WO2012128311A1 - 基材フィルムおよび該基材フィルムを備えた粘着シート - Google Patents
基材フィルムおよび該基材フィルムを備えた粘着シート Download PDFInfo
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- WO2012128311A1 WO2012128311A1 PCT/JP2012/057304 JP2012057304W WO2012128311A1 WO 2012128311 A1 WO2012128311 A1 WO 2012128311A1 JP 2012057304 W JP2012057304 W JP 2012057304W WO 2012128311 A1 WO2012128311 A1 WO 2012128311A1
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- Prior art keywords
- pressure
- meth
- sensitive adhesive
- wafer
- adhesive sheet
- Prior art date
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Classifications
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- 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
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- 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
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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 used during dicing or grinding
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
- H01L2221/6834—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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 used to protect an active side of a device or wafer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12042—LASER
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2848—Three or more layers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
Definitions
- the present invention relates to a substrate film used as a substrate for a surface protective pressure-sensitive adhesive sheet preferably used for protecting a circuit surface of a semiconductor wafer having a circuit formed on the surface, and in particular, has a height difference on the circuit surface.
- the present invention relates to a base film preferably used for an adhesive sheet for surface protection of a semiconductor wafer on which large bumps are formed.
- this invention relates to the adhesive sheet which equips this base material film with an adhesive layer and is preferably used as an adhesive sheet for surface protection of a semiconductor wafer.
- a surface protection sheet is attached to the circuit surface to alleviate the height difference of the circuit surface.
- the pressure-sensitive adhesive layer of the surface protective sheet is made thicker and the flowability of the pressure-sensitive adhesive is further increased, thereby bringing the pressure-sensitive adhesive layer and the wafer into close contact with each other. This is dealt with by eliminating the pressure difference due to bump bumps due to the cushioning properties of the layers.
- the thickness of the pressure-sensitive adhesive layer is increased and the fluidity thereof is increased, the pressure-sensitive adhesive easily wraps around the base portion of the bump.
- the pressure-sensitive adhesive attached to the base portion of the bump by the peeling operation of the surface protective sheet may cause in-layer destruction, and a part thereof may remain on the circuit surface. This is a problem that may occur even when a surface protective sheet using an energy ray curable adhesive is used. If the adhesive remaining on the circuit surface is not removed by solvent cleaning or the like, it remains as a foreign substance in the device and impairs the reliability of the completed device.
- Patent Document 1 Japanese Patent Laid-Open No. 2005-123382
- Japanese Patent Laid-Open No. 2005-123382 does not form an adhesive layer having a diameter smaller than the outer diameter of the semiconductor wafer to be attached on one side of the base sheet.
- a surface protective sheet provided with an opening and a portion where an adhesive layer formed on the outer periphery thereof is provided, and a grinding method using the surface protective sheet are disclosed.
- This surface protective sheet has a structure in which a double-sided PSA sheet punched into a ring shape is formed on one side of a base sheet, and since no adhesive is provided on the part that contacts the bump, it adheres to the base part of the bump. Can be used without adhering agent.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2004-288725 discloses that “a semiconductor element forming step of forming a plurality of pad electrodes at predetermined positions on an active surface of an IC wafer and a bump is formed on the pad”.
- a method for manufacturing a semiconductor device comprising: a bump forming step; and a back grinding step of grinding the IC wafer to a predetermined thickness on the inactive surface of the IC wafer.
- the bump forming step the peripheral portion of the IC wafer is A bump is formed, and a support member forming step is provided between the bump forming step and the back grind step to form or affix a support member on the peripheral portion.
- the support member A method of manufacturing a semiconductor device, characterized in that the inactive surface is ground in a state in which a peripheral portion of an IC wafer is supported. There has been disclosed.
- Patent Document 3 Japanese Patent Laid-Open No. 2005-109433
- a protective member that protects the back surface of a semiconductor wafer having bumps formed on the front surface and that does not have bumps formed thereon An outer periphery attaching portion that is attached to the outer peripheral region, a bump protection portion that is surrounded by the outer periphery attaching portion to support and protect the bump, and the outer periphery attaching portion and the bump protection portion are formed to accommodate the bump.
- a bump protecting member for grinding constituted by a concave portion to be made.
- the outer periphery of the bump forming surface of the wafer is surrounded by an adhesive layer, and a bump is formed by a substantially wafer-shaped substrate sheet (resin film) bonded on the adhesive layer.
- the bump formation surface is protected by covering the surface.
- the bumps are pressed against the resin film by the pressure of the grinder used for grinding. Therefore, bumps on the circuit surface may be crushed or dimples or cracks may be generated on the back surface of the wafer when grinding the back surface of the wafer.
- the hardness of the resin film is too high, such a problem appears remarkably.
- the shape retainability becomes insufficient, and the risk of damaging the wafer increases during transportation to the next process following grinding.
- Patent Document 4 discloses a surface protective adhesive sheet using a base material exhibiting special dynamic viscoelasticity as a surface protective adhesive sheet used for a wafer with bumps. This surface protective adhesive sheet was sufficient for bumps with relatively small bump height differences, but the backside grinding of semiconductor wafers with irregularities with height differences exceeding 150 ⁇ m was extremely thin. As a result, dimples and cracks may occur on the back surface of the wafer.
- the present invention has been made in view of the prior art as described above, and when the back surface is ground while the circuit surface of the wafer with bumps is protected by using the surface protection sheet, the bumps on the circuit surface are formed.
- the object is to prevent crushing and to suppress the occurrence of dimples and cracks on the ground surface.
- the present inventors have arranged a resin layer formed from a specific resin as a base film of the surface protection sheet, thereby providing viscoelasticity of the surface protection sheet.
- the present invention has been found that the bumps are not crushed even if the bumps are pressed against the sheet, and the height difference of the wafer surface with bumps can be alleviated, so that the occurrence of dimples and cracks on the ground surface can be suppressed. It came to complete.
- the present invention for solving the above problems includes the following gist.
- a base film of an adhesive sheet to be attached to a semiconductor wafer (A) a layer comprising a cured product obtained by energy-curing a compound containing a urethane (meth) acrylate oligomer and a thiol group-containing compound; (B) The base film comprised from the layer which consists of thermoplastic resins.
- a pressure-sensitive adhesive sheet further comprising a pressure-sensitive adhesive layer on the base film according to the above [1] or [2].
- the present invention has been made in view of the prior art as described above. According to the present invention, when the back surface is ground while the circuit surface of the bumped wafer is protected using the surface protection sheet. The bumps on the circuit surface can be prevented from being crushed, and the generation of dimples and cracks on the ground surface can be suppressed.
- the base film according to the present invention is a base film of an adhesive sheet to be attached to a semiconductor wafer, (A) a layer made of a cured product obtained by energy ray curing a compound containing a urethane (meth) acrylate oligomer and a thiol group-containing compound (hereinafter, sometimes abbreviated as “energy ray cured layer”); (B) It is characterized by comprising a layer made of a thermoplastic resin (hereinafter sometimes abbreviated as “thermoplastic resin layer”).
- the energy ray cured layer (A) which is one of the constituent layers of the base film, contains a urethane (meth) acrylate oligomer and a thiol group-containing compound, and an energy ray curable composition containing an energy ray curable monomer as necessary. Cured product.
- Urethane (meth) acrylate oligomer is a compound having a (meth) acryloyl group and having a urethane bond.
- a urethane (meth) acrylate oligomer has, for example, a hydroxyl group in a terminal isocyanate urethane prepolymer obtained by reacting a polyol compound such as a polyester type or a polyether type with a polyvalent isocyanate compound (meta) ) It is obtained by reacting acrylate.
- (meth) acryl is used in the meaning including both acryl and methacryl.
- the polyol compound is not particularly limited as long as it is a compound having two or more hydroxy groups, and known compounds can be used. Specifically, for example, any of an alkylene diol, a polyether type polyol, a polyester type polyol, and a polycarbonate type polyol may be used, but a better effect can be obtained by using a polyether type polyol.
- the polyol is not particularly limited, and may be a bifunctional diol, a trifunctional triol, or a tetrafunctional or higher polyol. From the viewpoint of availability, versatility, and reactivity, It is particularly preferred to use a diol. Accordingly, polyether type diols are preferably used.
- a polyether type diol which is a representative example of a polyether type polyol compound, is generally represented by HO-(-R-O-) n-H.
- R is a divalent hydrocarbon group, preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 3 or 4 carbon atoms.
- alkylene groups having 1 to 6 carbon atoms ethylene, propylene or tetramethylene is preferable, and propylene or tetramethylene is particularly preferable.
- particularly preferred polyether type diols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and more particularly preferred polyether type diols include polypropylene glycol and polytetramethylene glycol.
- n is the number of repetitions of (—R—O—), preferably about 10 to 250, more preferably about 25 to 205, and particularly preferably about 40 to 185.
- n is smaller than 10
- the urethane bond concentration of the urethane (meth) acrylate oligomer becomes high, and the compressive stress of the energy ray cured layer (A) becomes high.
- n is larger than 250, there is a concern that the compressive stress is hardly lowered.
- a terminal isocyanate urethane prepolymer having an ether bond (-(-R-O-) n-) introduced therein is produced by a reaction between a polyether-type diol and a polyvalent isocyanate compound.
- the urethane (meth) acrylate oligomer contains a structural unit derived from the polyether type diol.
- polyester polybasic acid components As the polybasic acid component used for the production of the polyester-type polyol compound, various known compounds generally known as polyester polybasic acid components can be used. Specifically, for example, dibasic acids such as adipic acid, maleic acid, succinic acid, oxalic acid, fumaric acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid and suberic acid, aromatic polybasic acids And the corresponding anhydrides and derivatives thereof, dimer acid, hydrogenated dimer acid and the like. In addition, in order to provide moderate hardness to a coating film, it is preferable to use an aromatic polybasic acid.
- dibasic acids such as adipic acid, maleic acid, succinic acid, oxalic acid, fumaric acid, malonic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid and suberic acid
- aromatic polybasic acids And the corresponding anhydrides and derivatives
- aromatic polybasic acid examples include dibasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid, polybasic acids such as trimellitic acid and pyromellitic acid, and the like. And corresponding acid anhydrides and derivatives thereof.
- the catalyst include tin compounds such as dibutyltin oxide and stannous octylate, and alkoxytitanium such as tetrabutyl titanate and tetrapropyl titanate.
- the polycarbonate type polyol compound is not particularly limited, and known ones can be used. Specifically, for example, a reaction product of the above-described glycols and alkylene carbonate can be used.
- the molecular weight calculated from the diol hydroxyl value of the polyol compound is preferably about 1000 to 10,000, and more preferably about 2000 to 9000.
- the molecular weight is lower than 1000, the crosslinking density of the urethane (meth) acrylate oligomer is increased, and the compressive stress of the energy ray cured layer (A) may be increased. If the molecular weight is too high, the urethane bond concentration becomes low, and the compressive stress may not easily decrease.
- the molecular weight of the polyether-type polyol compound is the number of polyether-type polyol functional groups ⁇ 56.11 ⁇ 1000 / hydroxyl value [mgKOH / g], which is a value calculated from the hydroxyl value of the polyether-type polyol compound.
- polyvalent isocyanate compound examples include aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, and dicyclohexylmethane-4.
- aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, and dicyclohexylmethane-4.
- aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, tolidine diisocyanate, tetramethylene xylylene diisocyanate, naphthalene-1,5-diisocyanate, and the like.
- isophorone diisocyanate hexamethylene diisocyanate, or xylylene diisocyanate because the viscosity of the urethane (meth) acrylate oligomer can be kept low and the handleability becomes good.
- a urethane (meth) acrylate oligomer is obtained by reacting a terminal isocyanate urethane prepolymer obtained by reacting a polyol compound as described above with a polyvalent isocyanate compound with a (meth) acrylate having a hydroxy group.
- the (meth) acrylate having a hydroxy group is not particularly limited as long as it is a compound having a hydroxy group and a (meth) acryloyl group in one molecule, and known ones can be used. Specifically, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meta ) Acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and other hydroxyalkyl (meth) acrylates, N -Dimethidyl ester of hydroxy group-containing (meth) acrylamide such as methylol (meth) acrylamide,
- the terminal isocyanate urethane prepolymer and the hydroxy group-containing (meth) acrylate are optionally mixed with a solvent and a catalyst.
- the reaction may be performed in the presence at about 60 to 100 ° C. for about 1 to 4 hours.
- the weight average molecular weight of the urethane (meth) acrylate oligomer thus obtained is not particularly limited, but the weight average molecular weight is usually 1000. It is preferably about ⁇ 100,000, more preferably 2,000 to 80,000.
- the weight average molecular weight 1000 or more the breaking elongation of the energy ray cured layer can be improved, and by making it 100000 or less, the resin viscosity of the urethane (meth) acrylate oligomer can be lowered.
- the handling property of the coating liquid for film is improved.
- the urethane (meth) acrylate oligomer obtained has a photopolymerizable double bond in the molecule, and has a property of being polymerized and cured by irradiation with energy rays to form a film.
- Said urethane (meth) acrylate oligomer can be used individually by 1 type or in combination of 2 or more types.
- the thiol group-containing compound is not particularly limited as long as it is a compound having at least one thiol group in the molecule, and known compounds can be used. Specifically, for example, nonyl mercaptan, 1-dodecanethiol, 1,2-ethanedithiol, 1,3-propanedithiol, triazinethiol, triazinedithiol, triazinetrithiol, 1,2,3-propanetrithiol, tetra Ethylene glycol-bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakisthioglucorate, dipentaerythritol hexakis (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl
- the content of the thiol group-containing compound is preferably 2 mmol or more, more preferably 3 to 100 mmol, particularly preferably 4 to 85 mmol with respect to 100 g (solid content) of the urethane (meth) acrylate oligomer.
- the energy ray cured layer (A) exhibits a specific viscoelasticity as described later, and can sufficiently relieve the height difference of the wafer surface with high bumps.
- the amount of the thiol group-containing compound is excessive, the elastic modulus of the energy ray cured layer (A) is remarkably lowered, and when the pressure-sensitive adhesive sheet using the base film is rolled up, the energy from the roll side portion is reduced.
- the constituent resin of the wire-cured layer (A) starts to bleed out, and long-term storage of the roll may be difficult.
- the content of the thiol group-containing compound is 100 mmol or less, it is possible to suppress the compound from remaining as an uncured product, and to prevent the resin from bleeding from the roll side portion.
- the molecular weight of the thiol group-containing compound is preferably 200 to 3000, more preferably 300 to 2000.
- the compatibility with the urethane (meth) acrylate oligomer is lowered, and the film forming property of the energy ray cured layer may be lowered.
- the energy ray polymerizable monomer is usually mixed and formed, and then cured. An energy ray cured layer is obtained.
- the energy ray curable monomer has an energy ray polymerizable double bond in the molecule, and particularly in the present invention, an acrylate ester compound having a relatively bulky group is preferably used.
- energy ray curable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
- the amount of the energy ray-curable monomer used is preferably 10 to 500 parts by weight, more preferably 30 to 300 parts by weight, based on 100 parts by weight (solid content) of the urethane (meth) acrylate oligomer.
- a technique called casting film formation can be preferably employed.
- a liquid compound (a liquid product obtained by diluting a mixture of the above components with a solvent if necessary) is cast into a thin film on a process sheet, for example, and then the coating film is irradiated with energy rays for polymerization. Cured to form a film.
- the stress applied to the resin during film formation is small, and the formation of fish eyes is small.
- the uniformity of the film thickness is also high, and the thickness accuracy is usually within 2%.
- ultraviolet rays, electron beams, etc. are used as the energy rays.
- the amount of irradiation varies depending on the type of energy beam.
- the ultraviolet intensity is preferably 50 to 300 mW / cm 2 and the ultraviolet irradiation amount is preferably about 100 to 1200 mJ / cm 2 .
- photopolymerization initiators include photopolymerization initiators such as benzoin compounds, acetophenone compounds, acylphosphinoxide compounds, titanocene compounds, thioxanthone compounds and peroxide compounds, and photosensitizers such as amines and quinones. Specific examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
- the use amount of the photopolymerization initiator is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total of the urethane (meth) acrylate oligomer and the energy ray curable monomer. Particularly preferred is 0.3 to 5 parts by weight.
- an inorganic filler such as calcium carbonate, silica, or mica, or a metal filler such as iron or lead may be added to the above-described compound.
- the energy ray cured layer (A) may contain additives such as colorants such as pigments and dyes.
- the above-mentioned energy ray cured layer (A) is laminated with a thermoplastic resin layer (B) described later to constitute a base film. As described above, the energy ray cured layer (A) may be laminated on the thermoplastic resin layer (B) after being formed on the process sheet, and directly on the thermoplastic resin layer (B). The cured layer (A) may be formed.
- the resulting energy ray hardened layer (A) exhibits unique viscoelasticity when a bump or the like formed on the wafer surface is pressed, rapidly deforms according to the shape of the bump, and applies pressure caused by the height difference of the bump. For relaxation, the bumps are not crushed even if they are pressed. Further, since the residual stress after deformation is small, the wafer can be stably held and the occurrence of dimples and cracks can be suppressed.
- the twist storage elastic modulus of the energy ray cured layer (A) is preferably in the range of 0.1 to 6 MPa, more preferably 0.3 to 3 MPa, and particularly preferably 0.5 to 2 MPa.
- the energy ray cured layer (A) leads to the physical properties of the pressure-sensitive adhesive sheet capable of preventing the bumps from being crushed and the generation of dimples.
- the compressive stress of the pressure-sensitive adhesive sheet described later can be adjusted to a desired range by using the thickness of the energy ray cured layer (A) or a specific urethane acrylate oligomer and a thiol group-containing compound.
- the thermoplastic resin layer (B) includes polyester resins such as polyethylene terephthalate (PET), polyolefin resins such as polyethylene (PE) and polypropylene (PP), polyimide (PI), polyetheretherketone (PEEK), and polychlorinated.
- Thermoplastic resins such as vinyl (PVC), polyvinylidene chloride resin, polyamide resin, polyurethane resin, polystyrene resin, acrylic resin, fluorine resin, cellulose resin, and polycarbonate resin are used. These thermoplastic resins can be used as a single layer or a multilayer product by laminating.
- thermoplastic resin layer (B) may be formed on one side of the energy ray cured layer (A) or may be formed on both sides.
- the thickness of the thermoplastic resin layer (B) is not particularly limited, but is preferably in the range of 10 to 1000 ⁇ m, more preferably 20 to 500 ⁇ m.
- the base film is formed by laminating the energy ray cured layer (A) and the thermoplastic resin layer (B).
- the energy ray cured layer (A) and the thermoplastic resin layer (B) may be directly laminated, or may be bonded via an adhesive layer.
- the manufacturing method of a base film is not specifically limited,
- the compound containing the said urethane (meth) acrylate oligomer, a thiol group containing compound, and an energy-beam curable monomer as needed is made into a thin film form on a process sheet.
- the coating film is dried if necessary, and a small amount of energy rays are irradiated to partially polymerize and cure the coating film to form a semi-cured layer.
- a thermoplastic resin layer (B) is formed on the semi-cured layer.
- the energy ray is irradiated to cure the semi-cured layer to obtain an energy ray cured layer (A), and the process sheet is removed.
- thermoplastic resin layer (B) is laminated
- a base film in which the thermoplastic resin layer (B) is formed on both surfaces of (A) can also be obtained.
- the pressure-sensitive adhesive sheet according to the present invention has a pressure-sensitive adhesive layer (C) formed on one side of the substrate film.
- the surface of the substrate film on which the pressure-sensitive adhesive layer is provided preferably the surface of the energy ray cured layer (A), may be subjected to corona treatment or a primer layer in order to improve the adhesion to the pressure-sensitive adhesive layer. Good.
- the type of the pressure-sensitive adhesive layer (C) is not specified as long as it has an appropriate removability to the wafer, and can be formed of various conventionally known pressure-sensitive adhesives.
- Such an adhesive is not limited at all, but an adhesive such as rubber-based, acrylic-based, silicone-based, or polyvinyl ether is used.
- an energy ray curable pressure-sensitive adhesive that is cured by irradiation with energy rays and becomes removable, a heat-foaming type, or a water swelling type pressure-sensitive adhesive can also be used.
- the energy ray curable (ultraviolet ray curable, electron beam curable) pressure-sensitive adhesive it is particularly preferable to use an ultraviolet curable pressure-sensitive adhesive.
- energy beam curable pressure-sensitive adhesives are described in, for example, JP-A-60-196956 and JP-A-60-223139.
- water-swelling pressure-sensitive adhesive those described in, for example, JP-B-5-77284 and JP-B-6-101455 are preferably used.
- the thickness of the pressure-sensitive adhesive layer (C) is not particularly limited, but is preferably in the range of 5 to 200 ⁇ m, more preferably 10 to 120 ⁇ m.
- a release sheet may be laminated on the pressure-sensitive adhesive layer in order to protect the pressure-sensitive adhesive layer before use.
- the release sheet is not particularly limited, and a release sheet base material treated with a release agent can be used.
- the release sheet substrate include films made of resins such as polyethylene terephthalate, polybutylene terephthalate, polypropylene, and polyethylene, or foamed films thereof, and papers such as glassine paper, coated paper, and laminated paper.
- the release agent include release agents such as silicone-based, fluorine-based, and long-chain alkyl group-containing carbamates.
- the method of providing the pressure-sensitive adhesive layer on the surface of the base film may transfer the pressure-sensitive adhesive layer formed by coating on the release sheet so as to have a predetermined film thickness to the surface of the base film, You may apply
- the pressure-sensitive adhesive sheet according to the present invention has a pressure-sensitive adhesive layer (C) formed on one side of the base film.
- the base film has a two-layer structure in which the thermoplastic resin layer (B) is laminated on one side of the energy beam cured layer (A)
- the pressure-sensitive adhesive layer (C) is the surface of the energy beam cured layer (A). It is preferable that it is provided.
- the pressure-sensitive adhesive sheet according to the present invention can take any shape such as a tape shape and a label shape.
- the unique viscoelasticity of the pressure-sensitive adhesive sheet can be easily evaluated by a compressive stress calculated from a load measured when a test piece having a bump having a predetermined shape is pushed into the pressure-sensitive adhesive sheet at a predetermined speed. Details of the measurement will be described later.
- the compressive stress of the pressure-sensitive adhesive sheet at 23 ° C. is preferably in the range of 0.01 to 1.0 MPa, more preferably 0.05 to 0.7 MPa, and particularly preferably 0.06 to 0.3 MPa. When the compressive stress is in the above range, the pressure-sensitive adhesive sheet exhibits viscoelasticity as described above, can prevent crushing of bumps and generation of dimples, and prevent resin from seeping out.
- the thickness of the energy ray cured layer (A) and the pressure-sensitive adhesive layer (C) in the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but when the pressure-sensitive adhesive sheet is applied to the circuit surface of a bumped wafer, the bumps on the circuit surface It is preferable to appropriately set the thickness of the energy ray cured layer (A) and the thickness of the pressure-sensitive adhesive layer (C) according to the height.
- the bump height is the height from the flat surface of the circuit surface (portion where no bump is formed) to the top of the bump, and is defined by the arithmetic average of the heights of a plurality of bumps.
- the pressure-sensitive adhesive sheet of the present invention can be used for processing semiconductor wafers as described below.
- Wafer back grinding method In wafer backside grinding, an adhesive sheet is applied to the circuit surface of a semiconductor wafer having a circuit formed on the surface to protect the circuit surface and grind the backside of the wafer to obtain a wafer having a predetermined thickness.
- the semiconductor wafer may be a silicon wafer or a compound semiconductor wafer such as gallium / arsenic. Formation of a circuit on the wafer surface can be performed by various methods including conventionally used methods such as an etching method and a lift-off method. In the semiconductor wafer circuit forming step, a predetermined circuit is formed.
- the thickness of the wafer before grinding is not particularly limited, but is usually about 500 to 1000 ⁇ m.
- the surface shape of the semiconductor wafer is not particularly limited, but the pressure-sensitive adhesive sheet of the present invention is preferably used for protecting the surface of a wafer having bumps formed on the circuit surface.
- the pressure-sensitive adhesive sheet of the present invention has the energy ray cured layer (A) and the pressure-sensitive adhesive layer (C) as described above, and has viscoelasticity capable of sufficiently following the bumps. For this reason, it is embedded in the wafer surface on which the bump is formed, the unevenness difference is eliminated, and the wafer can be held in a flat state. In addition, because of the high followability to the surface shape of the wafer, even if a strong shearing force is applied to the wafer when grinding the wafer back surface, the wafer can be prevented from vibrating and misaligned, and the wafer back surface can be ground to a flat and extremely thin thickness. Can do. Moreover, since a base film contains an energy-beam hardening layer (A), even if a bump is pressed on a base film, a bump will not be crushed.
- the back surface grinding is performed by a known method using a grinder, a suction table for fixing the wafer, etc. with the adhesive sheet attached. After the back grinding process, a process of removing the crushed layer generated by grinding may be performed.
- the thickness of the semiconductor wafer after back grinding is not particularly limited, but is preferably about 10 to 400 ⁇ m, particularly preferably about 25 to 300 ⁇ m.
- the pressure-sensitive adhesive sheet of the present invention it is possible to securely hold the wafer during backside grinding of the wafer and to prevent cutting water from entering the circuit surface.
- the pressure-sensitive adhesive sheet of the present invention can also be used as a dicing sheet.
- the adhesive sheet of the present invention is attached to the wafer and the wafer is cut.
- it is suitable for the case where the adhesive sheet of the present invention is attached to the circuit surface of the wafer and the wafer is cut while protecting the circuit surface with the adhesive sheet.
- the dicing sheet is generally attached by a device called a mounter, but is not particularly limited.
- the semiconductor wafer cutting means is not particularly limited. As an example, there is a method in which the peripheral portion of the dicing tape is fixed by a ring frame when the wafer is cut, and then the wafer is chipped by a known technique such as using a rotating round blade such as a dicer. Moreover, the dicing method using a laser beam may be used.
- the pressure-sensitive adhesive sheet of the present invention is preferably used in making a wafer with a high bump by the so-called tip dicing method. Specifically, from the wafer thickness from the surface of the semiconductor wafer on which a circuit having bumps is formed. Forming a groove with a shallow cutting depth, and sticking the adhesive sheet as a surface protective sheet on the circuit forming surface, and then grinding the back surface of the semiconductor wafer to reduce the wafer thickness and finally Is preferably used in a method of manufacturing a semiconductor chip, which is divided into individual chips.
- the pressure-sensitive adhesive sheet of the present invention high adhesion can be obtained between the chip and the pressure-sensitive adhesive layer, so that there is no infiltration of grinding water into the circuit surface and chip contamination can be prevented.
- the chip is picked up by a predetermined method.
- the chips in a wafer shape may be transferred to another pressure-sensitive adhesive sheet, and then chip pickup may be performed.
- a pressure-sensitive adhesive sheet composed of a thermoplastic resin layer, an energy ray cured layer and an acrylic pressure-sensitive adhesive layer was cut into a shape of 15 mm length ⁇ 15 mm width.
- the release sheet is removed from the adhesive sheet, and the bumped chip (bump height 250 ⁇ m, bump pitch 500 ⁇ m) made of a silicon wafer 10 mm long ⁇ 10 mm wide ⁇ 200 ⁇ m thick on the exposed adhesive layer surface is evenly distributed over the entire chip plane.
- the bumps were pushed down to a depth of 140 ⁇ m with a universal tensile and compression tester [manufactured by Instron, product name “Instron 5581 type”] at a speed of 0.6 mm / min.
- a load (compressive load) applied to the silicon wafer chip from the adhesive sheet was measured.
- the measurement was performed in an environment of a temperature of 23 ° C. and a relative humidity of 50%.
- the compressive stress was calculated from the measured compressive load and the surface area of the bumps on the entire pressed chip plane. It was assumed that the bump diameter was 280 ⁇ m and the load when the bump was pushed in half was measured.
- the bump surface area (39.9 mm 2 ) of the entire chip plane when 140 ⁇ m is pushed in is calculated from the surface area of one bump and the number of bumps (324), and the compressive stress is calculated from the following equation (1). .
- Compressive stress Compressive load / Bump surface area over the entire chip plane (1)
- Solder bumped wafer (8 inch silicon wafer with chip size 10mm x 10mm wide, 8mm silicon wafer, bump height 250 ⁇ m, bump pitch 500 ⁇ m, total thickness 720 ⁇ m) is affixed to adhesive sheet, fixed and ground to 250 ⁇ m thickness After that (using a grinder DGP8760 manufactured by DISCO Corporation), the back surface of the wafer was visually observed to confirm whether dimples were generated in the portion corresponding to the bumps on the back surface of the wafer. The case where no dimples were generated was designated as A, the case where slight dimples were confirmed to be produced but B which was not practically problematic was designated as C, and the case where obvious dimples were produced was designated as C. Also, the presence or absence of wafer cracks (wafer cracks) was visually confirmed.
- Adhesive sheet is affixed to a bumped wafer with a bump height of 250 ⁇ m using a Rintec “RAD3510” manufactured by Lintec Co., Ltd. “A” (distance from the back surface of the wafer to the base film surface of the pressure-sensitive adhesive sheet) and the total thickness “B” of the portion without bumps were measured, and “AB” was calculated as the height difference. It means that the unevenness
- the embedding property is an index of the adhesiveness of the adhesive sheet with respect to the gap between the bumps. The higher the embedding property, the more closely the adhesive sheet and the bumped wafer are in close contact with each other. When the embedding property is low, it means that the adhesion of the adhesive sheet is insufficient at the base portion of the bump.
- the prepared pressure-sensitive adhesive sheet was wound up in a roll shape, and the presence or absence of resin leaching was confirmed with an optical digital microscope (magnification 100 times) one week after the creation on the roll side.
- Example 1 At the end of a terminal isocyanate urethane prepolymer obtained by polymerizing polypropylene glycol (hereinafter referred to as PPG4000) having a molecular weight of 4000 calculated from the hydroxyl value and isophorone diisocyanate (hereinafter referred to as IPDI), 2-hydroxyethyl methacrylate (hereinafter referred to as “hydroxyl methacrylate”) is used.
- HEMA was reacted to obtain a polyether polyol-based urethane (meth) acrylate oligomer having a weight average molecular weight of 50,000.
- the weight average molecular weight was measured using a commercially available molecular weight measuring instrument (main product name “HLC-8220GPC”, manufactured by Tosoh Corporation; column product name “TSKGel SuperHZM-M”, manufactured by Tosoh Corporation; developing solvent tetrahydrofuran). It is the value obtained by using (hereinafter the same).
- PET polyethylene terephthalate
- SP-PET3811 thickness 38 ⁇ m
- the above-mentioned composition is applied to a thickness of 300 ⁇ m by a fountain die method. Then, a coating film was formed, and then a semi-cured layer was obtained by irradiation with ultraviolet rays from the coating film side.
- the ultraviolet irradiation device a belt conveyor type ultraviolet irradiation device (Igraphics: ECS-401GX) was used, and the high-pressure mercury lamp (Igraphics: H04-L41) was used as the ultraviolet source ⁇ irradiation conditions: lamp height 150 mm, Lamp output 3 kW (converted output 120 mW / cm), illuminance 271 mW / cm 2 with a light wavelength of 365 nm, light quantity 177 mJ / cm 2 (UV light quantity meter: UV-351 manufactured by Oak Manufacturing Co., Ltd.) ⁇ .
- lamp height 150 mm Lamp output 3 kW (converted output 120 mW / cm), illuminance 271 mW / cm 2 with a light wavelength of 365 nm, light quantity 177 mJ / cm 2 (UV light quantity meter: UV-351 manufactured by Oak Manufacturing Co., Ltd.) ⁇ .
- PET polyethylene terephthalate
- an acrylic copolymer having a weight average molecular weight of 500,000 and a glass transition temperature of -7 ° C. by solution polymerization in an ethyl acetate solvent using 70 parts by weight of butyl acrylate and 30 parts by weight of 2-hydroxyethyl acrylate was generated.
- 100 parts by weight of the solid content of this acrylic copolymer is reacted with 8 parts by weight of methacryloyloxyethyl isocyanate (80 equivalents with respect to 100 equivalents of hydroxy groups in the acrylic copolymer) to polymerize in the molecule.
- An ethyl acetate solution (30% solution) of an ultraviolet curable acrylic copolymer having a double bond was obtained.
- Example 2 Instead of TMMP 8 g used as the thiol group-containing compound in Example 1, tris [(3-mercaptopropionyloxy) -ethyl] isocyanurate (manufactured by Sakai Chemical Industry Co., Ltd .: TEMPIC, hexafunctional, solid content concentration 100 mass) %) A pressure-sensitive adhesive sheet was obtained and evaluated in the same manner as in Example 1 except that 1.0 g (2.1 mmol) was used. The results are shown in Tables 1 and 2.
- Example 3 A pressure-sensitive adhesive sheet was obtained and evaluated in the same manner as in Example 1 except that the amount of TMMP used as the thiol group-containing compound in Example 1 was changed to 40.0 g (100.4 mmol). The results are shown in Tables 1 and 2.
- Example 4 The procedure was carried out except that 40.0 g (196.4 mmol) of 1-dodecanethiol (manufactured by Aldrich, monofunctional, solid concentration 100 mass%) was used instead of TMMP 8 g used as the thiol group-containing compound in Example 1.
- TMMP 8 g used as the thiol group-containing compound in Example 1.
- a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 and evaluated. The results are shown in Tables 1 and 2.
- Example 5 Instead of TMMP 8 g used as the thiol group-containing compound in Example 1, tetraethylene glycol-bis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd .: EGMP-4, bifunctional, solid concentration 100 mass) %) A pressure-sensitive adhesive sheet was obtained and evaluated in the same manner as in Example 1 except that 8.0 g (21.5 mmol) was used. The results are shown in Tables 1 and 2.
- Example 6 In place of 8 g of TMMP used as the thiol group-containing compound in Example 1, pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd .: PEMP, tetrafunctional, solid content concentration: 100% by mass) A pressure-sensitive adhesive sheet was obtained and evaluated in the same manner as in Example 1 except that 0 g (16.4 mmol) was used. The results are shown in Tables 1 and 2.
- Example 7 Instead of 8 g of TMMP used as the thiol group-containing compound in Example 1, 8.0 g (18.5 mmol) of pentaerythritol tetrakisthioglycolate (manufactured by Sakai Chemical Industry Co., Ltd .: PETG, tetrafunctional, solid content concentration 100% by mass) ) was used and evaluated by the same method as in Example 1. The results are shown in Tables 1 and 2.
- Example 8 Instead of TMMP 8g used as the thiol group-containing compound in Example 1, dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd .: DPMP, hexafunctional, solid content concentration 100% by mass) A pressure-sensitive adhesive sheet was obtained and evaluated in the same manner as in Example 1 except that 8.0 g (10.2 mmol) was used. The results are shown in Tables 1 and 2.
- Example 9 instead of TMMP8g used as the thiol group-containing compound in Example 1, pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko KK: Karenz MT PE1, grade 2 tetrafunctional, solid content concentration 100% by mass) A pressure-sensitive adhesive sheet was obtained and evaluated in the same manner as in Example 1 except that 8.0 g (14.7 mmol) was used. The results are shown in Tables 1 and 2.
- Example 10 Instead of TMMP 8 g used as the thiol group-containing compound in Example 1, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H , 5H) -trione (Showa Denko Co., Ltd .: Karenz MT NR1, Grade 2 trifunctional, solid content concentration of 100% by mass), except that 8.0 g (14.1 mmol) was used. A pressure-sensitive adhesive sheet was obtained and evaluated. The results are shown in Tables 1 and 2.
- Example 11 Instead of TMMP 8 g used as the thiol group-containing compound in Example 1, 1,4-bis (3-mercaptobutyryloxy) butane (manufactured by Showa Denko KK: Karenz MT BD1, secondary bifunctional, solid content concentration (100% by mass) A pressure-sensitive adhesive sheet was obtained and evaluated in the same manner as in Example 1 except that 8.0 g (27.2 mmol) was used. The results are shown in Tables 1 and 2.
- Example 12 A pressure-sensitive adhesive sheet was obtained and evaluated in the same manner as in Example 1 except that the amount of TMMP used as the thiol group-containing compound in Example 1 was changed to 80.0 g (200.8 mmol). The results are shown in Tables 1 and 2.
- Example 1 a pressure-sensitive adhesive sheet was obtained and evaluated in the same manner as in Example 1 except that the thiol group-containing compound was not added. The results are shown in Tables 1 and 2.
- Example 2 The same as Example 1 except that a single layer film of polyethylene terephthalate (PET) film (Mitsubishi Chemical Polyester Co., Ltd .: T-100, thickness 188 ⁇ m) was used as the base film without forming an energy ray cured layer.
- PET polyethylene terephthalate
- An adhesive sheet was obtained by the method described above and evaluated. The results are shown in Tables 1 and 2.
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Abstract
Description
〔1〕半導体ウエハに貼付される粘着シートの基材フィルムであって、
(A)ウレタン(メタ)アクリレートオリゴマーとチオール基含有化合物とを含む配合物をエネルギー線硬化させた硬化物からなる層と、
(B)熱可塑性樹脂からなる層とから構成される基材フィルム。
(A)ウレタン(メタ)アクリレートオリゴマーとチオール基含有化合物とを含む配合物をエネルギー線硬化させた硬化物からなる層(以下、「エネルギー線硬化層」と略記することがある)と、
(B)熱可塑性樹脂からなる層(以下、「熱可塑性樹脂層」と略記することがある)とから構成されることを特徴としている。
基材フィルムの構成層のひとつであるエネルギー線硬化層(A)は、ウレタン(メタ)アクリレートオリゴマーとチオール基含有化合物とを含み、必要に応じエネルギー線硬化性モノマーを含む配合物をエネルギー線硬化させた硬化物である。
熱可塑性樹脂層(B)としては、ポリエチレンテレフタレート(PET)等のポリエステル樹脂、ポリエチレン(PE)、ポリプロピレン(PP)等のポリオレフィン系樹脂、ポリイミド(PI)、ポリエーテルエーテルケトン(PEEK)、ポリ塩化ビニル(PVC)、ポリ塩化ビニリデン系樹脂、ポリアミド系樹脂、ポリウレタン系樹脂、ポリスチレン系樹脂、アクリル系樹脂、フッ素系樹脂、セルロース系樹脂、ポリカーボネート系樹脂等の熱可塑性樹脂が使用される。これらの熱可塑性樹脂は単一層、または積層することによって複層品として用いることができる。
基材フィルムは、前記のように、エネルギー線硬化層(A)と熱可塑性樹脂層(B)とが積層されてなる。エネルギー線硬化層(A)と熱可塑性樹脂層(B)とは直接積層されていてもよく、接着剤層を介して接着されていてもよい。
粘着剤層(C)は、ウエハに対し適度な再剥離性があればその種類は特定されず、従来より公知の種々の粘着剤により形成され得る。このような粘着剤としては、何ら限定されるものではないが、たとえばゴム系、アクリル系、シリコーン系、ポリビニルエーテル等の粘着剤が用いられる。また、エネルギー線の照射により硬化して再剥離性となるエネルギー線硬化型粘着剤や、加熱発泡型、水膨潤型の粘着剤も用いることができる。
本発明に係る粘着シートは、上記基材フィルムの片面に粘着剤層(C)が形成されてなる。基材フィルムが、エネルギー線硬化層(A)の片面に熱可塑性樹脂層(B)が積層された2層構造の場合には、粘着剤層(C)はエネルギー線硬化層(A)の表面に設けられてなることが好ましい。本発明に係る粘着シートは、テープ状、ラベル状などあらゆる形状をとり得る。
本発明の粘着シートは、下記に示すように半導体ウエハの加工に用いることが出来る。
(ウエハ裏面研削方法)
ウエハの裏面研削においては、表面に回路が形成された半導体ウエハの回路面に粘着シートを貼付して回路面を保護しつつウエハの裏面を研削し、所定厚みのウエハとする。
本発明の粘着シートはダイシングシートとして使用することもできる。
ダイシングシートとして使用する際は、ウエハに本発明の粘着シートを貼付して、ウエハを切断する。特に、ウエハの回路面に本発明の粘着シートを貼付して、回路面を粘着シートで保護しながらウエハを切断する場合に好適である。ダイシングシートの貼付は、マウンターと呼ばれる装置により行われるのが一般的だが特に限定はされない。
さらにまた、本発明の粘着シートは、いわゆる先ダイシング法による高バンプ付ウエハのチップ化において好ましく用いられ、具体的には、バンプを有する回路が表面に形成された半導体ウエハ表面からそのウエハ厚さよりも浅い切込み深さの溝を形成し、該回路形成面に、上記粘着シートを表面保護シートとして貼付し、その後上記半導体ウエハの裏面研削をすることでウエハの厚みを薄くするとともに、最終的には個々のチップへの分割を行なう、半導体チップの製造方法に好ましく用いられる。
本発明の粘着シートを用いることで、チップと粘着剤層との間に高い密着性が得られるため、回路面への研削水の滲入がなく、チップの汚染を防止できる。
直径8mm、厚さ3mmのエネルギー線硬化層を用意し、粘弾性測定装置(Rheometrics社製、装置名:DYNAMIC ANALYZER RDA II)を用いて1Hzで23℃での捻り貯蔵弾性率を測定した。
熱可塑性樹脂層、エネルギー線硬化層とアクリル系粘着剤層からなる粘着シートを、縦15mm×横15mmの形状に裁断した。粘着シートから剥離シートを取り除いて、表出した粘着剤層面に縦10mm×横10mm×厚み200μmのシリコンウエハからなるバンプ付チップ(バンプ高さ250μm、バンプピッチ500μm)をチップ平面全体のバンプが均等に接触するように0.6mm/分の速度で、万能引張圧縮試験機[インストロン社製、製品名「インストロン5581型」]で深さ140μmまでバンプを押し込んだ。その際に粘着シートからシリコンウエハチップにかかる荷重(圧縮荷重)を測定した。測定は温度23℃、相対湿度50%の環境下で行った。測定された圧縮荷重と押し込まれたチップ平面全体のバンプの表面積から、圧縮応力を算出した。
なお、バンプの直径を280μmとし、バンプの半分まで押し込んだ時の荷重を測定していると仮定した。140μm押し込んだ際のチップ平面全体のバンプの表面積(39.9mm2)は、1バンプの表面積とバンプの数(324個)とから算出され、圧縮応力は以下の式(1)から算出される。
圧縮応力=圧縮荷重/チップ平面全体のバンプの表面積 ・・・(1)
ソルダーバンプ付ウエハ(チップサイズ縦10mm×横10mmのチップが整列している8インチシリコンウエハ、バンプ高さ250μm、バンプピッチ500μm、全厚720μm)を粘着シートに貼付、固定し、厚み250μmまで研削した後((株)ディスコ社製 グラインダーDGP8760を使用)、ウエハの裏面を目視にて観察し、ウエハ裏面のバンプに対応する部分にディンプルが発生していないか確認した。ディンプルが発生していないものをA、わずかにディンプルが発生しているのが確認されたが実用上問題ないものをB、明らかにディンプルが発生したものをCとした。
また、ウエハのクラック(ウエハのひび、割れ)の有無を目視にて確認した。
バンプ高さ250μmのバンプ付ウエハに粘着シートをリンテック(株)製ラミネーター「RAD3510」を用いて貼付し、直後にテクロック社製 定圧厚さ測定器:PG-02にてバンプの有る部分の全厚“A”(ウエハの裏面から粘着シートの基材フィルム面までの距離)、バンプが無い部分の全厚“B”を測定し、「A-B」を高低差として算出した。高低差が小さいほど、バンプ高さに起因する凹凸が粘着シートによって緩和されていることを意味する。
ウエハ表面に粘着シートを貼付した後、水を噴霧しつつウエハ裏面を全厚250μmまで研削し、ウエハ表面から粘着シートを剥がし、ウエハ表面への研削水の浸入の有無を光学デジタル顕微鏡(倍率100倍)にて確認した。
バンプ付ウエハの回路面に粘着シートをリンテック(株)製ラミネーター「RAD3510」を用いて貼付し、直後に光学デジタル顕微鏡(倍率300倍)にて観察し、バンプ間の埋め込み距離を測定した。なお、バンプ間の埋め込み距離は、次のように定義する。
作成した粘着シートをロール状に巻収し、ロール側部において、作成後1週間後に樹脂の浸み出しの有無を光学デジタル顕微鏡(倍率100倍)にて確認した。
水酸基価から算出した分子量4000のポリプロピレングリコール(以下PPG4000と記述)とイソホロンジイソシアナート(以下IPDIと記述)を重合させて得られる末端イソシアナートウレタンプレポリマーの末端に、2-ヒドロキシエチルメタクリレート(以下HEMAと記述)を反応させ、重量平均分子量が50000のポリエーテルポリオール系ウレタン(メタ)アクリレートオリゴマーを得た。なお、当該重量平均分子量は、市販の分子量測定機(本体製品名「HLC-8220GPC」、東ソー(株)製;カラム製品名「TSKGel SuperHZM-M」、東ソー(株)製;展開溶媒 テトラヒドロフラン)を用いて得た値である(以下、同様。)。
実施例1においてチオール基含有化合物として用いたTMMP8gに代えて、トリス[(3-メルカプトプロピオニロキシ)-エチル]イソシアヌレート(堺化学工業(株)製:TEMPIC、6官能、固形分濃度100質量%)1.0g(2.1mmol)を用いた以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
実施例1においてチオール基含有化合物として用いたTMMPの添加量を40.0g(100.4mmol)に変更した以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
実施例1においてチオール基含有化合物として用いたTMMP8gに代えて、1-ドデカンチオール(アルドリッチ社製、単官能、固形分濃度100質量%)40.0g(196.4mmol)を用いた以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
実施例1においてチオール基含有化合物として用いたTMMP8gに代えて、テトラエチレングリコール-ビス(3-メルカプトプロピオネート)(堺化学工業(株)製:EGMP-4、2官能、固形分濃度100質量%)8.0g(21.5mmol)を用いた以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
実施例1においてチオール基含有化合物として用いたTMMP8gに代えて、ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)(堺化学工業(株)製:PEMP、4官能、固形分濃度100質量%)8.0g(16.4mmol)を用いた以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
実施例1においてチオール基含有化合物として用いたTMMP8gに代えて、ペンタエリスリトールテトラキスチオグリコレート(堺化学工業(株)製:PETG、4官能、固形分濃度100質量%)8.0g(18.5mmol)を用いた以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
実施例1においてチオール基含有化合物として用いたTMMP8gに代えて、ジペンタエリスリトールヘキサキス(3-メルカプトプロピオネート)(堺化学工業(株)製:DPMP、6官能、固形分濃度100質量%)8.0g(10.2mmol)を用いた以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
実施例1においてチオール基含有化合物として用いたTMMP8gに代えて、ペンタエリスリトールテトラキス(3-メルカプトブチレート)(昭和電工(株)製:カレンズMT PE1、2級4官能、固形分濃度100質量%)8.0g(14.7mmol)を用いた以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
実施例1においてチオール基含有化合物として用いたTMMP8gに代えて、1,3,5-トリス(3-メルカプトブチルオキシエチル)-1,3,5-トリアジン-2,4,6-(1H,3H,5H)-トリオン(昭和電工(株)製:カレンズMT NR1、2級3官能、固形分濃度100質量%)8.0g(14.1mmol)を用いた以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
実施例1においてチオール基含有化合物として用いたTMMP8gに代えて、1,4-ビス(3-メルカプトブチリルオキシ)ブタン(昭和電工(株)製:カレンズMT BD1、2級2官能、固形分濃度100質量%)8.0g(27.2mmol)を用いた以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
実施例1においてチオール基含有化合物として用いたTMMPの添加量を80.0g(200.8mmol)に変更した以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
実施例1において、チオール基含有化合物を添加しなかった以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
基材フィルムとして、エネルギー線硬化層を形成せずに、ポリエチレンテレフタレート(PET)フィルム(三菱化学ポリエステル社製:T-100、厚み188μm)の単層フィルムを使用した以外は、実施例1と同様の方法にて粘着シートを得、評価を行った。結果を表1及び表2に示す。
Claims (3)
- 半導体ウエハに貼付される粘着シートの基材フィルムであって、
(A)ウレタン(メタ)アクリレートオリゴマーとチオール基含有化合物とを含む配合物をエネルギー線硬化させた硬化物からなる層と、
(B)熱可塑性樹脂からなる層とから構成される基材フィルム。 - 前記配合物におけるチオール基含有化合物の含有量が、ウレタン(メタ)アクリレートオリゴマー100gに対して、2mmol以上である請求項1に記載の基材フィルム。
- 請求項1または2に記載の基材フィルム上に、さらに粘着剤層を備える粘着シート。
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CN111433306B (zh) * | 2018-06-04 | 2022-05-10 | 株式会社Lg化学 | 背面研磨带 |
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US20140079947A1 (en) | 2014-03-20 |
KR102052120B1 (ko) | 2019-12-04 |
JP5762781B2 (ja) | 2015-08-12 |
KR20180034699A (ko) | 2018-04-04 |
KR20140079336A (ko) | 2014-06-26 |
KR102016578B1 (ko) | 2019-08-30 |
JP2012199406A (ja) | 2012-10-18 |
US9559073B2 (en) | 2017-01-31 |
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