WO2014030699A1 - 保護膜形成層付ダイシングシートおよびチップの製造方法 - Google Patents
保護膜形成層付ダイシングシートおよびチップの製造方法 Download PDFInfo
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- WO2014030699A1 WO2014030699A1 PCT/JP2013/072415 JP2013072415W WO2014030699A1 WO 2014030699 A1 WO2014030699 A1 WO 2014030699A1 JP 2013072415 W JP2013072415 W JP 2013072415W WO 2014030699 A1 WO2014030699 A1 WO 2014030699A1
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- protective film
- forming layer
- film forming
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- sheet
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- C—CHEMISTRY; METALLURGY
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- 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
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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
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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
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- 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
- H01L2221/68336—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 involving stretching of the auxiliary support post dicing
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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
- 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
- H01L2221/68377—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 with parts of the auxiliary support remaining in the finished device
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2223/00—Details relating to semiconductor or other solid state devices covered by the group H01L23/00
- H01L2223/544—Marks applied to semiconductor devices or parts
- H01L2223/54433—Marks applied to semiconductor devices or parts containing identification or tracking information
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2223/00—Details relating to semiconductor or other solid state devices covered by the group H01L23/00
- H01L2223/544—Marks applied to semiconductor devices or parts
- H01L2223/54473—Marks applied to semiconductor devices or parts for use after dicing
- H01L2223/54486—Located on package parts, e.g. encapsulation, leads, package substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/544—Marks applied to semiconductor devices or parts, e.g. registration marks, alignment structures, wafer maps
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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
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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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
- Y10T428/14—Layer or component removable to expose adhesive
- Y10T428/1471—Protective layer
Definitions
- the present invention relates to a dicing sheet with a protective film forming layer that can form a protective film on the back surface of the chip and can improve the manufacturing efficiency of the chip. Moreover, this invention relates to the manufacturing method of the chip
- chip a semiconductor chip having electrodes such as bumps on a circuit surface
- the electrodes are bonded to a substrate.
- the surface (chip back surface) opposite to the circuit surface of the chip may be exposed.
- the exposed chip back surface may be protected by an organic film.
- a chip having a protective film made of an organic film is obtained by applying a liquid resin to the back surface of a wafer by spin coating, drying and curing, and cutting the protective film together with the wafer.
- this method increases the number of steps and increases the product cost.
- the thickness accuracy of the protective film formed in this way is not sufficient, the product yield may be lowered.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2009-138026 discloses a protective film formed of a release sheet and an energy ray-curable component and a binder polymer component formed on the release sheet. A film for chip protection having a layer is disclosed.
- the chip protective film described in Patent Document 1 may shrink when the protective film forming layer is cured, which may cause a problem that the semiconductor wafer is warped.
- the above problem is remarkable in an extremely thin semiconductor wafer. If the semiconductor wafer is warped, the wafer may be damaged or the marking (printing) accuracy on the protective film may be reduced.
- Patent Document 2 Japanese Patent Application Laid-Open No. 2006-140348
- Japanese Patent Application Laid-Open No. 2006-140348 disclosed a substantially circular region composed of a protective film forming layer and a ring-shaped member composed of a re-peeling adhesive surrounding the region.
- a protective film forming and dicing sheet comprising a sheet having the above region on the upper surface is disclosed. If a semiconductor wafer is placed on the protective film forming layer of the protective film forming and dicing sheet and laser marking is performed with the peripheral edge of the sheet fixed by a ring frame, the warpage of the wafer is corrected. Since it is maintained, the printing accuracy is improved.
- this sheet also serves as a dicing sheet, it is not necessary to prepare a separate dicing sheet, and productivity is remarkably improved.
- a wafer is fixed on a protective film forming and dicing sheet, and the protective film forming layer is heated and cured in a state where the wafer is fixed, thereby forming a protective film on the wafer.
- the protective film forming and dicing sheet having the above configuration in the configuration in which the protective film forming layer and the sheet are laminated without using an adhesive, dicing is caused by the low adhesion between the protective film and the sheet. There was concern that the chip would fall out during the process.
- the adhesive strength between the two layers increases, and after dicing the wafer into pieces, the interface between the protective film and the adhesive layer is changed. There was a possibility that peeling could not be performed.
- the adhesive residue may adhere to the chip, and in the subsequent process, for example, the chip may adhere to the chip tray via the adhesive residue.
- the present invention has been made in view of the above circumstances. That is, according to the present invention, a semiconductor chip having a protective film with high uniformity and excellent printing accuracy can be easily manufactured, and the protective film and the dicing sheet can be easily peeled, and at the time of dicing.
- An object of the present invention is to provide a dicing sheet with a protective film-forming layer having excellent chip fixing ability.
- the present invention includes the following gist.
- a protective film in which a protective film-forming layer is detachably provided on an adhesive layer of an adhesive sheet in which an adhesive layer containing an adhesive component and a free epoxy group-containing compound is laminated on a base film Dicing sheet with forming layer.
- the protective film forming layer of the dicing sheet with the protective film forming layer according to any one of [1] to [7] is attached to a workpiece, and the following steps (1) to (3) are performed as follows: ), (2), (3) order, (2), (1), (3) order or (2), (3), (1) order manufacturing method of the chip with protective film: Step (1): a step of curing the protective film forming layer to obtain a protective film, Step (2): a step of dicing the workpiece and the protective film forming layer or the protective film, Process (3): The process of peeling a protective film formation layer or a protective film, and an adhesive sheet.
- Step (4) A step of performing laser printing on the protective film.
- the protective film forming layer or the protective film and the adhesive sheet can be easily peeled, In addition, the movement of the chip during dicing is suppressed, and a protective film having high uniformity and excellent printing accuracy can be easily formed on the back surface of the semiconductor chip.
- Sectional drawing of the dicing sheet with a protective film formation layer concerning this invention is shown.
- Sectional drawing of the dicing sheet with a protective film formation layer of the other aspect which concerns on this invention is shown.
- a dicing sheet 10 with a protective film forming layer has a protective film forming layer 4 on an adhesive layer 2 of an adhesive sheet 3 composed of a base film 1 and an adhesive layer 2.
- the protective film forming layer 4 is formed on the inner peripheral portion of the pressure-sensitive adhesive sheet 3 in substantially the same shape as the workpiece (semiconductor wafer or the like) to be attached.
- the pressure-sensitive adhesive layer 2 is exposed on the outer peripheral portion of the pressure-sensitive adhesive sheet 3.
- the protective film forming layer 4 having a smaller diameter than the pressure-sensitive adhesive sheet 3 is concentrically laminated on the pressure-sensitive adhesive layer 2 of the circular pressure-sensitive adhesive sheet 3.
- the exposed adhesive layer on the outer peripheral portion is used for fixing the ring frame 5 as shown in the figure.
- the dicing sheet 10 with a protective film forming layer can take any shape such as a long tape shape or a single-leaf label shape.
- the base film 1 is not particularly limited when the protective film forming layer 4 is thermally cured after the protective film forming layer 4 is peeled off from the pressure-sensitive adhesive sheet 3.
- low density polyethylene LDPE
- linear low Density polyethylene LLDPE
- ethylene / propylene copolymer polypropylene, polybutene, polybutadiene, polymethylpentene, ethylene / vinyl acetate copolymer, ethylene / (meth) acrylic acid copolymer, ethylene / methyl (meth) acrylate Copolymers, ethylene / (meth) ethyl acrylate copolymers, polyvinyl chloride, vinyl chloride / vinyl acetate copolymers, polyurethane films, films made of ionomers, and the like are used.
- “(meth) acryl” is used to mean both acrylic and methacrylic.
- the base film 1 is heat resistant in consideration of the durability of the pressure sensitive adhesive sheet 3.
- polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate
- polyolefin films such as polypropylene and polymethylpentene.
- the polypropylene film has heat resistance and is relatively flexible, and therefore has good expandability and pickup suitability, and is particularly preferably used.
- these cross-linked films and modified films by radiation and discharge can also be used.
- the base film may be a laminate of the above films.
- these synthetic resin films can be used in combination of two or more kinds or in combination. Furthermore, the thing which colored these films, or what gave printing etc. can be used.
- the film may be a sheet obtained by extrusion forming a thermoplastic resin, or may be a stretched film. A film obtained by thinning and curing a curable resin by a predetermined means is used. It may be broken.
- the thickness of the base film is not particularly limited, and is preferably 30 to 300 ⁇ m, more preferably 50 to 200 ⁇ m. By making the thickness of the base film within the above range, the base film is hardly broken even if cutting is performed by dicing. In addition, since sufficient flexibility is imparted to the dicing sheet with a protective film forming layer, it exhibits good adhesiveness to a workpiece (for example, a semiconductor wafer).
- the pressure-sensitive adhesive layer 2 in the present invention is composed of an epoxy group-containing compound, a pressure-sensitive adhesive component, and other additives as required.
- the pressure-sensitive adhesive layer 2 in the dicing sheet 10 with a protective film forming layer of the present invention is characterized by having an epoxy group-containing compound.
- the epoxy group-containing compound exists in a free state, and it is considered that a part of the epoxy-group-containing compound becomes an oil film at the interface between the pressure-sensitive adhesive layer 2 and the protective film forming layer 4 and functions as a release agent. That is, the presence of the epoxy group-containing compound at the interface between the pressure-sensitive adhesive layer 2 and the protective film-forming layer 4 prevents the pressure-sensitive adhesive layer 2 and the protective film-forming layer 4 from being excessively adhered to each other.
- the peeling force when peeling the protective film forming layer 4 (or protective film) from the adhesive sheet 3 is controlled to an appropriate range, and the pick-up force of the chip with the protective film forming layer 4 (or protective film) is reduced. Is done.
- the protective film forming layer and the protective film that is a cured product thereof are sometimes collectively referred to simply as “protective film forming layer”.
- Examples of the epoxy group-containing compound used in the present invention include compounds having at least one epoxy group in the molecule, such as bisphenol A type, bisphenol F type, bisphenol S type, biphenyl type, phenol novolac type, cresol.
- a novolac type epoxy resin can be used.
- the molecular weight of the epoxy group-containing compound is preferably relatively low, preferably 100 to 10,000, 300 to 2000, and preferably 350 to 1000.
- the epoxy group-containing compound present at the interface between the protective film-forming layer 4 and the adhesive layer 2 after application becomes easy to transfer to the protective film-forming layer 4, and is accompanied by the protective film-forming layer 4.
- the suitable range of the compounding ratio of the epoxy group-containing compound varies depending on the type of the epoxy group-containing compound and cannot be determined unconditionally, but generally in a total of 100 parts by mass of all the components constituting the pressure-sensitive adhesive layer 2, About 0.5 to 50 parts by mass, preferably about 2.5 to 25 parts by mass is used.
- the blending ratio of the epoxy group-containing compound described above indicates the composition at the time of preparation of the composition for forming the pressure-sensitive adhesive layer, but the epoxy group-containing compound is included in the pressure-sensitive adhesive layer in a free state. . That is, the pressure-sensitive adhesive layer contains a “free epoxy group-containing compound”.
- the free state means that the epoxy group-containing compound is in a substantially unreacted state with an adhesive component such as a (meth) acrylate polymer, and the epoxy group is contained in the matrix of the gel component in the adhesive component. It means that the contained compound is not taken in.
- the presence or absence of an unreacted epoxy group-containing compound can be determined by titration of the epoxy group of the sol component of the pressure-sensitive adhesive layer.
- the evaluation was based on the “epoxy index” represented by 1000 times the reciprocal of the epoxy equivalent.
- the “epoxy index” was a converted value of a value per 1 kg of the sample.
- the value of the epoxy index is preferably 0.05 eq / kg or more, more preferably 0.1 to 2.0 eq / kg.
- the value of this “epoxy index” is a value obtained by a measurement method in Examples described later.
- the epoxy group-containing compound and the adhesive component constituting the adhesive layer 2 react, the free state of the epoxy group-containing compound is not maintained, or the adhesive component and the protective film forming layer are bonded via the epoxy group-containing compound.
- the epoxy group-containing compound and the adhesive component are preferably non-reactive.
- the adhesive component contains a (meth) acrylic acid ester polymer
- the (meth) acrylic acid ester polymer can react with an epoxy group of an epoxy group-containing compound such as a carboxyl group or an amino group as described later. It is preferable that the functional group does not have a property or the ratio thereof is small.
- the pressure-sensitive adhesive layer in the present invention does not substantially contain a substance having an action of polymerizing the epoxy group-containing compound (epoxy curing agent).
- epoxy curing agent an epoxy curing agent is contained in the pressure-sensitive adhesive layer, the epoxy group-containing compound is bonded to the epoxy curing agent during storage of the dicing sheet with a protective film forming layer or when the protective film forming layer is thermally cured. There is a concern that a cured product is formed by reacting with each other, and the free state of the epoxy group-containing compound is not maintained.
- the component contained in the protective film-forming layer and the cured product generated from the epoxy group-containing compound generated in the pressure-sensitive adhesive layer are reacted and combined to form a protective film-forming layer (or protective film) and the pressure-sensitive adhesive layer.
- the epoxy curing agent that is preferably not substantially contained include amines, organic acids, acid anhydrides, phenol resins, urea resins, and polyamides.
- the pressure-sensitive adhesive layer in the present invention comprises a pressure-sensitive adhesive component and an epoxy group-containing compound as main components, and optionally contains other components.
- the pressure-sensitive adhesive component is not particularly limited as long as it imparts appropriate removability to the pressure-sensitive adhesive layer, and is formed from a general-purpose pressure-sensitive adhesive such as rubber, acrylic, silicone, urethane, or vinyl ether. May be. Among these, an acrylic pressure-sensitive adhesive is particularly preferably used.
- the adhesive component may be an energy ray curable adhesive component.
- the acrylic pressure-sensitive adhesive is mainly composed of a (meth) acrylic acid ester polymer obtained using a (meth) acrylic acid ester monomer having no reactive functional group and a reactive functional group-containing monomer used in combination as necessary as a main raw material. Ingredients.
- Examples of the (meth) acrylate monomer having no reactive functional group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth ) Hexyl acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, etc. are used.
- alkyl esters having aliphatic groups or aromatic groups such as (meth) acrylic acid cycloalkyl esters and (meth) acrylic acid benzyl esters are used as (meth) acrylic acid ester monomers having no reactive functional group. Also good. These monomers may be used alone or in combination of two or more.
- Examples of the reactive functional group-containing monomer include a hydroxyl group-containing monomer.
- Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, N-methylol acrylamide and the like.
- a hydroxyl group-containing monomer having an alcoholic hydroxyl group is preferable because it hardly reacts with the epoxy group of the epoxy group-containing compound.
- copolymerizable monomers other than (meth) acrylic acid ester monomers and reactive functional group-containing monomers having no reactive functional group used in (meth) acrylic acid ester polymers acrylonitrile, acrylamide, vinyl acetate, vinyl butyrate And vinyl esters.
- the (meth) acrylic acid ester polymer may be one having a group having a photopolymerizable carbon-carbon double bond in the side chain (hereinafter sometimes referred to as an energy beam crosslinkable polymer).
- the group having a photopolymerizable carbon-carbon double bond include a vinyl group, a (meth) acryloyl group, and a maleimide group.
- the (meth) acrylic acid ester polymer having a photopolymerizable carbon-carbon double bond in the side chain is a crosslinkable compound and has a function of reducing the adhesive strength of the adhesive layer by irradiation with energy rays.
- a hydroxyl group-containing (meth) acrylic acid ester polymer is synthesized using the hydroxyl group-containing monomer exemplified as the above-mentioned reactive functional group monomer, and methacryloyloxyethyl isocyanate or the like is synthesized therewith. It can be obtained by reacting a compound having both a functional group that reacts with a hydroxyl group and a group having a photopolymerizable carbon-carbon double bond.
- the (meth) acrylic acid ester polymer may be a polymer obtained by crosslinking an energy ray crosslinkable polymer by polyaddition of a photopolymerizable carbon-carbon double bond.
- the (meth) acrylic acid ester polymer corresponds to a cross-linked product of a compound that can be cross-linked by irradiation with energy rays to be described later, and has a function to be described later.
- Such a crosslinked product can be obtained by irradiating the pressure-sensitive adhesive layer containing the energy ray-crosslinkable polymer with energy rays and polyadding a photopolymerizable carbon-carbon double bond.
- the mass of the (meth) acrylic acid ester polymer is , Refers to the mass before the energy beam crosslinkable polymer is polymerized by polyaddition of photopolymerizable carbon-carbon double bonds.
- the molecular weight of the (meth) acrylic acid ester polymer is preferably 100,000 or more, particularly preferably 150,000 to 1,000,000.
- the glass transition temperature of the acrylic pressure-sensitive adhesive is usually 20 ° C. or less, preferably about ⁇ 70 to 0 ° C.
- the (meth) acrylic acid ester polymer may be crosslinked by a thermal crosslinking agent.
- Crosslinking can be performed by reacting a (meth) acrylic acid ester polymer before crosslinking with a thermal crosslinking agent when it has a structural unit derived from a reactive functional group-containing monomer.
- thermal crosslinking agent known materials such as polyvalent isocyanate compounds and chelate compounds can be used.
- polyvalent isocyanate compound toluylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, adducts of these polyvalent isocyanates and polyhydric alcohols, and the like are used.
- chelate compound ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate) or the like is used. These may be used alone or in combination.
- the thermal crosslinking agent is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer before crosslinking. It is used in the ratio.
- the mass of the (meth) acrylic acid ester polymer when the preferred range is determined based on the mass of the (meth) acrylic acid ester polymer, the mass of the (meth) acrylic acid ester polymer The mass derived from the thermal crosslinking agent is not included.
- the pressure-sensitive adhesive layer preferably contains a compound that can be cross-linked by irradiation with energy rays such as ultraviolet rays or a cross-linked product thereof.
- energy rays such as ultraviolet rays or a cross-linked product thereof.
- an adhesive layer hardens
- the pressure-sensitive adhesive layer contains a compound that can be cross-linked by irradiation with energy rays
- the resulting pressure-sensitive adhesive sheet has a large initial adhesive force, and the pressure-sensitive adhesive strength greatly decreases after irradiation with energy rays.
- the wafer and the chip can be securely held during dicing, and the adhesive force is greatly reduced by energy beam irradiation during pick-up, so that the chip with the protective film forming layer (or protective film) can be reliably picked up.
- the pressure-sensitive adhesive layer contains a cross-linked product of a compound that can be cross-linked by irradiation with energy rays
- the pressure-sensitive adhesive layer has increased cohesion due to the three-dimensional network structure of the cured product, and has moderately low adhesiveness. Yes. For this reason, it is possible to achieve both wafer and chip holding performance and chip pickup suitability.
- Examples of compounds that can be cross-linked by energy ray irradiation include (meth) acrylic acid ester polymers having a photopolymerizable carbon-carbon double bond group in the side chain as described above.
- Low molecular weight compounds having at least two or more photopolymerizable carbon-carbon double bonds in the molecule (hereinafter sometimes referred to as energy beam polymerizable low molecular weight compounds) are widely used. Specifically, trimethylol is used.
- Examples of the polymer of the compound that can be cross-linked by energy ray irradiation include the above-mentioned energy ray-crosslinkable polymer crosslinked by polyaddition of a photopolymerizable carbon-carbon double bond, and the above-mentioned energy ray-crosslinkable low molecular weight.
- a polymer obtained by irradiating the pressure-sensitive adhesive layer containing the compound with an energy ray and being crosslinked can be used.
- an energy beam crosslinkable low molecular weight compound or a cross-linked product thereof When using an energy beam crosslinkable low molecular weight compound or a cross-linked product thereof, a (meth) acrylic acid ester polymer and an energy beam polymerizable low molecular weight compound in the pressure-sensitive adhesive layer, or an energy beam crosslinkable low molecular weight used for forming a cross-linked product
- the compounding ratio with the compound is 10 to 1000 parts by weight, preferably 20 to 500 parts by weight, particularly preferably 50 to 200 parts by weight with respect to 100 parts by weight of the (meth) acrylic acid ester polymer. It is preferable.
- the adhesive component may contain a plasticizer, a tackifier, and the like.
- the pressure-sensitive adhesive layer 2 in the present invention is mainly composed of a pressure-sensitive adhesive component and an epoxy group-containing compound, but in addition to the pressure-sensitive adhesive component and the epoxy group-containing compound, other components are used within the range not impairing the gist of the present invention. May be blended.
- ultraviolet rays are used as energy rays, it is preferable to mix a photopolymerization initiator in the pressure-sensitive adhesive layer.
- the photopolymerization initiator examples include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, 2,4 -Diethylthioxanthone, ⁇ -hydroxycyclohexyl phenyl ketone, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, ⁇ -chloranthraquinone or 2,4,6-trimethylbenzoyl Examples thereof include diphenylphosphine oxide.
- the blending ratio of the photopolymerization initiator is about 0.1 to 10 parts by mass, preferably about 0.5 to 5 parts by mass with respect to 100 parts by mass of the compound that can be cross-linked by energy ray irradiation.
- Other components include inorganic fillers, antistatic agents, antioxidants, antioxidants, pigments, dyes and the like in addition to the photopolymerization initiators described above.
- the thickness of the pressure-sensitive adhesive layer 2 is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 2 to 80 ⁇ m, and particularly preferably 3 to 50 ⁇ m.
- the pressure-sensitive adhesive sheet 3 is formed by forming a pressure-sensitive adhesive layer 2 containing the above-mentioned pressure-sensitive adhesive component and a free epoxy group-containing compound on one surface of the above-described base film 1.
- the surface of the base film 1 in contact with the pressure-sensitive adhesive layer 2 may be subjected to corona treatment or other layers such as a primer.
- the protective film forming layer 4 in the present invention is not particularly limited, and for example, a thermosetting, thermoplastic, or energy ray curable protective film forming layer can be used. Among these, when a thermosetting protective film forming layer is used, since the problem of adhesion between the pressure-sensitive adhesive layer and the protective film becomes significant, the effects of the present invention are preferably exhibited. Further, the protective film forming layer 4 may be a single layer or a multilayer as long as the gist of the present invention is not impaired.
- the multilayer protective film forming layer includes an adhesive layer 4a that is a layer for contacting the workpiece and an adhesive proximity layer 4b that is in contact with the adhesive layer side.
- the adhesive layer 4a is not particularly limited as long as it has a function capable of adhering to the adherend. Further, the adhesive layer 4a itself can have a multilayer structure.
- the layer in contact with the pressure-sensitive adhesive layer side is referred to as “pressure-sensitive adhesive proximity layer 4b”.
- the pressure-sensitive adhesive proximity layer 4b is a layer that requires a function in consideration of being in contact with the pressure-sensitive adhesive layer and being exposed to the outermost layer after being attached to the adherend.
- the mode for the protective film forming layer is a mode for both the adhesive layer 4a and the pressure-sensitive adhesive proximity layer 4b.
- the only layer constituting the single layer serves as the function of the adhesive layer 4a and the pressure-sensitive adhesive proximity layer 4b.
- a mode for only one of the adjacent layers 4b also means a mode for a single layer constituting the single layer.
- the protective film-forming layer preferably contains a binder polymer component (A) and a curable component (B).
- Binder polymer component The binder polymer component (A) is used for imparting sufficient adhesion and film forming property (sheet processability) to the protective film forming layer.
- the binder polymer component (A) conventionally known acrylic polymers, polyester resins, urethane resins, acrylic urethane resins, silicone resins, rubber polymers, phenoxy resins, and the like can be used.
- the weight average molecular weight (Mw) of the acrylic polymer is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,200,000.
- Mw weight average molecular weight of the acrylic polymer
- the peeling force between the pressure-sensitive adhesive proximity layer 4b and the pressure-sensitive adhesive layer 2 is maintained at an appropriate level, and transfer failure of the protective film forming layer hardly occurs.
- the adhesion of the adhesive layer 4a to the adherend is maintained, and the protective film tends to be prevented from peeling off from the chip or the like.
- the glass transition temperature (Tg) of the acrylic polymer is preferably in the range of ⁇ 60 to 50 ° C., more preferably ⁇ 50 to 40 ° C., and particularly preferably ⁇ 40 to 30 ° C.
- Tg glass transition temperature
- the peeling force with the pressure-sensitive adhesive layer 2 may increase with respect to the pressure-sensitive adhesive proximity layer 4b, and transfer failure of the protective film forming layer may occur.
- the adhesiveness may be reduced, and transfer to a chip or the like may not be possible, or the protective film may be peeled off from the chip or the like after transfer.
- the acrylic polymer contains a (meth) acrylic acid ester monomer as a monomer constituting the acrylic polymer.
- (meth) acrylic acid ester monomers include alkyl (meth) acrylates having an alkyl group with 1 to 18 carbon atoms, specifically methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like.
- (meth) acrylate having a cyclic skeleton specifically cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Examples include dicyclopentenyloxyethyl (meth) acrylate and imide (meth) acrylate.
- examples of the monomer having a functional group include hydroxymethyl (meth) acrylate having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like; in addition, glycidyl (meth) having an epoxy group An acrylate etc. are mentioned.
- the acrylic polymer an acrylic polymer containing a monomer having a hydroxyl group as a monomer constituting the acrylic polymer is preferable because the compatibility with the curable component (B) described later is good.
- the acrylic polymer may be copolymerized with acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, or the like.
- the acrylic polymer may be crosslinked with a crosslinking agent.
- a crosslinking agent the same thing as what was illustrated as a crosslinking agent of the (meth) acrylic acid ester polymer of an adhesive layer can be used.
- the crosslinking agent is usually used in a ratio of 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the acrylic polymer before crosslinking.
- content of the other component which comprises a protective film formation layer when setting the preferable range on the basis of the mass of a binder polymer component (A), it is used as a crosslinking agent to the mass of a binder polymer component (A). Does not include derived mass.
- thermoplastic resin for maintaining the flexibility of the cured protective film may be blended. It is preferable for the adhesive layer 4a to incorporate such a thermoplastic resin.
- a thermoplastic resin preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 3,000 to 80,000.
- the glass transition temperature of the thermoplastic resin is preferably ⁇ 30 to 120 ° C., more preferably ⁇ 20 to 120 ° C.
- the thermoplastic resin include polyester resin, urethane resin, phenoxy resin, polybutene, polybutadiene, and polystyrene. These thermoplastic resins can be used individually by 1 type or in mixture of 2 or more types.
- the adhesive layer 4a follows the transfer surface of the protective film forming layer, and generation of voids and the like can be suppressed.
- thermosetting component As the curable component (B), a thermosetting component and / or an energy ray curable component is used, and a thermosetting component is particularly preferably used.
- thermosetting component examples include an epoxy thermosetting component, and the epoxy thermosetting component includes an epoxy compound and a thermosetting agent.
- the epoxy compound has an epoxy group.
- an epoxy-type compound a well-known epoxy-type compound can be used as curable resin.
- Specific examples of the epoxy compound include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, Examples thereof include epoxy compounds having two or more functional groups in the molecule, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin. These can be used individually by 1 type or in combination of 2 or more types.
- the epoxy compound is preferably 1 to 1000 parts by weight, more preferably 10 to 500 parts by weight, and particularly preferably 20 to 200 parts by weight with respect to 100 parts by weight of the binder polymer component (A). included. If the content of the thermosetting resin is less than 1 part by mass, sufficient adhesiveness may not be obtained, and if it exceeds 1000 parts by mass, the flexibility of the protective film forming layer derived from the binder polymer component (A) There is a concern that it is difficult to obtain a film-forming property.
- thermosetting agent functions as a curing agent for the epoxy compound and is also referred to as a thermoactive latent epoxy resin curing agent.
- a preferable thermosetting agent includes a compound having two or more functional groups other than an epoxy group capable of reacting with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an amino group, a carboxyl group, and an acid anhydride. Of these, phenolic hydroxyl groups, amino groups, acid anhydrides and the like are preferable, and phenolic hydroxyl groups and amino groups are more preferable.
- phenolic curing agent examples include polyfunctional phenolic resins, biphenols, novolac type phenolic resins, dicyclopentadiene type phenolic resins, zylock type phenolic resins, and aralkylphenolic resins.
- amine curing agent is DICY (dicyandiamide). These can be used individually by 1 type or in mixture of 2 or more types.
- the content of the thermosetting agent is preferably 0.1 to 500 parts by mass and more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the epoxy compound. If the content of the thermosetting agent is small, the reliability of the protective film forming layer may be reduced due to insufficient curing, and if it is excessive, the moisture absorption rate of the protective film forming layer may be increased and the reliability of the semiconductor device may be reduced. .
- the total amount of the epoxy compound and the thermosetting agent contained in the curable component is preferably 40 parts by mass or more, more preferably 60 parts by mass or more, particularly preferably with respect to 100 parts by mass of the binder polymer component (A). Is 75 to 250 parts by mass.
- ⁇ Energy ray curable component a low molecular compound (energy ray polymerizable compound) containing an energy ray polymerizable group and polymerized and cured when irradiated with energy rays such as ultraviolet rays and electron beams can be used.
- energy ray-curable components include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, and 1,4-butylene glycol.
- Photopolymerizable carbon-carbon such as acrylate compounds such as diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified acrylate, polyether acrylate and itaconic acid oligomer A compound containing a double bond can be used.
- the adhesive proximity layer 4b contains an energy ray curable component
- the energy ray curable component and the compound polymerizable by energy ray irradiation in the adhesive layer are polymerized at the same time, and the protective film forming layer and the adhesive
- the pressure-sensitive adhesive layer does not substantially contain a compound that can be polymerized by energy ray irradiation.
- the pressure-sensitive adhesive layer substantially contains a polymer of a compound that can be polymerized by irradiation with energy rays, such a problem does not occur.
- the protective film forming layer By imparting energy ray curability to the protective film forming layer, the protective film forming layer can be cured easily and in a short time, and the production efficiency of the chip with protective film is improved.
- the curing temperature of the thermosetting resin is about 100 to 200 ° C., and the curing time is about 2 hours.
- the energy ray-curable protective film forming layer is cured in a short time by energy ray irradiation, a protective film can be easily formed, which can contribute to improvement of production efficiency.
- thermosetting component is preferably used as the curable component.
- the protective film forming layer is thermosetting
- the problem that the adhesion between the protective film and the adhesive increases after the protective film forming layer is cured and the peeling becomes difficult is the thermosetting protective film forming layer.
- the dicing sheet with a protective film-forming layer of the present invention can eliminate excessive adhesion between the pressure-sensitive adhesive layer and the protective film. That is, the effect of the present invention is particularly preferably exhibited when the protective film forming layer is thermosetting.
- thermosetting component of the pressure-sensitive adhesive proximity layer 4b is an epoxy thermosetting component
- the epoxy group-containing compound present at the interface between the pressure-sensitive adhesive layer 2 and the pressure-sensitive adhesive proximity layer 4b also functions as a thermosetting component. Therefore, the influence on the properties of the pressure-sensitive adhesive proximity layer 4b is small, and the influence on the function of the protective film obtained by curing the protective film forming layer 4 is also small, which is more preferable.
- a coloring agent protective film formation layer contains a coloring agent (C).
- a coloring agent (C) By blending a colorant into the protective film forming layer, when a semiconductor device is incorporated in equipment, infrared rays generated from surrounding devices can be shielded, and malfunction of the semiconductor device due to them can be prevented. Visibility of characters when a product number or the like is printed on a protective film obtained by curing the protective film forming layer is improved. That is, in a semiconductor device or semiconductor chip on which a protective film is formed, the product number or the like is usually printed on the surface of the protective film by a laser marking method (a method in which the surface of the protective film is scraped off by laser light and printed).
- the colorant (C) organic or inorganic pigments and dyes are used.
- black pigments are preferable from the viewpoint of electromagnetic wave and infrared shielding properties.
- the black pigment include carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, and the like, but are not limited thereto. Carbon black is particularly preferable from the viewpoint of increasing the reliability of the semiconductor device.
- a colorant (C) may be used individually by 1 type, and may be used in combination of 2 or more type.
- the high curability of the protective film-forming layer in the present invention is particularly preferably exhibited when a colorant that lowers the transmittance of both visible light and / or infrared rays and ultraviolet rays is used, and the ultraviolet ray permeability is lowered.
- the colorant that reduces the transparency of both visible light and / or infrared and ultraviolet rays has an absorptivity or reflectivity in the visible light and / or infrared and ultraviolet wavelength regions. If it has, it will not specifically limit.
- the blending amount of the colorant (C) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, and particularly preferably as a mass ratio in the total solid content constituting the protective film forming layer. 1 to 15% by mass.
- the curing accelerator (D) may be used to adjust the curing rate of the protective film forming layer.
- the curing accelerator (D) is preferably used particularly when the epoxy compound and the thermosetting agent are used in combination in the curable component (B).
- Preferred curing accelerators include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl- Imidazoles such as 4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; Organic phosphines such as tributylphosphine, diphenylphosphine and triphenylphosphine; And tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphinetetraphenylborate. These can be used individually by 1 type or in mixture of 2 or more types.
- the curing accelerator (D) is contained in an amount of preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable component (B).
- the curing accelerator (D) By containing the curing accelerator (D) in an amount within the above range, it has excellent adhesive properties even when exposed to high temperatures and high humidity, and has high reliability even when exposed to severe reflow conditions. Can be achieved. If the content of the curing accelerator (D) is small, sufficient hardness and adhesive properties may not be obtained due to insufficient curing. If it is excessive, a curing accelerator having a high polarity will form a protective film under high temperature and high humidity. The reliability of the semiconductor device may be lowered by moving to the adhesion interface side in the layer and segregating.
- a coupling agent (E) having a group capable of reacting with an organic compound and a group capable of binding to a functional group on the surface of an inorganic substance is bonded to the chip of the protective film forming layer, adhesion and / or It may be used to improve the cohesiveness of the protective film. Moreover, the water resistance can be improved by using a coupling agent (E), without impairing the heat resistance of the protective film obtained by hardening
- the coupling agent (E) is particularly preferably used for the adhesive layer 4a from the viewpoint of improving the adhesion of the protective film forming layer to the chip.
- the coupling agent (E) a compound having a group that reacts with a functional group of the binder polymer component (A), the curable component (B), or the like as a group capable of reacting with an organic compound is preferably used.
- a silane coupling agent is desirable.
- Such coupling agents include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (methacryloxypropyl).
- the coupling agent (E) is usually 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on a total of 100 parts by weight of the binder polymer component (A) and the curable component (B). Preferably, it is contained at a ratio of 0.3 to 5 parts by mass. If the content of the coupling agent (E) is less than 0.1 parts by mass, the above effect may not be obtained, and if it exceeds 20 parts by mass, it may cause outgassing.
- the inorganic filler examples include silica, alumina, talc, calcium carbonate, titanium oxide, iron oxide, silicon carbide, boron nitride and other powders, beads formed by spheroidizing them, single crystal fibers, and glass fibers.
- silica filler and alumina filler are preferable.
- the said inorganic filler (F) can be used individually or in mixture of 2 or more types.
- the content of the inorganic filler (F) can be adjusted in the range of usually 1 to 80 parts by mass with respect to 100 parts by mass of the total solid content constituting the protective film forming layer.
- the photopolymerization initiator protective film forming layer contains an energy ray curable component
- the energy ray curable component is cured by irradiating with an energy ray such as ultraviolet rays.
- an energy ray such as ultraviolet rays.
- photopolymerization initiator (G) examples include benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal.
- a photoinitiator (G) can be used individually by 1 type or in combination of 2 or more types.
- the blending ratio of the photopolymerization initiator (G) is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the energy ray curable component. If the amount is less than 0.1 parts by mass, satisfactory transferability may not be obtained due to insufficient photopolymerization. If the amount exceeds 10 parts by mass, a residue that does not contribute to photopolymerization is generated, and the curability of the protective film forming layer is increased. May be insufficient.
- additives may be blended in the general-purpose additive protective film forming layer as necessary.
- additives include leveling agents, plasticizers, antistatic agents, antioxidants, ion scavengers, gettering agents, chain transfer agents, and the like.
- the maximum transmittance at a wavelength of 300 to 1200 nm which is a measure showing the transmittance of visible light and / or infrared rays and ultraviolet rays in the protective film forming layer, is preferably 20% or less, more preferably 0 to 15%. Further, it is more preferably more than 0% and not more than 10%, particularly preferably 0.001 to 8%.
- the maximum transmittance of the protective film forming layer at a wavelength of 300 to 1200 nm can be adjusted by the colorant (C).
- the maximum transmittance of the protective film forming layer is 3 for the cured protective film forming layer (thickness 25 ⁇ m) using a UV-vis spectrum inspection apparatus (manufactured by Shimadzu Corporation). The total light transmittance at 00 to 1200 nm was measured and set to the highest value (maximum transmittance).
- the thickness of the protective film forming layer is not particularly limited, but is preferably 3 to 300 ⁇ m, more preferably 5 to 250 ⁇ m, and particularly preferably 7 to 200 ⁇ m.
- the total thickness is as described above, and among these, the thickness of the pressure-sensitive adhesive proximity layer 4b is preferably 1 to 250 ⁇ m, more preferably 3 to 200 ⁇ m. Particularly preferred is 5 to 100 ⁇ m.
- the dicing sheet with a protective film forming layer may be provided with a release sheet for avoiding contact with the outside of the surface until it is used.
- a release sheet for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, Polyurethane film, ethylene vinyl acetate copolymer film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluorine A transparent film such as a resin film is used.
- crosslinked films are also used. Furthermore, these laminated films may be sufficient. Moreover, the film which colored these, an opaque film, etc. can be used.
- the release agent include release agents such as silicone-based, fluorine-based, and long-chain alkyl group-containing carbamates.
- the thickness of the release sheet is usually 10 to 500 ⁇ m, preferably 15 to 300 ⁇ m, particularly preferably about 20 to 250 ⁇ m.
- the thickness of the dicing sheet with a protective film forming layer is usually about 1 to 500 ⁇ m, preferably about 5 to 300 ⁇ m, and particularly preferably about 10 to 150 ⁇ m.
- the dicing sheet with a protective film forming layer is formed by providing the protective film forming layer 4 described above on the adhesive layer 2 of the adhesive sheet 3.
- the protective film forming layer may have a multilayer structure.
- the dicing sheet 10 with a protective film forming layer of the present invention is provided with a protective film forming layer 4 (or on the inner peripheral portion of the pressure sensitive adhesive sheet 3 composed of the base film 1 and the pressure sensitive adhesive layer 2. It is preferable that the multilayer protective film forming layer is detachably laminated and the pressure-sensitive adhesive layer 2 is exposed on the outer peripheral portion of the pressure-sensitive adhesive sheet 3.
- the protective film forming layer 4 (or the multilayer protective film forming layer) having a smaller diameter than the pressure-sensitive adhesive sheet 3 is preferably laminated on the pressure-sensitive adhesive layer 2 of the pressure-sensitive adhesive sheet 3 so as to be concentrically peelable.
- the protective film formation layer is comprised from the single
- the protective film forming layer-attached dicing sheet 10 having the above configuration is attached to the ring frame 5 in the pressure-sensitive adhesive layer 2 exposed on the outer peripheral portion of the pressure-sensitive adhesive sheet 3.
- annular double-sided tape or an adhesive layer may be separately provided on the margin for the ring frame (exposed adhesive layer on the outer periphery of the adhesive sheet).
- the double-sided tape has a configuration of pressure-sensitive adhesive layer / core material / pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer in the double-sided tape is not particularly limited. For example, rubber-based, acrylic-based, silicone-based, polyvinyl ether, or the like is used. .
- the adhesive layer is affixed to the ring frame at the outer periphery when a chip to be described later is manufactured.
- a polyester film for example, a polyester film, a polypropylene film, a polycarbonate film, a polyimide film, a fluororesin film, a liquid crystal polymer film and the like are preferably used.
- a protective film forming layer is formed on the release sheet.
- the protective film-forming layer is obtained by applying and drying a protective film-forming layer composition obtained by mixing the above-described components in an appropriate solvent on an appropriate release sheet.
- a composition for a protective film forming layer is applied onto a release sheet, dried to form a film, and this is bonded to another release sheet and sandwiched between two release sheets (release sheet / protective film) Forming layer / release sheet).
- the above operation is performed separately to prepare a plurality of protective film forming layers sandwiched between two release sheets, and one of each release sheet is peeled off to protect it.
- a multilayer protective film forming layer sandwiched between two release sheets is obtained.
- the protective film forming layer is sandwiched between two release sheets, one release sheet is released. Then, it is punched into a circle that is the same size or slightly larger than the workpiece (for example, a semiconductor wafer) to which the protective film forming layer is to be attached, and the periphery of the protective film forming layer that has been punched in a circular shape is removed. Also, in the state of being sandwiched between two release sheets, one release sheet and the protective film forming layer are die-cut, the protective film forming layer is removed together with the release sheet, and then the die-release is released The sheet may be peeled off.
- the workpiece for example, a semiconductor wafer
- the pressure-sensitive adhesive layer 2 may be applied directly on the base film 1 or formed on a process film such as a release film and then transferred onto the base film.
- Examples of the coating apparatus for forming the pressure-sensitive adhesive layer 2 include a roll coater, a knife coater, a roll knife coater, a fountain die coater, a slot die coater, and a reverse coater.
- the cohesive force of the pressure-sensitive adhesive layer may be controlled by irradiating energy rays after the pressure-sensitive adhesive layer is applied.
- the circular protective film forming layer 4 is affixed to the pressure-sensitive adhesive layer 2 of the pressure-sensitive adhesive sheet 3 prepared by the above-described method, etc., and is die-cut concentrically according to the outer diameter of the margin for the ring frame. Remove the periphery of the adhesive sheet.
- the pressure-sensitive adhesive is bonded before the pressure-sensitive adhesive sheet and the protective film-forming layer are bonded together in the production stage of the dicing sheet with the protective film-forming layer
- the adhesive layer may be irradiated with energy rays to polymerize a compound that can be polymerized by the energy rays, or after the adhesive sheet and the protective film forming layer are bonded together, the adhesive layer may be irradiated with energy rays to be polymerized. Good.
- the release sheet attached to the protective film forming layer is peeled to obtain the dicing sheet 10 with the protective film forming layer of the present invention.
- Chip manufacturing method Next, a method of using the dicing sheet 10 with a protective film forming layer according to the present invention will be described taking as an example the case where the sheet is applied to manufacture of a chip (for example, a semiconductor chip).
- a manufacturing method of a semiconductor chip using a dicing sheet with a protective film forming layer according to the present invention is a method in which a protective film forming layer of the above sheet is pasted on the back surface of a semiconductor wafer (work) on which a circuit is formed.
- Steps (1) to (3) can be performed by changing [(1), (2), (3)] or [(2), (1), (3)] or [(2), (3), (1)
- the semiconductor chip having a protective film on the back surface is obtained.
- Step (1) a step of curing the protective film forming layer to obtain a protective film
- Step (2) a step of dicing the semiconductor wafer (work) and the protective film forming layer or the protective film
- Process (3) The process of peeling a protective film formation layer or a protective film, and an adhesive sheet.
- the method for manufacturing a semiconductor chip according to the present invention further includes the following step (4) in addition to the above steps (1) to (3), and in any of the steps after the above step (1): Step (4) can also be performed.
- 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. Next, the opposite surface (back surface) of the circuit surface of the semiconductor wafer is ground.
- the grinding method is not particularly limited, and grinding may be performed by a known means using a grinder or the like. At the time of back surface grinding, an adhesive sheet called a surface protection sheet is attached to the circuit surface in order to protect the circuit on the surface.
- the circuit surface side (that is, the surface protection sheet side) of the wafer is fixed by a chuck table or the like, and the back surface side on which no circuit is formed is ground by a grinder.
- the thickness of the wafer after grinding is not particularly limited, but is usually about 20 to 500 ⁇ m.
- the crushed layer generated during back grinding is removed.
- the crushed layer is removed by chemical etching, plasma etching, or the like.
- the protective film forming layer of the dicing sheet with the protective film forming layer is attached to the back surface of the semiconductor wafer.
- the steps (1) to (3) are performed as [(1), (2), (3)] or [(2), (1), (3)] or [(2), (3), (1 )].
- steps (1) to (3) are performed in the order of [(1), (2), (3)] will be described.
- the step (4) is performed after the step (1) and before the step (2).
- the protective film forming layer of the dicing sheet with the protective film forming layer is attached to the back surface of the semiconductor wafer having a circuit formed on the front surface.
- the protective film forming layer is cured, and a protective film is formed on the entire surface of the wafer.
- a protective film is formed on the back surface of the wafer, and the strength is improved as compared with the case of the wafer alone, so that damage to the thinned wafer during handling can be reduced.
- the thickness of the protective film is excellent compared to a coating method in which a coating liquid for the protective film is directly applied to the back surface of the wafer or chip.
- the protective film forming layer has a thermosetting property in the dicing sheet with the protective film forming layer of the present invention
- a base film having excellent heat resistance slack due to deformation during thermosetting is suppressed
- the effect that dicing and pickup (peeling of the adhesive sheet from the protective film) becomes easy is preferably exhibited.
- the protective film is cured by the cured protective film forming layer (protective film).
- Laser printing is performed by the laser marking method, and the protective film is marked with a product number or the like by scraping the surface of the protective film over the adhesive sheet by irradiation with laser light.
- the dicing sheet with a protective film forming layer of the present invention since the warpage of the wafer can be suppressed even with an extremely thin wafer, the focal point of the laser beam is accurately determined and marking can be performed with high accuracy.
- a laminated body of a semiconductor wafer and a dicing sheet with a protective film forming layer (a laminated body of a semiconductor wafer, a protective film, and an adhesive sheet) is diced for each circuit formed on the wafer surface to form a semiconductor chip and a protective film.
- a laminate with the layered dicing sheet is obtained. Dicing is performed so as to cut both the wafer and the protective film.
- the dicing sheet with a protective film forming layer of the present invention since the pressure-sensitive adhesive sheet has sufficient adhesive force with respect to the protective film during dicing, chipping and chip jumping can be prevented, and the dicing suitability is excellent. Dicing is not particularly limited.
- the peripheral portion of the dicing sheet with a protective film forming layer (the outer peripheral portion of the adhesive sheet) is fixed with a ring frame, and then a rotating round blade such as a dicing blade is used.
- a known method for forming a wafer into chips is not limited as long as the protective film forming layer is completely cut, and is preferably 0 to 30 ⁇ m from the interface with the protective film forming layer.
- the pressure-sensitive adhesive sheet may be expanded.
- the dicing sheet with a protective film formation layer of this invention has the outstanding expandability.
- the protective film and the adhesive sheet are peeled off by picking up the diced semiconductor chip with a protective film by a general means such as a collet. As a result, a semiconductor chip having a protective film on the back surface (semiconductor chip with protective film) is obtained.
- the free epoxy group-containing compound contained in the pressure sensitive adhesive layer 2 forms an oil film-like thin film on the pressure sensitive adhesive surface, whereby the pressure sensitive adhesive layer 2 and the protective film forming layer are formed. It is considered that the interaction with (or the protective film) is reduced, and peeling between the pressure-sensitive adhesive layer 2 and the protective film forming layer (or the protective film) is facilitated. As a result, a semiconductor chip with a protective film forming layer (or protective film) can be easily picked up.
- a protective film having high thickness uniformity can be easily formed on the back surface of the chip, and cracks after the dicing process and packaging are less likely to occur.
- a chip with a protective film is obtained without replacing the wafer on which the protective film is formed with the dicing tape, as compared with the conventional process in which the wafer is diced. This simplifies the manufacturing process. Further, since the wafer weakened by grinding is not handled alone, the risk of wafer breakage is reduced. Further, the thinned wafer may be warped due to curing shrinkage of the protective film. However, since the wafer is held by the adhesive sheet, the warpage can be suppressed.
- the semiconductor device can be manufactured by mounting the semiconductor chip on a predetermined base by the face-down method. Further, a semiconductor device can be manufactured by adhering a semiconductor chip having a protective film on the back surface to another member (on the chip mounting portion) such as a die pad portion or another semiconductor chip.
- the dicing sheet with the protective film-forming layer of the present invention can be used. There is an effect that the semiconductor chip can be easily picked up. Conventionally, after the protective film forming layer is cured (after the step (1)), there is a problem that it is difficult to separate the chip with the protective film from the pressure-sensitive adhesive sheet (step (3)). However, according to the present invention, this problem is solved. Therefore, in the present invention, when the step (1) is performed before the step (3), that is, the steps (1) to (3) are performed in the order of [(1), (2), (3)] or [ (2), (1), (3)] can be preferably applied when performed in this order.
- the protective film-forming dicing sheet of the present invention is used.
- the semiconductor chip with the protective film can be easily picked up, and then the protective film-forming layer is cured (step (1)), whereby the semiconductor chip with the protective film is obtained.
- the protective film forming layer may be cured in a heating step at the time of resin sealing that is finally performed.
- ⁇ adhesive strength>, ⁇ pickup suitability>, and ⁇ adhesion to chip tray> were measured and evaluated as follows. Further, ⁇ Dicing sheet with protective film forming layer> was prepared using the following ⁇ Composition for protective film forming layer>, ⁇ Adhesive composition>, and ⁇ Base material>.
- thermosetting at 130 ° C. for 2 hours was performed.
- the adhesive sheet was peeled off from the cured protective film at 180 ° in accordance with JIS Z 0237: 2009, and the adhesive strength was measured.
- the adhesive force measurement when not performing the thermosetting process of the said protective film formation layer was also considered also considering the process of the order of the said process "(2), (3), (1)".
- a protective film forming layer of a dicing sheet with a protective film forming layer was attached to a polished surface of a silicon wafer having a thickness of 350 ⁇ m, a diameter of 6 inches and subjected to # 2000 polishing while heating to 70 ° C.
- the wafer with the protective film forming layer-attached dicing sheet attached thereto was placed in a heating oven at 130 ° C. for 2 hours to cure the protective film forming layer.
- the wafer was diced into chips of 3 mm ⁇ 3 mm size with a blade speed of 40 mm / second so that the base film was cut to a depth of 15 ⁇ m.
- the “epoxy index” of the pressure-sensitive adhesive was measured by an indicator titration method according to JIS K7236.
- the pressure-sensitive adhesive collected without being laminated on the substrate in the manufacturing process of the dicing tape was aged at room temperature for 1 week and then subjected to measurement.
- About 1.0 g of the pressure-sensitive adhesive for measurement was put into Soxhlet and extracted by refluxing an ethyl acetate solvent heated to a boiling point or higher with a water bath (manufactured by Shibata, SB-6) to obtain a sol component.
- the titration of the epoxy index was performed in a state where the ethyl acetate solvent was volatilized and the sol component was dissolved in about 50 ml of chloroform.
- the epoxy index in Table 1 is a converted value per kg of the pressure-sensitive adhesive before extraction.
- Binder polymer component acrylic polymer comprising 55 parts by mass of n-butyl acrylate, 10 parts by mass of methyl methacrylate, 20 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight: 900,000, glass transition (Temperature: -28 ° C) / 100 parts by mass
- B2 Thermally active latent epoxy resin curing agent Dicyandiamide (Asahi Denka, Adeka Hard)
- Adhesive A2 A pressure-sensitive adhesive composition was obtained in the same manner as pressure-sensitive adhesive A1, except that the amount of the epoxy group-containing compound was 20 parts by mass.
- Adhesive A3 In the adhesive A1, the energy ray crosslinkable polymer was replaced with the following, and the amount of the photopolymerization initiator (Ciba Specialty Chemicals, Irgacure (registered trademark) 184) was 3.25 parts by mass.
- a pressure-sensitive adhesive composition was obtained in the same manner as pressure-sensitive adhesive A1.
- Adhesive A4 A pressure-sensitive adhesive composition was prepared in the same manner as pressure-sensitive adhesive A1 except that 20 parts by mass of Epicoat (registered trademark) 828 (molecular weight 370) manufactured by Japan Epoxy Resin Co., Ltd. was used as the epoxy group-containing compound.
- a pressure-sensitive adhesive composition was prepared in the same manner as pressure-sensitive adhesive A1 except that 20 parts by mass of Epicoat (registered trademark) 806 (molecular weight of about 330) manufactured by Japan Epoxy Resin Co., Ltd. was used as the epoxy group-containing compound.
- Adhesive B1 A pressure-sensitive adhesive composition was prepared in the same manner as pressure-sensitive adhesive A1 except that the epoxy group-containing compound was not used.
- Adhesive B2 A pressure-sensitive adhesive composition was prepared in the same manner as the pressure-sensitive adhesive A3 except that the epoxy group-containing compound was not used.
- ⁇ Dicing sheet with protective film forming layer> The adhesive listed in Table 1 was applied to a release film (SP-PET 3811, thickness 38 ⁇ m, manufactured by Lintec Corporation) so that the coating amount after drying was 10 g / m 2 and dried at 100 ° C. for 1 minute.
- a pressure-sensitive adhesive sheet was obtained by laminating the material.
- the pressure-sensitive adhesive sheet other than Example 6 only the pressure-sensitive adhesive layer in the region attached to the wafer was irradiated with ultraviolet rays (irradiation condition: illuminance 230 mW / L) using an ultraviolet irradiation device (RAD-2000m / 12 manufactured by Lintec Corporation). Curing was performed by irradiating with cm 2 and a light amount of 800 mJ / cm 2 .
- the methyl ethyl ketone solution (solid concentration: 61% by mass) of the above protective film forming layer composition is dried on the release treatment surface of a release sheet (manufactured by Lintec, SP-PET3811, thickness: 38 ⁇ m) to a thickness of 25 ⁇ m.
- a release sheet manufactured by Lintec, SP-PET3811, thickness: 38 ⁇ m
- it applied and dried drying conditions: 120 degreeC in an oven for 2 minutes), and formed the protective film formation layer on the peeling sheet.
- a peel-treated surface of a polyethylene terephthalate film (SP-PET 381031, thickness 38 ⁇ m) was bonded to this protective film forming layer as another release sheet.
- the die is cut to the same size as the silicon wafer (diameter 8 inches) so as to cut only the protective film forming layer and other release sheets while leaving the release sheet, and then protection of the portion excluding the die-cut shape portion.
- the film-forming layer and other release sheets were removed, and a protective film-forming layer and other release sheets that were punched in a circle on the release sheet were obtained.
- a protective film forming layer formed on the release sheet on the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (for the pressure-sensitive adhesive sheet other than Example 6, the region irradiated with ultraviolet rays), and another release sheet that has been die-cut After peeling off and pasting, it was pasted and die-cut concentrically according to the outer diameter (diameter 260 mm) of the margin for the ring frame. Thereafter, the release sheet on the protective film forming layer was peeled off to obtain a dicing sheet with a protective film forming layer.
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Abstract
Description
[1]粘着成分と遊離のエポキシ基含有化合物とを含む粘着剤層が、基材フィルム上に積層されてなる粘着シートの粘着剤層上に、保護膜形成層を剥離可能に設けた保護膜形成層付ダイシングシート。
工程(1):保護膜形成層を硬化し保護膜を得る工程、
工程(2):ワークと、保護膜形成層または保護膜とをダイシングする工程、
工程(3):保護膜形成層または保護膜と、粘着シートとを剥離する工程。
工程(4):保護膜にレーザー印字を行う工程。
基材フィルム1としては、保護膜形成層4の熱硬化を、粘着シート3から保護膜形成層4を剥離後に行う場合には、特に限定されず、例えば低密度ポリエチレン(LDPE)、直鎖低密度ポリエチレン(LLDPE),エチレン・プロピレン共重合体、ポリプロピレン、ポリブテン、ポリブタジエン、ポリメチルペンテン、エチレン・酢酸ビニル共重合体、エチレン・(メタ)アクリル酸共重合体、エチレン・(メタ)アクリル酸メチル共重合体、エチレン・(メタ)アクリル酸エチル共重合体、ポリ塩化ビニル、塩化ビニル・酢酸ビニル共重合体、ポリウレタンフィルム、アイオノマー等からなるフィルムなどが用いられる。なお、本明細書において「(メタ)アクリル」は、アクリルおよびメタアクリルの両者を含む意味で用いる。
本発明における粘着剤層2は、エポキシ基含有化合物、粘着成分および必要に応じその他の添加剤から構成されている。
本発明の保護膜形成層付ダイシングシート10における粘着剤層2は、エポキシ基含有化合物を有することを特徴としている。粘着剤層2中で、エポキシ基含有化合物は遊離状態で存在し、粘着剤層2と保護膜形成層4との界面において一部が油膜状となり離型剤として機能すると考えられる。つまり、粘着剤層2と保護膜形成層4との界面にエポキシ基含有化合物が存在することで、粘着剤層2と保護膜形成層4とが過度に密着することが防止され、所要の工程後に、粘着シート3から保護膜形成層4(または保護膜)を剥離する際の剥離力が適切な範囲に制御され、保護膜形成層4(または保護膜)を伴ったチップのピックアップ力が低減される。以下では、特に使用態様を説明する場合に、保護膜形成層およびその硬化物である保護膜を総称して単に「保護膜形成層」と記載することがある。
粘着成分は、適度な再剥離性を粘着剤層に付与するものであればその種類は特に限定はされず、ゴム系、アクリル系、シリコーン系、ウレタン系、ビニルエーテル系など汎用の粘着剤から形成されてもよい。これらの中でも特にアクリル系粘着剤が好ましく用いられる。また、粘着成分は、エネルギー線硬化性の粘着成分であってもよい。
上記のように本発明における粘着剤層2は、粘着成分およびエポキシ基含有化合物を主成分とするが、粘着成分およびエポキシ基含有化合物に加えて、本発明の趣旨を損なわない範囲で他の成分が配合されていてもよい。エネルギー線として紫外線を用いる場合には、粘着剤層中に光重合開始剤を配合することが好ましい。光重合開始剤としては、具体的には、ベンゾフェノン、アセトフェノン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾイン安息香酸、ベンゾイン安息香酸メチル、ベンゾインジメチルケタール、2,4-ジエチルチオキサンソン、α―ヒドロキシシクロヘキシルフェニルケトン、ベンジルジフェニルサルファイド、テトラメチルチウラムモノサルファイド、アゾビスイソブチロニトリル、ベンジル、ジベンジル、ジアセチル、β―クロールアンスラキノンあるいは2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイドなどが挙げられる。
粘着シート3は、上記の基材フィルム1の片面に、上記の粘着成分および遊離のエポキシ基含有化合物を含む粘着剤層2が形成されてなる。基材フィルム1の粘着剤層2と接する面には粘着剤層2との密着性を向上するために、コロナ処理を施したりプライマー等の他の層を設けてもよい。
本発明における保護膜形成層4は特に限定されず、例えば熱硬化性、熱可塑性、エネルギー線硬化性の保護膜形成層を用いることができる。これらの中でも、熱硬化性の保護膜形成層を用いた場合に、粘着剤層と保護膜との密着の問題が顕著となるので、本発明の効果は好ましく発揮される。また、保護膜形成層4は、単層であってもよく、本発明の趣旨を損なわない範囲で多層であってもよい。
保護膜形成層4を多層構造とした場合の概略図を図2に示した。多層の保護膜形成層は、ワークに接するための層である接着層4aと、粘着剤層側に接する粘着剤近接層4bとを含む。接着層4aは被着体に接着しうる機能を有する限り、特に限定はされない。また接着層4a自体をさらに多層構造とすることもできる。
保護膜形成層に十分な接着性および造膜性(シート加工性)を付与するためにバインダーポリマー成分(A)が用いられる。バインダーポリマー成分(A)としては、従来公知のアクリルポリマー、ポリエステル樹脂、ウレタン樹脂、アクリルウレタン樹脂、シリコーン樹脂、ゴム系ポリマー、フェノキシ樹脂等を用いることができる。
架橋剤は、架橋前のアクリルポリマー100質量部に対して通常0.01~20質量部、好ましくは0.1~10質量部、より好ましくは0.5~5質量部の比率で用いられる。
硬化性成分(B)は、熱硬化性成分および/またはエネルギー線硬化性成分が用いられ、特に熱硬化性成分が好ましく用いられる。
熱硬化性成分としては、エポキシ系熱硬化性成分が挙げられ、エポキシ系熱硬化性成分は、エポキシ系化合物および熱硬化剤からなる。
エネルギー線硬化性成分としては、エネルギー線重合性基を含み、紫外線、電子線等のエネルギー線の照射を受けると重合硬化する低分子化合物(エネルギー線重合性化合物)を用いることができる。このようなエネルギー線硬化性成分として具体的には、トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールモノヒドロキシペンタアクリレート、ジペンタエリスリトールヘキサアクリレートあるいは1,4-ブチレングリコールジアクリレート、1,6-ヘキサンジオールジアクリレート、ポリエチレングリコールジアクリレート、オリゴエステルアクリレート、ウレタンアクリレート系オリゴマー、エポキシ変性アクリレート、ポリエーテルアクリレートおよびイタコン酸オリゴマーなどのアクリレート系化合物等の光重合性炭素-炭素二重結合を含む化合物を用いることができる。
保護膜形成層は、着色剤(C)を含有することが好ましい。保護膜形成層に着色剤を配合することで、半導体装置を機器に組み込んだ際に、周囲の装置から発生する赤外線等を遮蔽し、それらによる半導体装置の誤作動を防止することができ、また保護膜形成層を硬化して得た保護膜に、製品番号等を印字した際の文字の視認性が向上する。すなわち、保護膜を形成された半導体装置や半導体チップでは、保護膜の表面に品番等が通常レーザーマーキング法(レーザー光により保護膜表面を削り取り印字を行う方法)により印字されるが、保護膜が着色剤(C)を含有することで、保護膜のレーザー光により削り取られた部分とそうでない部分のコントラスト差が充分に得られ、視認性が向上する。着色剤(C)としては、有機または無機の顔料および染料が用いられる。これらの中でも電磁波や赤外線遮蔽性の点から黒色顔料が好ましい。黒色顔料としては、カーボンブラック、酸化鉄、二酸化マンガン、アニリンブラック、活性炭等が用いられるが、これらに限定されることはない。半導体装置の信頼性を高める観点からは、カーボンブラックが特に好ましい。着色剤(C)は、1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。本発明における保護膜形成層の高い硬化性は、可視光および/または赤外線と紫外線との両方の透過性を低下させる着色剤を用い、紫外線の透過性が低下した場合に、特に好ましく発揮される。可視光および/または赤外線と紫外線との両方の透過性を低下させる着色剤としては、上記の黒色顔料のほか、可視光および/または赤外線と紫外線との両方の波長領域で吸収性または反射性を有するものであれば特に限定されない。
硬化促進剤(D)を、保護膜形成層の硬化速度を調整するために用いてもよい。硬化促進剤(D)は、特に、硬化性成分(B)において、エポキシ系化合物と熱硬化剤とを併用する場合に好ましく用いられる。
有機化合物と反応しうる基と、無機物表面の官能基と結合しうる基を有するカップリング剤(E)を、保護膜形成層のチップに対する接着性、密着性および/または保護膜の凝集性を向上させるために用いてもよい。また、カップリング剤(E)を使用することで、保護膜形成層を硬化して得られる保護膜の耐熱性を損なうことなく、その耐水性を向上することができる。カップリング剤(E)は保護膜形成層のチップに対する接着性を向上させる観点から、接着層4aに用いることが特に好ましい。
無機充填材(F)を保護膜形成層に配合することにより、硬化後の保護膜における熱膨張係数を調整することが可能となり、半導体チップに対して硬化後の保護膜の熱膨張係数を最適化することで半導体装置の信頼性を向上させることができる。また、硬化後の保護膜の吸湿率を低減させることも可能となる。
保護膜形成層が、エネルギー線硬化性成分を含有する場合には、その使用に際して、紫外線等のエネルギー線を照射して、エネルギー線硬化性成分を硬化させる。この際、光重合開始剤(G)を含有させることで、重合硬化時間ならびに光線照射量を少なくすることができる。
保護膜形成層には、上記の他に、必要に応じて各種添加剤が配合されてもよい。各種添加剤としては、レベリング剤、可塑剤、帯電防止剤、酸化防止剤、イオン捕捉剤、ゲッタリング剤、連鎖移動剤などが挙げられる。
00~1200nmでの全光線透過率を測定し、透過率の最も高い値(最大透過率)とした。
保護膜形成層付ダイシングシートには、使用に供するまでの間、表面の外部との接触を避けるための剥離シートを設けてもよい。剥離シートとしては、たとえば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン酢酸ビニル共重合体フィルム、アイオノマー樹脂フィルム、エチレン・(メタ)アクリル酸共重合体フィルム、エチレン・(メタ)アクリル酸エステル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリイミドフィルム、フッ素樹脂フィルムなどの透明フィルムが用いられる。またこれらの架橋フィルムも用いられる。さらにこれらの積層フィルムであってもよい。また、これらを着色したフィルム、不透明フィルムなどを用いることができる。剥離剤としては、剥離剤としては、例えば、シリコーン系、フッ素系、長鎖アルキル基含有カルバメート等の剥離剤が挙げられる。
保護膜形成層付ダイシングシートは、粘着シート3の粘着剤層2上に、上述の保護膜形成層4を設けてなる。図2に示したように、保護膜形成層は多層構造であってもよい。図1、2で示したように、本発明の保護膜形成層付ダイシングシート10は、基材フィルム1と粘着剤層2とからなる粘着シート3の内周部に保護膜形成層4(または多層保護膜形成層)が剥離可能に積層され、粘着シート3の外周部に粘着剤層2が露出していることが好ましい。つまり、粘着シート3よりも小径の保護膜形成層4(または多層保護膜形成層)が、粘着シート3の粘着剤層2上に同心円状に剥離可能に積層されていることが好ましい。なお、図1においては、保護膜形成層は粘着剤近接層の単層から構成されている。以下、保護膜形成層がこのような単層構成である場合を例にとり説明する。
保護膜形成層付ダイシングシートの製造方法としては、次のような方法が挙げられる。まず、剥離シート上に保護膜形成層を形成する。保護膜形成層は、上記各成分を適宜の割合で、適当な溶媒中で混合してなる保護膜形成層用組成物を、適当な剥離シート上に塗布乾燥して得られる。また、剥離シート上に保護膜形成層用組成物を塗布、乾燥して成膜し、これを別の剥離シートと貼り合わせて、2枚の剥離シートに挟持された状態(剥離シート/保護膜形成層/剥離シート)としてもよい。多層保護膜形成層を作成する場合には、上記の操作を別途行い、2枚の剥離シートに挟持された保護膜形成層を複数準備し、それぞれの剥離シートの1枚を剥離して、保護膜形成層を露出させ、露出した保護膜形成層同士を積層することで、2枚の剥離シートに挟持された多層保護膜形成層を得る。
次に本発明に係る保護膜形成層付ダイシングシート10の利用方法について、該シートをチップ(例えば半導体チップ等)の製造に適用した場合を例にとって説明する。
工程(2):半導体ウエハ(ワーク)と、保護膜形成層または保護膜とをダイシングする工程、
工程(3):保護膜形成層または保護膜と粘着シートとを剥離する工程。
工程(4):保護膜にレーザー印字を行う工程。
保護膜形成層付ダイシングシートを25mmの幅に裁断して試料とし、70℃に加熱しながらシリコンミラーウエハに貼付した。その後保護膜形成層を硬化させるために130℃2時間の熱硬化を行った。硬化した保護膜から粘着シートをJIS Z 0237:2009に準拠して180°で剥離し、粘着力を測定した。なお、上記工程「(2)、(3)、(1)」の順の工程を想定した場合も考え、上記保護膜形成層の熱硬化工程を行わなかった場合の粘着力測定も行った。
厚み350μm、直径6インチ、♯2000研磨を行ったシリコンウエハの研磨面に保護膜形成層付ダイシングシートの保護膜形成層を70℃に加熱しながら貼付した。次いで、保護膜形成層付ダイシングシートを貼付したウエハを130℃の加熱オーブンに2時間投入して、保護膜形成層を硬化させた。次いで、ダイサー(ディスコ株式会社製、DFD651)を用いて、ブレード速度40mm/秒で、基材フィルムに15μmの深さに切り込みが入るようにして3mm×3mmのサイズのチップにウエハをダイスした。その際、チップ飛びの有無を目視で観察した。次いで、ダイボンダー(キャノンマシナリー社製、Bestem-D02)により50個のチップのピックアップを行い、ピックアップできた個数を調べた。なお、上記工程「(2)、(3)、(1)」の順の工程を想定して、上記保護膜形成層の熱硬化工程を行わなかった場合のピックアップ試験も行った。
ピックアップされたチップをプラスチックトレーに入れて1日放置後に、トレーを逆さまにしてチップがトレーに付着していないかどうかを確認した。
また、実施例および比較例において、粘着剤の「エポキシ指数」の測定は、JIS K7236に準拠し、指示薬滴定法にて行った。試料として、ダイシングテープの製造過程において基材上に積層しない状態で採取した粘着剤を、室温で1週間エージングしてから測定に供した。測定用の粘着剤約1.0gをソックスレー中に投入し、ウォーターバス(シバタ社製、SB-6)で沸点以上に加熱した酢酸エチル溶媒の還流により抽出してゾル成分を得た。エポキシ指数の滴定は、酢酸エチル溶媒を揮発し、前記ゾル成分をクロロホルム約50mlで溶解した状態で行った。なお、表1 におけるエポキシ指数は抽出前の粘着剤重量1kg当たりの換算値である。
保護膜形成層を構成する各成分と配合量を下記に示す(各成分/配合量)。
(A)バインダーポリマー成分:n-ブチルアクリレート55質量部、メチルメタクリレート10質量部、グリシジルメタクリレート20質量部、及び2-ヒドロキシエチルアクリレート15質量部からなるアクリルポリマー(重量平均分子量:90万、ガラス転移温度:-28℃) /100質量部
(B)硬化性成分
(B1)ビスフェノールA型エポキシ樹脂(エポキシ当量180-200)50質量部、ジシクロペンタジエン型エポキシ樹脂(大日本インキ化学工業(株)製エピクロンHP-7200HH)50質量部を組み合わせたエポキシ系化合物/(合計100質量部)
(B2)熱活性潜在性エポキシ樹脂硬化剤
ジシアンジアミド(旭電化製、アデカハードナー3636AS):2.8重量部
(C)着色剤:カーボンブラック10.0質量部
(D)硬化促進剤:2-フェニル-4,5-ジヒドロキシメチルイミダゾール(四国化成工業社製, キュアゾール2PHZ)2.8重量部
(E)シランカップリング剤:A-1110(日本ユニカー製)/1重量
(F)シリカフィラー:溶融石英フィラー(平均粒径8μm)/300重量部
厚み100μmのポリプロピレンフィルム CT265(三菱樹脂株式会社製)
(粘着剤A1)
(メタ)アクリル酸エステル重合体(2-エチルヘキシルアクリレート/酢酸ビニル/ヒドロキシエチルアクリレート= 45/40/5(質量比)、重量平均分子量= 約50万) に、メタクリロイルオキシエチルイソシアナートを80%当量(アクリルポリマー100質量部に対し16質量部)反応させたエネルギー線架橋性重合体100質量部に、光重合開始剤(チバ・スペシャリティケミカルズ社製、イルガキュア(登録商標)184)3.5質量部、エポキシ基含有化合物(大日本インキ化学工業(株) 製、商品名エピクロン(登録商標) EXA-4850-150、分子量約900)10質量部、およびイソシアナート化合物(東洋インキ製造社製、BHS-8515)1.07 質量部を配合(すべて固形分換算による配合比)し、粘着剤組成物とした。
エポキシ基含有化合物の配合量を20質量部とした以外は、粘着剤A1と同様にして粘着剤組成物とした。
粘着剤A1において、エネルギー線架橋性重合体を下記のものに代え、光重合開始剤(チバ・スペシャリティケミカルズ社製、イルガキュア(登録商標)184)の配合量を3.25質量部とした以外は、粘着剤A1と同様にして粘着剤組成物を得た。
(メタ)アクリル酸エステル重合体(ブチルアクリレート/アクリル酸メチル/ヒドロキシエチルアクリレート=50/35/15(質量比)、重量平均分子量= 約84万)に、メタクリロイルオキシエチルイソシアナートを80% 当量(アクリルポリマー100質量部に対し16質量部)反応させたエネルギー線架橋性重合体。
エポキシ基含有化合物としてジャパン・エポキシレジン社製、エピコート(登録商標)828(分子量370)を20質量部とした以外は粘着剤A1と同様にして粘着剤組成物とした。
エポキシ基含有化合物としてジャパン・エポキシレジン社製、エピコート(登録商標)806(分子量約330)を20質量部とした以外は粘着剤A1と同様にして粘着剤組成物とした。
(メタ)アクリル酸エステル重合体(ブチルアクリレート/メチルメタクリレート/ヒドロキシエチルアクリレート=70/25/5(質量比)、重量平均分子量=約50万)に、エポキシ基含有化合物( 大日本インキ化学工業(株)製、商品名エピクロン(登録商標)EXA-4850-150、分子量約900)10質量部、およびイソシアナート化合物(東洋インキ製造社製、BHS-8515)10.0質量部を配合(すべて固形分換算による配合比)し、粘着剤組成物とした。
エポキシ基含有化合物を使用しなかった以外は、粘着剤A1と同様にして粘着剤組成物とした。
エポキシ基含有化合物を使用しなかった以外は、粘着剤A3 と同様にして粘着剤組成物とした。
表1に記載の粘着剤を剥離フィルム(リンテック社製、SP-PET3811、厚さ38μm) に乾燥後の塗布量が10g/m2 となるように塗布し100℃ で1分乾燥した後、基材に積層することで粘着シートを得た。次いで、実施例6以外の粘着シートについて、ウエハに貼付される領域の粘着剤層のみに対して、紫外線照射装置(リンテック社製 RAD-2000m/12)を用いて紫外線(照射条件:照度230mW/cm2、光量800mJ/cm2)を照射することにより硬化を行った。
2 … 粘着剤層
3 … 粘着シート
4 … 保護膜形成層
4a… 接着層
4b… 粘着剤近接層
5 … リングフレーム
10… 保護膜形成層付ダイシングシート
Claims (9)
- 粘着成分と遊離のエポキシ基含有化合物とを含む粘着剤層が、基材フィルム上に積層されてなる粘着シートの粘着剤層上に、保護膜形成層を剥離可能に設けた保護膜形成層付ダイシングシート。
- 粘着剤層のエポキシ指数が、0.05eq/kg以上である請求項1に記載の保護膜形成層付ダイシングシート。
- 粘着成分が、エネルギー線硬化性である請求項1または2に記載の保護膜形成層付ダイシングシート。
- 粘着成分が、エネルギー線照射により架橋可能な化合物の架橋物を含有する請求項1または2に記載の保護膜形成層付ダイシングシート。
- 保護膜形成層がバインダーポリマー成分および硬化性成分を含有する請求項1~4の何れかに記載の保護膜形成層付ダイシングシート。
- 硬化性成分が、エポキシ系熱硬化性成分である請求項5に記載の保護膜形成層付ダイシングシート。
- 保護膜形成層が着色剤を含有する請求項1~6の何れかに記載の保護膜形成層付ダイシングシート。
- 請求項1~7のいずれかに記載の保護膜形成層付ダイシングシートの保護膜形成層を、ワークに貼付し、以下の工程(1)~(3)を、(1)、(2)、(3)の順、(2)、(1)、(3)の順または(2)、(3)、(1)の順に行う保護膜付チップの製造方法:
工程(1):保護膜形成層を硬化し保護膜を得る工程、
工程(2):ワークと、保護膜形成層または保護膜とをダイシングする工程、
工程(3):保護膜形成層または保護膜と、粘着シートとを剥離する工程。 - 前記工程(1)の後に何れかの工程において、下記工程(4)を行う請求項8に記載のチップの製造方法:
工程(4):保護膜にレーザー印字を行う工程。
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TW201422757A (zh) | 2014-06-16 |
US9754811B2 (en) | 2017-09-05 |
JP6274588B2 (ja) | 2018-02-07 |
JPWO2014030699A1 (ja) | 2016-07-28 |
TWI592458B (zh) | 2017-07-21 |
JP2016219841A (ja) | 2016-12-22 |
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