymerization initiator (C), Can reduce polymerization hardening time and light exposure.
作為光聚合起始劑(C)，具體而言可列舉：二苯甲酮、苯乙酮、安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮、2,4-二乙基噻吨酮(2,4-diethylthioxanthone)、1-羥基環己基苯基酮、苄基二 苯硫醚、一硫化四甲基秋蘭姆、偶氮二異丁腈、苯偶醯、二苯偶醯、二乙醯、β-氯蒽醌、(2,4,6-三甲基苄基二苯基)氧化膦、2-苯并噻唑-N,N-二乙基二硫胺甲酸酯、低聚{2-羥基-2-甲基-1-[4-(1-丙烯基)苯基]丙酮}、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等。 Specific examples of the photopolymerization initiator (C) include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, and benzoin benzene. Methyl formate, benzoin dimethyl ketal, 2,4-diethylthioxanthone, 1-hydroxycyclohexylphenyl ketone, benzyl di Phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzodiazone, dibenzodiazone, diethylhydrazone, β-chloroanthraquinone, (2,4,6-trimethylbenzyl Diphenyl) phosphine oxide, 2-benzothiazole-N, N-diethyldithiocarbamate, oligomeric {2-hydroxy-2-methyl-1- [4- (1-propenyl ) Phenyl] acetone}, 2,2-dimethoxy-1,2-diphenylethane-1-one, and the like.
該等可單獨使用，亦可併用2種以上。 These can be used alone or in combination of two or more.
當將能量線硬化型共聚物(A)(於調配選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分(B)的情形時，將能量線硬化型共聚物(A)、及選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分(B)之合計量設為100質量份)設為100質量份時，光聚合起始劑(C)較佳為以0.1質量份~10質量份、尤其是0.5質量份~6質量份之範圍之量使用。 When the energy ray-curable copolymer (A) (when at least one component (B) selected from the group consisting of energy ray-curable monomers and oligomers is blended, the energy ray-curable copolymer is prepared. (The total amount of (A) and at least one component (B) selected from the group consisting of energy ray-curable monomers and oligomers is set to 100 parts by mass)) When 100 parts by mass is set, photopolymerization starts The agent (C) is preferably used in an amount in the range of 0.1 to 10 parts by mass, especially 0.5 to 6 parts by mass.
能量線硬化性黏著劑中，除上述成分以外亦可調配適當其他成分。作為其他成分，例如可列舉不具有能量線硬化性之聚合物成分或低聚物成分(D)、交聯劑(E)等。 In the energy ray-curable adhesive, in addition to the above-mentioned components, other appropriate components may be blended. Examples of the other components include a polymer component or an oligomer component (D), a cross-linking agent (E), and the like, which do not have energy ray curability.
即，能量線硬化性黏著劑之一個形態係包含能量線硬化型共聚物(A)、以及視需要之從選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分(B)、光聚合起始劑(C)、不具有能量線硬化性之聚合物成分或低聚物成分(D)、及交聯劑(E)所組成之群中選擇的至少一種成分。 That is, one form of the energy ray-curable adhesive includes the energy ray-curable copolymer (A) and, if necessary, at least one component selected from the group consisting of energy ray-curable monomers and oligomers. (B) at least one component selected from the group consisting of a photopolymerization initiator (C), a polymer component or oligomer component (D) having no energy ray hardening property, and a crosslinking agent (E).
作為不具有能量線硬化性之聚合物成分或低聚物成分(D)，例如可列舉聚丙烯酸酯、聚酯、聚胺基甲酸酯、聚碳酸酯、聚烯烴等，較佳為重量平均分子量(Mw)為3000~250萬之聚合物或低聚物。 Examples of the polymer component or oligomer component (D) having no energy ray curability include polyacrylate, polyester, polyurethane, polycarbonate, polyolefin, and the like, and weight average is preferred. Polymers or oligomers with a molecular weight (Mw) of 3,000 to 2.5 million.
作為交聯劑(E)，可使用與能量線硬化型共聚物(A)等所具有之官能基具有反應性的多官能性化合物。作為此種多官能性化合物之例，可列舉：異氰酸酯化合物、環氧化合物、胺化合物、三聚氰胺化合物、氮丙啶化合物、肼化合物、醛化合物、噁唑啉化合物、金屬烷氧化物、金屬螯合物、金屬鹽、銨鹽、反應性酚樹脂等。 As the crosslinking agent (E), a polyfunctional compound having reactivity with a functional group included in the energy ray-curable copolymer (A) and the like can be used. Examples of such a polyfunctional compound include an isocyanate compound, an epoxy compound, an amine compound, a melamine compound, an aziridine compound, a hydrazine compound, an aldehyde compound, an oxazoline compound, a metal alkoxide, and a metal chelate. Substances, metal salts, ammonium salts, reactive phenol resins, etc.
藉由將該等其他成分(D)、(E)調配至能量線硬化性黏著劑，而可改善硬化前之黏著性及剝離性、硬化後之強度、與其他層之接著性、保存穩定性等。該等其他成分之調配量並無特別限定，可在相對於能量線硬化型共聚物(A)100質量份而為0質量份~40質量份之範圍內適當決定。 By blending these other components (D) and (E) to an energy ray hardening adhesive, it is possible to improve the adhesiveness and peelability before hardening, the strength after hardening, adhesion to other layers, and storage stability. Wait. The blending amount of these other components is not particularly limited, and can be appropriately determined within a range of 0 to 40 parts by mass based on 100 parts by mass of the energy ray-curable copolymer (A).
接著，以下說明能量線硬化性黏著劑係以不具有能量線硬化性之聚合物成分、與選自能量線硬化性之多官能單體及低聚物所組成之群中之至少一種的混合物為主成分之情形。 Next, the energy ray curable adhesive is described below as a mixture of a polymer component having no energy ray curability and at least one selected from the group consisting of energy ray curable polyfunctional monomers and oligomers as Principal component situation.
作為不具有能量線硬化性之聚合物成分，例如可使用與前述丙烯酸系共聚物(a1)相同之成分。能量線硬化性樹脂組成物中之不具有能量線硬化性之聚合物成分之含量，相對於前述能量線硬化性樹脂組成物之總質量，較佳為20質量%~99.9質量%，尤佳為30質量%~80質量%。 As the polymer component having no energy ray curability, for example, the same component as the acrylic copolymer (a1) can be used. The content of the polymer component having no energy ray curability in the energy ray curable resin composition is preferably 20% to 99.9% by mass relative to the total mass of the energy ray curable resin composition, and more preferably 30% to 80% by mass.
作為選自能量線硬化性之多官能單體及低聚物所組成之群中之至少一種成分，可選擇與前述成分(B)相同者。不具有能量線硬化性之聚合物成分、與選自能量線硬化性之多官能單體及低聚物所組成之群中之至少一種成分的調配比，將不具有能量線硬化性之聚合物成分設為100質量份時，選自多官能單體及低聚物所組成之群中之至少一種成分較佳為10質量份~150質量份，更佳為25質量份~100質量份。 As at least one component selected from the group consisting of energy ray-curable polyfunctional monomers and oligomers, the same component as the aforementioned component (B) can be selected. A blending ratio of a polymer component having no energy ray hardening property and at least one component selected from the group consisting of a multifunctional monomer and an oligomer having energy ray hardening property, a polymer having no energy ray hardening property When the component is 100 parts by mass, at least one component selected from the group consisting of a polyfunctional monomer and an oligomer is preferably 10 to 150 parts by mass, and more preferably 25 to 100 parts by mass.
於此情形時，亦可與上述同樣地適當調配光聚合起始劑(C)及交聯劑(E)。 In this case, the photopolymerization initiator (C) and the cross-linking agent (E) may be appropriately blended in the same manner as described above.
即，能量線硬化性黏著劑之一個形態係包含不具有能量線硬化性之聚合物成分、選自能量線硬化性之多官能單體及低聚物所組成之群中之至少一種成分、以及視需要之選自光聚合起始劑(C)及交聯劑(E)所組成之群中之至少一種成分。 That is, one form of the energy ray-curable adhesive includes a polymer component having no energy ray-curable properties, at least one component selected from the group consisting of energy ray-curable polyfunctional monomers and oligomers, and If necessary, at least one component selected from the group consisting of a photopolymerization initiator (C) and a crosslinking agent (E).
黏著劑層42之厚度只要可於使用保護膜形成用片3之各步驟中恰當地發揮功能，則並無特別限定。具體而言，較佳為1μm~50μm，更佳為2μm~30μm，又更佳為3μm~20μm。 The thickness of the adhesive layer 42 is not particularly limited as long as it can function properly in each step of using the sheet 3 for forming a protective film. Specifically, it is preferably 1 μm to 50 μm, more preferably 2 μm to 30 μm, and still more preferably 3 μm to 20 μm.
2.保護膜形成膜 2. Protective film formation film
保護膜形成膜1係用於在工件或對前述工件加工所得之加工物形成保護膜之膜。該保護膜由硬化之保護膜形成膜1所構成。作為工件，例如可列舉半導體晶圓等，作為對前述工件加工所得之加工物，例如可列舉半導體晶片，但本發明並不限定於該等。再者，於工件為半導體晶圓時，保護膜係形成於半導體晶圓之背面側(未形成有凸塊等電極之側)。 The protective film forming film 1 is a film for forming a protective film on a workpiece or a processed product obtained by processing the workpiece. This protective film is composed of a cured protective film forming film 1. Examples of the workpiece include a semiconductor wafer and the like, and examples of the processed product obtained by processing the workpiece include a semiconductor wafer, but the present invention is not limited thereto. When the workpiece is a semiconductor wafer, a protective film is formed on the back side of the semiconductor wafer (the side where electrodes such as bumps are not formed).
保護膜形成膜1可為包含單層之膜，亦可為包含複數層之膜，就透光率之控制容易性及製造成本之方面而言，較佳為包含單層。 The protective film-forming film 1 may be a film including a single layer or a film including a plurality of layers. In terms of ease of control of light transmittance and manufacturing cost, it is preferable to include a single layer.
保護膜形成膜1較佳為包含硬化性材料，作為此種材料之具體例，可列舉未硬化之硬化性接著劑。於此情形時，在保護膜形成膜1上重疊半導體晶圓等工件之後，使保護膜形成膜1硬化，藉此，可使由硬化之保護膜形成膜1構成之保護膜牢固地接著於工件，且可將具有耐久性之保護膜形成於晶片等。 The protective film-forming film 1 preferably contains a curable material, and specific examples of such a material include an uncured curable adhesive. In this case, after a workpiece such as a semiconductor wafer is superposed on the protective film forming film 1, the protective film forming film 1 is hardened, whereby the protective film composed of the cured protective film forming film 1 can be firmly adhered to the workpiece. , And a protective film having durability can be formed on a wafer or the like.
即，本發明一實施形態之保護膜形成用片之一個形態，係包含由未硬化之硬化性材料形成之保護膜形成膜。 That is, one aspect of the sheet for forming a protective film according to an embodiment of the present invention includes a protective film-forming film formed of an uncured hardening material.
保護膜形成膜1較佳為於常溫下具有黏著性，或藉由加熱而發揮黏著性。藉此，可於如上所述般在保護膜形成膜1重疊半導體晶圓等工件時使兩者貼合。因此，可於使保護膜形成膜1硬化前確實地進行定位。 The protective film-forming film 1 preferably has adhesiveness at room temperature or exhibits adhesiveness by heating. Thereby, when the protective film formation film 1 overlaps workpieces, such as a semiconductor wafer, as mentioned above, they can be bonded together. Therefore, the positioning can be surely performed before the protective film forming film 1 is cured.
構成具有此種特性之保護膜形成膜1之硬化性接著劑較佳為含有硬化性成分與黏合劑聚合物成分。作為硬化性成分，可使用熱硬化性成分、能量線硬化性成分、或該等之混合物，尤佳為使用熱硬化性成分。即，保護膜形成膜1較佳為由熱硬化性接著劑構成。 The curable adhesive constituting the protective film-forming film 1 having such characteristics preferably contains a curable component and an adhesive polymer component. As the curable component, a thermosetting component, an energy ray-curable component, or a mixture thereof can be used, and a thermosetting component is particularly preferably used. That is, the protective film-forming film 1 is preferably composed of a thermosetting adhesive.
作為熱硬化性成分，例如可列舉：環氧樹脂、酚樹脂、三聚氰胺樹脂、尿素樹脂、聚酯樹脂、胺基甲酸酯樹脂、丙烯酸樹脂、聚醯亞胺樹脂、苯并噁嗪(benzoxazine)樹脂等及該等之混合物。該等中，可較佳地使用環氧樹脂、酚樹脂及該等之混合物。 Examples of the thermosetting component include epoxy resin, phenol resin, melamine resin, urea resin, polyester resin, urethane resin, acrylic resin, polyimide resin, and benzoxazine. Resins, etc. and mixtures of these. Among these, epoxy resins, phenol resins, and mixtures thereof can be preferably used.
環氧樹脂具有受到加熱而三維網狀化而形成牢固之覆膜的性質。作為此種環氧樹脂，可使用以往公知之各種環氧樹脂，通常分子量(式量)較佳為300~2000左右，分子量更佳為300~500。更佳為將分子量為330~400之常 溫下為液狀之環氧樹脂、與分子量為400~2500、尤其是分子量為500~2000之常溫下為固體之環氧樹脂摻和而使用。另外，環氧樹脂之環氧當量較佳為50g/eq~5000g/eq。 The epoxy resin has a property of being three-dimensionally networked by heating to form a strong film. As such an epoxy resin, various conventionally known epoxy resins can be used. Generally, the molecular weight (formula) is preferably about 300 to 2000, and the molecular weight is more preferably 300 to 500. More preferably, the molecular weight is 330 ~ 400. Epoxy resin that is liquid at temperature is blended with epoxy resin that is solid at room temperature and has a molecular weight of 400 to 2500, especially 500 to 2000. The epoxy equivalent of the epoxy resin is preferably 50 g / eq to 5000 g / eq.
作為此種環氧樹脂，具體而言，可列舉：雙酚A、雙酚F、間苯二酚、苯基酚醛清漆、甲酚酚醛清漆等酚類之縮水甘油醚；丁二醇、聚乙二醇、聚丙二醇等醇類之縮水甘油醚；鄰苯二甲酸、間苯二甲酸、四氫鄰苯二甲酸等羧酸之縮水甘油醚；苯胺異氰尿酸酯等與氮原子鍵結之活性氫被縮水甘油基取代之縮水甘油型或烷基縮水甘油型之環氧樹脂；乙烯基環己烷二環氧化物、3,4-環氧環己基甲基-3,4-二環己烷羧酸酯、2-(3,4-環氧基)環己基-5,5-螺(3,4-環氧基)環己烷-間二噁烷等藉由使分子內之碳-碳雙鍵進行例如氧化而導入有環氧基之所謂的脂環型環氧化物。此外，亦可使用具有聯苯骨架、二環己二烯骨架、萘骨架等之環氧樹脂。 Specific examples of such epoxy resins include glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenyl novolac, and cresol novolac; butanediol, polyethylene Glycidyl ethers of alcohols such as glycols and polypropylene glycols; Glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; aniline isocyanurate and other nitrogen atoms Glycidyl or alkyl glycidyl epoxy resins with active hydrogen replaced by glycidyl groups; vinyl cyclohexane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-dicyclohexyl Alkyl carboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane, etc. The carbon double bond undergoes, for example, oxidation and a so-called alicyclic epoxide into which an epoxy group is introduced. In addition, an epoxy resin having a biphenyl skeleton, a dicyclohexadiene skeleton, a naphthalene skeleton, or the like can also be used.
該等中，可較佳地使用雙酚系縮水甘油型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂及苯酚酚醛清漆型環氧樹脂。該等環氧樹脂可單獨使用1種，或者亦可組合2種以上而使用。 Among these, a bisphenol-based glycidyl epoxy resin, an o-cresol novolac epoxy resin, and a phenol novolac epoxy resin can be preferably used. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.
於使用環氧樹脂時，較佳為併用熱活性型潛伏性環氧 樹脂硬化劑作為助劑。所謂「熱活性型潛伏性環氧樹脂硬化劑」係在室溫不會與環氧樹脂反應，藉由特定溫度以上之加熱而活化並與環氧樹脂反應之類型之硬化劑。熱活性型潛伏性環氧樹脂硬化劑之活化方法係有：藉由利用加熱之化學反應生成活性物質(陰離子、陽離子)之方法；於室溫附近穩定地分散於環氧樹脂中，於高溫下與環氧樹脂相溶、溶解，而開始硬化反應之方法；利用分子篩封入型之硬化劑於高溫溶出而開始硬化反應之方法；利用微膠囊之方法等。 When using an epoxy resin, it is preferable to use a thermally active latent epoxy in combination. The resin hardener acts as an auxiliary. The so-called "thermally active latent epoxy resin hardener" is a type of hardener that does not react with epoxy resin at room temperature and is activated by heating above a specific temperature and reacts with epoxy resin. The activation method of the thermally active latent epoxy resin hardener is: a method of generating an active material (anion, cation) by a chemical reaction by heating; stably dispersed in epoxy resin near room temperature, and at high temperature A method of dissolving and dissolving with an epoxy resin and starting a hardening reaction; a method of using a molecular sieve sealed type hardener to dissolve at a high temperature to start a hardening reaction; a method of using a microcapsule.
作為熱活性型潛伏性環氧樹脂硬化劑之具體例，可列舉：各種鎓鹽、或二元酸二醯肼化合物、二氰二胺、胺加成物硬化劑、咪唑化合物等高熔點活性氫化合物等。該等熱活性型潛伏性環氧樹脂硬化劑可單獨使用1種，或者組合2種以上而使用。此種熱活性型潛伏性環氧樹脂硬化劑以相對於環氧樹脂100重量份而較佳為0.1重量份~20重量份、更佳為0.2重量份~10重量份、又更佳為0.3重量份~5重量份之比率使用。 Specific examples of the heat-active latent epoxy resin hardener include various onium salts, or diacid dihydrazine compounds, dicyandiamine, amine adduct hardeners, and high-melting-point active hydrogens such as imidazole compounds. Compounds etc. These thermally active latent epoxy resin hardeners can be used alone or in combination of two or more. Such a thermally active latent epoxy resin hardener is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, and still more preferably 0.3 to 100 parts by weight of the epoxy resin. Use at a ratio of 5 parts by weight to 5 parts by weight.
作為酚系樹脂，可無特別限制地使用烷基酚、多酚、萘酚等酚類與醛類之縮合物等。具體而言，可使用苯酚酚醛清漆樹脂、鄰甲酚酚醛清漆樹脂、對甲酚酚醛清漆樹脂、第三丁基苯酚酚醛清漆樹脂、二環戊二烯甲酚樹脂、聚對乙烯基苯酚樹脂、雙酚A型酚醛清漆樹脂、或該等之改 質物等。 As the phenol-based resin, a condensate of phenols such as alkylphenols, polyphenols, naphthols, and aldehydes, and the like can be used without particular limitation. Specifically, phenol novolac resin, o-cresol novolac resin, p-cresol novolac resin, third butylphenol novolac resin, dicyclopentadiene cresol resin, poly-p-vinylphenol resin, Bisphenol A novolac resin, or a modification thereof Quality and so on.
該等酚系樹脂中所含之酚性羥基係藉由加熱而容易與上述環氧樹脂之環氧基發生加成反應，可形成耐衝擊性高之硬化物。因此，亦可併用環氧樹脂與酚系樹脂。 The phenolic hydroxyl group contained in these phenol-based resins easily undergoes an addition reaction with the epoxy group of the epoxy resin by heating, and can form a hardened product having high impact resistance. Therefore, an epoxy resin and a phenol resin may be used together.
作為能量線硬化性成分，可列舉黏著劑層42中之具有能量線硬化性之聚合物、或選自能量線硬化性之單體及低聚物所組成之群中之至少一種成分所列舉的成分。 Examples of the energy ray-curable component include an energy ray-curable polymer in the adhesive layer 42 or at least one component selected from the group consisting of energy ray-curable monomers and oligomers. ingredient.
黏合劑聚合物成分會對保護膜形成膜1賦予適度之黏性，而可提高保護膜形成用片3之操作性。黏合劑聚合物之重量平均分子量處於通常為5萬~200萬、較佳為10萬~150萬、尤佳為20萬~100萬之範圍。若重量平均分子量過低，則保護膜形成膜1之膜形成變得不充分，若過高，則與其他成分之相溶性變差，結果會阻礙均勻之膜形成。即，若重量平均分子量為上述下限值以上，則保護膜形成膜1之膜形成充分，若為上述上限值以下，則與其他成分之相溶性良好，結果為可形成均勻之膜。作為此種黏合劑聚合物，例如可使用丙烯酸系聚合物、聚酯樹脂、苯氧基樹脂、胺基甲酸酯樹脂、聚矽氧樹脂、橡膠系聚合物等，可尤佳地使用丙烯酸系聚合物。 The adhesive polymer component imparts a moderate viscosity to the protective film-forming film 1 and improves the operability of the protective film-forming sheet 3. The weight average molecular weight of the binder polymer is usually in the range of 50,000 to 2 million, preferably 100,000 to 1.5 million, and particularly preferably 200,000 to 1 million. If the weight average molecular weight is too low, the film formation of the protective film-forming film 1 becomes insufficient, and if it is too high, the compatibility with other components is deteriorated, and as a result, uniform film formation is hindered. That is, if the weight-average molecular weight is greater than or equal to the above lower limit value, the film formation of the protective film-forming film 1 is sufficient, and if it is less than or equal to the above upper limit value, compatibility with other components is good, and as a result, a uniform film can be formed. As such a binder polymer, for example, an acrylic polymer, a polyester resin, a phenoxy resin, a urethane resin, a silicone resin, a rubber-based polymer, or the like can be used, and an acrylic polymer is particularly preferably used. polymer.
作為丙烯酸系聚合物，例如可列舉包含(甲基)丙烯 酸酯單體與自(甲基)丙烯酸衍生物導出之結構單元的(甲基)丙烯酸酯共聚物。此處，作為(甲基)丙烯酸酯單體，可較佳地列舉烷基之碳數為1~18之(甲基)丙烯酸烷酯，具體而言，可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯等。另外，作為(甲基)丙烯酸衍生物，例如可列舉(甲基)丙烯酸、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸羥基乙酯等。 Examples of the acrylic polymer include (meth) propylene (Meth) acrylate copolymer of an ester monomer and a structural unit derived from a (meth) acrylic acid derivative. Here, as the (meth) acrylate monomer, preferred are alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl group, and specifically, methyl (meth) acrylate, (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. Examples of the (meth) acrylic acid derivative include (meth) acrylic acid, glycidyl (meth) acrylate, and hydroxyethyl (meth) acrylate.
上述中，若使用甲基丙烯酸縮水甘油酯等作為結構單元而於丙烯酸系聚合物中導入縮水甘油基，則與作為前述熱硬化性成分之環氧樹脂之相溶性提高，保護膜形成膜1之硬化後之玻璃轉移溫度(Tg)變高，而耐熱性提高。另外，上述中，若使用丙烯酸羥基乙酯等作為結構單元而於丙烯酸系聚合物導入羥基，則可控制對工件之密接性或黏著物性。 In the above, if glycidyl group is introduced into an acrylic polymer using glycidyl methacrylate or the like as a structural unit, compatibility with the epoxy resin as the thermosetting component is improved, and the protective film forming film 1 The glass transition temperature (Tg) after hardening becomes higher, and the heat resistance improves. In addition, in the above, if a hydroxyl group is introduced into an acrylic polymer using a hydroxyethyl acrylate or the like as a structural unit, the adhesion to the workpiece or the adhesive physical properties can be controlled.
使用丙烯酸系聚合物作為黏合劑聚合物時，前述聚合物之重量平均分子量較佳為10萬以上，尤佳為15萬~100萬。丙烯酸系聚合物之玻璃轉移溫度通常為20℃以下，較佳為-70℃~0℃左右，於常溫(23℃)下具有黏著性。 When an acrylic polymer is used as the binder polymer, the weight average molecular weight of the polymer is preferably 100,000 or more, particularly preferably 150,000 to 1 million. The glass transition temperature of the acrylic polymer is usually below 20 ° C, preferably about -70 ° C to 0 ° C, and has adhesiveness at normal temperature (23 ° C).
關於熱硬化性成分與黏合劑聚合物成分之調配比率，當將黏合劑聚合物成分設為100重量份時，熱硬化性成分 之調配量較佳為50重量份~1500重量份，更佳為70重量份~1000重量份，尤佳為80重量份~800重量份。若以此種比率調配熱硬化性成分與黏合劑聚合物成分，則於硬化前顯示出適度之黏性，可穩定地進行貼附作業，且於硬化後獲得覆膜強度優異之保護膜。 Regarding the blending ratio of the thermosetting component and the adhesive polymer component, when the adhesive polymer component is 100 parts by weight, the thermosetting component The blending amount is preferably 50 parts by weight to 1500 parts by weight, more preferably 70 parts by weight to 1,000 parts by weight, and even more preferably 80 parts by weight to 800 parts by weight. If a thermosetting component and an adhesive polymer component are blended at such a ratio, a moderate viscosity is exhibited before curing, a stable attaching operation can be performed, and a protective film having excellent film strength can be obtained after curing.
保護膜形成膜1亦可進一步含有選自著色劑及填料所組成之群中之至少一種成分。 The protective film-forming film 1 may further contain at least one component selected from the group consisting of a colorant and a filler.
作為著色劑，例如可使用無機系顏料、有機系顏料、有機系染料等公知之著色劑，就提高透光率之控制性之觀點而言，著色劑較佳為含有有機系之著色劑。就提高著色劑之化學穩定性(具體而言可例示難溶出、難發生移色、經時變化少之性質)之觀點而言，著色劑較佳為包含顏料之著色劑。 As the colorant, for example, a known coloring agent such as an inorganic pigment, an organic pigment, or an organic dye can be used. From the viewpoint of improving the controllability of light transmittance, the coloring agent preferably contains an organic coloring agent. From the viewpoint of improving the chemical stability of the colorant (specifically, the properties such as hardly dissolving out, color shift hardly, and little change over time), the colorant is preferably a coloring agent containing a pigment.
作為填料，可列舉結晶二氧化矽、熔融二氧化矽、合成二氧化矽等二氧化矽、或氧化鋁、玻璃球等無機填料。其中，較佳為二氧化矽，更佳為合成二氧化矽，尤佳為將成為半導體裝置之誤動作之主要原因的α線之線源盡可能去除之類型之合成二氧化矽。作為填料之形狀，可列舉球形、針狀、不定形等，較佳為球形，尤佳為圓球形。若填料為球形或圓球形，則不易產生光線之漫反射，而易於控制保護膜形成膜1之透光率之光譜圖譜。 Examples of the filler include silicon dioxide such as crystalline silicon dioxide, fused silicon dioxide, and synthetic silicon dioxide; or inorganic fillers such as alumina and glass balls. Among them, silicon dioxide is preferred, synthetic silicon dioxide is more preferred, and synthetic silicon dioxide of a type that removes as much as possible the source of the alpha rays, which is the main cause of malfunction of the semiconductor device, is more preferred. Examples of the shape of the filler include a spherical shape, a needle shape, and an irregular shape. A spherical shape is preferred, and a spherical shape is particularly preferred. If the filler is spherical or spherical, it is difficult to generate diffuse reflection of light, and it is easy to control the spectral spectrum of the light transmittance of the protective film-forming film 1.
作為選自著色劑及填料所組成之群中之至少一種成分之含量，相對於保護膜形成膜整體之質量，較佳為5質量%~75質量%。 The content of at least one component selected from the group consisting of a colorant and a filler is preferably 5% to 75% by mass relative to the mass of the entire protective film-forming film.
填料之平均粒徑較佳為0.005μm~20μm。 The average particle diameter of the filler is preferably 0.005 μm to 20 μm.
另外，保護膜形成膜1亦可含有偶合劑。藉由含有偶合劑，於保護膜形成膜1之硬化後，不會損害保護膜之耐熱性，且可使前述保護膜與工件之接著性及密接性提高，並且進一步亦可使耐水性(耐濕熱性)提高。作為偶合劑，就其通用性及成本優勢等而言，較佳為矽烷偶合劑。 The protective film-forming film 1 may contain a coupling agent. By containing a coupling agent, the heat resistance of the protective film is not impaired after the protective film-forming film 1 is hardened, and the adhesion and adhesion between the protective film and the workpiece can be improved, and the water resistance (water resistance Damp heat). As the coupling agent, a silane coupling agent is preferred in terms of its versatility and cost advantages.
作為矽烷偶合劑，例如可列舉：γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-(甲基丙烯醯氧基丙基)三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-6-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-6-(胺基乙基)-γ-胺基丙基甲基二乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、γ-脲基丙基三乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽基丙基)四硫化物、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、咪唑矽烷等。該等中，較佳為γ-縮水甘油氧基丙基三甲氧基矽烷。該等可單獨使用1種，或者混合2種以上而使用。 Examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6- (aminoethyl) -γ-amino group Propyltrimethoxysilane, N-6- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- Ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, imidazolesilane, etc. Among these, γ-glycidoxypropyltrimethoxysilane is preferred. These can be used individually by 1 type or in mixture of 2 or more types.
於保護膜形成膜1含有黏合劑聚合物成分及硬化性成分之情形，當將黏合劑聚合物成分及硬化性成分之質量份之合計設為100質量份時，偶合劑之含量較佳為0.1質量份~5質量份。 In the case where the protective film-forming film 1 contains a binder polymer component and a hardening component, when the total amount of the binder polymer component and the hardening component is 100 parts by mass, the content of the coupling agent is preferably 0.1 5 parts by mass.
為了調節硬化前之凝聚力，保護膜形成膜1亦可含有有機多元異氰酸酯化合物、有機多元亞胺化合物、有機金屬螯合物等交聯劑。另外，為了抑制靜電並使晶片之可靠性提高，保護膜形成膜1亦可含有抗靜電劑。又，為了提高保護膜之阻燃性能，使作為封裝之可靠性提高，保護膜形成膜1亦可含有磷酸化合物、溴化合物、磷系化合物等阻燃劑。 In order to adjust the cohesive force before hardening, the protective film-forming film 1 may contain a crosslinking agent such as an organic polyisocyanate compound, an organic polyimide compound, and an organic metal chelate compound. In addition, in order to suppress static electricity and improve the reliability of the wafer, the protective film forming film 1 may contain an antistatic agent. In addition, in order to improve the flame retardancy of the protective film and improve the reliability as a package, the protective film-forming film 1 may also contain flame retardants such as phosphoric acid compounds, bromine compounds, and phosphorus-based compounds.
即，保護膜形成膜1之一個形態係包含硬化性成分、黏合劑聚合物成分、以及視需要之從選自著色劑及填料所組成之群中之至少一種成分、偶合劑、交聯劑、抗靜電劑、及阻燃劑所組成之群中選擇的至少一種成分。 That is, one form of the protective film-forming film 1 includes a hardening component, an adhesive polymer component, and at least one component selected from the group consisting of a colorant and a filler, a coupling agent, a crosslinking agent, and At least one component selected from the group consisting of an antistatic agent and a flame retardant.
為了使作為保護膜之功能有效地發揮，保護膜形成膜1之厚度較佳為3μm~300μm，更佳為5μm~200μm，尤佳為7μm~100μm。 In order to effectively function as a protective film, the thickness of the protective film-forming film 1 is preferably 3 μm to 300 μm, more preferably 5 μm to 200 μm, and even more preferably 7 μm to 100 μm.
3.保護膜 3. Protective film
由本發明一實施形態之保護膜形成膜1形成之保護膜具備以下特性。 A protective film formed from the protective film-forming film 1 according to an embodiment of the present invention has the following characteristics.
保護膜於50℃之斷裂應變為0.1%以上且20%以下。藉由使該斷裂應變為20%以下，於在後述之條件下使第1支撐片4伸長(延伸)時，可恰當地分割第1支撐片4所具備之保護膜。若50℃之斷裂應變超過20%，則保護膜之分割容易變得不恰當，具體而言，於分割部分中容易產生形成保護膜之材料局部成為絲狀而未分割之現象(本說明書中稱為「拉絲現象」)。就更穩定地達成保護膜之恰當分割之觀點而言，保護膜之50℃之斷裂應變較佳為0.2%以上且15%以下，更佳為0.3%以上且13%以下，尤佳為0.5%以上且10%以下。 The breaking strain of the protective film at 50 ° C is 0.1% to 20%. When the breaking strain is 20% or less, when the first support sheet 4 is extended (extended) under the conditions described later, the protective film provided in the first support sheet 4 can be appropriately divided. If the breaking strain at 50 ° C exceeds 20%, the division of the protective film tends to become inappropriate. Specifically, in the divided portion, the material forming the protective film tends to become partially silky without being divided (referred to in this specification Is the "drawing phenomenon"). From the viewpoint of achieving a proper division of the protective film more stably, the breaking strain at 50 ° C of the protective film is preferably 0.2% or more and 15% or less, more preferably 0.3% or more and 13% or less, and even more preferably 0.5%. Above and below 10%.
再者，保護膜之「50℃之斷裂應變」可藉由後述試驗例所記載之方法進行測定。 The "breaking strain at 50 ° C" of the protective film can be measured by a method described in a test example described later.
保護膜之損耗正切之峰值溫度T1處於25℃至60℃之範圍內。藉由使損耗正切之峰值溫度T1處於上述範圍內，於後述條件(具體而言為第1分割步驟中之使第1支撐片4伸長時之保護膜的溫度T2保持在40℃至70℃之範圍內)下使第1支撐片4伸長(延伸)時，可恰當地分割第1支撐片4所具備之保護膜。於溫度T1過低時，保護膜會軟質化，保護膜之50℃之斷裂應變容易超過20%。於溫度T1過高時，保護膜會硬質化，在使第1支撐片4延伸時難以恰當地進行保護膜之分割。就更穩定地達成保護膜之恰當分割之觀點而言，溫度T2較佳為損耗正切之峰值溫度T1以上。 The peak temperature T1 of the loss tangent of the protective film is in the range of 25 ° C to 60 ° C. By keeping the peak temperature T1 of the loss tangent within the above range, the temperature T2 of the protective film when the first support sheet 4 is extended in the first division step is maintained at a temperature of 40 ° C to 70 ° C. When the first support sheet 4 is extended (extended), the protective film provided in the first support sheet 4 can be appropriately divided. When the temperature T1 is too low, the protective film will soften, and the breaking strain at 50 ° C of the protective film will easily exceed 20%. When the temperature T1 is too high, the protective film is hardened, and it is difficult to properly divide the protective film when the first support sheet 4 is extended. From the viewpoint of achieving a proper division of the protective film more stably, the temperature T2 is preferably equal to or higher than the peak temperature T1 of the loss tangent.
再者，保護膜之「損耗正切之峰值溫度」可藉由後述試驗例所記載之方法進行測定。 In addition, the "peak temperature of loss tangent" of a protective film can be measured by the method described in the test example mentioned later.
保護膜於25℃之儲存彈性模數較佳為3.0×109Pa以上且5.0×1011Pa以下，更佳為5.0×109Pa以上且1.0×1011Pa以下。藉由使保護膜之25℃之儲存彈性模數為3.0×109Pa以上，於使附有保護膜之半導體晶片自第1支撐片4分離時，不易產生保護膜附有瑕疵之不良情形。 The storage elastic modulus of the protective film at 25 ° C. is preferably 3.0 × 10 9 Pa or more and 5.0 × 10 11 Pa or less, and more preferably 5.0 × 10 9 Pa or more and 1.0 × 10 11 Pa or less. When the storage elastic modulus of the protective film at 25 ° C. is 3.0 × 10 9 Pa or more, when the semiconductor wafer with the protective film is separated from the first support sheet 4, it is not easy to cause defects such as defects in the protective film.
保護膜於25℃之損耗正切較佳為0.01以上且0.4以下。藉由使保護膜之25℃之損耗正切為0.4以下，於使附有保護膜之半導體晶片自第1支撐片4分離時，不易產生保護膜有瑕疵之不良情形。保護膜之25℃之損耗正切更佳為0.03以上且0.3以下，尤佳為0.05以上且0.2以下。 The loss tangent of the protective film at 25 ° C is preferably 0.01 or more and 0.4 or less. When the loss tangent of the protective film at 25 ° C. is 0.4 or less, when the semiconductor wafer with the protective film is separated from the first support sheet 4, it is difficult to cause defects such as defects in the protective film. The 25 ° C loss tangent of the protective film is more preferably 0.03 or more and 0.3 or less, and even more preferably 0.05 or more and 0.2 or less.
再者，保護膜之「25℃之儲存彈性模數」及「25℃之損耗正切」可藉由後述試驗例所記載之方法進行測定。 The "storage elastic modulus at 25 ° C" and the "loss tangent at 25 ° C" of the protective film can be measured by the methods described in the test examples described later.
保護膜之波長為1064nm之透光率較佳為40%以上且100%以下。藉由使保護膜之波長為1064nm之透光率為40%以上，可讓用於隱形切割之雷射光有效率地到達半導體晶圓等工件內。就穩定地使雷射光有效率地到達半導體晶圓的觀點而言，保護膜之波長為1064nm之透光率較佳為50%以上且99.9%以下，更佳為60%以上且99.5%以下。 The light transmittance of the protective film having a wavelength of 1064 nm is preferably 40% or more and 100% or less. With the protective film having a wavelength of 1064 nm and a light transmittance of 40% or more, the laser light used for stealth cutting can efficiently reach a workpiece such as a semiconductor wafer. From the viewpoint of stably enabling laser light to efficiently reach the semiconductor wafer, the transmittance of the protective film at a wavelength of 1064 nm is preferably 50% or more and 99.9% or less, and more preferably 60% or more and 99.5% or less.
保護膜於50℃之斷裂應力較佳為1.0×103Pa以上且2.0×107Pa以下。藉由使該斷裂應力為2.0×107Pa以下，於後述條件下使第1支撐片4伸長(延伸)時，可恰當地分割第1支撐片4所具備之保護膜。就更穩定地達成保護膜之恰當分割之觀點而言，保護膜之50℃之斷裂應力更佳為5.0×103Pa以上且1.9×107Pa以下，更佳為5.0×103Pa以上且1.8×107Pa以下，又更佳為8.0×103Pa以上且1.7×107Pa以下。 The breaking stress of the protective film at 50 ° C. is preferably 1.0 × 10 3 Pa or more and 2.0 × 10 7 Pa or less. When the breaking stress is 2.0 × 10 7 Pa or less, when the first support sheet 4 is extended (extended) under the conditions described later, the protective film provided in the first support sheet 4 can be appropriately divided. From the viewpoint of more appropriately achieving proper division of the protective film, the fracture stress at 50 ° C. of the protective film is more preferably 5.0 × 10 3 Pa or more and 1.9 × 10 7 Pa or less, and more preferably 5.0 × 10 3 Pa or more and 1.8 × 10 7 Pa or less, more preferably 8.0 × 10 3 Pa or more and 1.7 × 10 7 Pa or less.
再者，保護膜之「50℃之斷裂應力」可藉由後述試驗例所記載之方法進行測定。 The "breaking stress at 50 ° C" of the protective film can be measured by a method described in a test example described later.
即，本發明之保護膜形成用片之一個形態係具有前述保護膜形成膜，且前述保護膜形成膜具有以下特性：50℃之斷裂應變為0.1%以上且20%以下，且損耗正切之峰值溫度T1處於25℃至60℃之範圍內。 That is, one form of the sheet for forming a protective film according to the present invention has the aforementioned protective film-forming film, and the aforementioned protective film-forming film has the following characteristics: the breaking strain at 50 ° C is 0.1% to 20%, and the peak of the loss tangent is The temperature T1 is in a range of 25 ° C to 60 ° C.
前述保護膜形成膜可進一步具有以下之至少一種特性：25℃之儲存彈性模數為3.0×109Pa以上且5.0×1011Pa以下；25℃之損耗正切為0.01以上且0.4以下；波長為1064nm之透光率為40%以上且100%以下；50℃之斷裂應力為1.0×103Pa以上且2.0×107Pa以下。 The protective film-forming film may further have at least one of the following characteristics: the storage elastic modulus at 25 ° C is 3.0 × 10 9 Pa or more and 5.0 × 10 11 Pa or less; the loss tangent at 25 ° C is 0.01 or more and 0.4 or less; the wavelength is The light transmittance at 1064nm is 40% to 100%; the fracture stress at 50 ° C is 1.0 × 10 3 Pa to 2.0 × 10 7 Pa.
再者，此處所謂之「特性」係指保護膜形成膜之化學特性或物理化學特性。 In addition, the "characteristics" referred to herein refer to chemical characteristics or physicochemical characteristics of the protective film-forming film.
4.治具用黏著劑層 4. Adhesive layer for fixture
作為構成治具用黏著劑層5之黏著劑，較佳為具有所需之黏著力及再剝離性之黏著劑，例如可使用丙烯酸系黏著劑、橡膠系黏著劑、聚矽氧系黏著劑、胺基甲酸酯系黏著劑、聚酯系黏著劑、聚乙烯醚系黏著劑等。該等中，較佳為與環狀架等治具之密接性高，於切割步驟等中可有效抑制保護膜形成用片3自環狀架等剝落的丙烯酸系黏著劑。再者，亦可於治具用黏著劑層5之厚度方向中介置作為芯材之基材。 As the adhesive constituting the adhesive layer 5 for a jig, an adhesive having a desired adhesive force and re-peelability is preferable. For example, an acrylic adhesive, a rubber adhesive, a polysiloxane adhesive, Urethane-based adhesives, polyester-based adhesives, polyvinyl ether-based adhesives, and the like. Among these, an acryl-based adhesive having high adhesion to a jig such as a ring-shaped frame, and capable of effectively suppressing peeling of the protective film-forming sheet 3 from the ring-shaped frame or the like in a cutting step or the like is preferable. Furthermore, a base material as a core material may be interposed in the thickness direction of the adhesive layer 5 for a jig.
另一方面，就相對於環狀架等治具之接著性之觀點而言，治具用黏著劑層5之厚度較佳為5μm~200μm，更佳為10μm~100μm。 On the other hand, the thickness of the adhesive layer 5 for a jig is preferably 5 μm to 200 μm, and more preferably 10 μm to 100 μm from the viewpoint of adhesiveness of a jig such as a ring frame.
5.剝離片 5. Release sheet
本發明一實施形態之保護膜形成用片3的剝離片6，係於至使用保護膜形成用片3之前的期間，對保護膜形成膜1及治具用黏著劑層5進行保護。 The release sheet 6 of the protective film forming sheet 3 according to one embodiment of the present invention protects the protective film forming film 1 and the adhesive layer 5 for jigs before the protective film forming sheet 3 is used.
剝離片6之構成為任意，可例示利用剝離劑等對塑膠膜進行剝離處理而成之片。作為塑膠膜之具體例，可列舉：聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等聚酯膜；及聚丙烯或聚乙烯等聚烯烴膜。作為剝離劑，可使用聚矽氧系剝離劑、氟系剝離劑、長鏈烷基系剝離劑等，該等中較佳為廉價且可獲得穩定性能之聚矽 氧系剝離劑。剝離片6之厚度並無特別限制，通常為20μm~250μm左右。 The configuration of the release sheet 6 is arbitrary, and examples thereof include a sheet obtained by peeling a plastic film using a release agent or the like. Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; and polyolefin films such as polypropylene or polyethylene. . As the release agent, a polysiloxane-based release agent, a fluorine-based release agent, a long-chain alkyl-based release agent, or the like can be used. Among these, a polysilicon that is inexpensive and obtains stable performance is preferred. Oxygen-based release agent. The thickness of the release sheet 6 is not particularly limited, but is usually about 20 μm to 250 μm.
6.保護膜形成用片之製造方法 6. Manufacturing method of sheet for forming protective film
保護膜形成用片3較佳為分別製作包含保護膜形成膜1之積層體(本說明書中稱為「積層體I」)及包含第1支撐片4之積層體(本說明書中稱為「積層體II」)之後，使用積層體I及積層體II，將保護膜形成膜1與第1支撐片4積層而製造，但並不限定於此。 The sheet 3 for forming a protective film is preferably a laminated body including the protective film forming film 1 (referred to as "laminated body I" in this specification) and a laminated body including the first support sheet 4 (referred to as "laminated body in this specification"). Body II "), and using the laminated body I and the laminated body II, the protective film-forming film 1 and the first support sheet 4 are laminated and manufactured, but it is not limited thereto.
製造積層體I時，於第1剝離片之剝離面形成保護膜形成膜1。具體而言，調製含有構成保護膜形成膜1之硬化性接著劑、及視需要進一步含有溶劑之保護膜形成膜用之塗佈劑，利用輥式塗佈機、刀式塗佈機、輥刀式塗佈機、氣刀式塗佈機、模具塗佈機、棒式塗佈機、凹版塗佈機、簾幕式塗佈機等塗佈機，於第1剝離片之剝離面塗佈前述塗佈劑並使其乾燥，而將保護膜形成膜1形成於第1剝離片之剝離面。接著，於保護膜形成膜1之露出面重疊第2剝離片之剝離面並壓接，而獲得由兩片剝離片夾著保護膜形成膜1而成之積層體(積層體I)。 When manufacturing the laminated body I, the protective film forming film 1 is formed on the peeling surface of a 1st peeling sheet. Specifically, a coating agent for a protective film-forming film containing a curable adhesive constituting the protective film-forming film 1 and, if necessary, a solvent is further prepared, and a roll coater, a knife coater, and a roll knife are used. Coater, air knife coater, die coater, bar coater, gravure coater, curtain coater and other coaters, apply the aforementioned to the release surface of the first release sheet The coating agent is dried and the protective film-forming film 1 is formed on the release surface of the first release sheet. Next, the exposed surface of the protective film-forming film 1 is laminated with the release surface of the second release sheet and pressure-bonded to obtain a laminated body (laminated body I) in which the protective film-forming film 1 is sandwiched between the two release sheets.
該積層體I可視需要實施半切(half cut)，使保護膜形成膜1(及第2剝離片)成為所需之形狀，例如圓形等。於此情形，半切所產生之保護膜形成膜1及第2剝離片之多餘 部分適當去除即可。 This laminated body I can be subjected to a half cut if necessary, so that the protective film forming film 1 (and the second release sheet) has a desired shape, such as a circle or the like. In this case, the protective film forming film 1 and the second release sheet produced by the half-cutting are redundant. Partial removal is sufficient.
另一方面，當製造積層體II時，於第3剝離片之剝離面塗佈含有構成黏著劑層42之黏著劑、及視需要進一步含有溶劑之黏著劑層用之塗佈劑，並使其乾燥，而於第3剝離片之剝離面形成黏著劑層42。之後，於黏著劑層42之露出面壓接基材41，而獲得包括含有基材41及黏著劑層42之第1支撐片4、與第3剝離片之積層體(積層體II)。 On the other hand, when manufacturing the laminated body II, the release surface of the third release sheet is coated with an adhesive containing the adhesive layer 42 and, if necessary, a coating agent for an adhesive layer further containing a solvent, and then After drying, the adhesive layer 42 is formed on the release surface of the third release sheet. Then, the base material 41 is pressure-bonded on the exposed surface of the adhesive layer 42 to obtain a laminated body (laminated body II) including the first support sheet 4 containing the base material 41 and the adhesive layer 42 and the third release sheet.
此處，於黏著劑層42包含能量線硬化性黏著劑時，可在該階段對黏著劑層42照射能量線而使黏著劑層42硬化，亦可在積層保護膜形成膜1之後照射能量線而使黏著劑層42硬化。又，於在積層保護膜形成膜1之後使黏著劑層42硬化時，可在切割步驟前使黏著劑層42硬化，亦可在切割步驟後使黏著劑層42硬化。 Here, when the adhesive layer 42 contains an energy ray-curable adhesive, the adhesive layer 42 may be irradiated with energy rays at this stage to harden the adhesive layer 42, or the energy rays may be irradiated after the protective film is laminated on the protective film formation film 1 As a result, the adhesive layer 42 is hardened. In addition, when the adhesive layer 42 is hardened after the protective film is formed by laminating the protective film 1, the adhesive layer 42 may be hardened before the cutting step, or the adhesive layer 42 may be hardened after the cutting step.
作為能量線，通常使用紫外線、電子束等。能量線之照射量根據能量線之種類而不同，於例如紫外線時，以光量計較佳為50mJ/cm2~1000mJ/cm2，更佳為100mJ/cm2~500mJ/cm2。另外，於電子束時，較佳為10krad~1000krad左右。 As the energy rays, ultraviolet rays, electron beams, and the like are generally used. The irradiation amount of the energy ray varies according to the type of the energy ray. In the case of ultraviolet rays, for example, it is preferably 50 mJ / cm 2 to 1000 mJ / cm 2 in terms of light amount, and more preferably 100 mJ / cm 2 to 500 mJ / cm 2 . In the case of the electron beam, it is preferably about 10 krad to 1000 krad.
如此獲得積層體I及積層體II後，將積層體I中之第2剝離片剝離，並且將積層體II中之第3剝離片剝離，將積層 體I露出之保護膜形成膜1與積層體II露出之第1支撐片4之黏著劑層42重疊並壓接。第1支撐片4亦可視需要進行半切，而成為所需之形狀，例如具有較保護膜形成膜1大之直徑之圓形等。於此情形時，藉由半切而產生之第1支撐片4之多餘部分適當去除即可。 After obtaining the laminated body I and the laminated body II in this manner, the second release sheet in the laminated body I is peeled off, and the third release sheet in the laminated body II is peeled off, and the laminated body is laminated. The protective film-forming film 1 exposed from the body I and the adhesive layer 42 of the first support sheet 4 exposed from the laminated body II are overlapped and crimped. The first supporting sheet 4 may be cut in half as needed to have a desired shape, such as a circle having a larger diameter than the protective film forming film 1. In this case, the excess portion of the first support piece 4 generated by half cutting may be appropriately removed.
如此而獲得保護膜形成用片3，其包含：第1支撐片4，係於基材41上積層黏著劑層42而成；保護膜形成膜1,係積層於第1支撐片4中積層有黏著劑層42之側；及第1剝離片，其積層於保護膜形成膜1中與面對第1支撐片4之面為相反側之面。最後，將第1剝離片剝離之後，於保護膜形成膜1中與面對第1支撐片4之面為相反側之面的周緣部，形成治具用黏著劑層5。治具用黏著劑層5亦可藉由與上述黏著劑層42相同之方法進行塗佈而形成。 In this way, a protective film-forming sheet 3 is obtained, which includes: a first support sheet 4 formed by laminating an adhesive layer 42 on a substrate 41; a protective film-forming film 1 formed by laminating the first support sheet 4 The side of the adhesive layer 42; and the first release sheet, which is laminated on the protective film-forming film 1 and the side opposite to the side facing the first support sheet 4. Finally, after the first release sheet is peeled off, a peripheral edge portion of the protective film-forming film 1 on the surface opposite to the surface facing the first support sheet 4 forms an adhesive layer 5 for a jig. The adhesive layer 5 for a jig can also be formed by coating in the same manner as the above-mentioned adhesive layer 42.
7.保護膜形成用片之使用方法 7. Use of protective film forming sheet
以下，作為一例說明使用本發明一實施形態之保護膜形成用片3，而由作為工件之半導體晶圓製造附有保護膜之晶片的方法。 Hereinafter, as an example, a method of manufacturing a wafer with a protective film from a semiconductor wafer as a work using the sheet 3 for forming a protective film according to an embodiment of the present invention will be described.
(1)第1貼附步驟 (1) First attaching step
首先，使上述本發明一實施形態之保護膜形成用片3所具備之保護膜形成膜1中與面對第1支撐片4之面為相反側之面露出。圖1所示之保護膜形成用片3係如圖2所示， 將剝離片6剝離即可。 First, the protective film-forming film 1 included in the protective film-forming sheet 3 according to the embodiment of the present invention is exposed on a surface opposite to the surface facing the first support sheet 4. The sheet 3 for forming a protective film shown in FIG. 1 is shown in FIG. 2. The release sheet 6 may be peeled.
接著，將露出之上述面貼附於作為工件之半導體晶圓7之一面，具體而言係貼附於與電路形成面為相反側之面(背面)，而獲得具備保護膜形成用片3與工件1之第1積層體10(圖3)。圖3所示之第1積層體10進一步具備治具用黏著劑層5及環狀架8。如前所述，治具用接著劑層5為保護膜形成用片3之一要件，於第1貼附步驟中，在將保護膜形成用片3之保護膜形成膜1貼附於半導體晶圓7時，將保護膜形成用片3之治具用接著劑層5貼附於環狀架8即可。 Next, the exposed surface is attached to one surface of the semiconductor wafer 7 as a workpiece, and specifically, is attached to a surface (back surface) opposite to the circuit formation surface to obtain a sheet 3 with a protective film and The first laminated body 10 of the work 1 (FIG. 3). The first laminated body 10 shown in FIG. 3 further includes an adhesive layer 5 for a jig and a ring frame 8. As described above, the adhesive layer 5 for jigs is one of the requirements of the sheet 3 for forming a protective film. In the first attaching step, the protective film forming film 1 of the sheet 3 for forming a protective film is attached to a semiconductor crystal. At the time of circle 7, the jig adhesive layer 5 for the protective film forming sheet 3 may be attached to the ring frame 8.
即，第1貼附步驟之一個形態包括：使本發明一實施形態之保護膜形成用片所具備之保護膜形成膜中與面對第1支撐片之面為相反側之面露出；及將前述露出之面貼附於工件之一面，而獲得具備前述保護膜形成用片與前述工件之第1積層體。 That is, one aspect of the first attaching step includes exposing a protective film-forming film included in the protective film-forming sheet according to an embodiment of the present invention on a surface opposite to the surface facing the first support sheet; and The exposed surface is adhered to one surface of a workpiece, and a first laminated body including the sheet for forming a protective film and the workpiece is obtained.
加熱時間及加熱溫度根據構成膜之材料而不同，較佳為例如於90℃~170℃加熱0.5小時~5小時。 The heating time and heating temperature vary depending on the material constituting the film, and it is preferably, for example, heated at 90 ° C to 170 ° C for 0.5 hours to 5 hours.
(2)第1硬化步驟 (2) First hardening step
使藉由第1貼附步驟而獲得之第1積層體10之保護膜形成用片3所具備的保護膜形成膜1硬化，而獲得保護膜。用於獲得保護膜之硬化條件係根據構成保護膜形成膜1之材料而適當設定。於保護膜形成膜1為熱硬化性接著劑時，在特定溫度下將保護膜形成膜1加熱恰當之時間即可。 另外，於保護膜形成膜1並非熱硬化性接著劑時，另行實施加熱處理。 The protective film forming film 1 included in the protective film forming sheet 3 of the first laminated body 10 obtained in the first attaching step is cured to obtain a protective film. The hardening conditions for obtaining the protective film are appropriately set depending on the material constituting the protective film forming film 1. When the protective film-forming film 1 is a thermosetting adhesive, the protective film-forming film 1 may be heated at a specific temperature for an appropriate time. When the protective film-forming film 1 is not a thermosetting adhesive, a heat treatment is separately performed.
即，第1硬化步驟之一個形態係包括藉由使前述第1積層體中之保護膜形成膜硬化，而獲得保護膜。 That is, one aspect of the first curing step includes obtaining a protective film by hardening the protective film-forming film in the first laminated body.
(3)第1分割步驟 (3) The first division step
於將經過前述第1硬化步驟之第1積層體10之保護膜形成用片3所具備的保護膜之溫度T2保持在40℃至70℃之範圍內之狀態下，使保護膜形成用片3所具備之第1支撐片4伸長(延伸)，而將保護膜與半導體晶圓7一起分割。結果如圖4所示般獲得第2積層體20，係於第1支撐片4之一面上，配置有將半導體晶圓7與保護膜之積層體以於厚度方向產生切割面的方式分割而成之複數(例如為2~20,000)個附有保護膜之晶片9。 The protective film forming sheet 3 is maintained in a state where the temperature T2 of the protective film provided in the protective film forming sheet 3 of the first laminated body 10 having undergone the first hardening step is within a range of 40 ° C to 70 ° C. The first supporting sheet 4 provided is stretched (extended), and the protective film is divided together with the semiconductor wafer 7. As a result, as shown in FIG. 4, a second laminated body 20 was obtained. The second laminated body 20 was attached to one surface of the first support sheet 4, and the laminated body of the semiconductor wafer 7 and the protective film was arranged so as to generate a cutting surface in the thickness direction. A plurality of (for example, 2 to 20,000) wafers 9 with a protective film.
即，第1分割步驟之一個形態包括：於將經過前述第1硬化步驟之前述第1積層體中前述保護膜之溫度T2保持在40℃至70℃之範圍內的狀態下，使前述第1支撐片伸長，將前述工件與前述保護膜之積層體分割，藉此獲得於前述第1支撐片之一面上配置有複數個附有保護膜之晶片的第2積層體。 That is, one aspect of the first dividing step includes: maintaining the temperature T2 of the protective film in the first laminated body that has undergone the first hardening step within a range of 40 ° C. to 70 ° C. The support sheet is extended, and the laminated body of the workpiece and the protective film is divided to obtain a second laminated body in which a plurality of wafers with protective films are arranged on one surface of the first support sheet.
使第1支撐片4伸長之方法並無限定。可如圖4所示，自第1支撐片4中之與與面對環狀架8之面相反之面側壓抵環狀之構件R，且使環狀架8與環狀之構件R之鉛垂方向之 相對位置變化，藉此使第1支撐片4伸長。即，藉由前述伸長而於支撐片4產生之應力中，係包含與水平方向或半導體晶圓7之背面平行之方向的向量。 The method for extending the first support sheet 4 is not limited. As shown in FIG. 4, the ring-shaped member R can be pressed against the ring-shaped member R from the side of the first support sheet 4 opposite to the side facing the ring-shaped frame 8, and the ring-shaped member 8 and the ring-shaped member R can be pressed. Of vertical direction The relative position is changed, thereby extending the first support sheet 4. That is, the stress generated in the support sheet 4 by the elongation includes a vector in a direction parallel to the horizontal direction or the back surface of the semiconductor wafer 7.
通常，進行第1支撐片4之延伸時，位於第1支撐片4與半導體晶圓7之間的構件為保護膜形成膜1。保護膜形成膜1通常由可藉由硬化而形成保護膜之材料，即硬化性材料構成，其典型例為未硬化之硬化性接著劑。此種材料被賦予拉伸力時，直至斷裂之前的變形量(斷裂應變)大，有使第1支撐片4伸長(延伸)亦無法分割之情形。因此，於第1支撐片4之延伸時，係將保護膜形成膜1冷卻到0℃至-20℃左右(具體而言，通常係藉由將第1積層體10冷卻而達成)，而使保護膜形成膜1之斷裂應變降低。然而，通常與加熱相比，進行冷卻需要相對昂貴之冷卻設備，且冷卻所需之能量較加熱所需之能量多。因此，將保護膜形成膜1冷卻，通常為將第1積層體10冷卻，會導致附有保護膜之晶片之製造方法中之初期投資及運轉成本增大。 Generally, when the first support sheet 4 is extended, a member located between the first support sheet 4 and the semiconductor wafer 7 is the protective film forming film 1. The protective film-forming film 1 is generally composed of a hardening material, which is a material capable of forming a protective film by hardening, and a typical example thereof is an unhardened hardening adhesive. When a tensile force is applied to such a material, the amount of deformation (breaking strain) before breaking is large, and the first support sheet 4 may not be able to be stretched (extended). Therefore, when the first support sheet 4 is extended, the protective film-forming film 1 is cooled to about 0 ° C to -20 ° C (specifically, it is usually achieved by cooling the first laminated body 10) so that The breaking strain of the protective film forming film 1 is reduced. However, compared to heating, cooling is generally required for relatively expensive cooling equipment, and the energy required for cooling is greater than the energy required for heating. Therefore, cooling the protective film-forming film 1 to cool the first laminated body 10 usually results in an increase in initial investment and operating costs in a method for manufacturing a wafer with a protective film.
與此相對，本發明一實施形態之附有保護膜之晶片之製造方法中，進行第1支撐片4之延伸時位於第1支撐片4與半導體晶圓7之間的構件為保護膜。由於保護膜係保護膜形成膜1硬化而獲得，故其斷裂應變較保護膜形成膜1之斷裂應變低。因此，不易產生起因於斷裂應變之分割不良。然而，由於保護膜為已硬化之材料，故有斷裂應力變 高之情形，有因斷裂應力高而產生分割不良之可能性。因此，本發明一實施形態之附有保護膜之晶片之製造方法中，於第1支撐片4之延伸時，係設為將保護膜之溫度T2保持在40℃至70℃之範圍內之狀態。 In contrast, in the method for manufacturing a wafer with a protective film according to an embodiment of the present invention, a member located between the first supporting sheet 4 and the semiconductor wafer 7 when the first supporting sheet 4 is extended is a protective film. Since the protective film is obtained by hardening the protective film forming film 1, its breaking strain is lower than that of the protective film forming film 1. Therefore, it is not easy to cause poor division due to the strain at break. However, since the protective film is a hardened material, there is a change in fracture stress. If it is high, there is a possibility of poor partition due to high fracture stress. Therefore, in the method for manufacturing a wafer with a protective film according to an embodiment of the present invention, when the first support sheet 4 is extended, the temperature T2 of the protective film is maintained in a range of 40 ° C to 70 ° C. .
即，與以往之冷延伸相反地進行熱延伸，藉此而使保護膜產生分割不良之可能性降低。若將保護膜之溫度T2升高至40℃左右，則與室溫(23℃)狀態相比斷裂應力之下降變得明顯，可穩定地獲得源於熱延伸之效果(分割不良之降低)。另一方面，若使第1支撐片4之延伸時之保護膜之溫度T2超過70℃，則因保護膜之斷裂應變增大、第1支撐片4之機械特性變化(楊氏模數下降、軟質化等)所引起之作業不良(具體例可列舉延伸量之下降、第1支撐片4對載物台之熔著等)等不良情形明顯化之可能性變高。因此，藉由將第1支撐片4之延伸時之保護膜之溫度T2設為70℃以下，可使附有保護膜之晶片之製造中產生不良情形之可能性穩定地降低。就使此種產生不良情形之可能性更穩定地降低之觀點而言，第1支撐片4之延伸時之保護膜之溫度T2較佳為設為42℃以上且65℃以下，更佳為設為43℃以上且60℃以下，尤佳為設為45℃以上且55℃以下。 That is, the hot stretching is performed in contrast to the conventional cold stretching, thereby reducing the possibility of occurrence of poor division of the protective film. If the temperature T2 of the protective film is increased to about 40 ° C, the decrease in fracture stress becomes apparent compared with the room temperature (23 ° C) state, and the effect due to thermal elongation (reduction of poor division) can be obtained stably. On the other hand, if the temperature T2 of the protective film when the first supporting sheet 4 is extended exceeds 70 ° C, the mechanical strain of the first supporting sheet 4 changes due to the increase in the breaking strain of the protective film (the Young's modulus decreases, Defects such as softening, etc. (specific examples include a decrease in elongation amount, adhesion of the first support sheet 4 to the stage, etc.) are likely to become apparent. Therefore, by setting the temperature T2 of the protective film when the first support sheet 4 is extended to 70 ° C. or less, the possibility of occurrence of a defect in the manufacture of the wafer with the protective film can be stably reduced. From the viewpoint of stably reducing the possibility of such a bad situation, the temperature T2 of the protective film at the time of the extension of the first support sheet 4 is preferably 42 ° C or higher and 65 ° C or lower, more preferably The temperature is 43 ° C or higher and 60 ° C or lower, and more preferably 45 ° C or higher and 55 ° C or lower.
(4)第1拾取步驟 (4) 1st picking step
第1拾取步驟中，將藉由實施第1分割步驟而獲得的第 2積層體20所具備之複數個附有保護膜之晶片9分別自第1支撐片4分離，而獲得個別之附有保護膜之晶片9作為加工物。該分離方法並無限定。可如圖5所示，使用頂起銷P及真空吸附筒夾C。如此，可獲得附有保護膜之晶片9。即，第1拾取步驟之一個形態係包括藉由將前述第2積層體所具備之前述複數個附有保護膜之晶片分別自前述第1支撐片分離，而獲得前述附有保護膜之晶片作為加工物。 In the first picking step, the first 2 The plurality of wafers 9 with a protective film provided in the multilayer body 20 are separated from the first support sheet 4 respectively, and individual wafers 9 with a protective film are obtained as processed objects. The separation method is not limited. As shown in FIG. 5, a jacking pin P and a vacuum suction collet C can be used. In this way, a wafer 9 with a protective film can be obtained. That is, one aspect of the first picking step includes separating the plurality of wafers with a protective film provided in the second laminated body from the first supporting sheet, respectively, to obtain the wafers with a protective film as the Processed.
(5)改質層形成步驟 (5) Modification layer forming step
於開始第1分割步驟之前係進行改質層形成步驟，係以聚焦於設定在半導體晶圓7(工件)內部之焦點的方式照射紅外線區域(例如為1064nm)之雷射光，而於半導體晶圓7內部形成改質層。第1分割步驟中，藉由使對經過改質層形成步驟之半導體晶圓7貼合之第1支撐片伸長，而於分割預定線處進行半導體晶圓7之分割。即，改質層形成步驟之一個形態係包括在開始前述第1分割步驟之前，以聚焦於設定在前述工件內部之焦點的方式照射紅外線區域之雷射光，而於前述工件內部形成改質層。 Before the first division step is performed, a modified layer forming step is performed, which irradiates laser light in an infrared region (for example, 1064 nm) so as to focus on a focal point set inside the semiconductor wafer 7 (workpiece), and the semiconductor wafer is 7 A modified layer is formed inside. In the first dicing step, the first support sheet bonded to the semiconductor wafer 7 that has undergone the modified layer forming step is extended, and the semiconductor wafer 7 is diced at a predetermined dicing line. That is, one form of the modified layer forming step includes irradiating laser light in an infrared region so as to focus on a focus set inside the workpiece before starting the first dividing step, and forming a modified layer inside the workpiece.
8.保護膜形成用片之其他實施形態 8. Other Embodiments of Sheet for Forming Protective Film
(1)第1支撐片不具有治具用黏著劑層之情形 (1) Case where the first support sheet does not have an adhesive layer for jigs
圖6係本發明其他實施形態之一的保護膜形成用片之剖面圖。如圖6所示，本實施形態之保護膜形成用片3A之構成為具備：第1支撐片4，係於基材41之一面積層黏著劑 層42而成；保護膜形成膜1，其積層於第1支撐片4中之積層有黏著劑層42之側；及剝離片6，其積層於保護膜形成膜1中與面對第1支撐片4之面為相反側之面。實施形態中之保護膜形成膜1係以於面方向與工件大致相同或較工件稍大之方式形成，且以於面方向上較第1支撐片4小之方式形成。未積層有保護膜形成膜1之部分之黏著劑層42可貼附於環狀架等治具。 6 is a cross-sectional view of a sheet for forming a protective film according to another embodiment of the present invention. As shown in FIG. 6, the protective film-forming sheet 3A of this embodiment is configured to include a first support sheet 4, which is an adhesive layer on an area of a substrate 41. Layer 42; protective film forming film 1 laminated on side of adhesive layer 42 in first support sheet 4; and release sheet 6 laminated on protective film forming film 1 and facing first support The surface of the sheet 4 is the surface on the opposite side. The protective film forming film 1 in the embodiment is formed so that the surface direction is substantially the same as or slightly larger than the workpiece, and is formed so as to be smaller than the first support sheet 4 in the surface direction. The adhesive layer 42 in a portion where the protective film forming film 1 is not laminated can be attached to a jig such as a ring frame.
本實施形態之保護膜形成用片3A之各構件之材料及厚度等與前述保護膜形成用片3之各構件之材料及厚度相同。然而，於黏著劑層42包含能量線硬化性黏著劑時，較佳為使黏著劑層42中之要與保護膜形成膜1接觸之部分之能量線硬化性黏著劑硬化，除此以外之部分不使能量線硬化性黏著劑硬化。藉此，可提高使保護膜形成膜1硬化而成之保護膜之平滑性(巨觀)，並且可將對環狀架等治具之接著力維持為高。 The material and thickness of each member of the protective film forming sheet 3A of this embodiment are the same as those of the respective members and thickness of the protective film forming sheet 3. However, when the adhesive layer 42 contains an energy ray-curable adhesive, it is preferable to harden the energy ray-curable adhesive in a portion of the adhesive layer 42 that is to be in contact with the protective film-forming film 1. Does not harden the energy ray hardening adhesive. Thereby, the smoothness (giant view) of the protective film formed by curing the protective film forming film 1 can be improved, and the adhesive force to a jig such as a ring frame can be maintained high.
再者，亦可於保護膜形成用片3A之第1支撐片4之黏著劑層42中與基材41為相反側之周緣部，另行設置與前述保護膜形成用片3之治具用黏著劑層5相同之治具用黏著劑層。 Furthermore, in the adhesive layer 42 of the first support sheet 4 of the protective film forming sheet 3A, a peripheral edge portion on the side opposite to the base material 41 may be separately provided for adhesion to the jig of the protective film forming sheet 3. The adhesive layer for a jig is the same as the adhesive layer 5.
(2)第1支撐片不具有黏著劑層之情形 (2) Case where the first support sheet does not have an adhesive layer
如圖11所示，本發明其他實施形態之一的保護膜形成 用片3B所具備之第1支撐片亦可不具備黏著劑層，而(僅)由基材構成。於此情形時，基材中之保護膜形成膜側之面相當於第1支撐片之第1面。 As shown in FIG. 11, a protective film is formed according to another embodiment of the present invention. The first support sheet provided in the sheet 3B may not include an adhesive layer, and may be (only) a base material. In this case, the surface on the protective film forming film side in the base material corresponds to the first surface of the first support sheet.
於第1支撐片由基材構成時，較佳為在保護膜形成膜中與面對基材(第1支撐片)之面為相反側之面的周緣部，設置與圖1所示之治具用黏著劑層5相同之治具用黏著劑層。 When the first support sheet is composed of a base material, it is preferable that a peripheral edge portion of a surface opposite to the surface facing the base material (first support sheet) in the protective film-forming film is provided with the treatment shown in FIG. 1. The adhesive layer 5 for a jig is the same as the adhesive layer 5 for a jig.
(3)第1支撐片為剝離片之情形 (3) When the first support sheet is a release sheet
本發明之其他實施形態之一的保護膜形成用片所具備之第1支撐片可為具有剝離面之剝離片。於此情形時，剝離面相當於第1支撐片之第1面。剝離片之具體構成並無限定。 The first support sheet included in the protective film forming sheet according to another embodiment of the present invention may be a release sheet having a release surface. In this case, the peeling surface corresponds to the first surface of the first support sheet. The specific structure of the release sheet is not limited.
(4)具備第2支撐片之情形 (4) When the second support sheet is provided
本發明之其他實施形態之一的保護膜形成用片係可具備第2支撐片，係積層於保護膜形成膜之與面對第1支撐片之面為相反之面側。第2支撐片可為剝離片，且以剝離面與保護膜形成膜相向之方式配置。 The sheet for forming a protective film according to another embodiment of the present invention may include a second support sheet, which is layered on the side of the protective film forming film opposite to the surface facing the first support sheet. The second support sheet may be a release sheet, and may be disposed so that the release surface faces the protective film-forming film.
(5)將第1支撐片自保護膜形成膜剝離之情形 (5) When the first support sheet is peeled from the protective film-forming film
如圖2至圖5所示，上述本發明一實施形態之附有保護膜之晶片9之製造方法中，於第1硬化步驟中由保護膜形成 膜1形成保護膜之後，於第1拾取步驟中自第1支撐片4分離保護膜，具體而言為分離作為附有保護膜之晶片9之一部分的保護膜之分割體。 As shown in FIG. 2 to FIG. 5, in the manufacturing method of the wafer 9 with a protective film according to the embodiment of the present invention, the protective film is formed in the first hardening step. After the film 1 is formed into a protective film, the protective film is separated from the first support sheet 4 in the first pickup step, specifically, a divided body of the protective film that is a part of the wafer 9 with the protective film attached.
本發明之其他實施形態之一的附有保護膜之晶片之製造方法中，保護膜形成膜自第1支撐片剝離之後被硬化而成為保護膜。此種製造方法之一例如下。 In the method for manufacturing a wafer with a protective film according to another embodiment of the present invention, the protective film-forming film is cured after being peeled from the first support sheet to become a protective film. One example of such a manufacturing method is as follows.
即，本實施形態之製造方法之一個形態係如圖7~圖10所示般，包括：積層步驟，係使本發明一實施形態之保護膜形成用片所具備之保護膜形成膜1中與面對第1支撐片之面為相反側之面露出，將前述露出之面貼附於半導體晶圓等工件7之一面，且將前述保護膜形成用片之第1支撐片自保護膜形成膜1剝離，藉此獲得具備前述工件7與前述保護膜形成膜1之第3積層體11；第2硬化步驟，係藉由使前述第3積層體11所具備之前述保護膜形成膜1硬化，而獲得保護膜；第2貼附步驟，係將具備第3基材132及積層於第3基材132之一面側之第3黏著劑層131的加工用片13中之前述第3黏著劑層側131之面，與經過前述第2硬化步驟之前述第3積層體11中之前述保護膜側之面貼合，藉此獲得具備前述加工用片13與前述第3積層體11之第4積層體12；第2分割步驟，係於將前述第4積層體12所具備之前述保護膜之溫度T3保持在40℃至70℃之範圍內的狀態下，使前述第4積層體12所具備之前述加工用片13伸長，將前 述保護膜與前述工件7一起分割，藉此獲得第5積層體14，該第5積層體14係於前述加工用片13之一面上配置有將前述工件7與前述保護膜之積層體以於厚度方向產生切割面的方式分割而成之複數個附有保護膜之晶片9；及第2拾取步驟，係將前述第5積層體14所具備之複數個附有保護膜之晶片9分別自前述加工用片13分離，而獲得附有保護膜之晶片9作為加工物；進一步包括改質層形成步驟，該改質層形成步驟係於開始前述第2分割步驟之前，以聚焦於設定在前述工件7內部之焦點的方式照射紅外線區域之雷射光，而於前述工件7內部形成改質層。 That is, one aspect of the manufacturing method of this embodiment is as shown in FIG. 7 to FIG. 10, and includes a lamination step of bringing the protective film forming film 1 included in the protective film forming sheet of one embodiment of the present invention into The surface facing the first supporting sheet is exposed on the opposite side. The exposed surface is attached to one surface of a workpiece 7 such as a semiconductor wafer, and the first supporting sheet of the protective film forming sheet is formed from a protective film. 1 is peeled off to obtain the third laminated body 11 including the workpiece 7 and the protective film forming film 1; the second hardening step is to harden the protective film forming film 1 provided in the third laminated body 11, A protective film is obtained; in the second attaching step, the third adhesive layer in the processing sheet 13 including the third substrate 132 and the third adhesive layer 131 laminated on one side of the third substrate 132 is provided. The surface of the side 131 is bonded to the surface of the protective film side in the third laminated body 11 that has undergone the second hardening step, thereby obtaining a fourth laminated layer including the processing sheet 13 and the third laminated body 11.体 12; the second division step is based on the above-mentioned fourth laminated body 12 State temperature T3 of the protective film remains in the range of 40 ℃ to 70 deg.] C, so that the body 12 includes the machining of a fourth layered elongate sheet 13, the front The protective film is divided with the workpiece 7 to obtain a fifth laminated body 14. The fifth laminated body 14 is arranged on one surface of the processing sheet 13, and a laminated body of the workpiece 7 and the protective film is disposed on the surface. A plurality of wafers 9 with a protective film, which are divided in such a manner that a cutting surface is generated in the thickness direction; and a second picking step is to separate the plurality of wafers 9 with a protective film provided in the fifth laminated body 14 from the foregoing The processing sheet 13 is separated to obtain a protective film-attached wafer 9 as a processed product. The modified sheet further includes a reforming layer forming step, which is performed prior to the start of the second division step to focus on the workpiece set The internal focal point 7 radiates laser light in the infrared region, and a modified layer is formed inside the aforementioned workpiece 7.
此處，加工用片13所具備之第3基材132具有與支撐片4所具備之基材41相同之特徵即可。又，加工用片13所具備之第3黏著劑層131具有與支撐片4所具備之黏著劑層42相同之特徵即可。另外，第2分割步驟中之溫度T3較佳為上述溫度T1以上。 Here, the third base material 132 included in the processing sheet 13 may have the same characteristics as the base material 41 included in the support sheet 4. The third adhesive layer 131 included in the processing sheet 13 may have the same characteristics as the adhesive layer 42 included in the support sheet 4. The temperature T3 in the second division step is preferably equal to or higher than the temperature T1.
以上說明之實施形態係為了使本發明理解容易而記載，並非限定本發明。因此，上述實施形態所揭示之各要件亦包括屬於本發明技術範圍之所有設計變更或均等物。 The embodiments described above are described in order to make the present invention easy to understand, and do not limit the present invention. Therefore, the requirements disclosed in the above embodiments also include all design changes or equivalents belonging to the technical scope of the present invention.
例如，亦可於第1支撐片4中之基材41與黏著劑層42之間介置其他層。另外，亦可於包含基材41之第1支撐片4之第1面積層其他層。作為其他層，例如可列舉底塗層等 用於調整基材41與黏著劑層42之間之接著性的層、調整支撐片4與保護膜形成膜1之間之接著性的層。 For example, another layer may be interposed between the substrate 41 and the adhesive layer 42 in the first support sheet 4. In addition, another layer may be provided on the first area layer of the first support sheet 4 including the base material 41. Examples of the other layer include an undercoat layer and the like. A layer for adjusting the adhesiveness between the substrate 41 and the adhesive layer 42, and a layer for adjusting the adhesiveness between the support sheet 4 and the protective film-forming film 1.
(實施例) (Example)
以下藉由實施例等更具體地說明本發明，但本發明之範圍並不限定於該等實施例等。 Hereinafter, the present invention will be described more specifically with examples and the like, but the scope of the present invention is not limited to these examples and the like.
〔實施例1〕 [Example 1]
將以下之各成分以表1所示之調配比(固體成分換算)進行混合，且以固體成分濃度相對於保護膜形成膜用塗佈劑之總質量而成為50質量%之方式利用甲基乙基酮進行稀釋，而調製保護膜形成膜用塗佈劑。 Each of the following components was mixed at the mixing ratio (solid content conversion) shown in Table 1, and methyl solid was used so that the concentration of the solid content was 50% by mass relative to the total mass of the coating film-forming coating agent. The ketone is diluted to prepare a coating agent for a protective film forming film.
(A-1)黏合劑聚合物：使丙烯酸正丁酯10質量份、丙烯酸甲酯70質量份、甲基丙烯酸縮水甘油酯5質量份及丙烯酸2-羥基乙酯15質量份共聚而成之(甲基)丙烯酸酯共聚物(重量平均分子量：40萬，玻璃轉移溫度：-1℃) (A-1) Binder polymer: copolymerized by 10 parts by mass of n-butyl acrylate, 70 parts by mass of methyl acrylate, 5 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate ( (Meth) acrylate copolymer (weight average molecular weight: 400,000, glass transition temperature: -1 ° C)
(A-2)黏合劑聚合物：使丙烯酸甲酯85質量份、及丙烯酸2-羥基乙酯15質量份共聚而成之(甲基)丙烯酸酯共聚物(重量平均分子量：40萬，玻璃轉移溫度：-6℃) (A-2) Adhesive polymer: (meth) acrylic acid ester copolymer (weight average molecular weight: 400,000, glass transition) obtained by copolymerizing 85 parts by mass of methyl acrylate and 15 parts by mass of 2-hydroxyethyl acrylate. Temperature: -6 ℃)
(A-3)黏合劑聚合物：使丙烯酸正丁酯55質量份、丙烯酸甲酯10質量份、甲基丙烯酸縮水甘油酯20質量份及丙烯酸2-羥基乙酯15質量份共聚而成之(甲基)丙烯酸酯共聚物(重量平均分子量：80萬，玻璃轉移溫度：-28℃) (A-3) Binder polymer: copolymerized by 55 parts by mass of n-butyl acrylate, 10 parts by mass of methyl acrylate, 20 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate ( (Meth) acrylate copolymer (weight average molecular weight: 800,000, glass transition temperature: -28 ° C)
(B-1)雙酚A型環氧樹脂(三菱化學公司製造，jER828，環氧當量為184g/eq~194g/eq) (B-1) Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828, epoxy equivalent is 184g / eq ~ 194g / eq)
(B-2)雙酚A型環氧樹脂(三菱化學公司製造，jER1055，環氧當量為800g/eq~900g/eq) (B-2) Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER1055, epoxy equivalent is 800g / eq ~ 900g / eq)
(B-3)二環戊二烯型環氧樹脂(DIC公司製造，Epiclon HP-7200HH，環氧當量為255g/eq~260g/eq) (B-3) Dicyclopentadiene type epoxy resin (manufactured by DIC, Epiclon HP-7200HH, epoxy equivalent is 255g / eq ~ 260g / eq)
(B-4)甲酚酚醛清漆型環氧樹脂(日本化藥公司製造，EOCN-104，環氧當量為220g/eq) (B-4) Cresol novolac epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104, epoxy equivalent is 220g / eq)
(C)熱活性潛伏性環氧樹脂硬化劑：二氰二胺(ADEKA公司製造，Adeka Hardener EH-3636AS，活性氫量為21g/eq) (C) Thermally active latent epoxy resin hardener: dicyandiamine (manufactured by ADEKA, Adeka Hardener EH-3636AS, active hydrogen content is 21 g / eq)
(D)硬化促進劑：2-苯基-4,5-二羥基甲基咪唑(四國化成工業公司製造，Curezol 2PHZ) (D) Hardening accelerator: 2-phenyl-4,5-dihydroxymethylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., Curezol 2PHZ)
(E-1)環氧基改質球狀二氧化矽填料(Admatechs公司製造，SC2050MA，平均粒徑為0.5μm) (E-1) Epoxy modified spherical silica filler (manufactured by Admatechs, SC2050MA, average particle size: 0.5 μm)
(E-2)乙烯基改質球狀二氧化矽填料(Admatechs公司製造，YA050C-MJA，平均粒徑為0.05μm) (E-2) Vinyl modified spherical silica filler (manufactured by Admatechs, YA050C-MJA, average particle size: 0.05 μm)
(E-3)不定形二氧化矽填料(龍森公司製造，SV-10，平均粒徑為8μm) (E-3) Amorphous silica filler (manufactured by Lonson Corporation, SV-10, average particle size: 8 μm)
(F)矽烷偶合劑：γ-縮水甘油氧基丙基三甲氧基矽烷(信越化學工業公司製造，KBM403，甲氧基當量：12.7mmol/g，分子量：236.3) (F) Silane coupling agent: γ-glycidyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403, methoxy equivalent: 12.7 mmol / g, molecular weight: 236.3)
於在聚對苯二甲酸乙二酯(PET)膜之單面形成聚矽氧系之剝離劑層而成之剝離片(LINTEC公司製造，SP-PET381031)上，利用刀式塗佈機，以最終獲得之保護膜形成膜之厚度成為25μm之方式塗佈前述保護膜形成膜用塗佈劑之後，利用烘箱於120℃乾燥2分鐘，而形成保護膜形成膜。然後於保護膜形成膜上，重疊在PET膜之單面形成聚矽氧系之剝離劑層而成之剝離片(LINTEC公司製造，SP-PET251130)之剝離面，並使兩者貼合，而獲得保護膜形成用片。 On a release sheet (manufactured by LINTEC, SP-PET381031) formed by forming a polysiloxane-based release agent layer on one side of a polyethylene terephthalate (PET) film, a knife coater was used to After the coating film for the protective film-forming film was applied so that the thickness of the finally obtained protective film-forming film became 25 μm, it was dried in an oven at 120 ° C. for 2 minutes to form a protective film-forming film. Then, on the protective film forming film, the release surface of a release sheet (manufactured by LINTEC, SP-PET251130) formed by superposing a polysiloxane-based release agent layer on one side of the PET film, and bonding the two together, and A sheet for forming a protective film was obtained.
〔實施例2〕 [Example 2]
調製如下之保護膜形成膜用塗佈劑，即，將構成保護膜形成膜之各成分之種類及調配量設為表1之實施例2之列所示之組成，且以固體成分濃度成為50%之方式利用甲基乙基酮進行稀釋，除此以外，以與實施例1相同之方式製造保護膜形成用片。 A coating agent for a protective film-forming film was prepared by setting the type and amount of each component constituting the protective film-forming film to the composition shown in the column of Example 2 in Table 1, and setting the solid content concentration to 50 A sheet for forming a protective film was produced in the same manner as in Example 1 except that the method was used for dilution with methyl ethyl ketone.
〔比較例1〕 [Comparative Example 1]
調製如下之保護膜形成膜用塗佈劑，即，將構成保護膜形成膜之各成分之種類及調配量設為表1之比較例1之列所示之組成，且以固體成分濃度成為50%之方式利用甲基乙基酮進行稀釋，除此以外，以與實施例1相同之方式製造保護膜形成用片。 A coating agent for a protective film-forming film was prepared by setting the type and amount of each component constituting the protective film-forming film to the composition shown in the column of Comparative Example 1 in Table 1, and setting the solid content concentration to 50 A sheet for forming a protective film was produced in the same manner as in Example 1 except that the method was used for dilution with methyl ethyl ketone.
〔比較例2〕 [Comparative Example 2]
調製如下之保護膜形成膜用塗佈劑，即，將構成保護膜形成膜之各成分之種類及調配量設為表1之比較例2之列所示之組成，且以固體成分濃度成為50%之方式利用甲基乙基酮進行稀釋，除此以外，以與實施例1相同之方式製造保護膜形成用片。再者，(E-3)不定形二氧化矽填料(SV-10)使用預先利用珠磨機於甲基乙基酮中分散24小時而成者。 A coating agent for a protective film-forming film was prepared by setting the type and amount of each component constituting the protective film-forming film to the composition shown in the column of Comparative Example 2 in Table 1, and setting the solid content concentration to 50 A sheet for forming a protective film was produced in the same manner as in Example 1 except that the method was used for dilution with methyl ethyl ketone. The (E-3) amorphous silica filler (SV-10) was prepared by dispersing it in methyl ethyl ketone for 24 hours using a bead mill in advance.
〔試驗例1〕<黏彈性之測定> [Test Example 1] <Measurement of Viscoelasticity>
(1)硬化物樣品之製作 (1) Production of hardened samples
將實施例及比較例中所製作之保護膜形成用片之兩片剝離片剝離，且以厚度成為200μm之方式積層所獲得之保護膜形成膜。將所獲得之保護膜形成層在烘箱內(大氣環境下)於130℃加熱2小時，而獲得厚度為200μm之保護膜作為硬化物樣品。 The protective film-forming film obtained by peeling off the two peeling sheets of the protective film-forming sheet produced in the Example and the comparative example, and laminating | stacking it so that thickness might be 200 micrometers. The obtained protective film-forming layer was heated in an oven (under the atmosphere) at 130 ° C. for 2 hours, and a protective film having a thickness of 200 μm was obtained as a hardened sample.
(2)硬化後之50℃之斷裂應變之測定 (2) Determination of fracture strain at 50 ° C after hardening
切割所獲得之硬化物樣品，準備寬度5mm×長度20mm×厚度200μm之試驗片。使用動態機械分析裝置(TA Instruments公司製造，DMA Q800)，進行試驗片之拉伸試驗(夾盤間距：5mm)。於溫度為50℃之環境下保持1分鐘之後，一面以1N/分鐘之固定增加率增加負重一面進行拉伸試驗。自其結果獲得斷裂應變。將結果示於表2。 The obtained hardened sample was cut to prepare a test piece having a width of 5 mm × length of 20 mm × thickness of 200 μm. The tensile test (chuck pitch: 5 mm) of the test piece was performed using a dynamic mechanical analyzer (manufactured by TA Instruments, DMA Q800). After holding for 1 minute in an environment at a temperature of 50 ° C, a tensile test was performed while increasing the load at a fixed increase rate of 1 N / minute. From this result, the strain at break is obtained. The results are shown in Table 2.
(3)硬化物樣品之損耗正切之峰值溫度之測定 (3) Determination of the peak temperature of the loss tangent of the hardened sample
切割硬化物樣品，準備寬度4.5mm×長度20mm×厚度200μm之試驗片。使用動態機械分析裝置(TA Instruments公司製造，DMA Q800)，於下述條件下進行儲存彈性模數及損耗模數之測定。 The hardened sample was cut to prepare a test piece having a width of 4.5 mm × length of 20 mm × thickness of 200 μm. Using a dynamic mechanical analyzer (manufactured by TA Instruments, DMA Q800), the storage elastic modulus and the loss modulus were measured under the following conditions.
測定模式：拉伸模式 Measurement mode: Stretch mode
測定開始溫度：0℃ Measurement start temperature: 0 ° C
測定結束溫度：300℃ Measurement end temperature: 300 ° C
升溫速度：3℃/分鐘 Heating rate: 3 ° C / min
頻率：11Hz Frequency: 11Hz
測定環境：大氣 Measurement environment: atmosphere
根據所獲得之儲存彈性模數及損耗模數算出損耗正 切(tanδ)，將該值成為最大之溫度設為損耗正切之峰值溫度。將結果示於表2。 Calculate the positive loss based on the obtained storage elastic modulus and loss modulus Tang (tan δ), and the temperature at which this value becomes the maximum is the peak temperature of the loss tangent. The results are shown in Table 2.
(4)硬化物樣品之25℃之儲存彈性模數及損耗正切之測定 (4) Determination of storage elastic modulus and loss tangent of the hardened sample at 25 ° C
根據上述儲存彈性模數及損耗模數之測定資料，求出25℃之儲存彈性模數及25℃之損耗正切。將結果示於表2。 According to the measurement data of the storage elastic modulus and the loss modulus, the storage elastic modulus at 25 ° C. and the loss tangent at 25 ° C. are obtained. The results are shown in Table 2.
(5)硬化後之50℃之斷裂應力之測定 (5) Determination of fracture stress at 50 ° C after hardening
切割所獲得之硬化物樣品，準備寬度5mm×長度20mm×厚度200μm之試驗片。使用動態機械分析裝置(TA Instruments公司製造，DMA Q800)，進行試驗片之拉伸試驗(夾盤間距：5mm)。於溫度為50℃之環境下保持1分鐘之後，一面以1N/分鐘之固定之增加率增加負重，一面進行拉伸試驗。自其結果獲得斷裂應力。其結果為，實施例1中為1.71×107Pa，實施例2中為1.02×107Pa、比較例1中為8.90×106Pa，比較例2中為2.27×107Pa。。 The obtained hardened sample was cut to prepare a test piece having a width of 5 mm × length of 20 mm × thickness of 200 μm. A tensile test (chuck pitch: 5 mm) of the test piece was performed using a dynamic mechanical analyzer (manufactured by TA Instruments, DMA Q800). After holding for 1 minute in an environment with a temperature of 50 ° C, a tensile test was performed while increasing the load at a fixed increase rate of 1 N / minute. The fracture stress is obtained from the result. As a result, it was 1.71 × 10 7 Pa in Example 1, 1.02 × 10 7 Pa in Example 2, 8.90 × 10 6 Pa in Comparative Example 1, and 2.27 × 10 7 Pa in Comparative Example 2. .
〔試驗例2〕<分割性之評價> [Test Example 2] <Evaluation of Dividability>
於厚度100μm、外徑8吋之矽晶圓所構成之工件上，使用貼附裝置(LINTEC公司製造，RAD-3600F/12)於70℃貼附切割加工成與矽晶圓相同形狀之保護膜形成膜之後，在烘箱內(大氣環境下)於130℃加熱2小時使其硬化，而製作附有保護膜之晶圓。 On a workpiece made of a silicon wafer with a thickness of 100 μm and an outer diameter of 8 inches, a protective film (adhesive device manufactured by LINTEC Corporation, RAD-3600F / 12) was cut and processed into the same shape as the silicon wafer at 70 ° C After the film is formed, it is heated in an oven (under the atmosphere) at 130 ° C for 2 hours to harden it, and a wafer with a protective film is produced.
使用貼附裝置(LINTEC公司製造，RAD-2700F/12) ，將隱形切割用切割帶(LINTEC公司製造，Adwill D-821HS)貼附於附有保護膜之晶圓之保護膜面。此時，亦進行切割帶對環狀架之貼附。 Use attachment device (manufactured by LINTEC, RAD-2700F / 12) , Attach a dicing tape for invisible dicing (manufactured by LINTEC, Adwill D-821HS) to the protective film surface of a wafer with a protective film. At this time, the attachment of the cutting tape to the endless frame is also performed.
使用雷射照射裝置，隔著切割帶及保護膜而照射在晶圓內部聚光之雷射(波長：1064nm)。此時，沿著以形成5mm×5mm之晶片體之方式設定之切割預定線一面掃描一面照射。 A laser irradiation device is used to irradiate a laser (wavelength: 1064 nm) which is focused on the inside of the wafer through a dicing tape and a protective film. At this time, irradiation is performed while scanning along a predetermined cutting line set to form a 5 mm × 5 mm wafer body.
然後，使用延伸裝置(DISCO公司製造，DDS2300)，於溫度為50℃之環境下，以速度100mm/秒、延伸量10mm將貼合於附有保護膜之晶圓之切割帶延伸。 Then, using a stretching device (manufactured by DISCO Corporation, DDS2300), the dicing tape attached to the wafer with the protective film was stretched at a speed of 100 mm / sec and an extension amount of 10 mm in an environment at a temperature of 50 ° C.
其結果，在於所有切割預定線處被分割之晶圓同樣地保護膜亦被分割，時將保護膜分割性設為良好(表2中「A」)，將於分割後之保護膜確認到拉絲現象之情形(表2中「B」)、或有保護膜未被分割之部位之情形(表2中「C」)判定為不良。將結果示於表2。 As a result, the protective film is also divided in the same way for all the wafers that are divided at the predetermined cutting line. When the protective film is set to be good ("A" in Table 2), the drawing of the protective film after the division is confirmed. It was judged to be a defective case ("B" in Table 2) or a case where a protective film was not divided ("C" in Table 2). The results are shown in Table 2.
〔試驗例3〕<保護膜之強度之評價> [Test Example 3] <Evaluation of Strength of Protective Film>
於試驗例2中進行之分割性評價後，使用上述延伸裝置，且使用將熱源設定為550℃之IR(Infrared，紅外線)爐，將具備被分割之晶圓及保護膜(即複數個附有保護膜之晶片)以及切割帶之積層體(第4積層體)加熱5分鐘，藉此矯正切割帶延伸時產生之切割帶之鬆弛。然後，使用固晶機(Canon Machinery公司製造，Bestem-D02)，於進行過3mm之延伸之狀態下，自切割帶之與面對被分割晶 圓及保護膜之面為相反的面側壓抵頂起銷，且利用真空吸附筒夾將被頂出之附有保護膜之晶片拉起，藉此拾取附有保護膜之晶片。 After the severability evaluation performed in Test Example 2, the above-mentioned extension device was used, and an IR (Infrared) furnace with a heat source set to 550 ° C was provided with a divided wafer and a protective film (that is, a plurality of The wafer of the protective film) and the laminated body (the fourth laminated body) of the dicing tape are heated for 5 minutes, thereby correcting the slack of the dicing tape generated when the dicing tape is extended. Then, using a solid crystal machine (Bestem-D02, manufactured by Canon Machinery Co., Ltd.), in a state of 3mm extension, the surface of the self-cutting tape and the surface of the divided crystal The sides of the circle and the protective film are pressed against the ejector pins on the opposite side, and the ejected wafer with the protective film is pulled up by a vacuum suction collet, thereby picking up the wafer with the protective film.
對所拾取之附有保護膜之晶片進行觀察，將未確認到壓抵於保護膜之銷之痕跡之情形判定為良好(表2中「A」)，將確認到無問題程度之銷之痕跡的情形判定為合格(表2中「B」)，將確認到銷之痕跡之情形判定為不良(表2中「C」)。將結果示於表2。再者，關於本評價，由於比較例2之保護膜在試驗例2中未恰當地被分割，故而僅對具備實施例1及2以及比較例1(評價對象設為被割斷之一部分)之保護膜之第4積層體進行本評價。 Observe the picked-up wafer with the protective film, and judge that no trace of the pin pressed against the protective film is judged to be good ("A" in Table 2). The situation was judged to be acceptable ("B" in Table 2), and the situation where the trace of the pin was confirmed was judged to be poor ("C" in Table 2). The results are shown in Table 2. In addition, in this evaluation, since the protective film of Comparative Example 2 was not properly divided in Test Example 2, only the protection provided with Examples 1 and 2 and Comparative Example 1 (the evaluation target is a part that is cut off) is provided. The fourth laminated body of the film was subjected to this evaluation.
根據表2可知，具備50℃之斷裂應變為20%以下且損耗正切之峰值溫度T1處於25℃至60℃之範圍內之保護膜之實施例之保護膜形成用片的分割性優異，並且保護膜之強度亦優異。 According to Table 2, it can be seen that the sheet for forming a protective film of the example having the protective film having a breaking strain at 50 ° C of 20% or less and a peak temperature T1 of the loss tangent in the range of 25 ° C to 60 ° C has excellent slicability and protection The strength of the film is also excellent.
[產業上之可利用性] [Industrial availability]
本發明之保護膜形成用片適合用於包括將保護膜一 面加熱一面分割之步驟之情形，因此於產業上極其有用。 The sheet for forming a protective film of the present invention is suitably used for The step of heating and dividing is extremely industrially useful.
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| TW104127314A TWI668290B (en) | 2014-08-22 | 2015-08-21 | Sheet for forming protective film and method of manufacturing semiconductor tip having protective film |
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| KR102221484B1 (en) * | 2014-03-24 | 2021-02-26 | 린텍 가부시키가이샤 | Protective film forming film, protective film forming sheet and work product manufacturing method |
| SG11201607716PA (en) * | 2014-03-24 | 2016-11-29 | Lintec Corp | Protection membrane forming film, protection membrane forming utilization sheet, production method and inspection method for workpiece or processed product, workpiece determined as adequate product, and processed product determined as adequate product |
-
2015
- 2015-08-21 JP JP2016544263A patent/JP6589209B2/en active Active
- 2015-08-21 TW TW108122914A patent/TWI706023B/en active
- 2015-08-21 CN CN201580044561.4A patent/CN106660332B/en active Active
- 2015-08-21 SG SG11201701272UA patent/SG11201701272UA/en unknown
- 2015-08-21 TW TW104127316A patent/TWI672354B/en active
- 2015-08-21 WO PCT/JP2015/073503 patent/WO2016027883A1/en active Application Filing
- 2015-08-21 MY MYPI2017700479A patent/MY182846A/en unknown
- 2015-08-21 CN CN201580044562.9A patent/CN106660333B/en active Active
- 2015-08-21 WO PCT/JP2015/073545 patent/WO2016027888A1/en active Application Filing
- 2015-08-21 KR KR1020177004497A patent/KR102368140B1/en active IP Right Grant
- 2015-08-21 TW TW104127314A patent/TWI668290B/en active
- 2015-08-21 KR KR1020177004494A patent/KR102376017B1/en active IP Right Grant
- 2015-08-21 SG SG11201701270QA patent/SG11201701270QA/en unknown
- 2015-08-21 TW TW108128902A patent/TWI712670B/en active
- 2015-08-21 JP JP2016544268A patent/JPWO2016027888A1/en active Pending
- 2015-08-21 MY MYPI2017700515A patent/MY186759A/en unknown
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2017
- 2017-02-16 PH PH12017500285A patent/PH12017500285A1/en unknown
- 2017-02-16 PH PH12017500284A patent/PH12017500284B1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090053518A1 (en) * | 2006-03-28 | 2009-02-26 | Lintec Corporation | Sheet for Forming a Protective Film for Chips |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI712670B (en) | 2020-12-11 |
| SG11201701270QA (en) | 2017-03-30 |
| WO2016027883A1 (en) | 2016-02-25 |
| TWI668290B (en) | 2019-08-11 |
| CN106660333A (en) | 2017-05-10 |
| WO2016027888A1 (en) | 2016-02-25 |
| CN106660332B (en) | 2020-08-07 |
| KR102368140B1 (en) | 2022-02-25 |
| SG11201701272UA (en) | 2017-04-27 |
| KR20170044108A (en) | 2017-04-24 |
| JPWO2016027888A1 (en) | 2017-06-01 |
| PH12017500285B1 (en) | 2017-06-28 |
| MY186759A (en) | 2021-08-18 |
| PH12017500284A1 (en) | 2017-07-03 |
| CN106660333B (en) | 2018-11-06 |
| TW201614024A (en) | 2016-04-16 |
| MY182846A (en) | 2021-02-05 |
| KR20170044652A (en) | 2017-04-25 |
| JPWO2016027883A1 (en) | 2017-06-01 |
| JP6589209B2 (en) | 2019-10-16 |
| KR102376017B1 (en) | 2022-03-17 |
| CN106660332A (en) | 2017-05-10 |
| PH12017500285A1 (en) | 2017-06-28 |
| TW201938728A (en) | 2019-10-01 |
| PH12017500284B1 (en) | 2017-07-03 |
| TW201940622A (en) | 2019-10-16 |
| TW201614023A (en) | 2016-04-16 |
| TWI706023B (en) | 2020-10-01 |
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