WO2018158857A1 - 粘着シート - Google Patents
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- WO2018158857A1 WO2018158857A1 PCT/JP2017/007978 JP2017007978W WO2018158857A1 WO 2018158857 A1 WO2018158857 A1 WO 2018158857A1 JP 2017007978 W JP2017007978 W JP 2017007978W WO 2018158857 A1 WO2018158857 A1 WO 2018158857A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive sheet
- acrylic
- sheet according
- Prior art date
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- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- 238000001721 transfer moulding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
Classifications
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- 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
-
- 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
- C09J7/387—Block-copolymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
-
- 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
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Definitions
- the present invention relates to an adhesive sheet.
- chip size package (CSP) technology has attracted attention as a mounting technology.
- a package in a form of only a chip that does not use a substrate represented by a wafer level package (WLP)
- WLP wafer level package
- a chip to be fixed on a substrate needs to be fixed on another support. Therefore, for example, an adhesive sheet is used as a support for temporarily fixing a chip when manufacturing a semiconductor device (Patent Documents 1 to 4).
- JP 2011-134811 A JP 2012-062373 A JP 2012-168394 A JP 2012-129649 A
- chip displacement the movement of the semiconductor element when sealing the semiconductor element
- An object of the present invention is to prevent chip misalignment when sealing a semiconductor element on an adhesive sheet, and particularly when peeling the adhesive sheet from an adherend when the semiconductor element has a polyimide film. It is providing the adhesive sheet which can make compatible both peelability.
- the present invention is a pressure-sensitive adhesive sheet used when sealing a semiconductor element on a pressure-sensitive adhesive sheet
- the pressure-sensitive adhesive sheet includes a base material and a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive layer has a value determined by a die pull test for silicon in an atmosphere of 100 ° C. of 3.0 N / die or more, and the pressure-sensitive adhesive layer is attached to a polyimide film and heated at 190 ° C. for 1 hour.
- a pressure-sensitive adhesive sheet having an adhesive strength with respect to the polyimide film in an atmosphere at 40 ° C. of 1.0 N / 25 mm or less is obtained.
- the pressure-sensitive adhesive sheet has 0 pressure-sensitive adhesive force on the polyimide film in a 40 ° C. atmosphere after the pressure-sensitive adhesive layer is attached to the polyimide film and heated at 190 ° C. for 1 hour. It is preferably 1 N / 25 mm or more.
- the pressure-sensitive adhesive sheet has a pressure-sensitive adhesive force to the polyimide film at room temperature of 0.4 N after the pressure-sensitive adhesive layer is attached to the polyimide film and heated at 190 ° C. for 1 hour. / 25 mm or more and 10.0 N / 25 mm or less is preferable.
- the storage elastic modulus of the substrate at 100 ° C. is preferably 1 ⁇ 10 7 Pa or more.
- the pressure-sensitive adhesive layer is preferably made of an acrylic pressure-sensitive adhesive composition or a silicone-based pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive layer is preferably made of an acrylic pressure-sensitive adhesive composition.
- the acrylic pressure-sensitive adhesive composition contains an acrylic copolymer, and the acrylic copolymer is a copolymer component derived from a (meth) acrylic acid alkyl ester.
- the alkyl of the (meth) acrylic acid alkyl ester preferably has 6 to 10 carbon atoms.
- the proportion of the mass of the copolymer component derived from the (meth) acrylic acid alkyl ester in the total mass of the acrylic copolymer is 90% by mass or more. Is preferred.
- the acrylic copolymer preferably includes an acrylic copolymer containing 2-ethyl hexyl (meth) acrylate as a main monomer.
- the acrylic copolymer preferably includes a copolymer component derived from a monomer having a hydroxyl group.
- the proportion of the mass of the copolymer component derived from the monomer having a hydroxyl group in the mass of the entire acrylic copolymer is preferably 3% by mass or more.
- the acrylic pressure-sensitive adhesive composition cross-links a composition containing at least the acrylic copolymer and a cross-linking agent mainly composed of a compound having an isocyanate group. It is preferable that the crosslinked product obtained by this is included.
- the acrylic pressure-sensitive adhesive composition contains a pressure-sensitive adhesive auxiliary containing an oligomer having a reactive group.
- the pressure-sensitive adhesive composition comprises at least the acrylic copolymer, the pressure-sensitive adhesive aid, and a cross-linking agent mainly composed of a compound having an isocyanate group. It is preferable to include a crosslinked product obtained by crosslinking the product.
- the pressure-sensitive adhesive layer is made of a silicone-based pressure-sensitive adhesive composition, and the silicone-based pressure-sensitive adhesive composition contains an addition polymerization type silicone resin.
- tip at the time of sealing the semiconductor element on an adhesive sheet, and the favorable at the time of peeling an adhesive sheet from a to-be-adhered body in case a semiconductor element has a polyimide film especially It is possible to provide a pressure-sensitive adhesive sheet that can achieve both excellent peelability.
- FIG. 1 shows a schematic cross-sectional view of the pressure-sensitive adhesive sheet 10 of the present embodiment.
- the pressure-sensitive adhesive sheet 10 has a base material 11 and a pressure-sensitive adhesive layer 12 containing a pressure-sensitive adhesive composition.
- the base material 11 has a first base material surface 11a and a second base material surface 11b opposite to the first base material surface 11a.
- the adhesive layer 12 is laminated
- a release sheet RL is laminated as shown in FIG.
- the shape of the pressure-sensitive adhesive sheet 10 can take any shape such as a tape shape and a label shape.
- the pressure-sensitive adhesive layer 12 of the pressure-sensitive adhesive sheet 10 has a value obtained by a die pull test for silicon in an atmosphere of 100 ° C. of 3.0 N / die or more, and the pressure-sensitive adhesive layer 12 is pasted on a polyimide film. Then, after being heated at 190 ° C. for 1 hour, the adhesive strength to the polyimide film in a 40 ° C. atmosphere (hereinafter sometimes referred to as “adhesive strength in a 40 ° C. atmosphere after heating”) is 1.0 N / 25 mm.
- die shift in some cases.
- the semiconductor element on the pressure-sensitive adhesive sheet is sealed, the semiconductor element moves and is displaced (hereinafter referred to as “die shift” in some cases). Can be prevented.
- the die shift is presumed that the semiconductor element does not slide sideways on the adhesive layer 12, but the semiconductor element peels once from the adhesive layer 12 and moves again after moving. And it shows that it becomes difficult that a semiconductor element peels from the adhesive layer 12, so that the value calculated
- the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet 10 under the above conditions pressure-sensitive adhesive strength in a 40 ° C. atmosphere after heating
- the polyimide film is deposited.
- the adhesive strength is a value measured by a 180 ° peeling method at a peeling speed (pulling speed) of 300 mm / min and a width of the pressure sensitive adhesive sheet of 25 mm, and more specifically, after heating.
- the adhesive strength in a 40 ° C. atmosphere is measured by the method described in Examples described later.
- the value obtained by this die pull test is preferably 3.2 N / die or more, preferably 3.4 N / die or more and 15 N / die or less. It is more preferable that If the value obtained in the die pull test is less than 3.0 N / die, there is a risk of die shifting, and if it exceeds 15 N / die, the circuit surface of the semiconductor element may be destroyed when the semiconductor element is peeled from the adhesive sheet. There is.
- silicone in the atmosphere of 100 degreeC of the adhesive layer 12 can be measured by the method described in the Example mentioned later.
- required by this die pull test the following methods are mentioned.
- required by this die pull test can be adjusted by changing the composition of the adhesive composition used with the adhesive layer 12.
- the adhesive strength of the adhesive sheet 10 under the above conditions is preferably 0.8 N / 25 mm or less, more preferably 0.5 N / 25 mm or less. It is.
- the lower limit of the adhesive strength of the adhesive sheet 10 under the above conditions is preferably 0.1 N / 25 mm or more.
- the adhesive strength of the adhesive sheet 10 (adhesive strength in a 40 ° C. atmosphere after heating)
- the following methods may be mentioned.
- the composition of the pressure-sensitive adhesive composition used in the pressure-sensitive adhesive layer 12 the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet 10 (pressure-sensitive adhesive force in a 40 ° C. atmosphere after heating) can be adjusted.
- the pressure-sensitive adhesive sheet 10 has a pressure-sensitive adhesive force to the polyimide film at room temperature after the pressure-sensitive adhesive layer 12 is attached to the polyimide film and heated at 190 ° C. for 1 hour (hereinafter referred to as “pressure-sensitive adhesive force at room temperature after heating”). Is preferably 0.4 N / 25 mm or more and 10.0 N / 25 mm or less, and more preferably 1.0 N / 25 mm or more and 8.0 N / 25 mm or less. If the adhesive strength at room temperature after heating of the adhesive sheet 10 is within the above range, the adhesive sheet 10 does not peel off from the base material 11 or the adherend at room temperature after heating. It can be easily peeled off by heating. In this specification, room temperature is 23 ° C.
- the substrate 11 is a member that supports the pressure-sensitive adhesive layer 12.
- a sheet material such as a synthetic resin film can be used.
- synthetic resin films include 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.
- examples of the substrate 11 include these cross-linked films and laminated films.
- the base material 11 preferably includes a polyester-based resin, and more preferably includes a material having a polyester-based resin as a main component.
- the material having a polyester-based resin as a main component means that the proportion of the mass of the polyester-based resin in the entire material constituting the base material is 50% by mass or more.
- the polyester resin is, for example, any resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, and copolymer resins of these resins. Is preferred, and polyethylene terephthalate resin is more preferred.
- the lower limit of the storage elastic modulus at 100 ° C. of the substrate 11 is preferably 1 ⁇ 10 7 Pa or more, more preferably 1 ⁇ 10 8 Pa or more, from the viewpoint of dimensional stability during processing.
- the upper limit of the storage elastic modulus at 100 ° C. of the substrate 11 is preferably 1 ⁇ 10 12 Pa or less from the viewpoint of workability.
- the storage elastic modulus at 100 degrees C of the base material 11 is a value of the tensile elastic modulus measured at a frequency of 1 Hz using a viscoelasticity measuring device.
- the substrate to be measured is cut into a width of 5 mm and a length of 20 mm, and a viscoelasticity measuring device (manufactured by TA Instruments, DMAQ800) is used. Measure.
- the first substrate surface 11a may be subjected to at least one surface treatment such as a primer treatment, a corona treatment, and a plasma treatment.
- the adhesive material is apply
- the pressure-sensitive adhesive used for the pressure-sensitive adhesive treatment of the substrate 11 include pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and urethane-based pressure-sensitive adhesives.
- the thickness of the substrate 11 is preferably 10 ⁇ m or more and 500 ⁇ m or less, more preferably 15 ⁇ m or more and 300 ⁇ m or less, and further preferably 20 ⁇ m or more and 250 ⁇ m or less.
- the pressure-sensitive adhesive layer 12 includes a pressure-sensitive adhesive composition.
- the pressure-sensitive adhesive contained in this pressure-sensitive adhesive composition is not particularly limited, and various types of pressure-sensitive adhesives can be applied to the pressure-sensitive adhesive layer 12.
- Examples of the adhesive contained in the adhesive layer 12 include a rubber adhesive, an acrylic adhesive, a silicone adhesive, a polyester adhesive, and a urethane adhesive.
- the kind of adhesive is selected in consideration of the use and the kind of adherend to be attached.
- the pressure-sensitive adhesive layer 12 is preferably made of an acrylic pressure-sensitive adhesive composition or a silicone-based pressure-sensitive adhesive composition, and more preferably made of an acrylic pressure-sensitive adhesive composition. By forming the pressure-sensitive adhesive layer 12 from an acrylic pressure-sensitive adhesive composition, it is possible to effectively reduce adhesive residue.
- an acrylic adhesive composition contains an acrylic copolymer.
- a part or all of the acrylic acid alkyl ester (CH 2 ⁇ CR 1 COOR 2 ) is a (meth) acrylic acid alkyl ester in which the alkyl group R 2 has 6 to 10 carbon atoms.
- Examples of (meth) acrylic acid alkyl esters in which the alkyl group R 2 has 6 to 10 carbon atoms include n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Isooctyl acrylate, n-octyl (meth) acrylate, and n-decyl (meth) acrylate.
- R 2 is preferably a linear or branched alkyl group, more preferably 2-ethylhexyl (meth) acrylate, and more preferably 2-ethylhexyl acrylate.
- the acrylic copolymer preferably includes an acrylic copolymer containing 2-ethylhexyl (meth) acrylate as a main monomer.
- the main monomer is 2-ethylhexyl (meth) acrylate
- the ratio of the weight of the copolymer component derived from 2-ethylhexyl (meth) acrylate to the total weight of the acrylic copolymer is It means 50% by mass or more.
- Examples of the (meth) acrylic acid alkyl ester (CH 2 ⁇ CR 1 COOR 2 ) in which the alkyl group R 2 has 1 to 5 or 11 to 20 carbon atoms include, for example, methyl (meth) acrylate, (meth) acrylic Ethyl acetate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate And stearyl (meth) acrylate.
- the (meth) acrylic acid alkyl ester may be used alone or in combination of two or more.
- the acrylic copolymer is used.
- the first copolymer component in the acrylic copolymer is a (meth) acrylic acid alkyl ester
- a copolymer component other than the (meth) acrylic acid alkyl ester in the acrylic copolymer hereinafter referred to as “th”
- the type and number of “second copolymer component” are not particularly limited.
- a functional group-containing monomer having a reactive functional group is preferable.
- a reactive functional group of a 2nd copolymer component when using the crosslinking agent mentioned later, it is preferable that it is a functional group which can react with the said crosslinking agent.
- This reactive functional group is preferably at least one substituent selected from the group consisting of, for example, a carboxyl group, a hydroxyl group, an amino group, a substituted amino group, and an epoxy group. More preferably, it is any substituent.
- Examples of the monomer having a carboxyl group include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, and citraconic acid. Examples include acids.
- carboxyl group-containing monomers acrylic acid is preferable from the viewpoint of reactivity and copolymerization.
- a carboxyl group-containing monomer may be used independently and may be used in combination of 2 or more type.
- hydroxyl group-containing monomer examples include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic acid 3- And (meth) acrylic acid hydroxyalkyl esters such as hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- 2-hydroxyethyl (meth) acrylate is preferred from the viewpoint of hydroxyl reactivity and copolymerization.
- a hydroxyl-containing monomer may be used independently and may be used in combination of 2 or more type.
- Examples of the acrylate ester having an epoxy group include glycidyl acrylate and glycidyl methacrylate.
- the second copolymer component in the acrylic copolymer in addition to the above, for example, an alkoxyalkyl group-containing (meth) acrylic acid ester, a (meth) acrylic acid ester having an aromatic ring, non-crosslinkable acrylamide And a copolymer component derived from at least one monomer selected from the group consisting of (meth) acrylic acid ester having a non-crosslinkable tertiary amino group, vinyl acetate, and styrene.
- alkoxyalkyl group-containing (meth) acrylic acid ester examples include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, and ethoxyethyl (meth) acrylate. It is done.
- examples of the (meth) acrylic acid ester having an aromatic ring include phenyl (meth) acrylate.
- non-crosslinkable acrylamides include acrylamide and methacrylamide.
- Examples of the (meth) acrylic acid ester having a non-crosslinkable tertiary amino group include (meth) acrylic acid (N, N-dimethylamino) ethyl and (meth) acrylic acid (N, N-dimethylamino). And propyl. These monomers may be used independently and may be used in combination of 2 or more type.
- the second copolymer component in the acrylic copolymer is a copolymer derived from a monomer having a nitrogen atom-containing ring from the viewpoint of improving the polarity of the pressure-sensitive adhesive and improving the adhesion and the adhesive strength. Polymer components are also preferred.
- Monomers having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N- Examples include vinyl morpholine, N-vinyl caprolactam, and N- (meth) acryloyl morpholine.
- N- (meth) acryloylmorpholine is preferable. These monomers may be used independently and may be used in combination of 2 or more type.
- the acrylic copolymer preferably includes a copolymer component derived from a monomer having a hydroxyl group.
- the acrylic copolymer contains a copolymer component derived from a monomer having a hydroxyl group
- a crosslinking agent described later when used, the cohesiveness of the pressure-sensitive adhesive is improved by crosslinking with a hydroxyl group as a crosslinking point, As a result, the adhesiveness of the pressure-sensitive adhesive sheet is improved. Therefore, the die pull test value is improved.
- the ratio of the mass of the copolymer component derived from the monomer having a hydroxyl group to the total mass of the acrylic copolymer is preferably 3% by mass or more, and the upper limit is 9.9% by mass or less. It is preferable.
- the proportion of the mass of the copolymer component derived from the carboxyl group-containing monomer is preferably 1% by mass or less, 0.05 More preferably, the content is from 1% by mass to 1% by mass.
- the weight average molecular weight (Mw) of the acrylic copolymer is preferably from 300,000 to 2,000,000, more preferably from 600,000 to 1,500,000, and even more preferably from 800,000 to 1,200,000. preferable. If the weight average molecular weight Mw of an acrylic copolymer is 300,000 or more, an adhesive sheet can be peeled without the residue of the adhesive to a to-be-adhered body. If the weight average molecular weight Mw of an acrylic copolymer is 2 million or less, an adhesive sheet can be reliably affixed on a to-be-adhered body.
- the weight average molecular weight (Mw) of the acrylic copolymer is a standard polystyrene conversion value measured by a gel permeation chromatography (GPC) method.
- the acrylic copolymer can be produced according to a conventionally known method using the above-mentioned various raw material monomers.
- the form of copolymerization of the acrylic copolymer is not particularly limited, and may be any of a block copolymer, a random copolymer, or a graft copolymer.
- the content of the acrylic copolymer in the acrylic pressure-sensitive adhesive composition is preferably 40% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 90% by mass or less. preferable.
- an acrylic adhesive composition contains an acrylic copolymer and an adhesion aid.
- the acrylic pressure-sensitive adhesive composition contains a pressure-sensitive adhesive agent, for example, the initial tack of the pressure-sensitive adhesive sheet is improved, and peeling when the pressure-sensitive adhesive sheet is attached to the frame can be prevented.
- the adhesion assistant preferably contains an oligomer having a reactive group (hereinafter, the adhesion assistant containing an oligomer having a reactive group may be referred to as a “reactive adhesion assistant”).
- the oligomer is preferably a polymer having a molecular weight of less than 10,000.
- the reactive group in the reactive adhesive aid is a kind selected from the group consisting of a hydroxyl group, an isocyanate group, an amino group, an oxirane group, an acid anhydride group, an alkoxy group, an acryloyl group, and a methacryloyl group.
- the above functional groups are preferable, and a hydroxyl group is more preferable.
- One type or two or more types of reactive groups may be included in the reactive adhesive aid.
- the reactive tackifier having a hydroxyl group may further have another reactive group as described above.
- the number of reactive groups may be one or two or more in one molecule constituting the reactive adhesion assistant.
- the reactive adhesive aid is preferably a rubber material having a reactive group.
- the pressure-sensitive adhesive composition contains a rubber-based material having a reactive group, the effect of improving the elongation at break and reducing the adhesive residue is further enhanced, and it becomes easier to increase the die pull test value.
- the rubber-based material is not particularly limited, but a polybutadiene-based resin and a hydrogenated product of a polybutadiene-based resin are preferable, and a hydrogenated product of a polybutadiene-based resin is more preferable.
- the polybutadiene-based resin include resins having 1,4-repeating units, resins having 1,2-repeating units, and resins having both 1,4-repeating units and 1,2-repeating units.
- the hydrogenated product of the polybutadiene resin of the present embodiment includes a hydride of a resin having these repeating units.
- the polybutadiene resin and the hydrogenated product of the polybutadiene resin preferably have reactive groups at both ends.
- the reactive groups at both ends may be the same or different.
- the reactive groups at both ends are preferably one or more functional groups selected from the group consisting of a hydroxyl group, an isocyanate group, an amino group, an oxirane group, an acid anhydride group, an alkoxy group, an acryloyl group, and a methacryloyl group. More preferably, it is a hydroxyl group.
- both ends are hydroxyl groups.
- the adhesion assistant may contain a non-reactive adhesion assistant, and the non-reactive adhesion assistant may be used in combination with the above-mentioned reactive adhesion assistant.
- the non-reactive adhesion assistant include esters such as acetylcitric acid triester.
- the content of the pressure-sensitive adhesive assistant in the pressure-sensitive adhesive composition is preferably 3% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less. If the content rate of the adhesion promoter in an adhesive composition is 3 mass% or more, generation
- the acrylic pressure-sensitive adhesive composition according to this embodiment includes a cross-linked product obtained by cross-linking a composition containing the above-mentioned acrylic copolymer and a cross-linking agent. Further, the pressure-sensitive adhesive composition according to this embodiment includes a cross-linked product obtained by cross-linking a composition in which the above-mentioned acrylic copolymer, the above-mentioned reactive pressure-sensitive adhesive assistant, and a cross-linking agent are blended. It is also preferable.
- examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent, an amine crosslinking agent, and an amino resin crosslinking agent. These cross-linking agents may be used alone or in combination of two or more.
- a cross-linking agent that is a compound having an isocyanate group is preferable.
- isocyanate-based crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, Polyvalent isocyanates such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, and lysine isocyanate Compounds.
- Polyvalent isocyanates such as diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyan
- polyvalent isocyanate compound may be a trimethylolpropane adduct type modified product of these compounds, a burette type modified product reacted with water, or an isocyanurate type modified product having an isocyanurate ring.
- the acrylic pressure-sensitive adhesive composition is a crosslinked product obtained by crosslinking a composition containing at least the acrylic copolymer described above and a crosslinking agent containing a compound having an isocyanate group as a main component. It is preferable to include. Further, the pressure-sensitive adhesive composition according to the present embodiment is a composition comprising at least the above-mentioned acrylic copolymer, the above-mentioned reactive pressure-sensitive adhesive aid, and a cross-linking agent mainly composed of a compound having an isocyanate group. It is also preferable to contain a cross-linked product obtained by cross-linking.
- the cohesiveness of the pressure-sensitive adhesive is further improved by crosslinking while the die pull test value is further improved, thereby obtaining the effect of suppressing adhesive residue on the adherend. It is done.
- the content of the crosslinking agent in the acrylic pressure-sensitive adhesive composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass with respect to 100 parts by mass of the acrylic copolymer. Part to 15 parts by mass, more preferably 5 parts to 10 parts by mass. If the content of the crosslinking agent in the acrylic pressure-sensitive adhesive composition is within such a range, the die pull test value can be improved.
- the isocyanate-based crosslinking agent is more preferably a compound having an isocyanurate ring (isocyanurate-type modified product).
- the compound having an isocyanurate ring is preferably blended so that the isocyanate group is 0.7 equivalent or more and 1.5 equivalent or less with respect to the hydroxyl equivalent of the acrylic copolymer. If the compounding quantity of the compound which has an isocyanurate ring is 0.7 equivalent or more, the adhesive strength will not become too high after heating, the adhesive sheet will be easily peeled off, and the adhesive residue can be reduced. If the compounding quantity of the compound which has an isocyanurate ring is 1.5 equivalent or less, it can prevent that an initial stage adhesive force becomes low too much, or can prevent a sticking fall.
- the acrylic pressure-sensitive adhesive composition in the present embodiment contains a crosslinking agent
- the acrylic pressure-sensitive adhesive composition preferably further contains a crosslinking accelerator.
- the crosslinking accelerator is preferably selected and used as appropriate according to the type of the crosslinking agent.
- the acrylic pressure-sensitive adhesive composition contains a polyisocyanate compound as a cross-linking agent
- a silicone-type adhesive composition contains a silicone resin, and it is preferable that an addition polymerization type silicone resin is included.
- a silicone pressure-sensitive adhesive composition containing an addition polymerization type silicone resin is referred to as an addition reaction type silicone pressure-sensitive adhesive composition.
- the addition reaction type silicone pressure-sensitive adhesive composition contains a main agent (addition polymerization type silicone resin) and a crosslinking agent.
- the addition reaction type silicone pressure-sensitive adhesive composition has an advantage that it can be used only by primary curing at low temperature and does not require secondary curing at high temperature.
- the conventional peroxide curable silicone pressure-sensitive adhesive requires secondary curing at a high temperature such as 150 ° C. or higher. Therefore, by using the addition reaction type silicone pressure-sensitive adhesive composition, it is possible to produce a pressure-sensitive adhesive sheet at a relatively low temperature, use the base material 11 having excellent energy economy and relatively low heat resistance. Thus, the pressure-sensitive adhesive sheet 10 can be manufactured. Further, since no by-product is produced during curing unlike the peroxide curable silicone pressure-sensitive adhesive, there are no problems such as odor and corrosion.
- the addition reaction type silicone pressure-sensitive adhesive composition is usually composed of a main agent composed of a mixture of a silicone resin component and a silicone rubber component, a hydrosilyl group (SiH group) -containing crosslinking agent, and a curing catalyst used as necessary.
- the silicone resin component is an organopolysiloxane having a network structure obtained by hydrolyzing organochlorosilane or organoalkoxysilane and then performing a dehydration condensation reaction.
- the silicone rubber component is a diorganopolysiloxane having a linear structure.
- organo group examples include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group, both of the silicone resin component and the silicone rubber component.
- the aforementioned organo groups are partially vinyl, hexenyl, allyl, butenyl, pentenyl, octenyl, (meth) acryloyl, (meth) acryloylmethyl, (meth) acryloylpropyl, and cyclohexenyl. It is substituted with an unsaturated group such as a group.
- An organo group having a vinyl group that is easily available industrially is preferred.
- cross-linking proceeds by an addition reaction between the unsaturated group in the main agent and the hydrosilyl group in the cross-linking agent to form a network structure, thereby exhibiting adhesiveness.
- the number of unsaturated groups such as vinyl groups is usually 0.05 or more and 3.0 or less, preferably 0.1 or more and 2.5, per 100 organo groups. It is as follows. By setting the number of unsaturated groups to 100 or more organo groups to 0.05 or more, it is possible to prevent the reactivity with the hydrosilyl group from being lowered and difficult to cure, and to impart appropriate adhesive strength. . By setting the number of unsaturated groups per 100 organo groups to 3.0 or less, the crosslink density of the pressure-sensitive adhesive is increased, thereby preventing the adhesive force and cohesive force from being increased and adversely affecting the adherend surface.
- organopolysiloxane as described above examples include KS-3703 manufactured by Shin-Etsu Chemical Co., Ltd. (the number of vinyl groups is 0.6 with respect to 100 methyl groups), Toray Dow BY23-753 manufactured by Corning Co., Ltd. (the number of vinyl groups is 0.1 with respect to 100 methyl groups), and BY24-162 (the number of vinyl groups is 1.4 with respect to 100 methyl groups). Etc.).
- SD4560PSA, SD4570PSA, SD4580PSA, SD4584PSA, SD4585PSA, SD4587L, and SD4592PSA manufactured by Toray Dow Corning Co., Ltd. can also be used.
- organopolysiloxane which is a silicone resin component
- silicone rubber component KS-3800 manufactured by Shin-Etsu Chemical Co., Ltd. (the number of vinyl groups is methyl) is used. 7.6 for 100 groups), BY24-162 manufactured by Toray Dow Corning Co., Ltd. (for which the number of vinyl groups is 1.4 for 100 methyl groups), BY24- 843 (having no unsaturated group), SD-7292 (having 5.0 vinyl groups per 100 methyl groups), and the like.
- addition polymerization type silicone resin as described above are described in, for example, JP-A-10-219229.
- the cross-linking agent usually has 0.5 to 10 hydrogen atoms bonded to silicon atoms, preferably 1 to one unsaturated group (vinyl group, etc.) of the silicone resin component and the silicone rubber component. It mix
- the number By setting the number to 0.5 or more, the reaction between the unsaturated group (vinyl group and the like) and the hydrosilyl group does not proceed completely, and curing failure is prevented.
- the addition reaction type silicone pressure-sensitive adhesive composition preferably contains a curing catalyst together with the aforementioned addition reaction type silicone component (main agent comprising a silicone resin component and a silicone rubber component) and a crosslinking agent.
- This curing catalyst is used for promoting the hydrosilylation reaction between the unsaturated group in the silicone resin component and the silicone rubber component and the SiH group in the crosslinking agent.
- the curing catalyst is a platinum-based catalyst, that is, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reaction product of chloroplatinic acid and an alcohol solution, a reaction product of chloroplatinic acid and an olefin compound, chloroplatinic acid and vinyl.
- Examples thereof include a reaction product with a group-containing siloxane compound, a platinum-olefin complex, a platinum-vinyl group-containing siloxane complex, and a platinum-phosphorus complex.
- Specific examples of the curing catalyst as described above are described in, for example, JP-A-2006-28311 and JP-A-10-147758. More specifically, examples of commercially available products include SRX-212 manufactured by Toray Dow Corning Co., Ltd., and PL-50T manufactured by Shin-Etsu Chemical Co., Ltd.
- the blending amount thereof is usually 5 mass ppm or more and 2000 mass ppm or less, preferably 10 mass, with respect to the total amount of the silicone resin component and the silicone rubber component as platinum content. It is mass ppm or more and 500 mass ppm or less.
- the addition reaction type silicone pressure-sensitive adhesive composition an adhesive force is exhibited even at room temperature by blending the above-mentioned components, but the addition reaction type silicone pressure-sensitive adhesive composition is applied to the substrate 11 or a release sheet RL described later.
- the silicone resin component and the silicone rubber component by the crosslinking agent are irradiated with heat or active energy rays. It is preferable to promote the crosslinking reaction.
- a pressure-sensitive adhesive sheet having stable adhesive force can be obtained by accelerating the crosslinking reaction by irradiation with heat or active energy rays.
- the heating temperature is usually 60 ° C. or higher and 140 ° C. or lower, preferably 80 ° C. or higher and 130 ° C. or lower. Heating at 60 ° C. or higher prevents the silicone resin component and silicone rubber component from being insufficiently cross-linked and prevents the adhesive force from becoming insufficient. Heating at 140 ° C. or lower causes heat shrinkage to the substrate. Wrinkles can be prevented from being deteriorated or discolored.
- an active energy ray having energy quanta in an electromagnetic wave or a charged particle beam that is, an active light such as an ultraviolet ray or an electron beam
- an active light such as an ultraviolet ray or an electron beam
- a photopolymerization initiator is not required.
- a photopolymerization initiator is present.
- the photopolymerization initiator in the case of crosslinking by ultraviolet irradiation is not particularly limited, and any photopolymerization initiator conventionally used in an ultraviolet curable resin is appropriately selected and used. be able to.
- photopolymerization initiator examples include benzoins, benzophenones, acetophenones, ⁇ -hydroxy ketones, ⁇ -amino ketones, ⁇ -diketones, ⁇ -diketone dialkyl acetals, anthraquinones, thioxanthones, and other compounds. Is mentioned. These photopolymerization initiators may be used alone or in combination of two or more. Further, the amount used is usually 0.01 parts by mass or more and 30 parts by mass or less, preferably 0.05 parts by mass with respect to 100 parts by mass of the total amount of the addition reaction type silicone component and the crosslinking agent used as the main agent. It is selected in the range of 20 parts by mass or less.
- the acceleration voltage of the electron beam is generally 130 kV or more and 300 kV or less, preferably 150 kV or more and 250 kV or less.
- the acceleration voltage of 130 kV or more it is possible to prevent the adhesive force from becoming insufficient due to insufficient crosslinking between the silicone resin component and the silicone rubber component.
- By irradiating with an acceleration voltage of 300 kV or less It can prevent that an adhesive layer and a base material deteriorate or discolor.
- a preferable range of the beam current is 1 mA or more and 100 mA or less.
- the dose of the irradiated electron beam is preferably 1 Mrad or more and 70 Mrad or less, and more preferably 2 Mrad or more and 20 Mrad or less.
- a dose of 1 Mrad or more it is possible to prevent the pressure-sensitive adhesive layer and the substrate from being deteriorated or discolored, and to prevent the adhesiveness from becoming insufficient due to insufficient crosslinking.
- a dose of 70 Mrad or less it is possible to prevent a decrease in cohesive force due to deterioration or discoloration of the pressure-sensitive adhesive layer, and it is possible to prevent the base material from being deteriorated or contracted.
- the irradiation amount in the case of ultraviolet irradiation is appropriately selected.
- the light amount is preferably 100 mJ / cm 2 or more and 500 mJ / cm 2 or less, and the illuminance is preferably 10 mW / cm 2 or more and 500 mW / cm 2 or less.
- Heating and irradiation with active energy rays are preferably performed in a nitrogen atmosphere in order to prevent reaction inhibition by oxygen.
- the pressure-sensitive adhesive composition may contain other components as long as the effects of the present invention are not impaired.
- other components that can be included in the pressure-sensitive adhesive composition include organic solvents, flame retardants, tackifiers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, antiseptics, antifungal agents, and plastics. Agents, antifoaming agents, colorants, fillers, wettability adjusting agents and the like.
- the addition reaction type silicone pressure-sensitive adhesive composition may contain a non-reactive polyorganosiloxane such as polydimethylsiloxane and polymethylphenylsiloxane as an additive.
- the pressure-sensitive adhesive composition according to this embodiment include the following pressure-sensitive adhesive compositions, but the present invention is not limited to such examples.
- an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer.
- an acrylic copolymer obtained by copolymerizing a hydroxyl group-containing monomer wherein the adhesion assistant contains a rubber material having a reactive group as a main component, and the crosslinking agent is an isocyanate crosslinking agent.
- a certain adhesive composition is mentioned.
- an acrylic copolymer, a pressure-sensitive adhesive aid, and a crosslinking agent are included, and the acrylic copolymer is at least 2-ethylhexyl acrylate, a carboxyl group-containing monomer.
- an acrylic copolymer obtained by copolymerizing a hydroxyl group-containing monomer the pressure-sensitive adhesive composition is a hydroxylated hydrogenated polybutadiene at both terminals, and the crosslinking agent is an isocyanate-based crosslinking agent Is mentioned.
- an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, and An acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acrylate, wherein the adhesion assistant contains a rubber material having a reactive group as a main component, and the crosslinking agent is an isocyanate crosslinking agent And a pressure-sensitive adhesive composition.
- an acrylic copolymer, an adhesion assistant, and a crosslinking agent are included, and the acrylic copolymer includes at least 2-ethylhexyl acrylate, acrylic acid, and A pressure-sensitive adhesive composition which is an acrylic copolymer obtained by copolymerizing 2-hydroxyethyl acrylate, wherein the pressure-sensitive adhesive aid is a hydroxylated hydrogenated polybutadiene at both ends, and the cross-linking agent is an isocyanate-based cross-linking agent Things.
- the proportion of the copolymer component derived from 2-ethylhexyl acrylate in the total mass of the acrylic copolymer is 80% by mass or more and 95% by mass. %
- the proportion of the mass of the copolymer component derived from the carboxyl group-containing monomer is 1% by mass or less, and the remainder is preferably another copolymer component. It preferably contains a copolymer component derived from a hydroxyl group-containing monomer.
- the thickness of the pressure-sensitive adhesive layer 12 is appropriately determined according to the use of the pressure-sensitive adhesive sheet 10.
- the thickness of the pressure-sensitive adhesive layer 12 is preferably 5 ⁇ m or more and 60 ⁇ m or less, and more preferably 10 ⁇ m or more and 50 ⁇ m or less.
- the thickness of the pressure-sensitive adhesive layer 12 is 5 ⁇ m or more, the pressure-sensitive adhesive layer 12 easily follows the unevenness of the chip circuit surface, and the generation of a gap can be prevented. Therefore, for example, there is no possibility that the interlayer insulating material, the sealing resin, and the like enter the gaps in the irregularities on the circuit surface of the semiconductor chip, and the electrode pads for wiring connection on the chip circuit surface are blocked.
- the semiconductor chip When the thickness of the pressure-sensitive adhesive layer 12 is 60 ⁇ m or less, the semiconductor chip is unlikely to sink into the pressure-sensitive adhesive layer, and a step between the semiconductor chip portion and the resin portion that seals the semiconductor chip is less likely to occur. Therefore, there is no fear that the wiring is disconnected due to a step during rewiring.
- the release sheet RL is not particularly limited.
- the release sheet RL preferably includes a release substrate and a release agent layer formed by applying a release agent on the release substrate.
- the release sheet RL may include a release agent layer only on one side of the release substrate, or may include a release agent layer on both sides of the release substrate.
- the release substrate include a paper substrate, a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper substrate, and a plastic film.
- the paper substrate include glassine paper, coated paper, and cast coated paper.
- plastic film examples include polyester films (for example, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate), polyolefin films (for example, polypropylene, polyethylene, and the like), and the like.
- release agent examples include olefin-based resins, rubber-based elastomers (for example, butadiene-based resins and isoprene-based resins), long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins, and silicone-based resins.
- the release agent is preferably a non-silicone-based release agent.
- the thickness of the release sheet RL is not particularly limited.
- the thickness of the release sheet RL is usually 20 ⁇ m or more and 200 ⁇ m or less, and preferably 25 ⁇ m or more and 150 ⁇ m or less.
- the thickness of the release agent layer is not particularly limited.
- the thickness of the release agent layer is preferably 0.01 ⁇ m or more and 2.0 ⁇ m or less, and preferably 0.03 ⁇ m or more and 1.0 ⁇ m or less. More preferred.
- the thickness of the plastic film is preferably 3 ⁇ m or more and 50 ⁇ m or less, and more preferably 5 ⁇ m or more and 40 ⁇ m or less.
- the manufacturing method of the adhesive sheet 10 is not particularly limited.
- the adhesive sheet 10 is manufactured through the following processes. First, the pressure-sensitive adhesive composition is applied on the first base material surface 11a of the base material 11 to form a coating film. Next, this coating film is dried to form the pressure-sensitive adhesive layer 12. Then, release sheet RL is stuck so that adhesive layer 12 may be covered.
- another manufacturing method of the adhesive sheet 10 it manufactures through the following processes. First, an adhesive composition is applied on the release sheet RL to form a coating film. Next, the coating film is dried to form the pressure-sensitive adhesive layer 12, and the first base material surface 11 a of the base material 11 is bonded to the pressure-sensitive adhesive layer 12.
- a coating liquid pressure-sensitive adhesive liquid for application
- the organic solvent include toluene, ethyl acetate, and methyl ethyl ketone.
- the method for applying the coating liquid is not particularly limited. Examples of the coating method include spin coating, spray coating, bar coating, knife coating, roll knife coating, roll coating, blade coating, die coating, and gravure coating.
- the coating liquid In order to prevent the organic solvent and the low boiling point component from remaining in the pressure-sensitive adhesive layer 12, it is preferable to apply the coating liquid to the substrate 11 or the release sheet RL, and then heat and dry the coating film.
- a crosslinking agent is blended in the pressure-sensitive adhesive composition, it is preferable to heat the coating film in order to promote the crosslinking reaction and improve the cohesive force.
- the pressure-sensitive adhesive sheet 10 is used when sealing a semiconductor element.
- the pressure-sensitive adhesive sheet 10 is not mounted on a metal lead frame, and is preferably used when sealing a semiconductor element that is stuck on the pressure-sensitive adhesive sheet 10.
- the pressure-sensitive adhesive sheet 10 is not used when sealing a semiconductor element mounted on a metal lead frame, but seals a semiconductor element that is stuck to the pressure-sensitive adhesive layer 12.
- PSP, WLP, etc. are mentioned as a form which packages a semiconductor element, without using metal lead frames.
- the pressure-sensitive adhesive sheet 10 according to the present embodiment has an adhesive strength in a 40 ° C. atmosphere after heating of 1.0 N / 25 mm or less, so that even a relatively large adherend can be easily peeled off.
- the pressure-sensitive adhesive sheet 10 according to the present embodiment can suppress the occurrence of adhesive residue even when the pressure-sensitive adhesive sheet 10 is peeled off in a temperature atmosphere higher than room temperature (for example, a temperature atmosphere of 30 to 60 ° C.).
- a temperature atmosphere higher than room temperature for example, a temperature atmosphere of 30 to 60 ° C.
- the pressure-sensitive adhesive sheet 10 is peeled off at a low speed or the pressure-sensitive adhesive sheet 10 is peeled off at a temperature atmosphere higher than room temperature, thereby reducing the pressure-sensitive adhesive property at the time of peeling.
- the pressure-sensitive adhesive sheet 10 is preferably used for a panel scale package that is relatively large, has a complicated structure, and has a high possibility of breakage during peeling.
- the panel of the panel scale package include circular, elliptical, and quadrangular panels in plan view.
- the diameter is preferably about 200 mm to 450 mm.
- each side is preferably about 300 mm to 800 mm in size.
- the pressure-sensitive adhesive sheet 10 includes a step of attaching a frame member in which a plurality of openings are formed to the pressure-sensitive adhesive sheet 10; a step of attaching a semiconductor chip to the pressure-sensitive adhesive layer 12 exposed at the openings of the frame member; It is preferably used in a process including a step of covering the semiconductor chip with a sealing resin, a step of thermosetting the sealing resin, and a step of peeling the adhesive sheet 10 after thermosetting.
- FIGS. 2A to 2E are schematic views illustrating the method for manufacturing the semiconductor device according to the present embodiment.
- the manufacturing method of the semiconductor device according to the present embodiment includes a step of attaching the frame member 20 in which a plurality of openings 21 are formed on the adhesive sheet 10 (adhesive sheet attaching step), and an opening 21 of the frame member 20.
- a step of bonding the semiconductor chip CP to the exposed adhesive layer 12 (bonding step), a step of covering the semiconductor chip CP with the sealing resin 30 (sealing step), and a step of thermosetting the sealing resin 30 ( A thermosetting step) and a step of peeling the pressure-sensitive adhesive sheet 10 (peeling step) are carried out after thermosetting.
- thermosetting step and a step of peeling the pressure-sensitive adhesive sheet 10 (peeling step) are carried out after thermosetting.
- each step will be described.
- the frame member 20 is formed in a lattice shape and has a plurality of openings 21.
- the frame member 20 is preferably formed of a material having heat resistance. Examples of the material of the frame member include metals such as copper and stainless steel, and heat resistant resins such as polyimide resin and glass epoxy resin.
- the opening 21 is a hole that penetrates the front and back surfaces of the frame member 20.
- the shape of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated in the frame.
- the depth of the hole of the opening 21 is not particularly limited as long as the semiconductor chip CP can be accommodated.
- FIG. 2B shows a schematic diagram for explaining a step of attaching the semiconductor chip CP to the adhesive layer 12.
- the semiconductor chip CP is manufactured, for example, by performing a back grinding process for grinding the back surface of the semiconductor wafer on which the circuit is formed and a dicing process for separating the semiconductor wafer into individual pieces.
- a semiconductor chip CP semiconductor element
- the dicing apparatus is not particularly limited, and a known dicing apparatus can be used.
- the dicing conditions are not particularly limited. Note that a laser dicing method, a stealth dicing method, or the like may be used instead of the dicing method using a dicing blade.
- an expanding process may be performed in which the dicing sheet is extended to widen the interval between the plurality of semiconductor chips CP.
- the semiconductor chip CP can be picked up using a conveying means such as a collet. Further, by performing the expanding step, the adhesive force of the adhesive layer of the dicing sheet is reduced, and the semiconductor chip CP can be easily picked up.
- the energy ray polymerizable compound is blended in the adhesive composition or the adhesive layer of the dicing sheet, the energy ray polymerizable compound is applied to the adhesive layer by irradiating the adhesive layer from the substrate side of the dicing sheet. Harden.
- the energy ray polymerizable compound When the energy ray polymerizable compound is cured, the cohesive force of the adhesive layer is increased, and the adhesive force of the adhesive layer can be reduced.
- the energy rays include ultraviolet rays (UV) and electron beams (EB), and ultraviolet rays are preferable.
- UV ultraviolet rays
- EB electron beams
- the energy beam irradiation may be performed at any stage after the semiconductor wafer is pasted and before the semiconductor chip is peeled off (pickup). For example, the energy beam may be irradiated before or after dicing, or the energy beam may be irradiated after the expanding step.
- the material of the sealing resin 30 is a thermosetting resin, and examples thereof include an epoxy resin.
- the epoxy resin used as the sealing resin 30 may include, for example, a phenol resin, an elastomer, an inorganic filler, a curing accelerator, and the like.
- the method for covering the semiconductor chip CP and the frame member 20 with the sealing resin 30 is not particularly limited. In the present embodiment, an embodiment using a sheet-like sealing resin 30 will be described as an example.
- the sheet-shaped sealing resin 30 is placed so as to cover the semiconductor chip CP and the frame member 20, and the sealing resin 30 is heated and cured to form the sealing resin layer 30A. In this way, the semiconductor chip CP and the frame member 20 are embedded in the sealing resin layer 30A.
- the temperature condition range for heat curing by the vacuum laminating method is, for example, 80 ° C. or more and 120 ° C. or less.
- a laminated sheet in which the sheet-shaped sealing resin 30 is supported by a resin sheet such as polyethylene terephthalate may be used.
- the resin sheet may be peeled off from the sealing resin 30 and the sealing resin 30 may be heated and cured.
- Examples of such a laminated sheet include an ABF film (manufactured by Ajinomoto Fine Techno Co., Ltd.).
- a transfer molding method may be employed.
- the semiconductor chip CP and the frame member 20 adhered to the pressure-sensitive adhesive sheet 10 are accommodated inside the mold of the sealing device.
- a fluid resin material is injected into the mold to cure the resin material.
- the heating and pressure conditions are not particularly limited.
- a temperature of 150 ° C. or higher and a pressure of 4 MPa to 15 MPa are maintained for 30 seconds to 300 seconds.
- the pressure is released, the cured product is taken out from the sealing device, and left in an oven, and a temperature of 150 ° C. or higher is maintained for 2 hours to 15 hours. In this way, the semiconductor chip CP and the frame member 20 are sealed.
- the first heat pressing process may be performed before the process of thermosetting the sealing resin 30 (thermosetting process).
- the semiconductor chip CP and the pressure-sensitive adhesive sheet 10 with the frame member 20 covered with the sealing resin 30 are sandwiched by plate members from both sides, and pressed under conditions of a predetermined temperature, time, and pressure. .
- the sealing resin 30 is easily filled into the gap between the semiconductor chip CP and the frame member 20.
- corrugation of 30 A of sealing resin layers comprised with the sealing resin 30 can also be planarized by implementing a heat press process.
- the plate member for example, a metal plate such as stainless steel can be used.
- the sealing body 50 When the pressure-sensitive adhesive sheet 10 is peeled after the thermosetting step, the semiconductor chip CP and the frame member 20 sealed with the sealing resin 30 are obtained. Hereinafter, this may be referred to as a sealing body 50.
- FIG. 2D The schematic diagram explaining the process of sticking the reinforcing member 40 to the sealing body 50 is shown by FIG. 2D.
- a rewiring process and a bumping process for forming a rewiring layer on the exposed circuit surface of the semiconductor chip CP are performed.
- a process (reinforcing member attaching process) of attaching the reinforcing member 40 to the sealing body 50 is performed as necessary. May be.
- FIG. As illustrated in FIG. 2D, the sealing body 50 is supported in a state of being sandwiched between the adhesive sheet 10 and the reinforcing member 40.
- the reinforcing member 40 includes a heat-resistant reinforcing plate 41 and a heat-resistant adhesive layer 42.
- the reinforcing plate 41 include a plate-like member containing a heat resistant resin such as a polyimide resin and a glass epoxy resin.
- the adhesive layer 42 adheres the reinforcing plate 41 and the sealing body 50.
- the adhesive layer 42 is appropriately selected according to the material of the reinforcing plate 41 and the sealing resin layer 30A.
- the adhesive layer 42 is preferably a glass cloth including a thermoplastic resin.
- the thermoplastic resin contained bismaleimide triazine resin (BT resin) is preferable.
- the adhesive layer 42 is sandwiched between the sealing resin layer 30A of the sealing body 50 and the reinforcing plate 41, and is further sandwiched between the reinforcing plate 41 side and the adhesive sheet 10 side by plate members, respectively. It is preferable to carry out the second hot pressing step of pressing under the conditions of temperature, time and pressure.
- the sealing body 50 and the reinforcing member 40 are temporarily fixed by the second heating press process. In order to cure the adhesive layer 42 after the second heat pressing step, it is preferable to heat the temporarily fixed sealing body 50 and the reinforcing member 40 under conditions of a predetermined temperature and time.
- the conditions for heat curing are appropriately set according to the material of the adhesive layer 42, and are, for example, 185 ° C., 80 minutes, and 2.4 MPa.
- a metal plate such as stainless steel can be used as the plate-like member.
- FIG. 2E The schematic explaining the process of peeling the adhesive sheet 10 is shown by FIG. 2E.
- the adhesive sheet 10 when the base material 11 of the adhesive sheet 10 is bendable, the adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A while being bent.
- peeling angle (theta) is not specifically limited, It is preferable to peel the adhesive sheet 10 with peeling angle (theta) of 90 degree
- the peeling angle ⁇ is 90 degrees or more, the pressure-sensitive adhesive sheet 10 can be easily peeled from the frame member 20, the semiconductor chip CP, and the sealing resin layer 30A.
- the peeling angle ⁇ is preferably 90 degrees or more and 180 degrees or less, and more preferably 135 degrees or more and 180 degrees or less.
- the temperature atmosphere at the time of peeling the pressure-sensitive adhesive sheet 10 may be room temperature, but when there is a concern about the destruction of each member of the adherend and the interface between the members at the time of peeling, the pressure-sensitive adhesive of the pressure-sensitive adhesive For the purpose of lowering, the pressure-sensitive adhesive sheet 10 may be peeled in a temperature atmosphere higher than room temperature.
- the temperature atmosphere higher than room temperature is preferably in the range of 30 to 60 ° C, more preferably in the range of 35 to 50 ° C.
- the aforementioned reinforcing member sticking step may be performed as necessary.
- “bendable” means, for example, that it can be wound in a roll shape and has a flexibility that can sufficiently prevent damage even when wound in a roll shape. Means.
- the reinforcing member 40 When the reinforcing member 40 is attached, the reinforcing member 40 is peeled off from the sealing body 50 at the stage where the support by the reinforcing member 40 becomes unnecessary after the rewiring process and the bumping process are performed. Thereafter, the sealing body 50 is separated into individual semiconductor chips CP (individualization step).
- a method for dividing the sealing body 50 into individual pieces is not particularly limited.
- the semiconductor wafer can be separated into pieces by the same method as that used when dicing the semiconductor wafer.
- the step of dividing the sealing body 50 into pieces may be performed in a state where the sealing body 50 is adhered to a dicing sheet or the like.
- the adhesive sheet 10 it is possible to prevent the chip from being displaced when sealing the semiconductor element on the adhesive sheet, and in particular, when the semiconductor element has a polyimide film, the adhesive sheet is attached to the adherend.
- the pressure-sensitive adhesive sheet 10 having good releasability that hardly causes adhesive residue when peeled off.
- the adhesive sheet 10 may be a sheet piece, and may be provided in a state in which a plurality of adhesive sheets 10 are laminated.
- the pressure-sensitive adhesive layer 12 may be covered with the base material 11 of another pressure-sensitive adhesive sheet to be laminated.
- the pressure-sensitive adhesive sheet 10 may be a belt-like sheet or may be provided in a state of being wound in a roll shape. The pressure-sensitive adhesive sheet 10 wound up in a roll shape can be used by being unwound from a roll and cut into a desired size.
- the sealing resin 30 may be an energy ray curable resin that is cured by energy rays such as ultraviolet rays.
- the adhesive sheet 10 may be used in a method for manufacturing a semiconductor device that seals a semiconductor element without using a frame member.
- a passivation film such as polyimide resin may be provided on the circuit surface of the semiconductor chip CP.
- the adhesive sheet 10 is more easily peeled off.
- the sealing body 50 When the pressure-sensitive adhesive sheet 10 is peeled off, the sealing body 50 may be held by suction means such as a suction table. If it is the adhesive sheet 10, it can peel without destroying the sealing body 50, and it can peel, without moving the sealing body 50 from an adsorption
- Wafer single-sided mirror silicon wafer with a thickness of 750 ⁇ m and an 8-inch size
- Back grinding tape E-8180HR (manufactured by Lintec Corporation)
- dicing tape D-174A (manufactured by Lintec Corporation)
- Grinding device “DFG-8540” manufactured by DISCO Corporation
- a double-sided tape DF (TL-4100S-50, manufactured by Lintec Corporation) is applied to the entire surface of the backing aluminum plate AB (150 mm ⁇ 75 mm size) shown in FIG.
- the semiconductor chips CP were arranged in two rows in the direction along the short side of the rectangular shape of the aluminum plate AB and in four columns in the direction along the long side. At that time, the semiconductor chip CP was gently and vertically installed so that the corner of the semiconductor chip CP was not applied to the adhesive layer 12.
- the sample prepared in the above (d) was vacuum laminated using a vacuum laminator under the following conditions. When vacuum laminating, as shown in FIG. 3E, two release films LF (thickness: 38 ⁇ m) were arranged on the top and bottom, and vacuum laminating was performed.
- Vacuum laminator NISSHINBO ⁇ Temperature: 100 °C -Pressure: 100 Pa, Degree of vacuum: No setting (full pull), Press: No setting (differential pressure from atmospheric pressure) ⁇ Lamination speed: High speed mode ⁇ Program: 60 seconds after evacuation, 40 seconds with high speed lamination ⁇ After temperature setting, lamination was performed after 1 hour, and before the actual sample lamination, the sample was idled once.
- the sample vacuum-laminated in (e) above was placed on a pull tester (“Dage4000” manufactured by Nordson Advanced Technology Co., Ltd.) and preheated to 100 ° C.
- G As shown in FIG.
- the pull block PB with the double-sided tape DF2 (TL-4100S-50, manufactured by Lintec Corporation) is placed on the semiconductor chip CP as shown in FIG. 3G.
- a force of 2N was applied per second.
- a die pull test is performed as shown in FIG. 3H, the displacement and force of the load cell are measured, and the force peak value is applied to one die (semiconductor chip CP). (Unit: N / die).
- the semiconductor chip on the adhesive sheet is sealed with a sealing resin (ABF film of Ajinomoto Fine Techno Co., Ltd., GX T-31). did.
- the sealing conditions are as follows. -Preheating temperature: 100 ° C for both table and diaphragm ⁇ Vacuum evacuation: 60 seconds ⁇ Dynamic press mode: 30 seconds ⁇ Static press mode: 10 seconds Then, the semiconductor chip on the adhesive sheet after embedding was observed visually and under a microscope to confirm whether the semiconductor chip was misaligned or not. .
- the pressure-sensitive adhesive sheet prepared in Example 1 was cut to a width of 25 mm, and the pressure-sensitive adhesive surface of the cut pressure-sensitive adhesive sheet was attached to an adherend (polyimide film) with a load of 2 kgf.
- adherend polyimide film
- Kapton 100H product name
- This polyimide film-attached pressure-sensitive adhesive sheet is stored for 0.5 hours in an environment of 25 ° C. and 50% relative humidity, and then using a thermostat (PHH-202, manufactured by ESPEC Corporation) under the conditions of 190 ° C. and 1 hour. Heated.
- the pressure-sensitive adhesive sheet with the polyimide film was stored for 1 hour in an environment of 25 ° C. and 50% relative humidity, and then the peeling angle was 180 °, the peeling speed was 300 mm / min, and the adhesive was allowed to occur at room temperature and 40 ° C. atmosphere.
- the adhesive strength after heating of the adhesive sheet when the sheet was peeled from the polyimide film was measured.
- a measuring device a measuring device with a thermostatic bath (manufactured by A & D, TENSILON) was used.
- the adhesive strength after heating was measured in the same manner as described above.
- the pressure-sensitive adhesive sheet produced in Example 1 was cut to a width of 25 mm, and the pressure-sensitive adhesive surface of the cut pressure-sensitive adhesive sheet and an adherend (a semiconductor wafer provided with a circuit surface having a polyimide film; diameter 150 mm, thickness 200 ⁇ m) The surfaces were pasted together. At this time, bonding was performed by applying a load of 2 kgf. After the pressure-sensitive adhesive sheet affixed to the semiconductor wafer is stored in an environment of 25 ° C. and 50% relative humidity for 0.5 hours, it is subjected to conditions of 190 ° C. and 1 hour using a thermostat (PHH-202, manufactured by ESPEC Corporation). And heated.
- a thermostat PH-202, manufactured by ESPEC Corporation
- the adhesive sheet affixed to the semiconductor wafer is stored in an environment of 25 ° C. and 50% relative humidity for 1 hour, and then the peeling angle is set to 180 °, the peeling speed is set to 300 mm / min, and the adhesive sheet is attached in an atmosphere of 40 ° C.
- the sheet was peeled from the semiconductor wafer.
- a peeling device a measuring device with a thermostatic bath (manufactured by A & D, TENSILON) was used. The semiconductor wafer after peeling an adhesive sheet was observed visually and the residue of the semiconductor wafer surface was confirmed.
- Example 1 Preparation of adhesive sheet.
- the following materials polymer, pressure-sensitive adhesive, cross-linking agent, and diluting solvent) were blended and sufficiently stirred, and the pressure-sensitive adhesive liquid for coating according to Example 1 (pressure-sensitive adhesive composition) Prepared).
- Acrylic ester copolymer 40 parts by mass (solid content)
- the acrylic ester copolymer was prepared by copolymerizing 92.8% by mass of 2-ethylhexyl acrylate, 7.0% by mass of 2-hydroxyethyl acrylate, and 0.2% by mass of acrylic acid.
- the weight average molecular weight of the obtained polymer was 850,000.
- Adhesion aid hydroxylated hydrogenated polybutadiene at both ends (Nippon Soda Co., Ltd .; GI-1000), 5 parts by mass (solid content)
- Crosslinking agent Aliphatic isocyanate having hexamethylene diisocyanate (isocyanurate-type modified product of hexamethylene diisocyanate) [manufactured by Nippon Polyurethane Industry Co., Ltd .; Coronate HX], 3.5 parts by mass (solid content)
- Diluting solvent Methyl ethyl ketone was used, and the solid content concentration of the coating adhesive solution was adjusted to 30% by mass.
- Comparative Example 1 The pressure-sensitive adhesive sheet according to Comparative Example 1 was used except that 5 parts by mass (solid content) of tributyl acetyl citrate (ATBC) [manufactured by Taoka Chemical Industry Co., Ltd.] was used as a pressure-sensitive adhesive aid contained in the pressure-sensitive adhesive layer. It was produced in the same manner as in Example 1.
- ATBC tributyl acetyl citrate
- Comparative Example 2 The pressure-sensitive adhesive sheet according to Comparative Example 2 was produced in the same manner as in Example 1 except that the polymer contained in the pressure-sensitive adhesive layer was different from that in Example 1.
- the polymer used in Comparative Example 2 was composed of 80.8% by mass of 2-ethylhexyl acrylate, 7% by mass of 2-hydroxyethyl acrylate, 12% by mass of N-acryloylmorpholine, and 0.2% by mass of acrylic acid. Prepared by copolymerization. The weight average molecular weight of the obtained polymer was 760,000.
- Comparative Example 3 The pressure-sensitive adhesive sheet according to Comparative Example 3 was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive layer did not contain a pressure-sensitive adhesive aid.
- Table 1 shows the evaluation results of the pressure-sensitive adhesive sheets according to Example 1 and Comparative Examples 1 to 3.
- the pressure-sensitive adhesive sheet according to Example 1 has a value obtained by a die pull test for silicon in an atmosphere of 100 ° C. of the pressure-sensitive adhesive layer of 3.0 N / die or more, and the pressure-sensitive adhesive sheet After the adhesive layer is attached to the polyimide film and heated at 190 ° C for 1 hour, the adhesive force to the polyimide film in a 40 ° C atmosphere is 1.0 N / 25 mm or less, so that die shift can be prevented and after heating It was confirmed that the peelability of the film was also good.
- the pressure-sensitive adhesive sheet according to Comparative Example 1 is considered to have failed to prevent die shift because the value obtained by the die pull test for silicon in an atmosphere of 100 ° C.
- the pressure-sensitive adhesive sheet according to Comparative Examples 2 to 3 had a pressure-sensitive adhesive strength of 1.0 N / 25 mm with respect to the polyimide film in a 40 ° C. atmosphere after the pressure-sensitive adhesive layer was attached to the polyimide film and heated at 190 ° C. for 1 hour. Since it exceeds, it is thought that it is inferior to peelability after a heating.
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Abstract
Description
[粘着シート]
図1には、本実施形態の粘着シート10の断面概略図が示されている。
粘着シート10は、基材11と、粘着剤組成物を含む粘着剤層12とを有する。
基材11は、第一基材面11a、及び第一基材面11aとは反対側の第二基材面11bを有する。本実施形態の粘着シート10においては、第一基材面11aに粘着剤層12が積層されている。粘着剤層12の上には、図1に示されているように、剥離シートRLが積層されている。
粘着シート10の形状は、例えば、テープ状、及びラベル状等、あらゆる形状をとり得る。
ダイプル試験で求められる値が3.0N/ダイ以上であれば、粘着シート上の半導体素子を封止する際に、半導体素子が移動して位置がずれること(以下、「ダイシフト」と称する場合がある)を防止できる。このような理由は、必ずしも明らかではないが、次のようなメカニズムによると推定する。すなわち、ダイシフトは、半導体素子が粘着剤層12上を横滑りしているわけではなく、半導体素子が一度粘着剤層12から剥離し、移動した後に再び粘着していると推定する。そして、ダイプル試験で求められる値が高いほど、半導体素子が粘着剤層12から剥離することが困難となることを示す。そのため、ダイプル試験で求められる値とダイシフトとの間に相関関係があると推定する。
また、前記条件下での粘着シート10の粘着力(加熱後の40℃雰囲気での粘着力)が1.0N/25mm以下であると、加熱後であっても、特に、ポリイミド膜が被着面である場合に、粘着シート10を被着体から剥離する際に糊残りが発生することもない。
なお、本明細書において、粘着力は、180°引き剥がし法により、剥離速度(引っ張り速度)300mm/分、粘着シートの幅25mmにて測定した値であり、より具体的には、加熱後の40℃雰囲気での粘着力は、後述の実施例に記載の方法により測定される。
ダイプル試験で求められる値が、3.0N/ダイ未満であると、ダイシフトするおそれがあり、15N/ダイを超えると粘着シートから半導体素子を剥離するときに、半導体素子の回路面を破壊するおそれがある。
なお、このダイプル試験で求められる値を調整する方法としては、以下のような方法が挙げられる。例えば、粘着剤層12で用いる粘着剤組成物の組成を変更することで、このダイプル試験で求められる値を調整できる。
前記条件下での粘着シート10の粘着力(加熱後の40℃雰囲気での粘着力)の下限値は、0.1N/25mm以上であることが好ましい。
粘着シート10の加熱後の室温での粘着力が、上記範囲の粘着力であれば、粘着シート10は、加熱後の室温においては基材11または被着体から剥がれ落ちることがなく、剥離時には、加熱することで容易に剥離することができる。
なお、本明細書において、室温とは、23℃である。
基材11は、粘着剤層12を支持する部材である。
基材11としては、例えば、合成樹脂フィルム等のシート材料等を用いることができる。合成樹脂フィルムとしては、例えば、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、及びポリイミドフィルム等が挙げられる。その他、基材11としては、これらの架橋フィルム及び積層フィルム等が挙げられる。
基材11としては、ポリエチレンテレフタレートフィルム、またはポリエチレンナフタレートフィルムが好ましく、ポリエチレンテレフタレートフィルムがより好ましい。
なお、本明細書において、基材11の100℃での貯蔵弾性率は、粘弾性測定機器を用いて、周波数1Hzで測定した引張弾性率の値である。測定する基材を幅5mm、長さ20mmに切断し、粘弾性測定機器(ティー・エイ・インスツルメント社製、DMAQ800)を使用し、周波数1Hz、引張モードにより、100℃の貯蔵粘弾率を測定する。
本実施形態に係る粘着剤層12は、粘着剤組成物を含んでいる。この粘着剤組成物に含まれる粘着剤としては、特に限定されず、様々な種類の粘着剤を粘着剤層12に適用できる。粘着剤層12に含まれる粘着剤としては、例えば、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、及びウレタン系粘着剤等が挙げられる。なお、粘着剤の種類は、用途及び貼着される被着体の種類等を考慮して選択される。粘着剤層12は、アクリル系粘着剤組成物、またはシリコーン系粘着剤組成物からなることが好ましく、アクリル系粘着剤組成物からなることがより好ましい。粘着剤層12がアクリル系粘着剤組成物からなることにより、効果的に糊残りを減少させることができる。
粘着剤層12がアクリル系粘着剤組成物からなる場合、アクリル系粘着剤組成物は、アクリル系共重合体を含むことが好ましい。この場合、アクリル系共重合体は、(メタ)アクリル酸アルキルエステル(CH2=CR1COOR2(R1は水素またはメチル基、R2は直鎖、分岐鎖または環状(脂環式)のアルキル基))に由来する共重合体成分を含むことが好ましい。また、アクリル酸アルキルエステル(CH2=CR1COOR2)の一部または全部が、アルキル基R2の炭素数が6~10である(メタ)アクリル酸アルキルエステルであることが好ましい。アルキル基R2の炭素数が6~10である(メタ)アクリル酸アルキルエステルとしては、(メタ)アクリル酸n-ヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n-オクチル、及び(メタ)アクリル酸n-デシル等が挙げられる。これらの中でも、R2が直鎖または分岐鎖のアルキル基であることが好ましく、(メタ)アクリル酸2-エチルヘキシルがより好ましく、アクリル酸2-エチルヘキシルがさらに好ましい。
本実施形態においては、アクリル系共重合体は、(メタ)アクリル酸2-エチルヘキシルを主たるモノマーとするアクリル系共重合体を含むことが好ましい。
本明細書において、(メタ)アクリル酸2-エチルヘキシルを主たるモノマーとするとは、アクリル系共重合体全体の質量に占める、(メタ)アクリル酸2-エチルヘキシル由来の共重合体成分の質量の割合が50質量%以上であることを意味する。
(メタ)アクリル酸アルキルエステルは、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。
なお、本明細書における「(メタ)アクリル酸」は、「アクリル酸」及び「メタクリル酸」の双方を表す場合に用いる表記であり、他の類似用語についても同様である。
本実施形態においては、アクリル系共重合体は、前記CH2=CR1COOR2を主たるモノマーとするアクリル系共重合体を含むことが好ましい。
本明細書において、CH2=CR1COOR2を主たるモノマーとするとは、アクリル系共重合体全体の質量に占める、CH2=CR1COOR2由来の共重合体成分の質量の割合が50質量%以上であることを意味する。
芳香族環を有する(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸フェニル等が挙げられる。
非架橋性のアクリルアミドとしては、例えば、アクリルアミド、及びメタクリルアミド等が挙げられる。
非架橋性の3級アミノ基を有する(メタ)アクリル酸エステルとしては、例えば、(メタ)アクリル酸(N,N-ジメチルアミノ)エチル、及び(メタ)アクリル酸(N,N-ジメチルアミノ)プロピル等が挙げられる。
これらのモノマーは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。
窒素原子含有環を有するモノマーとしては、N-ビニル-2-ピロリドン、N-メチルビニルピロリドン、N-ビニルピペリドン、N-ビニルピペラジン、N-ビニルピラジン、N-ビニルピロール、N-ビニルイミダゾール、N-ビニルモルホリン、N-ビニルカプロラクタム、及びN-(メタ)アクリロイルモルホリン等が挙げられる。窒素原子含有環を有するモノマーとしては、N-(メタ)アクリロイルモルホリンが好ましい。
これらのモノマーは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。
アクリル系共重合体が、水酸基を有するモノマーに由来する共重合体成分を含むことで、後述する架橋剤を使用する場合に、水酸基を架橋点とした架橋により粘着剤の凝集性が向上し、その結果、粘着シートの接着性が向上する。よって、ダイプル試験値が向上する。
アクリル系共重合体全体の質量に占める、水酸基を有するモノマーに由来する共重合体成分の質量の割合は、3質量%以上であることが好ましく、上限としては、9.9質量%以下であることが好ましい。
アクリル系共重合体の重量平均分子量(Mw)は、ゲル・パーミエーション・クロマトグラフィー(Gel Permeation Chromatography;GPC)法により測定される標準ポリスチレン換算値である。
アクリル系粘着剤組成物が反応性粘着助剤を含むことで、上記の効果に加えて、破断伸度を向上させ糊残りを減少させることができる。また、ダイプル試験値を上昇させることが容易となる。
ポリブタジエン系樹脂としては、1,4-繰り返し単位を有する樹脂、1,2-繰り返し単位を有する樹脂、並びに1,4-繰り返し単位及び1,2-繰り返し単位の両方を有する樹脂が挙げられる。本実施形態のポリブタジエン系樹脂の水素添加物は、これらの繰り返し単位を有する樹脂の水素化物も含む。
また、粘着剤組成物全体の質量に占める、反応性粘着助剤の質量の割合は、3質量%以上50質量%以下であることが好ましく、5質量%以上30質量%以下であることがより好ましい。
また、本実施形態に係る粘着剤組成物は、前述のアクリル系共重合体と、前述の反応性粘着助剤と、さらに架橋剤とを配合した組成物を架橋させて得られる架橋物を含むことも好ましい。
また、多価イソシアネート化合物は、これら化合物のトリメチロールプロパンアダクト型変性体、水と反応させたビュウレット型変性体、またはイソシアヌレート環を有するイソシアヌレート型変性体であってもよい。
また、本実施形態に係る粘着剤組成物は、前述のアクリル系共重合体と、前述の反応性粘着助剤と、イソシアネート基を有する化合物を主成分とする架橋剤とを少なくとも配合した組成物を架橋させて得られる架橋物を含むことも好ましい。
前述の架橋物を含むアクリル系粘着剤組成物であれば、ダイプル試験値がより向上されつつ、架橋により粘着剤の凝集性がより向上するため、被着体への糊残りの抑制効果が得られる。
粘着剤層12がシリコーン系粘着剤組成物をからなる場合、シリコーン系粘着剤組成物は、シリコーン樹脂を含むことが好ましく、付加重合型シリコーン樹脂を含むことが好ましい。本明細書において、付加重合型シリコーン樹脂を含むシリコーン系粘着剤組成物を付加反応型シリコーン系粘着剤組成物と称する。
したがって、付加反応型シリコーン系粘着剤組成物を用いることにより、比較的低温での粘着シートの製造が可能となり、エネルギー経済性に優れており、かつ、比較的耐熱性の低い基材11を用いて粘着シート10を製造することも可能となる。また、過酸化物硬化型シリコーン系粘着剤のように硬化時に副生物を生じないので、臭気及び腐食等の問題もない。
シリコーン樹脂成分は、オルガノクロルシランまたはオルガノアルコキシシランを加水分解した後、脱水縮合反応を行うことにより得られる網状構造のオルガノポリシロキサンである。
シリコーンゴム成分は、直鎖構造を有するジオルガノポリシロキサンである。
オルガノ基としては、シリコーン樹脂成分、及びシリコーンゴム成分ともに、例えば、メチル基、エチル基、プロピル基、ブチル基、及びフェニル基等である。前述のオルガノ基は、一部、ビニル基、ヘキセニル基、アリル基、ブテニル基、ペンテニル基、オクテニル基、(メタ)アクリロイル基、(メタ)アクリロイルメチル基、(メタ)アクリロイルプロピル基、及びシクロヘキセニル基等のような不飽和基に置換されている。工業的に入手が容易なビニル基を有するオルガノ基が好ましい。
付加反応型シリコーン系粘着剤組成物においては、主剤における不飽和基と、架橋剤におけるヒドロシリル基との付加反応によって架橋が進行して網状の構造が形成され、粘着性が発現する。
この硬化触媒は、シリコーン樹脂成分及びシリコーンゴム成分中の不飽和基と、架橋剤中のSiH基とのヒドロシリル化反応を促進させるために使用される。
硬化触媒としては、白金系の触媒、すなわち、塩化白金酸、塩化白金酸のアルコール溶液、塩化白金酸とアルコール溶液との反応物、塩化白金酸とオレフィン化合物との反応物、塩化白金酸とビニル基含有シロキサン化合物との反応物、白金-オレフィン錯体、白金-ビニル基含有シロキサン錯体、及び白金-リン錯体等が挙げられる。前述のような硬化触媒の具体例は、例えば、特開2006-28311号公報及び特開平10-147758号公報に記載されている。
より具体的には、市販品として、例えば東レ・ダウコーニング株式会社製のSRX-212、及び信越化学工業株式会社製のPL-50T等が挙げられる。
紫外線照射により架橋させる場合の光重合開始剤としては、特に制限はなく、従来、紫外線硬化型樹脂に慣用されている光重合開始剤の中から、任意の光重合開始剤を適宜選択して用いることができる。この光重合開始剤としては、例えばベンゾイン類、ベンゾフェノン類、アセトフェノン類、α-ヒドロキシケトン類、α-アミノケトン類、α-ジケトン類、α-ジケトンジアルキルアセタール類、アントラキノン類、チオキサントン類、その他化合物等が挙げられる。
これらの光重合開始剤は、単独で用いてもよく、二種以上を組み合わせて用いてもよい。また、その使用量は、主剤として用いられる前記付加反応型シリコーン成分と架橋剤との合計量100質量部に対し、通常、0.01質量部以上30質量部以下、好ましくは0.05質量部以上20質量部以下の範囲で選定される。
照射される電子線の線量は、1Mrad以上70Mrad以下が好ましく、2Mrad以上20Mrad以下がより好ましい。1Mrad以上の線量で照射することにより、粘着剤層及び基材が劣化したり変色したりするのを防止し、架橋不足により粘着性が不十分になるのを防止することができる。70Mrad以下の線量で照射することにより、粘着剤層が劣化したり変色したりすることによる凝集力の低下を防止し、基材が劣化したり収縮したりするのを防止することができる。
紫外線照射の場合の照射量としては、適宜選択されるが、光量は、100mJ/cm2以上500mJ/cm2以下、照度は、10mW/cm2以上500mW/cm2以下であることが好ましい。
加熱及び活性エネルギー線の照射は、酸素による反応阻害を防止するため、窒素雰囲気下で行うことが好ましい。
付加反応型シリコーン系粘着剤組成物には、添加剤として、ポリジメチルシロキサン及びポリメチルフェニルシロキサン等のような非反応性のポリオルガノシロキサンが含まれていてもよい。
本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、粘着助剤と、架橋剤とを含み、前記アクリル系共重合体が、少なくともアクリル酸2-エチルヘキシル、カルボキシル基含有モノマー、及び水酸基含有モノマーを共重合して得られるアクリル系共重合体であり、前記粘着助剤が、反応性基を有するゴム系材料を主成分として含み、前記架橋剤が、イソシアネート系架橋剤である粘着剤組成物が挙げられる。
本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、粘着助剤と、架橋剤とを含み、前記アクリル系共重合体が、少なくともアクリル酸2-エチルヘキシル、カルボキシル基含有モノマー、及び水酸基含有モノマーを共重合して得られるアクリル系共重合体であり、前記粘着助剤が、両末端水酸基水素化ポリブタジエンであり、前記架橋剤が、イソシアネート系架橋剤である粘着剤組成物が挙げられる。
本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、粘着助剤と、架橋剤とを含み、前記アクリル系共重合体が、少なくともアクリル酸2-エチルヘキシル、アクリル酸、及びアクリル酸2-ヒドロキシエチルを共重合して得られるアクリル系共重合体であり、前記粘着助剤が、反応性基を有するゴム系材料を主成分として含み、前記架橋剤が、イソシアネート系架橋剤である粘着剤組成物が挙げられる。
本実施形態に係る粘着剤組成物の一例として、アクリル系共重合体と、粘着助剤と、架橋剤とを含み、前記アクリル系共重合体が、少なくともアクリル酸2-エチルヘキシル、アクリル酸、及びアクリル酸2-ヒドロキシエチルを共重合して得られるアクリル系共重合体であり、前記粘着助剤が、両末端水酸基水素化ポリブタジエンであり、前記架橋剤が、イソシアネート系架橋剤である粘着剤組成物が挙げられる。
本実施形態に係る粘着剤組成物のこれらの例においては、前記アクリル系共重合体全体の質量に占める、アクリル酸2-エチルヘキシル由来の共重合体成分の質量の割合が80質量%以上95質量%以下であり、カルボキシル基含有モノマー由来の共重合体成分の質量の割合が1質量%以下であり、残部が他の共重合体成分であることが好ましく、他の共重合体成分としては、水酸基含有モノマー由来の共重合体成分を含むことが好ましい。
剥離シートRLとしては、特に限定されない。例えば、取り扱い易さの観点から、剥離シートRLは、剥離基材と、剥離基材の上に剥離剤が塗布されて形成された剥離剤層とを備えることが好ましい。また、剥離シートRLは、剥離基材の片面のみに剥離剤層を備えていてもよいし、剥離基材の両面に剥離剤層を備えていてもよい。
剥離基材としては、例えば、紙基材、この紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙、及びプラスチックフィルム等が挙げられる。紙基材としては、グラシン紙、コート紙、及びキャストコート紙等が挙げられる。プラスチックフィルムとしては、ポリエステルフィルム(例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、及びポリエチレンナフタレート等)、並びにポリオレフィンフィルム(例えば、ポリプロピレン、及びポリエチレン等)等が挙げられる。
剥離剤としては、例えば、オレフィン系樹脂、ゴム系エラストマー(例えば、ブタジエン系樹脂、及びイソプレン系樹脂等)、長鎖アルキル系樹脂、アルキド系樹脂、フッ素系樹脂、並びにシリコーン系樹脂等が挙げられる。粘着剤層が、シリコーン系粘着剤組成物からなる場合には、剥離剤は、非シリコーン系の剥離剤であることが好ましい。
剥離剤層の厚みは、特に限定されない。剥離剤を含む溶液を塗布して剥離剤層を形成する場合、剥離剤層の厚みは、0.01μm以上2.0μm以下であることが好ましく、0.03μm以上1.0μm以下であることがより好ましい。
剥離基材としてプラスチックフィルムを用いる場合、当該プラスチックフィルムの厚みは、3μm以上50μm以下であることが好ましく、5μm以上40μm以下であることがより好ましい。
粘着シート10の製造方法は、特に限定されない。
例えば、粘着シート10は、次のような工程を経て製造される。
まず、基材11の第一基材面11aの上に粘着剤組成物を塗布し、塗膜を形成する。次に、この塗膜を乾燥させて、粘着剤層12を形成する。その後、粘着剤層12を覆うように剥離シートRLを貼着する。
また、粘着シート10の別の製造方法としては、次のような工程を経て製造される。まず、剥離シートRLの上に粘着剤組成物を塗布し、塗膜を形成する。次に、塗膜を乾燥させて、粘着剤層12を形成し、この粘着剤層12に基材11の第一基材面11aを貼り合わせる。
有機溶媒及び低沸点成分が粘着剤層12に残留することを防ぐため、コーティング液を基材11または剥離シートRLに塗布した後、塗膜を加熱して乾燥させることが好ましい。
粘着剤組成物に架橋剤が配合されている場合には、架橋反応を進行させて凝集力を向上させるためにも、塗膜を加熱することが好ましい。
粘着シート10は、半導体素子を封止する際に使用される。粘着シート10は、金属製リードフレームに搭載されておらず、粘着シート10上に貼着された状態の半導体素子を封止する際に使用されることが好ましい。具体的には、粘着シート10は、金属製リードフレームに搭載された半導体素子を封止する際に使用されるのではなく、粘着剤層12に貼着された状態の半導体素子を封止する際に使用されることが好ましい。金属製リードフレームを用いずに半導体素子をパッケージングする形態としては、PSP及びWLP等が挙げられる。
パネルスケールパッケージのパネルとしては、例えば、平面視で円形、楕円形、及び四角形等のパネルが挙げられる。例えば、パネルが円形である場合には、直径200mm以上450mm以下程度のサイズであることが好ましい。また例えば、パネルが四角形の場合には、各々の辺が300mm以上800mm以下程度のサイズであることが好ましい。パネルが上記のサイズであれば、被着体から粘着シート10を剥離する際に、良好に剥離することができる。
粘着シート10は、複数の開口部が形成された枠部材を粘着シート10に貼着させる工程と、前記枠部材の開口部にて露出する粘着剤層12に半導体チップを貼着させる工程と、前記半導体チップを封止樹脂で覆う工程と、前記封止樹脂を熱硬化させる工程と、熱硬化させた後、粘着シート10を剥離する工程と、を有するプロセスにおいて使用されることが好ましい。
本実施形態に係る粘着シート10を用いて半導体装置を製造する方法を説明する。
図2A~図2Eには、本実施形態に係る半導体装置の製造方法を説明する概略図が示されている。
本実施形態に係る半導体装置の製造方法は、粘着シート10に複数の開口部21が形成された枠部材20を貼着させる工程(粘着シート貼着工程)と、枠部材20の開口部21にて露出する粘着剤層12に半導体チップCPを貼着させる工程(ボンディング工程)と、半導体チップCPを封止樹脂30で覆う工程(封止工程)と、封止樹脂30を熱硬化させる工程(熱硬化工程)と、熱硬化させた後、粘着シート10を剥離する工程(剥離工程)と、を実施する。必要に応じて、熱硬化工程の後に、封止樹脂30で封止された封止体50に補強部材40を貼着させる工程(補強部材貼着工程)を実施してもよい。
以下、各工程について説明する。
図2Aには、粘着シート10の粘着剤層12に枠部材20を貼着させる工程を説明する概略図が示されている。なお、粘着シート10の粘着剤層12上に剥離シートRLが貼着されている場合には、予め剥離シートRLを剥離する。
本実施形態に係る枠部材20は、格子状に形成され、複数の開口部21を有する。枠部材20は、耐熱性を有する材質で形成されていることが好ましい。枠部材の材質としては、例えば、銅及びステンレス等の金属、並びにポリイミド樹脂及びガラスエポキシ樹脂等の耐熱性樹脂等が挙げられる。
開口部21は、枠部材20の表裏面を貫通する孔である。開口部21の形状は、半導体チップCPを枠内に収容可能であれば、特に限定されない。開口部21の孔の深さも、半導体チップCPを収容可能であれば、特に限定されない。
図2Bには、粘着剤層12に半導体チップCPを貼着させる工程を説明する概略図が示されている。
枠部材20に粘着シート10を貼着させると、それぞれの開口部21において開口部21の形状に応じて粘着剤層12が露出する。各開口部21の粘着剤層12に半導体チップCPを貼着させる。半導体チップCPを、その回路面を粘着剤層12で覆うように貼着させる。
ダイシング装置は、特に限定されず、公知のダイシング装置を用いることができる。また、ダイシングの条件についても、特に限定されない。なお、ダイシングブレードを用いてダイシングする方法に代えて、レーザーダイシング法またはステルスダイシング法等を用いてもよい。
ダイシングシートの接着剤組成物または接着剤層に、エネルギー線重合性化合物が配合されている場合には、ダイシングシートの基材側から接着剤層にエネルギー線を照射し、エネルギー線重合性化合物を硬化させる。エネルギー線重合性化合物を硬化させると、接着剤層の凝集力が高まり、接着剤層の接着力を低下させることができる。エネルギー線としては、例えば、紫外線(UV)及び電子線(EB)等が挙げられ、紫外線が好ましい。エネルギー線の照射は、半導体ウェハの貼付後、半導体チップの剥離(ピックアップ)前のいずれの段階で行ってもよい。例えば、ダイシングの前もしくは後にエネルギー線を照射してもよいし、エキスパンド工程の後にエネルギー線を照射してもよい。
図2Cには、粘着シート10に貼着された半導体チップCP及び枠部材20を封止する工程を説明する概略図が示されている。
封止樹脂30の材質は、熱硬化性樹脂であり、例えば、エポキシ樹脂等が挙げられる。封止樹脂30として用いられるエポキシ樹脂には、例えば、フェノール樹脂、エラストマー、無機充填材、及び硬化促進剤等が含まれていてもよい。
封止樹脂30で半導体チップCP及び枠部材20を覆う方法は、特に限定されない。本実施形態では、シート状の封止樹脂30を用いた態様を例に挙げて説明する。シート状の封止樹脂30を半導体チップCP及び枠部材20を覆うように載置し、封止樹脂30を加熱硬化させて、封止樹脂層30Aを形成する。このようにして、半導体チップCP及び枠部材20が封止樹脂層30Aに埋め込まれる。シート状の封止樹脂30を用いる場合には、真空ラミネート法により半導体チップCP及び枠部材20を封止することが好ましい。この真空ラミネート法により、半導体チップCPと枠部材20との間に空隙が生じることを防止できる。真空ラミネート法による加熱硬化の温度条件範囲は、例えば、80℃以上120℃以下である。
図2Dには、封止体50に補強部材40を貼着させる工程を説明する概略図が示されている。
粘着シート10を剥離した後、露出した半導体チップCPの回路面に対して再配線層を形成する再配線工程及びバンプ付け工程が実施される。
このような再配線工程及びバンプ付け工程における封止体50の取り扱い性を向上させるため、必要に応じて、封止体50に補強部材40を貼着させる工程(補強部材貼着工程)を実施してもよい。補強部材貼着工程を実施する場合には、粘着シート10を剥離する前に実施することが好ましい。図2Dに示すように、封止体50は、粘着シート10及び補強部材40によって挟まれた状態で支持されている。
補強板41としては、例えば、ポリイミド樹脂及びガラスエポキシ樹脂等の耐熱性樹脂を含む板状の部材が挙げられる。
接着層42は、補強板41と封止体50とを接着させる。接着層42としては、補強板41及び封止樹脂層30Aの材質に応じて適宜選択される。例えば、封止樹脂層30Aがエポキシ系樹脂を含み、補強板41がガラスエポキシ樹脂を含んでいる場合には、接着層42としては、熱可塑性樹脂を含んだガラスクロスが好ましく、接着層42に含まれる熱可塑性樹脂としては、ビスマレイミドトリアジン樹脂(BTレジン)が好ましい。
図2Eには、粘着シート10を剥離する工程を説明する概略図が示されている。
本実施形態では、粘着シート10の基材11が屈曲可能である場合、粘着シート10を屈曲させながら、枠部材20、半導体チップCP及び封止樹脂層30Aから容易に剥離することができる。剥離角度θは、特に限定されないが、90度以上の剥離角度θで粘着シート10を剥離することが好ましい。剥離角度θが90度以上であれば、粘着シート10を、枠部材20、半導体チップCP及び封止樹脂層30Aから容易に剥離することができる。剥離角度θは、90度以上180度以下が好ましく、135度以上180度以下がより好ましい。このように粘着シート10を屈曲させながら剥離を行うことで、枠部材20、半導体チップCP及び封止樹脂層30Aにかかる負荷を低減しながら剥離することができ、粘着シート10の剥離による、半導体チップCP及び封止樹脂層30Aの損傷を抑制することができる。粘着シート10を剥離する際の温度雰囲気は、室温であってもよいが、剥離時における被着体の各部材及び部材間の界面の破壊が懸念される場合には、粘着剤の粘着性の低下を目的として、室温よりも高い温度雰囲気において粘着シート10を剥離してもよい。室温よりも高い温度雰囲気としては、30~60℃の範囲が好ましく、35~50℃の範囲がより好ましい。粘着シート10を剥離した後、前述の再配線工程及びバンプ付け工程等が実施される。粘着シート10の剥離後、再配線工程及びバンプ付け工程等の実施前に、必要に応じて、前述の補強部材貼着工程を実施してもよい。
なお、本明細書において、「屈曲可能」とは、例えば、ロール状に巻くことが可能であり、かつロール状に巻いても損傷が充分に抑制される程度の柔軟性を有していることを意味する。
その後、封止体50を半導体チップCP単位で個片化する(個片化工程)。封止体50を個片化させる方法は特に限定されない。例えば、前述の半導体ウェハをダイシングする際に使用した方法と同様の方法で個片化させることができる。封止体50を個片化させる工程は、封止体50をダイシングシート等に貼着させた状態で実施してもよい。封止体50を個片化することで、半導体チップCP単位の半導体パッケージが製造され、この半導体パッケージは、実装工程においてプリント配線基板等に実装される。
本発明は、前記実施形態に限定されず、本発明の目的を達成できる範囲での変形及び改良等は、本発明に含まれる。なお、以下の説明では、前記実施形態で説明した部材等と同一であれば、同一符号を付してその説明を省略または簡略する。
また、粘着シート10は、シート片であってもよく、複数枚の粘着シート10が積層された状態で提供されてもよい。この場合、例えば、粘着剤層12は、積層される別の粘着シートの基材11によって覆われていてもよい。
また、粘着シート10は、帯状のシートであってもよく、ロール状に巻き取られた状態で提供されてもよい。ロール状に巻き取られた粘着シート10は、ロールから繰り出されて所望のサイズに切断する等して使用することができる。
粘着シートの評価は、以下に示す方法に従って行った。
粘着剤層の100℃の雰囲気でのシリコンに対するダイプル試験で求められる値を測定した。具体的には、下記の(a)~(h)の手順に沿って測定した。
(a)測定対象の半導体チップ(シリコン)を、下記の条件にてウェハを研削および個片化することにより作製した。
・ウェハ:厚さ750μm、8インチサイズの片面ミラーシリコンウェハ
・バックグラインドテープ:E-8180HR(リンテック株式会社製)、ダイシングテープ:D-174A(リンテック株式会社製)
・グラインド装置:株式会社ディスコ製の「DFG-8540」
・ダイシング装置:株式会社ディスコ製の「DFD651」
・標準ダイシング条件:ブレード=27HECC、35,000rpm、カットモードA、50mm/s
・チップ厚み:200μm(ウェハミラー面とは逆の面を研削し、♯2000仕上げとした。)、チップサイズ:6.4mm×6.4mm(6.435mmステップ)
(b)図3Aに示す裏打ち用のアルミニウム板AB(150mm×75mmサイズ)に、図3Bに示すように、両面テープDF(TL-4100S-50、リンテック株式会社製)を全面に貼り付け、その後、両面テープDFの剥離フィルムを剥離した。
(c)実施例1で作製した粘着剤層12を試料フィルムとし、図3Cに示すように、両面テープDFに、基材が両面テープDFと接するように粘着シートを貼り付け、その後、粘着シートの剥離フィルムを剥離した。
(d)図3Dに示すように、半導体チップCP(8個)を、回路面CPAが粘着剤層12に接するようにして、粘着剤層12上にピンセットを用いて、2.5cm間隔で両面テープDFを貼ったアルミニウム板ABの中央部に設置した。半導体チップCPは、アルミニウム板ABの長方形形状の短辺に沿った方向に2行、長辺に沿った方向に4列の配置とした。その際に、粘着剤層12に半導体チップCPの角を当てないように、半導体チップCPを優しく垂直に設置した。
(e)上記の(d)で作製したサンプルを、真空ラミネーターを用いて、下記の条件にて、真空ラミネートした。なお、真空ラミネートをする際には、図3Eに示すように、上下に剥離フィルムLF(厚み:38μm)を2枚配置し、真空ラミネートをした。
・真空ラミネーター:NISSHINBO社製
・温度:100℃
・圧力:100Pa、真空度:設定なし(全引き)、プレス:設定なし(大気圧との差圧)
・ラミネート速度:高速モード
・プログラム:真空引き60秒間後に、高速ラミネートで40秒間
・温度設定後、1時間後以降にラミネートを行い、実際のサンプルラミネートの前には、一度空運転した。
(f)上記の(e)で真空ラミネートしたサンプルを、プル試験機(ノードソン・アドバンスト・テクノロジー株式会社製の「Dage4000」)に載せて、100℃に予熱した。
(g)図3Fに示すように、両面テープDF2(TL-4100S-50、リンテック株式会社製)が貼り付けられたプルブロックPBを、図3Gに示すように、半導体チップCP上に置き、5秒間2Nの力を加えた。1分間経過後に、下記の条件にて、図3Hに示すようにして、ダイプル試験を行い、ロードセルの変位及び力を測定し、力のピーク値を、1つのダイ(半導体チップCP)にかかる力(単位:N/ダイ)とした。
・雰囲気の温度:100℃
・試験速度:200μm/s
(h)その後、半導体チップCPをプルブロックPBから取り外した後に、上記の(g)のようにして、別の半導体チップCPにて、ダイプル試験を行い、6個のチップについて、1つのダイにかかる力を求めた。そして、得られた有効データの平均値を、ダイプル試験で求められる値(単位:N/ダイ)とした。
比較例1~3で作製した粘着剤層についても、上記と同様にして、100℃の雰囲気でのシリコンに対するダイプル試験で求められる値を測定した。
実施例1で作製した粘着シートの粘着剤層(粘着面)に、半導体チップ(シリコンミラーチップ、チップサイズ:2.3mm×1.7mm、チップ厚み:0.2mm)8000個を、粘着シートの粘着面と半導体チップの回路面とが接するように、80行100列の配列で設置した。この際、チップの2.3mmの長さの辺と平行な方向と、チップの配列の列方向が一致するようにした。また、隣り合うチップ同士の距離は、チップの長方形形状の中心間の距離が5mmとなるようにした。その後、真空加熱加圧ラミネーター(ROHM and HAAS社製の「7024HP5」)を用いて、封止樹脂(味の素ファインテクノ株式会社製ABFフィルム、GX T-31)で粘着シート上の半導体チップを封止した。封止条件は、下記の通りである。
・予熱温度:テーブル及びダイアフラムとも100℃
・真空引き:60秒間
・ダイナミックプレスモード:30秒間
・スタティックプレスモード:10秒間
そして、埋め込み後の粘着シート上の半導体チップを目視及び顕微鏡にて観察し、半導体チップの位置ずれの有無を確認した。半導体チップの位置ずれがない場合を「A」と判定し、半導体チップの位置ずれがある場合を「B」と判定した。なお、埋め込みを行う前後で半導体チップが20μm以上移動した場合に、「位置ずれがある」と判定した。
比較例1~3で作製した粘着シートについても、上記と同様にして、半導体チップの位置ずれの有無を確認した。
実施例1で作製した粘着シートを25mm幅に切断し、切断した粘着シートの粘着面を、被着体(ポリイミドフィルム)に2kgfの荷重をかけて貼付した。ポリイミドフィルムとしては、東レ・デュポン株式会社製の厚さ25μmのカプトン100H(製品名)を用いた。
このポリイミドフィルム付き粘着シートを、25℃50%相対湿度の環境下で0.5時間保管した後、恒温器(エスペック株式会社製、PHH-202)を用いて、190℃及び1時間の条件で加熱した。加熱後、ポリイミドフィルム付き粘着シートを、25℃50%相対湿度の環境下で1時間保管した後に、剥離角度を180°とし、剥離速度を300mm/minとし、室温及び40℃雰囲気下で、粘着シートをポリイミドフィルムから剥離した際の、粘着シートの加熱後の粘着力をそれぞれ測定した。測定機として、恒温槽付測定機(株式会社A&D製、TENSILON)を用いた。
比較例1~3で作製した粘着シートについても、上記と同様にして、加熱後の粘着力を測定した。
実施例1で作製した粘着シートを25mm幅に切断し、切断した粘着シートの粘着面と、被着体(ポリイミド膜を有する回路面が設けられた半導体ウェハ;直径150mm、厚さ200μm)の回路面とを貼り合わせた。この際、2kgfの荷重をかけて貼り合わせを行った。
半導体ウェハに貼付した粘着シートを、25℃50%相対湿度の環境下で0.5時間保管した後、恒温器(エスペック株式会社製、PHH-202)を用いて、190℃及び1時間の条件で加熱した。加熱後、半導体ウェハに貼付した粘着シートを、25℃50%相対湿度の環境下で1時間保管した後に、剥離角度を180°とし、剥離速度を300mm/minとし、40℃雰囲気下で、粘着シートを半導体ウェハから剥離した。剥離装置として、恒温槽付測定機(株式会社A&D製、TENSILON)を用いた。粘着シートを剥離した後の半導体ウェハを目視にて観察し、半導体ウェハ表面の残渣を確認した。テープ剥離後に、糊残りなく剥離できた場合を「C」と判定し、糊残りがあり、半導体ウェハ表面が汚染されている場合を「D」として、剥離性を評価した。
比較例1~3で作製した粘着シートについても、上記と同様にして、半導体ウェハ表面の残渣を確認した。
(実施例1)
(1)粘着剤組成物の調製
以下の材料(ポリマー、粘着助剤、架橋剤、及び希釈溶剤)を配合し、十分に撹拌して、実施例1に係る塗布用粘着剤液(粘着剤組成物)を調製した。
アクリル酸エステル共重合体は、アクリル酸2-エチルヘキシル92.8質量%と、アクリル酸2-ヒドロキシエチル7.0質量%と、アクリル酸0.2質量%とを共重合して調製した。得られた重合体の重量平均分子量は、850,000であった。
シリコーン系剥離層を設けた38μmの透明ポリエチレンテレフタレートフィルムからなる剥離フィルム〔リンテック株式会社製;SP-PET382150〕の剥離層面側に、調製した塗布用粘着剤液を、コンマコーター(登録商標)を用いて塗布し、90℃及び90秒間の加熱を行い、続いて115℃及び90秒間の加熱を行い、塗膜を乾燥させて、粘着剤層を作製した。粘着剤層の厚さは50μmであった。
塗布用粘着剤液の塗膜を乾燥させた後、粘着剤層と、基材とを貼り合わせて、実施例1に係る粘着シートを得た。なお、基材として、透明ポリエチレンテレフタレートフィルム〔帝人デュポンフィルム株式会社製;PET50KFL12D、厚さ50μm、100℃での貯蔵弾性率3.1×109Pa〕を用い、基材の易接着面に粘着剤層を貼り合わせた。
比較例1に係る粘着シートは、粘着剤層に含まれる粘着助剤として、アセチルクエン酸トリブチル(ATBC)〔田岡化学工業株式会社製〕、5質量部(固形分)を用いたこと以外は、実施例1と同様に作製した。
比較例2に係る粘着シートは、粘着剤層に含まれるポリマーが実施例1と異なること以外は、実施例1と同様に作製した。
比較例2で用いたポリマーは、アクリル酸2-エチルヘキシル80.8質量%と、アクリル酸2-ヒドロキシエチル7質量%と、N-アクリロイルモルホリン12質量%と、アクリル酸0.2質量%とを共重合して調製した。得られた重合体の重量平均分子量は、760,000であった。
比較例3に係る粘着シートは、粘着剤層が粘着助剤を含まないこと以外は、実施例1と同様に作製した。
一方、比較例1に係る粘着シートは、粘着剤層の100℃の雰囲気でのシリコンに対するダイプル試験で求められる値が3.0N/ダイ未満であるため、ダイシフトを防止することができなかったと考えられる。また、比較例2~3に係る粘着シートは、粘着剤層をポリイミドフィルムに貼付して190℃で1時間加熱した後の、40℃雰囲気でのポリイミドフィルムに対する粘着力が1.0N/25mmを超えているため、加熱後の剥離性に劣ると考えられる。
Claims (15)
- 粘着シート上の半導体素子を封止する際に使用される粘着シートであって、
当該粘着シートは、基材と、粘着剤組成物を含む粘着剤層とを備え、
前記粘着剤層は、100℃の雰囲気でのシリコンに対するダイプル試験で求められる値が3.0N/ダイ以上であり、かつ、
前記粘着剤層をポリイミドフィルムに貼付して190℃で1時間加熱した後の、40℃雰囲気での前記ポリイミドフィルムに対する粘着力が1.0N/25mm以下である、
粘着シート。 - 前記粘着シートは、前記粘着剤層をポリイミドフィルムに貼付して190℃で1時間加熱した後の、40℃雰囲気での前記ポリイミドフィルムに対する粘着力が0.1N/25mm以上である、
請求項1に記載の粘着シート。 - 前記粘着シートは、前記粘着剤層をポリイミドフィルムに貼付して190℃で1時間加熱した後の、室温での前記ポリイミドフィルムに対する粘着力が0.4N/25mm以上10.0N/25mm以下である、
請求項1または請求項2に記載の粘着シート。 - 前記基材の100℃での貯蔵弾性率は、1×107Pa以上である、
請求項1から請求項3のいずれか1項に記載の粘着シート。 - 前記粘着剤層は、アクリル系粘着剤組成物またはシリコーン系粘着剤組成物からなる、
請求項1から請求項4のいずれか1項に記載の粘着シート。 - 前記粘着剤層は、アクリル系粘着剤組成物からなる、
請求項5に記載の粘着シート。 - 前記アクリル系粘着剤組成物は、アクリル系共重合体を含み、
前記アクリル系共重合体は、(メタ)アクリル酸アルキルエステルに由来する共重合体成分を含み、
前記(メタ)アクリル酸アルキルエステルのアルキル基の炭素数が6~10である、
請求項6に記載の粘着シート。 - 前記アクリル系共重合体全体の質量に占める、(メタ)アクリル酸アルキルエステルに由来する共重合体成分の質量の割合が、90質量%以上である、
請求項7に記載の粘着シート。 - 前記アクリル系共重合体は、(メタ)アクリル酸2エチル-ヘキシルを主たるモノマーとするアクリル系共重合体を含む、
請求項7または請求項8に記載の粘着シート。 - 前記アクリル系共重合体は、水酸基を有するモノマーに由来する共重合体成分を含む、
請求項7から請求項9のいずれか一項に記載の粘着シート。 - 前記アクリル系共重合体全体の質量に占める、前記水酸基を有するモノマーに由来する共重合体成分の質量の割合が、3質量%以上である、
請求項10に記載の粘着シート。 - 前記アクリル系粘着剤組成物は、前記アクリル系共重合体と、イソシアネート基を有する化合物を主成分とする架橋剤とを少なくとも配合した組成物を架橋させて得られる架橋物を含む、
請求項7から請求項11のいずれか一項に記載の粘着シート。 - 前記アクリル系粘着剤組成物は、反応性基を有するオリゴマーを含む粘着助剤を含有する、
請求項6から請求項11のいずれか一項に記載の粘着シート。 - 前記粘着剤組成物は、前記アクリル系共重合体と、前記粘着助剤と、イソシアネート基を有する化合物を主成分とする架橋剤とを少なくとも配合した組成物を架橋させて得られる架橋物を含む、
請求項13に記載の粘着シート。 - 前記粘着剤層は、シリコーン系粘着剤組成物からなり、前記シリコーン系粘着剤組成物は、付加重合型シリコーン樹脂を含む、
請求項5に記載の粘着シート。
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