[go: up one dir, main page]

WO2004090962A1 - Base film for semiconductor wafer processing - Google Patents

Base film for semiconductor wafer processing Download PDF

Info

Publication number
WO2004090962A1
WO2004090962A1 PCT/JP2004/004943 JP2004004943W WO2004090962A1 WO 2004090962 A1 WO2004090962 A1 WO 2004090962A1 JP 2004004943 W JP2004004943 W JP 2004004943W WO 2004090962 A1 WO2004090962 A1 WO 2004090962A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
base film
semiconductor wafer
less
processing
Prior art date
Application number
PCT/JP2004/004943
Other languages
French (fr)
Japanese (ja)
Inventor
Koji Furuya
Original Assignee
Teijin Dupont Films Japan Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Teijin Dupont Films Japan Limited filed Critical Teijin Dupont Films Japan Limited
Priority to JP2005505286A priority Critical patent/JPWO2004090962A1/en
Publication of WO2004090962A1 publication Critical patent/WO2004090962A1/en

Links

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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • 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 groups H01L21/18 - H01L21/326 or H10D48/04 - H10D48/07 e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a base film for processing a semiconductor wafer using a biaxially oriented film containing polyethylene-1,2,6-naphthalenedicarboxylate as a main component. More specifically, when used as a base material of a pack grinding tape or a base material of a dicing tape in semiconductor wafer processing, particularly in a pack grinding process or a dicing process, a bag having excellent dimensional stability, smoothness, and strength.
  • the present invention relates to a base film for grinding tape or dicing tape.
  • plastic films such as polyolefin and its copolymer, polychlorinated vinyl and its copolymer, polyester, polycarbonate, polyamide, and polyimide have been used as the base film of the adhesive film and the release film of the dicing tape.
  • plastic films such as polyolefin and its copolymer, polychlorinated vinyl and its copolymer, polyester, polycarbonate, polyamide, and polyimide have been used as the base film of the adhesive film and the release film of the dicing tape.
  • polyester films are being used.
  • a germanium compound is applied to a polymerization catalyst for the purpose of preventing a decrease in the yield of a silicon wafer caused by impurities contained in the polyester / reflective film and the silicone resin release layer
  • Japanese Patent Laid-Open A method is disclosed.
  • a technology relating to a release film for protecting an adhesive layer in storage of a knock grind tape or a dicing tape is disclosed in Japanese Patent Application Laid-Open No. H11-2010. .
  • the conventional polishing method has problems such as damage to the wafer and longer polishing time than before. For example, a plasma etching method has been devised as a processing technique. Is coming.
  • the processing temperature is higher than that of the conventional processing method.
  • mechanical strength are becoming issues.
  • the adhesive strength of the adhesive is reduced by calorie heat or UV irradiation, and then the tape is expanded to pick up each cut chip, or the chips are removed from the tape side.
  • the push-up method There is a gap between the chips by using the push-up method.1 It is often said that if the tape shrinks greatly when the heat of calorie heats up, a chip pick-up force S occurs and the production efficiency of semiconductor wafers deteriorates. ing.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 5-1755332
  • Patent Document 2 Japanese Patent Application Laid-Open No. Hei 11-5838
  • Patent Literature 3 Japanese Patent Application Laid-Open No. H10-102-148081
  • Patent Document 4 Japanese Patent Application Laid-Open No. H11-20110
  • the object of the present invention is to solve the problems of the prior art and to solve the problems of the prior art, and to use the semiconductor wafer at a high temperature and a high humidity when used as a substrate of a back grinding tape or a substrate of a dicing tape.
  • Excellent dimensional stability, smoothness, «strength, and! The purpose is to obtain a semiconductor film base film with good caroet aptitude. Further objects and advantages of the present invention will become apparent from the following description.
  • the present invention is also achieved by the semiconductor wafer and the base film for processing according to the first aspect of the present invention, wherein the base film for processing a semiconductor wafer is for a pack grinding tape or a dicing tape.
  • the above objects and advantages of the present invention are: Third, the amount of extracted oligomer in the film is 0.8% by weight or less, and the refractive index in the thickness direction of the film is 1.8%.
  • the present invention is also attained by the base film for semiconductor wafers according to the first aspect of the present invention, which has a value of not less than 501 and not more than 1.515.
  • a back grinding tape having an adhesive layer on one surface of the base film for a back grinding tape of the first or second invention, and an adhesive layer on one surface of the base film for a dicing tape of the first or second invention. This is achieved by at least one of the dicing tapes.
  • a pack grind tape composite further comprising a release film on the pressure-sensitive adhesive layer of the pack grind tape of the fourth present invention, and a release further on the pressure-sensitive adhesive layer of the dicing tape of the fourth present invention This is achieved by at least one of the dicing tabs having a film.
  • the base film for processing a semiconductor wafer of the present invention is excellent in dimensional stability, smoothness and mechanical strength under high temperature, especially under high humidity.
  • it is suitable for semiconductor wafers, dicing tapes used for processing, or pad grinding tapes.
  • the base film for semiconductor wafers is mainly composed of polyethylene-12,61-naphthalenedicarboxylate (hereinafter sometimes referred to as PEN), and may be a copolymer or a mixture.
  • PEN polyethylene-12,61-naphthalenedicarboxylate
  • the main dicarboxylic acid component is naphthalenedicarboxylic acid
  • the main glycol component is ethylene glycolone.
  • examples of the naphthalenedicarboxylic acid include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and the like.
  • —Naphthalenedicarboxylic acid is preferred.
  • Mainly means that at least 80 mo 1% of the total repeating units are ethylene-1,2,6-naphthalenedicarboxylate, which is a component of the polymer which is a component of the film of the present invention. It is more preferably at least 90% mo, particularly preferably at least 95% mo. In other words, it is sufficient that the polyethylene-1,2,6-naphthalenedicarboxylate film of the present invention does not extremely lose its original properties and that dimensional stability and high strength can be ensured when used under high temperatures.
  • a compound having two esteno-1 ⁇ functional groups in the molecule is used as the copolymerization component of the copolymer other than the main component ethylene-1,2,6-naphthalenedicanoleboxylate. be able to.
  • Examples of such compounds include oxalic acid, adipic acid, phthalic acid, sebacic acid, dodecanedicarboxylic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, Dicarboxylic acids such as phenylindanedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, tetralindicarboxylic acid, decalindicarboxylic acid and diphenyletherdicarboxylic acid can be preferably used.
  • oxycarboxylic acids such as p-oxybenzoic acid and p-oxochetoxybenzoic acid can also be preferably used.
  • propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexanemethylene glycol, neopentyl glycol, ethylene oxide adduct of bisphenol sulfone, ethylene oxide adduct of bisphenol A, diethylene glycol And dihydric alcohols such as polyethylene oxide glycol are also preferably used.
  • These compounds can be used alone or in combination of two or more.
  • isophthalic acid, terephthalic acid, 4,4'-diphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, p-oxybenzoic acid 1S are used as the acid component, and tris are used as the glycolone component.
  • Methylene glycolone, hexamethylene glycol neopentyl glycol and bisphenol sulfone ethylene oxide adducts are preferred.
  • polyethylene 1,2,6-naphthalenedicarboxylate used in the present invention may partially or entirely block terminal hydroxyl groups and / or carboxyl groups with a monofunctional compound such as benzoic acid or methoxypolyalkylene glycol. It may be what you did.
  • the polyethylene-1,2,6-naphthalenediole reoxyxylate used in the present invention can be used to obtain a substantially linear polymer with an extremely small amount of a trifunctional or higher functional esteno-forming compound such as glycerin or pentaerythritol. It may be copolymerized within the range.
  • the film of the present invention may be a mixture of polyethylene-1,2,6-naphthalene dicarboxylate as a main component and other organic polymers.
  • organic polymers include polyethylene terephthalate, polyethylene isophthalate, polytrimethylene terephthalate, polyethylene-1,4,4′-tetramethylenediphenyldicarboxylate, polyethylene-1,2,7-naphthalenedicarboxylate, polytrimethylene-1,2, Examples include 6-naphthalenedicarboxylate, polyneopentylene-1,2,6-naphthalenedicarboxylate, and poly (bis (4-ethylenoxyphenyl) sulfone) -1,2,6-naphthalenedicarboxylate.
  • polyethylene isophthalate polytrimethylene terephthalate, polytrimethylene-1,2,6-naphthalenedicarboxylate, poly (bis (4-ethyleneoxyphen-nore) sunolefon) 1,2,6-naphthalenedicarbonate ⁇ boxylate
  • polyethylene isophthalate polytrimethylene terephthalate
  • polytrimethylene-1,2,6-naphthalenedicarboxylate polytrimethylene-1,2,6-naphthalenedicarboxylate
  • poly (bis (4-ethyleneoxyphen-nore) sunolefon) 1,2,6-naphthalenedicarbonate ⁇ boxylate is preferred.
  • the organic polymer mixed with these PENs may be used alone or in combination of two or more.
  • the proportion of the organic polymer mixed with PEN is at most 20 mo 1%, preferably at most 10 mo 1%, particularly preferably at most 5 mo 1%, in the repeating unit of the polymer. You.
  • the production of such a mixture can be carried out by a generally known method for producing a polyester fiber.
  • the polyester used in the present invention can be obtained by a conventionally known method.
  • a method of directly obtaining a low-polymerization degree polyester by a reaction of dicarboxylic acid and dalicol, or a method of subjecting a lower alkyl ester of dicarboxylic acid and glycol to a transesterification reaction using a known transesterification catalyst The polymerization reaction may be carried out in the presence of a heavy vehicle.
  • the ester exchange reaction catalyst include compounds containing sodium, potassium, magnesium, calcium, dumbbell, strontium, titanium, zirconium, manganese, and konoleto, and these may be used alone or in combination of two or more. .
  • Antimony trioxide, antimony tetroxide, antimony pentoxide, antimony trichloride, antimony tribromide, antimony glycolate, antimony acetate, antimony compounds such as antimony trioxide, antimony acetate, and germanium dioxide are typical examples of heavy insect media. Titanium compounds such as germanium compounds, tetraethino retitanate, tetrapropyl titanate, tetraphenyl titanate or partial hydrochloride thereof, titanium-noreammonium oxalate, titanium potassium oxalate, and titanium trisacetyl acetate Can be Among the above polymerization catalysts, germanium conjugates are particularly preferably used.
  • the resulting transesterification product is added to the obtained transesterification reaction product in a ffi state.
  • the germanium compound used for the polycondensation reaction catalyst for example, (a) amorphous germanium oxide (mouth) fine crystalline germanium oxide (c) a solution in which germanium oxide is dissolved in water can be preferably used. .
  • germanium oxides such as crystalline germanium dioxide, amorphous germanium dioxide, germanium tetraethoxide, and germanium tetra-n-butoxide can be preferably used.
  • Germanium dioxide and amorphous germanium dioxide can be preferably used.
  • Germanium metal remaining in the metal The element is preferably from 10 to 100 ppm by weight, more preferably from 10 to 500 ppm by weight, and still more preferably from 10 to 200 ppm by weight.
  • concentration of germanium in the metal element was determined by setting the dried sample on a scanning electron microscope (SEM, trade name “S570” manufactured by Hitachi Measuring Instruments Service Co., Ltd.) and connecting the energy to it. It is a value obtained by quantitative analysis using a dispersive X-ray microanalyzer (XMA, trade name: AX-700, manufactured by HORIBA, Ltd.).
  • ⁇ preferably contains a phosphorus compound for the purpose of deactivating the transesterification catalyst before the polymerization reaction.
  • phosphorus compounds include phosphoric acid, phosphorous acid, phosphonic acid, phosphonate compounds and derivatives thereof, and these may be used in battle insects or in combination of two or more.
  • a phosphonate compound represented by the following formula (I) is preferable as the phosphorus compound.
  • R 1 and R 2 are an alkyl group having 1 to 4 carbon atoms
  • X is one CH 2 — or one CH (Y) ⁇ (Y represents a phenyl group).
  • R 1 and R 2 may be the same or different.
  • Particularly preferred phosphorus compounds are carbomethoxymethanephosphonic acid, carbethoxymethanephosphonic acid, canolevopropoxymethanephosphonic acid, phenolic olevobutoxymethanephosphonic acid, carpomethoxy-phosphonopheninoleacetic acid, and canolevoethoxyphosphono Dimethylacetate, carbopropoxy-phosphonophenylacetate, and carbopoxy-phosphonophene / lexanoic acid dimethyl / leestenole, jetty / leestene / le, dipropinole ester and dibutyl ester.
  • the reason why these phosphonate compounds are preferable is that the reaction with the metal compound proceeds relatively slowly as compared with the phosphorus compound which is usually used as a stabilizer. Long contact time of the compound As a result, the amount of catalyst added to the polyester can be reduced, and even if a large amount of stabilizer is added to the catalyst, the thermal stability of the polyester is impaired! / This is for you.
  • the timing of the recommendation of these phosphorus compounds may be any time after the transesterification reaction is substantially completed, for example, under atmospheric pressure before the start of the polycondensation reaction, under reduced pressure after the start of the polycondensation reaction. At the end of polycondensation reaction or after completion of polycondensation reaction, ie polymer You may add after obtaining.
  • the content of the phosphorus compound is preferably 20 to: L 00 weight ppm in polyethylene mono 2,6-naphthalenedicarboxylate as the phosphorus element in the phosphorus compound.
  • the polyethylene-1,2,6-naphthalenedicarboxylate used in the present invention may be prepared by using 2,6-naphthalenedicarboxylic acid and ethylene glycol as raw materials, and may be 2,6-naphthalenedicarboxylate represented by 2,6-dimethylnaphthalate. Esteno W ⁇ -forming derivatives of acid and ethylene dalicol may be used as raw materials.
  • the transesterification reaction is carried out under a pressure of not less than 0.05 MPa and not more than 0.2 OMPa, so that the amount of the metal compound added can be further reduced.
  • polyester used in the present invention can be formed into chips after melt polymerization, and then subjected to solid-phase polymerization under calorific heat or in an inert gas stream such as nitrogen.
  • solid-state polymerization is also preferably performed in the present invention.
  • the intrinsic viscosity of the polymer containing polyethylene-1,6-naphthalenedicarboxylate as a main component is 0.40 (preferably not less than 1 1 / ⁇ and not more than 0.90 dl Zg).
  • the intrinsic viscosity is a value (unit: d1 / g) measured at 25 ° C using o-chlorophenol as a solvent.
  • the base particles for processing semiconductor wafers of the present invention have a small percentage of inert particles in order to impart slipperiness to the film.
  • inert particles for example, particles such as spherical silica, porous silica, calcium carbonate, alumina, titanium dioxide, potassium chloride, barium sulfate, zeolite, or organic particles such as silicone resin particles and cross-linked polystyrene particles Can be mentioned.
  • the inorganic particles are synthetic products rather than natural products because the particle size is uniform.
  • the crystal morphology, hardness, specific gravity, and color of the particles are not particularly limited, and can be used according to the purpose.
  • calcium carbonate examples include calcium carbonate, porous silica, spherical silica, and chao. Phosphorus, talc, magnesium carbonate, palladium carbonate, calcium sulfate, calcium sulfate, potassium sulfate, lithium phosphate, canolecum phosphate, magnesium phosphate, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, lithium fluoride, etc. be able to.
  • calcium carbonate particles spherical silica particles, porous silica particles, and plate-like aluminum silicate are particularly preferred.
  • organic particles examples include organic particles and crosslinked polymer particles.
  • organic salt particles include, for example, terephthalates such as calcium phosphate, calcium, norium, zinc, manganese, and magnesium.
  • crosslinked polymer particle examples include an insect or copolymer of a vinyl monomer such as dibienolebenzene, styrene, acryloleic acid or methacrylic acid.
  • fine particles such as polytetrafluoroethylene, a silicone resin, a benzoguanamine resin, a thermosetting epoxy resin, an unsaturated polyester resin, a hydrophobizable urea resin, and a hydrophobizable phenol resin are also preferably exemplified.
  • silicone resin particles and crosslinked polystyrene particles are particularly preferred.
  • the average particle size of each type of particles is preferably 0.05 to 5 ⁇ , and 0.08 ⁇ to 3.5. ⁇ am is more preferable, and it is particularly preferable that it is 0.10 m or more and 3 m or less. Further, the total amount of inert particles contained in the film is preferably 0.05% by weight or more and 3% by weight or less, more preferably 0.08% by weight or more and 2.0% by weight or less. It is particularly preferred that the content be 0.1% by weight or more and 1.0% by weight or less. ,
  • the inert particles to be added to the film may be a single component selected from those exemplified above, or may be a multicomponent containing two or more components.
  • a single component: ⁇ may contain two or more types of particles with different average particle sizes!
  • the average of inert particles is determined by using a CP-50 centrifugal particle size analyzer (Centrifugal P a • rticle Size Ann a 1 yzer) j manufactured by Shimadzu Corporation. From the integrated curve of particles of each particle size and their abundance calculated based on the centrifugal sedimentation curve obtained from the measurement. This is a value obtained by reading the particle size corresponding to 0% by weight (see “Particle Size Measurement Technology”, published by Nikkan Kogyo Shimbun, p. 1979, p. '
  • calcium carbonate particles having an average particle size of 0.3 to 111 or more and 0.8 zm or less are contained in an amount of 0.05 to 0.4% by weight and / or an average particle size of 0 to 0.4% by weight.
  • Spherical particles having a particle size of 1 ⁇ m or more and 0.6 m or less are used in an amount of 0.3% by weight or more and 0.5% by weight or less, and the Z or average vertical diameter is 0.1 Zm or more and 0.6 ⁇ m.
  • particles of the same type of inert particles having different particle sizes may be simultaneously contained.
  • the film of the present invention may contain a nucleating agent, an antioxidant, a heat stabilizer, a lubricant, a flame retardant, an antistatic agent, a polysiloxane, etc., depending on the use.
  • the addition time of the inert particles and other additives is not particularly limited as long as it is a stage before the film formation of polyethylene 1,261-naphthalenedicarboxylate. It can also be added during film formation. From the viewpoint of uniform dispersion, it is preferable to add inactive particles and other additives to ethylene glycol and add them at a high concentration during polymerization to form a master chip, and dilute the obtained master chip with an additive-free chip. Good.
  • the semiconductor wafer and the base film for processing according to the present invention are biaxially oriented films containing the above-mentioned polyethylene-12,61-naphthalenedicarboxylate as a main component.
  • the base film (which may be abbreviated as a film) in the present invention may be a single layer or a plurality of layers of two or more layers. It is preferable for achieving both flatness of the surface and winding property of the base film.
  • a co-extrusion method, an extrusion laminating method, a coating method, and the like can be used, and are not particularly limited. It is preferable to form a plurality of layers by a co-extrusion method in which each resin is extruded from a plurality of extruders using 6-naphthalene dicanolepoxylate.
  • the base film for processing a semiconductor wafer of the present invention is used for back grinding tape. Or preferably for dicing tape! / ,.
  • the film of the present invention has a heat shrinkage of not more than 1.0% in both the film forming direction and the width direction when subjected to heat treatment at 200 for 10 minutes.
  • the heat shrinkage of the film of the present invention is more preferably from ⁇ 0.20% to 0.80%, particularly preferably from 0.10% to 0.60%.
  • the film forming direction is a traveling direction when a film is formed, and may be referred to as a longitudinal direction, a longitudinal direction, a continuous direction, a film direction or an MD direction of the film.
  • the width direction is a direction orthogonal to the film forming direction in the in-plane direction of the film, and may be referred to as a lateral direction or TD.
  • the heat shrinkage ratio after heat treatment at 200 ° C for 10 minutes exceeds 1.0%, the dimensional shrinkage of the base film will increase when the temperature rises in the semiconductor wafer processing process. On the other hand, since the wafer thermally expands, the wafer may fall off the adhesive of the tape during the processing process, or in some cases, the thickness of the wafer may be too thin.
  • the heat shrinkage is less than 0.20%: ⁇ , that is, when the thermal expansion occurs, the thermal expansion of the base film becomes larger than the thermal expansion of the wafer. May move to the wafer surface from the part.
  • any of the 8 8 ⁇ in which the shrinkage or expansion of the film is large beyond the scope of the present invention is not preferable because the semiconductor wafer mounted on the tape warps due to the difference from the expansion coefficient of the wafer. Also, if the expansion coefficient of the film is larger than the expansion coefficient of the semiconductor wafer, it warps with the wafer side inward and causes chips to stick together, so that the expansion of the film, that is, the heat shrinkage rate becomes negative. Direction must be suppressed as much as possible.
  • the oligomer extraction amount of the film of the present invention is preferably 0.8% by weight or less under the condition of extracting with chloroform for 24 hours. It is more preferably 0.6% by weight or less, particularly preferably 0.5% by weight. / 0 or less. Oligomer extraction is 0.8 It exceeds weight 0/0 when the semiconductor Ueno, was used as a working base film: ⁇ a, your a processing temperature environment or a pressure-sensitive adhesive layer Coating process in step! / Polyolomer may precipitate on the surface of the base film, causing problems such as contamination in the processing step and a decrease in the adhesive strength between the pressure-sensitive adhesive layer and the base film.
  • the most effective way to suppress the precipitation of oligomers on the film surface is to reduce the amount of oligomers contained in the film, and it is preferable to reduce the amount of oligomer extracted for this application.
  • the intrinsic viscosity of polyethylene-2,6-naphthalenedicarboxylate be 0.45 dl / g or more and 0.90 dlZg or less. It is more preferably from 0.48 to 0.85 d1 / g, particularly preferably from 0.50 to 0.80 d1 / g. If the intrinsic viscosity of poly (1,6-naphthalenedicanolepoxylate) is less than the lower limit, the amount of finolem extracted oligomer will be too large, but will exceed the upper limit; ⁇ indicates excessive load in the polymerization and film forming process May be required.
  • the intrinsic viscosity of the film is preferably 0.40 to 0.90 d1 / g.
  • the intrinsic viscosity is a value (unit: d1 / g) measured at 25 ° C using o-chlorophenol as a solvent. Refractive index in the thickness direction>
  • the refractive index (nz) in the thickness direction of the film of the present invention is preferably from 1.501 to 1.515. It is more preferably 1.503 or more and 1.513 or less, particularly preferably 1.504 or more and 1.52 or less.
  • the refractive index in the thickness direction is less than 1.501, the laminating property of the film is degraded, so that burrs are generated on the cut end surface of the film.
  • the refractive index in the thickness direction exceeds 1.515, the film becomes brittle, and when the tape is used as a base film for pack grind tape or dicing tape, the film tears when peeling. Sometimes.
  • the variation in the thickness of the film of the present invention is preferably 15% or less, more preferably 10% or less, and particularly preferably 8% or less based on the average thickness of the film.
  • the smaller the variation in film thickness the more uniform the bonding strength between the back grinding tape and the semiconductor wafer and the bonding surface between the dicing chip and the semiconductor wafer, and stable taping becomes possible.
  • Back grinding and dicing can be performed, and a chip suitable for high definition and high density can be supplied.
  • the Young's modulus of the film of the present invention is preferably 540 OMPa or more and 690 OMPa or less in both the film forming direction and the width direction of the film. OMPa or less, particularly preferably 560 OMPa or more and 670 OMPa or less. The difference between the Young's moduli in both directions is preferably 100 OMPa or less.
  • the Young's modulus is less than 540 OMPa, the rigidity of the film will be insufficient, and it will be difficult to reduce the thickness of the base film for semiconductor wafer processing utilizing the high elastic modulus of polyethylene-2,61-naphthalenedicarboxylate film. Sometimes. On the other hand, if the Young's modulus exceeds 690 OMPa, a large amount of chips tend to be generated when cutting the film, which may contaminate processing in a clean state. Furthermore, when picking up each cut chip, it is difficult to push up the chip from the expanding tape side of the tape, which reduces production efficiency.
  • the center line average surface roughness (Ra) on at least one side of the film of the present invention is preferably 3 nm or more and 80 nm or less, more preferably 5 nm or more and 60 nm or less, and particularly preferably 7 nm or more and 5 Onm or less. It is. Further, the film is preferably composed of two or more layers, and the sum of Ra on both surfaces of the film is preferably 10 nm or more, and more preferably 14 nm or more.
  • the center line average roughness (R a) is determined by the method specified in JISB-0601, the cutoff is 0.25 mm, and the measurement probe is 3 ⁇ ⁇ .
  • Ra Ra is less than 3 nm, the film will not slide easily, and the film surface will be abraded when transported during film production or when the film is wound, or the film will be in a whirl state. When the film is wound, it is difficult for air trapped between the film and the film to escape, and the air traps generated may impair the flatness of the film. On the other hand, if Ra exceeds 80 nm, the film slips too much, so that misalignment may frequently occur when winding the film or winding it after applying an adhesive layer on the film surface to form a tape. There is.
  • the density of the film of the present invention is preferably 1.356 gZcm 3 or more and 1.364 gZcm 3 or less. More preferably, 1.357 ⁇ . It is not less than 111 3 and not more than 1.36 2 gZcm 3 . If the density is less than 1.356 gZ cm 3 , the crystallinity of the film is low; the semiconductor wafer may have insufficient dimensional stability in the processing step. If the density exceeds 1.364 gZ cm 3 , the crystallinity will be too high and the toughness of the film will be lost. Become.
  • the density of the film is a value measured by the floatation method at 25 ° C during a density gradient using an aqueous solution of calcium nitrate as a solvent.
  • the average thickness of the film of the invention is preferably from 9 in to 150 ⁇ , more preferably from 9 m to 125 m, and particularly preferably from 12 ⁇ m to 100; If the average thickness of the film is less than 9 m, there will be an age at which the strength of Nada, Ueno, and surface humidification as a support in Uenoka will be insufficient. On the other hand, if the average thickness of the film exceeds 150 ⁇ , the stiffness of the film becomes extremely strong, and even if the adhesive strength of the tape is slightly strong: In the case of ⁇ , the wafer may be damaged when the tape is peeled off, or dicing may occur. Later, the force to expand the film may be too great.
  • the film of the present invention preferably has a coefficient of dynamic friction ( ⁇ d) between the films of 0.5 or less. If the number of friction ( ⁇ d) exceeds 0.5, the handleability during the film forming process and during the application of the adhesive layer will deteriorate, for example, when running on a roll in the process. Or, when wound up in a roll, drawbacks such as scratches may occur.
  • ⁇ d coefficient of dynamic friction
  • the heat shrinkage of the film was determined by calculating the heat shrinkage (SMD) in the film forming direction and the thermal TO ratio (S TD) in the width direction. It is preferable that the absolute value of the difference (
  • SMD heat shrinkage
  • S TD thermal TO ratio
  • the back grinding tape in the present invention has an adhesive layer on the above-mentioned base for back grinding tape-one side of the film.
  • a silicon wafer is stabilized by using a back grinding tape in which an adhesive layer is laminated on one side of a base film for a pack grinding tape for fixing the silicon wafer. It can be fixed in a state.
  • the dicing tape in the present invention has the single-sided pressure-sensitive adhesive layer of the above-mentioned base film for dicing tape.
  • a dicing tape in which an adhesive layer is laminated on one surface of a base film for dicing tape is used for fixing silicon wafers, and silicon wafers are fixed. Can be fixed in a stable state.
  • the base film for a back grinding tape or a dicing tape of the present invention may be provided with a coating layer on at least one surface thereof for the purpose of improving the adhesiveness with an adhesive.
  • the coating layer is preferably made of at least one water-soluble or water-dispersible polymer resin selected from a polyester resin, a urethane resin, an acryl resin, and a butyl resin, and particularly contains both a polyester resin and an attaryl resin. Power S preferred ,.
  • the polyester resin of the coating layer used in the present invention has a glass transition point (T g) of 0 to: L 00 ° C, more preferably 10 to 90 ° C.
  • the polyester resin is soluble in water. Or, a dispersible polyester / resin is preferred, but it may contain some organic solvent.
  • the powerful polyester resin includes a polybasic acid or an ester / ester derivative thereof and a polyol or an estero conductor thereof as described below.
  • polybasic acid components include terephthalenic acid, isophthalenic acid, phthalenic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sepasic acid, trimellitic acid, Examples include melitic acid, dimer acid, and 5-sodium sulfonic acid.
  • a copolymerized polyester resin is synthesized using two or more of these acid components.
  • an unsaturated polycarboxylic acid such as maleic acid, itaconic acid and the like, and hydroxycarboxylic acids such as p-hydroxybenzoic acid.
  • the polyol components include ethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylene glycolone, and dimethylolone.
  • the acryl resin of the coating layer used in the present invention has a glass transition point (Tg) of 150 to 50 ° C, more preferably 150 to 25 ° C.
  • Tg glass transition point
  • the acryl resin is preferably water-soluble or dispersible acryl, but may contain some organic solvent.
  • Such an acryl resin can be copolymerized from the following acrylic monomers.
  • the acrylic monomer include alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butynole, isobutyl, t-butynole, and 2-ethylhexyl). Group, cyclohexyl group, etc.); hydroxy such as 2-hydroxyethyl acrylate, 2-hydroxyethynolemethacrylate, 2-hydroxypropinolate tallate, 2-hydroxypropyl / methacrylate, etc.
  • the composition used in the present invention is preferably used in the form of a water-based coating solution such as a watery night, an aqueous dispersion, or an emulsion in order to form a fine grain.
  • a water-based coating solution such as a watery night, an aqueous dispersion, or an emulsion in order to form a fine grain.
  • other resins other than the above composition for example, a polymer having an oxazoline group, a crosslinking agent such as melamine, epoxy, and aziridine, an antistatic agent, a coloring agent, a surfactant, ⁇ ]
  • a strong lubricant may be added as necessary for the purpose of improving the slipperiness or blocking resistance of the film.
  • the solid content concentration of the aqueous coating solution is usually 20% by weight or less, and preferably 1 to 10% by weight. If the proportion is less than 1% by weight, the coatability on the polyester film will be insufficient, while if it exceeds 20% by weight, the stability of the coating and the coating property may be degraded.
  • the coating layer is applied firmly to the unstretched film or uniaxially stretched film by applying the aqueous coating solution, and then stretched in two or one direction and thermally fixed. Can be opened.
  • a coating method a roll coat method, a gravure coat method, a roll brush method, a spray method, an air knife coat method, an impregnation method, a curtain coat method, or the like can be used or in combination.
  • the pressure-sensitive adhesive constituting the back-grinding tape and the dicing tape of the present invention known pressure-sensitive adhesives can be widely used, but an ataryl-based pressure-sensitive adhesive is preferred.
  • the ataryl adhesive specifically, copolymers with acryl-based polymers and other functional monomers selected from combat insect polymers and copolymers having an acrylic acid ester as a main structural unit. Combinations and mixtures of these polymers are used.
  • acrylic acid esters of alkyl alcohols having 1 to 10 carbon atoms, methacryloleic acid esters of alkyl alcohols having 1 to 10 carbon atoms, vinyl esters of acetic acid, acrylonitrile, and butyl alkyl ether can be preferably used.
  • the above acrylic copolymers can be used alone or in combination of two or more! / You can.
  • the functional monomer for example, atalylic acid, methacrylic acid, maleic acid, 2-hydroxyxethynoleate tallate, 2-hydroxyethyl methacrylate, and the like are used.
  • a cross-linking agent examples include a polyvalent isocyanate compound, a polyvalent epoxy compound, a polyvalent aziridine compound, and a chelate compound.
  • polyvalent isocyanate compounds include toluylene diisocyanate, diphene / lemethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Etc. are used.
  • polyepoxy compound include ethylene glycol diglycidyl ether, terephthalic acid diglycidyl ester atalylate, and the like.
  • polyvalent aziridine compound specifically, tris-2,4,6-((1-aziridinole)-1,3,5-triazine, tris [1-1 (2-methinole) -aziridininole] phosphinoxide, hexa [ 11- (2-Methinole) -aziridininole] Triphosphatriazine or the like is used.
  • the chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), and the like.
  • the molecular weight of the acrylic copolymer obtained by polymerizing these monomers is 1.0 X 10 5 to: 10.0 X 10 5 , preferably 4.0 X 10 5 to 8.5. 0 X 1 0 5.
  • a pressure-sensitive adhesive layer which can be hardened by irradiating a UV ray to reduce the adhesive force at the time of pickup can be used.
  • a pressure-sensitive adhesive containing the above acrylonitrile-based copolymer as a main component and a radiation-polymerizable compound.
  • Such radiation-polymerizable compounds are disclosed, for example, in JP-A-60-196,956 and JP-A-60-223,139.
  • low molecular weight compounds having at least two or more photopolymerizable carbon-carbon double bonds in a molecule that can be three-dimensionally reticulated by light irradiation are widely used, specifically, trimethylol propane triatalylate, and tetramethylol.
  • a polyurethane acrylate oligomer can be used in addition to the above-mentioned atalylate compound.
  • the urethane atalylate-based oligomer is composed of a polyester compound such as a polyester type or a polyethenolate type, and a polyvalent isocyanate compound such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, Hydroxyl groups are present in the terminal isocyanate urethane prepolymer obtained by reacting 3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane 4,4-diisocyanate, etc.
  • This urethane acrylate oligomer is a radiation polymerizable compound having at least one carbon-carbon double bond.
  • Such a urethane acrylate copolymer has a molecular weight of 300 to If a wafer having a size of 300,000, preferably 300,000 to 100,000, and more preferably 400,000 to 800, is used, the wafer chip can be used even for semiconductor wafers and rough surfaces. This is preferable because the adhesive does not adhere to the chip surface during the pick-up. Further, in order to use a urethane acrylate oligomer as a radiation polymerizable compound, at least a photopolymerizable single-carbon double bond must be included in the molecule as disclosed in JP-A-60-196,956.
  • an extremely excellent pressure-sensitive adhesive sheet can be obtained.
  • the adhesive force of the adhesive sheet before irradiation with the ultraviolet ray is sufficiently large, and the adhesive force after irradiation is sufficiently reduced so that the adhesive does not remain on the chip surface when picking up the wafer chip.
  • the pressure-sensitive adhesive layer may contain, in addition to the pressure-sensitive adhesive and the crosslinkable polymerizable compound as described above, a compound that is colored by irradiation with radiation.
  • a compound to be colored to the adhesive layer by such Nada line irradiation, the sheet is colored after the adhesive sheet is irradiated with radiation, and therefore, the wafer sensor is detected by an optical sensor. In this case, the detection accuracy is improved, and no malfunction occurs when picking up a wafer chip. Further, an effect is obtained that whether or not radiation has been applied to the pressure-sensitive adhesive sheet can be immediately determined visually.
  • the compound colored by irradiation with the thigh line include leuco dye.
  • leuco dye triphenylenomethane type, phenololean type, phenothiazine type, auramine type and spiropyran type dyes for poor use are preferably used.
  • Developers preferably used with these leuco dyes include conventionally used electron acceptors such as phenol formalin resin prepolymers, aromatic carboxylic acid derivatives, and activated clay, and the like.
  • Various known color formers can be used in combination.
  • Such a compound that is colored by irradiation with X-rays may be included in the adhesive layer after being dissolved in an organic solvent or the like, or may be included in the adhesive layer in the form of fine powder. .
  • This compound is present in the pressure-sensitive adhesive layer in an amount of 0.01 to 10% by weight, preferably 0.5 to 5% by weight. Desirable, used in an amount of / 0 .
  • the back-grinding tape is usually stored in the form of a back-grid tape in which the surface of the pressure-sensitive adhesive layer is protected by a release film;
  • the release film is peeled off and used in the Indian process. That is, the back grinding tape composite of the present invention further has a release film on the adhesive layer of the back grinding tape.
  • Such a release film is obtained by laminating a silicone release layer on one side of a base film made of polyester, and bonding the silicone release layer surface to the adhesive layer surface of the pack grind tape to form a back grind tape.
  • a silicone release layer is obtained by laminating a silicone release layer on one side of a base film made of polyester, and bonding the silicone release layer surface to the adhesive layer surface of the pack grind tape to form a back grind tape.
  • the release film may further have a primer layer between the silicone release layer and the base film made of polyester.
  • the dicing tape is usually stored in the state of a dicing tape composite in which the surface of the pressure-sensitive adhesive layer is protected by a release film, and the release film is peeled and removed in the dicing process. That is, the dicing tape composite of the present invention further has a release film on the adhesive layer of the dicing tape.
  • a strong release film is made by laminating a silicone release layer on one side of a base film made of polyester.
  • the silicone release layer surface and the adhesive layer surface of the dicing tape are bonded together to form a dicing tape: I do.
  • the release film may further have a primer layer between the silicone release layer and the base film made of polyester.
  • the polyester base film constituting the release film of the present invention may be composed of the same polyester as the base finolem for processing a semiconductor wafer of the present invention, or may be composed of a different polyester.
  • Preferable examples of such polyesters include polyesters containing polyethylene terephthalate and polyethylene_2,6-naphthalenedicarboxylate as main components.
  • “mainly” means that at least 8% of Omo 1% of the repeating unit in the polymer component is ethylene terephthalate or ethylene-1,6-naphthalenedicarboxylate, and more preferably 90%. mo 1% or more, particularly preferably 95 mo 1% or more.
  • the polyester base film which constitutes the release film, is hardened by UV irradiation after curing, dicing, and curing.
  • the light transmittance of the base film is preferably 85% or more.
  • the silicone release layer constituting the release film of the present invention can be formed by applying a coating liquid containing, for example, a curable silicone resin to one surface of a polyester base film, followed by drying and curing.
  • a curable silicone resin include a condensation reaction system, an addition reaction system, an ultraviolet or electron beam curing system, and a reaction system with a deviation, and one or more of such curable silicone resins can be used.
  • the method for producing the base film of the present invention will be described in detail.
  • the polyethylene-2,6-naphthalenedicarboxylate film of the present invention can be obtained by, for example, melt-extruding a resin at a normal extrusion temperature, that is, at a temperature not lower than the melting point (hereinafter referred to as Tm) (Tm + 70 ° C).
  • Tm melting point
  • the obtained film-like melt is quenched on the surface of a rotary cooling drum to obtain an unstretched film having an intrinsic viscosity of 0.40 to 0.90 dl Zg.
  • a static adhesion method of applying an electrostatic charge to the film-like melt is known.
  • polyethylene 1,2,6-naphthalenedioxy propyloxylate has a high electrical resistance of a molten material, so that the above-mentioned electrostatic adhesion to the cooling drum may be insufficient.
  • quaternary sulfonic acid with 0.1 to 10 mmo 1% of esteno-forming functional group based on all bifunctional carboxylic acid components of polyethylene 1,2,6-naphthalene dicanoleboxylate It is preferred to include phosphonium.
  • the unstretched film thus obtained is stretched in the longitudinal direction by a factor of 2.8 to 3.5 times at a temperature of 120 to 170 ° (more preferably, a temperature of 130 to 160 ° C).
  • the film is stretched at a draw ratio of 2.8 to 3.6 times at 120 to 150 ° C in the transverse direction at the next V, and becomes a biaxial film.
  • the elongation ratio is preferably in the range of 0.90 to 1.15 times the longitudinal stretching ratio in order to keep the thickness variation of the film within a desired range.
  • the biaxially oriented film thus obtained may have a biaxially oriented film of from 235 to 255 ° C, more preferably from 240 to 250 ° C.
  • the polyester refinolem of the present invention is heat-treated after winding.
  • the method of heat treatment after winding is not specified, but a hanging-type loosening treatment method is particularly preferable.
  • the suspended fiber treatment method is as follows: the film to be processed is dropped downward by its own weight through a mouthpiece installed above, heated by calories in the middle, and then turned almost horizontally while being cooled by rollers below.
  • winding is performed after the winding tension is cut off by an ep-mouth.
  • the hanging distance is preferably about 2 to 10 m.
  • the heat treatment after the film forming step is performed in the film forming step (relaxation treatment after heat setting) if the heat shrinkage at 200 ° C. of the obtained biaxially oriented polyester film is within a desired range. Even if it is performed, even if it is performed by a relaxation heat treatment after the film is formed and once wound up, the processing method is not particularly limited.
  • a preferred heating method is infrared heat because the film can be immediately calo-heated.
  • a preferred relaxation heat treatment is a treatment in which the film temperature is set to 200 to 240 ° C. If the film temperature is lower than 200 ° C, it is difficult to reduce the heat shrinkage at 200 ° C.
  • the film temperature exceeds 240 ° C
  • the flatness tends to be worse.
  • ⁇ the oligomer may precipitate and the film may become white. This whitening depends on the pressure history. For example, if a hanging belt is transported over the film part of a film roll, it will be 200. Even if it is less than C, the belt and the infested part are whitened: ⁇ .
  • the film fi3 ⁇ 4 can be measured using a non-inverting infrared spectrometer (eg, a Burns ⁇ n radiometer).
  • the suspension relaxation heat treatment method is preferable to the heat treatment in the film forming process because the heat shrinkage in a wide range of buoy / REM can be suppressed more uniformly.
  • polyester base films that make up release films have been known for some time. Or can be obtained by methods that are accumulated in the art. That is, the unstretched polyester film that has been melted and extruded is uniaxially stretched, then stretched in a direction perpendicular to the stretching direction, and further subjected to a heat setting treatment.
  • ⁇ can be applied, for example, by applying a coating liquid containing a component of a release layer to a polyester base film and drying by heating.
  • a known coating method can be applied as a 'coating liquid' coating method, and for example, a low / coater method or a blade coater method can be used.
  • Each composite is obtained by laminating the release film obtained by the above method on a pack grind tape dicing tape.
  • the film is held in an oven set at a temperature of 200 ° C without tension for 10 minutes, and the dimensional change before and after the heat treatment is calculated as the heat shrinkage S (%) by the following equation (1). . ⁇
  • L. Distance between gauges before heat treatment
  • L distance between gauges after heat treatment.
  • the sample width is 20 mm and length is 200 mm
  • the distance between gauge points before heat treatment is 150 mm.
  • the heat shrinkage was determined by measuring in both the machine direction (MD) and width direction (TD) of the film.
  • the oligomer deposition rate as a percentage of the total area occupied by oligomers (appearing as white spots) with respect to the total area of the photograph is evaluated.
  • the refractive index in the thickness direction (z) of the film was determined at 25 ° C using a Na-D line.
  • the measurement is performed in both the film forming direction (MD) and the width direction (TD) of the finolem, and the Young's modulus is calculated from the tangent at the top of the obtained load-elongation curve.
  • the cut-off is 0.25 mm
  • the measuring probe is 3 ⁇ .
  • a surface roughness meter (trade name “Surfcom SE-3CK” manufactured by Tokyo Seimitsu Co., Ltd.) ) Measure at.
  • Film thickness ⁇ ⁇ Using a micrometer (trade name “K-402B” manufactured by Anritsu Corporation), the film thickness is 10 cm in each of the film forming direction (MD) and width direction (TD). The film thickness is measured at a total of 300 locations. The average value of the film thickness at 300 locations was calculated and the average film thickness t was calculated. ( ⁇ ).
  • the film was made in the J ⁇ direction (MD) and the width direction (MD) at a needle pressure of 30 g and a running speed of 25 mmsec.
  • TD Measure over a length of 2m each, and get a chart.
  • the maximum thickness t ( ⁇ ) and the minimum thickness t 2 ( ⁇ ) are read from this chart. Average thickness t of the film thus obtained.
  • ( ⁇ ) and the maximum thickness ( ⁇ , the minimum thickness t 2 ( ⁇ m), and force), and calculate the thickness variation D (%) using the following equation (3): D t 2 ) / t. ] X 1 00... (3)
  • a stack of two 75mm (width) x 10 Omm (length) cut huinolems (sampnoles), a weight of 200 g is placed as a load W (g), and the upper film is slid at a speed of 150 mmZ. Calculate the number of moving and shaking from the force F d (g) when sliding. The film is measured after conditioning for 24 hours at 23 ° C and 65% R ⁇ . Number of dynamics F d , W
  • the film was held for 10 minutes in an oven set at a temperature of 200 ° C without tension, and before and after each heat treatment in the film forming direction (MD) and width direction (TD). From the dimensional change, (1)
  • the heat shrinkage S (%) is calculated by the following equation (1), as in the case of the heat shrinkage, and the absolute value of the difference in the heat shrinkage in both directions is calculated.
  • L0 distance between gauge points before heat treatment
  • L distance between gauge points after heat treatment
  • the density of the biaxially oriented polyethylene-1,6-naphthalenedicarboxylate film was measured according to JIS C2151.
  • dicing depth 20 ⁇ from tape surface
  • four push-up pins diameter of suction holder: 28 ⁇
  • collet pyramid collet
  • throw-up distance 2mm
  • dicing size 8111111 It is 8111111.
  • Polymer C a polyethylene-1,6-naphthalenediene ruboxylate polymer having an intrinsic viscosity of 0.62 dlZg (referred to as “Polymer C”) was obtained. 170 ° C of this polymer C After being dried for 6 hours in the extruder, it is melted at a temperature of 30 ° C and melted through a slit die with an opening of l mm. The surface finish is 0.3 S, and the rotating drum has a surface temperature of 50 ° C. This was extruded to obtain an unstretched film.
  • the unstretched film thus obtained is stretched 3.3 times in the direction (orientation) at 144, and then stretched 3.4 times in the transverse direction (width direction) at 140 ° C. Further heat-setting at 243 ° C for 5 seconds ⁇ ⁇ Shrink 5% in the width direction (tow-in) and apply a biaxially oriented PEN film with a thickness of 16 ⁇ m and an intrinsic viscosity of 0.5 2 d 1 / g to 1 It was wound up into a 300-Om width in a 50-Omm width.
  • the obtained biaxially oriented PEN film is dripped downward by its own weight via the nip roller installed above, and the infrared excitation filter is set so that the finolem ⁇ J becomes 2225 ° C on the way.
  • the roller After heating with a heating device, the roller is turned almost horizontally while cooling with a roll roller located 4 m below the roller installed above, winding off the winding tension with a nip roller, and winding and relaxing heat treatment. went. Relaxation was performed by using the difference in speed between the upper nip roller and the nip roller that shuts off the winding tension.
  • Example 1 shows the property evaluation results of the obtained film of Example 1.
  • a good pick-up operation could be performed without causing a malfunction due to a malfunction of the diponder device due to a change in the thermal dimension of the film, a variation in the thickness of the film or the flatness of the film.
  • the semiconductor layer in the adhesive layer coating process was not contaminated, and the processing process was not contaminated.Further, the film was not broken by peeling off the tape, and the processing performance in manufacturing semiconductor wafers was good. .
  • Example 2 The same operation as in Example 1 was repeated except that the stretching ratio in the direction of »was changed to 2.9 times, the stretching ratio in the horizontal direction was changed to 3.1 times, and the suspension relaxation heat treatment was not performed. A 5 ⁇ m biaxially oriented PEN film was obtained.
  • Table 1 shows the property evaluation results of the obtained film of Example 2.
  • the film thickness and workability of the example film there was no failure due to the malfunction of the die bonder device due to the change in the thermal dimension of the film, the thickness variation of the film, the flatness of the film, etc. Was.
  • the inside of the adhesive layer coating process and the semiconductor No dyeing was observed, and no film was broken by tape peeling, and the workability in the production of semiconductor wafers was good.
  • Example 3 a two-layer film was formed as follows. First, add 0.03 parts of manganese acetate tetrahydrate to a mixture of 100 parts of dimethyl 2,6-naphthalenedicarboxylate and 60 parts of ethylene glycol, and gradually raise the temperature from 150 ° C to 240 ° C. The transesterification was carried out while performing the reaction. Way, the reaction of antimony trioxide was added 0.024 parts at which point 1 70 ° C, further average elevation diameter 0.5 0.1 5 wt carbonate Cal Shiumu particles ⁇ 0 /. Was added. And the reaction temperature is 220.
  • each of these polymers After drying each of these polymers at 170 ° C for 6 hours, they are fed to two separate extruders, each melted at 300 ° C, and co-extruded to form slits with an opening of 1 mm.
  • the mixture was extruded through a die onto a rotating drum having a surface finish of 0.3 S and a surface of ⁇ J at 50 ° C to obtain a two-layer unstretched film.
  • This unstretched film was successively biaxially stretched in the same manner as in Example 1 and heat-set to obtain a film thickness of 16 ⁇ m (polymer A layer side: 10 ⁇ m, polymer B layer side: 6 ⁇ ⁇ ).
  • a biaxially oriented PEN film having a viscosity of 0.54 d 1 / g was wound up in a roll shape of 300 Om with a width of 150 Omm.
  • the obtained biaxially oriented PEN film was subjected to a relaxation treatment using the same suspension-type relaxation heat treatment apparatus.
  • the biaxially oriented PEN film after the relaxation treatment thus obtained was used as Example 3.
  • Table 1 shows the property evaluation results of the obtained films of the examples.
  • the film and workability of these films there was no failure due to a malfunction of the die bonder unit due to a change in the thermal dimension of the film, a variation in the thickness of the film, or the flatness of the film, and a good pick-up operation was performed. Further, the inside of the adhesive layer coating step, the semiconductor wafer, and the processing step were not contaminated, and further, the film was not broken by tape peeling, and the workability in the production of the semiconductor wafer was good.
  • a 50m film of "Kapton; Type H” manufactured by Toray DuPont was used.
  • Table 1 shows the characteristics of the film. Although the thermal dimensional change of the film was excellent, the dimensional stability under high humidity was poor due to the high water absorption.
  • This polymer was dried at 170 ° C for 3 hours, fed to an extruder, melted at 290 ° C, passed through a slit die with an opening of 1 mm, surface finish 0.3 S, surface It was extruded on a rotating drum at a temperature of 25 ° C to obtain an unstretched film.
  • the unstretched film obtained in this way is increased 3.2 times in the longitudinal direction (film forming direction) at 90 ° C. Stretched, then stretched 3.8 times in the transverse direction (width direction) at 120 ° C, and heat-set at 210 ° C for 5 seconds.
  • a biaxially oriented polyethylene terephthalate film having 16, ⁇ ⁇ and an intrinsic viscosity of 0.55 dl Zg was wound into a roll of 3500 m in width of 1500 mm. After that, the obtained biaxially oriented polyethylene terephthalate film is suspended downward by its own weight through a nip roller installed above, and the infrared heating device is set so that the film temperature becomes 180 ° C in the middle.
  • Table 1 shows the property evaluation results of the obtained film of Comparative Example 2.
  • the chip was misaligned due to the poor dimensional stability of the film, and malfunctions occurred due to malfunction of the diponder device.
  • the amount of oligomer “a” contaminating the inside of the adhesive layer coating step and the inside of the semiconductor wafer processing step was found. Also, the oligomer precipitation rate on the film surface after heating was high.
  • Example 3 As Comparative Example 3, the same operation as in Example 2 was repeated except that the stretching ratio in the longitudinal direction was changed to 3.6 times and the stretching ratio in the transverse direction was changed to 3.7 times. An axially oriented PEN film was obtained.
  • Table 1 shows the results of evaluating the characteristics of the fi / rem of Comparative Example 3 obtained.
  • the thermal dimensional change of the film exceeds 1.0% in both the vertical and horizontal directions of the film, resulting in wafer processability, chip displacement, etc., and failure due to malfunction of the diponder device. occured.
  • Comparative Example 4 the same operation as in Example 1 was repeated except that the stretching ratio in the horizontal direction was changed to 3.6 times and the stretching ratio in the horizontal direction was changed to 3.9 times, and the suspension-type relaxation fiber treatment was performed. Thus, a biaxially oriented PEN film having a thickness of 20 m was obtained. Table 1 shows the results of the regeneration evaluation of the obtained film of Comparative Example 4. The change in the thermal dimension of the film exceeded 1.0% in the longitudinal direction of the film, and in the case of the wafer and the workability, the chip was misaligned and the die bonder device failed due to malfunction.
  • Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Layer Configuration Single Layer Single Layer Two Layer Single Layer Single Layer Single Layer Single Layer Polymer Polymer C Polymer C Polymer AI Bolima B-One Polymer C Polymer C Added particles
  • Type Spherical silica Spherical silica Calcium carbonate I Spherical silica-Spherical silica Spherical silica Spherical silica Particle size U m 0.4 0.4 0.5 0.1-0.4 0.4 0.4 Amount added% by weight 0.20 0.20 0.15 0.05 1 0.20 0.20 0.20 0.20 Longitudinal stretching magnification 3.3 2.9 3.3 ⁇ 3.2 3.6 3.6 imJ3 ⁇ 4. 145 145 145 1 90 145 145 Lateral stretching magnification ⁇ 3.4 3.1 3.1 ⁇ 3.8 3.7 3.9
  • 2,6-Naphthalenediphenyl dimethyl sulfonate (100 parts) and ethylene glycol (60 parts) are mixed with 0.03 parts of manganese acetate tetrahydrate, and the temperature is gradually raised from 150 ° C to 240 ° C. While performing an estenole exchange reaction. During the reaction, when the reaction temperature reached 170 ° C, 0.024 parts of antimony trioxide was added, and spherical silica particles having an average particle diameter of 0.6 ⁇ m and a particle diameter ratio of 1.1 were added. 1% by weight was added.
  • reaction temperature reached 220 ° C.
  • 0.042 parts corresponding to 2 mmol% of 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt was added.
  • an ester exchange reaction was subsequently carried out, and after the transesterification reaction was completed, 0.023 parts of trimethinol phosphate was added.
  • the reaction product was transferred to a polymerization reactor, heated to 290 ° C, and subjected to a polycondensation reaction under a high vacuum of 0.2 mmHg or less.
  • Polyethylene-1,2,6-naphthalene di- ore-boxylate polymer (polymer D) with an intrinsic viscosity of 0.43 d1 / g measured at night and polyethylene-1,2,6 with an intrinsic viscosity of 0.69 dlZg —A naphthalenedicarboxylate polymer (Polymer E) was obtained.
  • Polymer E was further solid-phase polymerized to have an intrinsic viscosity of 0.78 dlZg (Polymer F).
  • Polymer E 170 After drying at C for 6 hours, it is fed to an extruder, melted at a melting temperature of 305 ° C, extruded through a slit die with an opening of lmm, onto a rotating drum with a surface finish of 0.3 S and a surface of 50 ° C. An unstretched film was obtained.
  • the unstretched film thus obtained is stretched 3.0 times in the longitudinal direction (film forming direction) at 145 ° C, and then stretched 3.0 times in the transverse direction ( ⁇ ⁇ direction) at 140 ° C in the next step. Then heat-set at 246 ° C for 5 seconds. @ 3 ⁇ 4 ⁇ Shrink 4% in the width direction (tow-in) and apply a 30 ⁇ m thick, 0.59 d 1 / g biaxially oriented PEN film to the 1 It was wound up in a 50 Omm width and 300 Om mouth shape.
  • the obtained biaxially oriented PEN film is dripped downward by its own weight via a roll-up roller installed at the top, and the infrared temperature is adjusted so that the film temperature becomes 225 ° C on the way.
  • the nip roller was placed 4 m below the roller placed above, and the direction was changed almost horizontally while cooling with a nip roller. Winding tension was cut off by a nip roller, and then the film was wound and subjected to relaxation heat treatment. Relaxation cuts off the winding tension with the upper nip roller. I went there.
  • Example 4 The biaxially oriented PAN film thus obtained after the relaxation treatment was used as Example 4.
  • Table 2 shows the property evaluation results of the obtained film of Example 4.
  • a good pick-up operation could be performed without a failure due to a malfunction of the die bonder device due to a change in the thermal dimension of the film, a variation in the thickness of the film or the flatness of the film.
  • the semiconductor wafer and the processing step were not contaminated in the adhesive layer coating step, the film was not broken by tape peeling, and the workability in the production of the semiconductor wafer was good.
  • Example 5 The same operation as in Example 4 was repeated except that polymer F was used in Example 4, to obtain a 50- ⁇ m-thick biaxially oriented PAN film.
  • the biaxially oriented PEN film thus obtained was used as Example 5.
  • Table 2 shows the property evaluation results of the obtained film of Example 5.
  • the heat and workability of the film of the example there was no failure due to the malfunction of the diponder device due to the change in the thermal dimension of the film, the variation in the thickness of the film, the flatness of the film, and the like, and a good pick-up operation was performed.
  • the inside of the adhesive layer coating process, the semiconductor coating, and the inside of the processing process were not contaminated, and further, the film was not broken by tape peeling, and the workability in the production of semiconductor wafers was good.
  • Example 4 the same as Example 4, except that the film was stretched 3.3 times in the machine direction at 145 ° C, and then stretched 3.3 times in the direction at 140 ° C. The operation was repeated to obtain a biaxially oriented ⁇ ⁇ ⁇ film having a thickness of 30 ⁇ m.
  • the biaxially-oriented film obtained in this manner was used as Example 6.
  • Table 2 shows the property evaluation results of the obtained films of the examples.
  • a good pick-up operation could be performed without causing a failure due to a malfunction of the diponder device due to a change in the thermal dimension of the film, a variation in the thickness of the film or the flatness of the film.
  • the inside of the adhesive layer coating step, the semiconductor wafer, and the processing step were not contaminated, and the tape was not broken by peeling off the tape.
  • the flexibility in the production of semiconductor wafers was good.
  • Example 7 The same operation as in Example 4 was repeated except that Polymer D was used in Example 4, to obtain a biaxially oriented PAN film having a thickness of 50 ⁇ m.
  • the biaxially oriented PEN finolem thus obtained was used as Example 7.
  • Table 2 shows the property evaluation results of the obtained film of Example 7.
  • a good pick-up operation was performed without any failure due to malfunction of the die bonder due to changes in the thermal dimensions of the film, variations in the thickness of the film, and flatness of the film.
  • contamination in the process due to oligomer precipitation on the film surface occurred.
  • Example 6 the same operation as in Example 6 was repeated except that the amount of the inert particles contained in the film was set to 0.01% by weight and the heat setting was set to 233 ° C. A 30 ⁇ m biaxially oriented PEN film was obtained. The biaxially oriented PEN film / rem obtained in this manner was used as Example 8.
  • Table 2 shows the property evaluation results of the obtained film of Example 8.
  • the thermal dimensional change of the film is small, the difference in the thermal shrinkage in the vertical and horizontal directions exceeds the desired range, so that there is a slight problem in the stability in the production of semiconductor wafers. It was hot.
  • Example 4 except that the film was stretched 2.7 times in the ifc direction at 145 ° C, and stretched 2.7 times in the horizontal direction at 140 ° C in Example 4. The same operation as in 4 was repeated to obtain a biaxially oriented ⁇ ⁇ ⁇ film having a thickness of 30 ⁇ .
  • the biaxially-oriented film obtained in this manner was referred to as Run # 9.
  • Table 2 shows the property evaluation results of the obtained films of the examples. Deterioration of the film process, although the thermal dimensional change of the film is small, the refractive index in the film thickness direction is high, causing contamination in the process due to film chips, etc., and film tearing at the time of tape peeling. did. [Table 2]

Landscapes

  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Dicing (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

A base film for semiconductor wafer processing is disclosed which mainly contains polyethylene-2,6-naphthalene dicarboxylate, exhibits excellent dimensional stability, smoothness, mechanical strength under high temperature, high humidity conditions, and has an excellent processing aptitude. This base film for semiconductor wafer processing is a biaxially oriented film mainly containing polyethylene-2,6-naphthalene dicarboxylate. The thermal shrinkage rate of this base film when heat-treated at 200˚C for 10 minutes is not more than 1.00% in both the film-forming direction and the width direction.

Description

明細書 半導体ウェハ加工用ベースフィルム  Description Base film for processing semiconductor wafers
技術分野 Technical field
本発明は、 ポリエチレン一 2， 6一ナフタレンジカルボキシレートを主たる成分 としてなる二軸配向フィルムを用いた半導体ウェハ加工用ベースフィルムに関する。 更に詳しくは、 半導体ウェハ加工、 特にパックグラインドエ程またはダイシングェ 程において、 パックグラインドテープの基材あるいはダイシングテープの基材とし て用いた際、 優れた寸法安定性、 平滑性、 «強度を有するバックグラインドテー プ用またはダイシングテープ用ベースフィルムに関する。  The present invention relates to a base film for processing a semiconductor wafer using a biaxially oriented film containing polyethylene-1,2,6-naphthalenedicarboxylate as a main component. More specifically, when used as a base material of a pack grinding tape or a base material of a dicing tape in semiconductor wafer processing, particularly in a pack grinding process or a dicing process, a bag having excellent dimensional stability, smoothness, and strength. The present invention relates to a base film for grinding tape or dicing tape.
従来の技術  Conventional technology
半導体製造におけるウェハ裏面の研磨工程 （バックグラインド工程） と、 完成し ■ たウェハから I Cチップを切断する工程 （ダイシング工程） では、 種々の粘着剤を 積層した粘着テープがゥェハの固定用に使用される。 バックグラインドエ程にぉ ヽ て表面に回路形成されたゥヱハは粘着テープに固定された状態で裏面を研磨され、 UV照射や加熱などにより粘着剤の粘着力が された後、 次のダイシング工程へ 移動する。 ダイシングェ程では粘着テープに固定されたウェハが個々の I Cチップ 単位に力ッティングされ、 パックグラインドエ程と同様に UV照射や加熱などによ り粘着剤の粘着力が低減された後、 一つづつ取り出される。 取り出された I Cチッ プは次のボンディング工程、 モールディング工程に移送される。  In the process of polishing the back surface of the wafer (back grinding process) in semiconductor manufacturing and the process of cutting IC chips from the completed wafer (dicing process), adhesive tapes laminated with various adhesives are used for fixing wafers. You. After the back-grinding process, the back surface is polished while the circuit is formed on the front surface while being fixed to the adhesive tape, and the adhesive strength of the adhesive is increased by UV irradiation or heating. Moving. In the dicing process, the wafers fixed on the adhesive tape are force-tipped into individual IC chips, and the adhesive force of the adhesive is reduced by UV irradiation or heating, as in the pack grinding process, and then one by one. Taken out. The extracted IC chip is transferred to the next bonding step and molding step.
従来、 ダイシングテープの粘着フィルム及び離形フィルムの基材フィルムとして は、 ポリオレフイン及びその共重合体、 ポリ塩化ビュル及ぴその共重合体、 ポリエ ステル、 ポリカーボネート、 ポリアミド、 ポリイミド等のプラスチックフィルムが 用いられており、 最近では«的強度、 寸法安定性、 耐熱 14、 価格等の点で、 例え ば、 特開平 5—1 7' 5 3 3 2号公報、 特開平 1— 5 8 3 8号公報に示されたように ポリエステルフィルムが用いられるようになってきている。 一方、 ポリエステ/レフ イルム及ぴシリコーン樹脂離形層に含まれている不純物に起因するシリコンウェハ の歩留り低下を防止する目的で、 重合触媒にゲルマニウム化合物を適用する （特開 ¥ 1 0 - 2 1 4 8 0 1号公報） 方法が開示されている。 また、 同様な低汚染性の観 点からノ ックグラインドテープやダイシングテープの保管における粘着層保護用の 離型フィルムに関する技術が特開平 1 1— 2 0 1 0 5号公報により開示されている。 ところで、 近頃の半導体の高集積化に伴い、 半導体ウェハの薄肉化が急速に進行 している中で、 ウエノヽ厚みの薄肉化に適した新たな半導体ウェハ加工技術が考案さ れてきている。特にウェハ厚みが非常に薄くなってきたために従来の研磨方法では、 ウェハの破損や従来よりも研磨に時間がかかる等の課題があり、 加工技術として例 えばプラズマでエッチングをする方法等が考案されてきている。 Conventionally, plastic films such as polyolefin and its copolymer, polychlorinated vinyl and its copolymer, polyester, polycarbonate, polyamide, and polyimide have been used as the base film of the adhesive film and the release film of the dicing tape. Recently, for example, in terms of target strength, dimensional stability, heat resistance 14, and price, see, for example, Japanese Patent Application Laid-Open Nos. 5-17'5332 and 1-5838. As indicated, polyester films are being used. On the other hand, a germanium compound is applied to a polymerization catalyst for the purpose of preventing a decrease in the yield of a silicon wafer caused by impurities contained in the polyester / reflective film and the silicone resin release layer (Japanese Patent Laid-Open A method is disclosed. Further, from the viewpoint of the same low contamination, a technology relating to a release film for protecting an adhesive layer in storage of a knock grind tape or a dicing tape is disclosed in Japanese Patent Application Laid-Open No. H11-2010. . By the way, in recent years, as semiconductor wafers have become more highly integrated, semiconductor wafers have been rapidly becoming thinner, and new semiconductor wafer processing techniques suitable for thinner wafers have been devised. In particular, since the wafer thickness has become extremely thin, the conventional polishing method has problems such as damage to the wafer and longer polishing time than before. For example, a plasma etching method has been devised as a processing technique. Is coming.
しかしながら、 新たに考案された加工方法では、 従来の加工方法に比べて加工温 度が高温になるため、 従来のポリエステルフィルムを ¾|才とした半導体ウエノ、加工 用フィルムでは、 その熱寸法安定性や機械強度が課題となってきている。 また、 ダ イシング工程では一般にテープ剥離の際、 カロ熱や UV照射により粘着剤の粘着力を 弱めた後、 切断した各チップをピックアップするためにテープのエキスパンドを行 う方法やテープ側からチップを突上げる方法を用いてチップ間に隙間を開けている 1 カロ熱時のテープの寸法収縮が大きいとチップのピックアップ不良力 S発生し、 半 導体ウェハの生産効率が悪くなることが誦となってきている。  However, with the newly devised processing method, the processing temperature is higher than that of the conventional processing method. And mechanical strength are becoming issues. In addition, in the dicing process, when the tape is peeled, generally, the adhesive strength of the adhesive is reduced by calorie heat or UV irradiation, and then the tape is expanded to pick up each cut chip, or the chips are removed from the tape side. There is a gap between the chips by using the push-up method.1 It is often said that if the tape shrinks greatly when the heat of calorie heats up, a chip pick-up force S occurs and the production efficiency of semiconductor wafers deteriorates. ing.
一方、 フィルムとしてポリイミドを用いた 、 p及 τΚ率が高いために、 より 高レ、寸法安定性が求められている。  On the other hand, when polyimide is used as the film, the p and τΚ ratios are high, so that higher levels and dimensional stability are required.
さらに、 半導体ウェハの生産性を向上させるために、 工程内のクリーン化や加工 性の改良が常に追求されている。  Furthermore, in order to improve the productivity of semiconductor wafers, cleanliness in the process and improvement of workability are constantly pursued.
(特許文献 1 ) 特開平 5— 1 7 5 3 3 2号公報  (Patent Document 1) Japanese Patent Application Laid-Open No. 5-1755332
(特許文献 2 ) 特開平 1一 5 8 3 8号公報  (Patent Document 2) Japanese Patent Application Laid-Open No. Hei 11-5838
(特許文献 3 ) 特開平 1 0— 2 1 4 8 0 1号公報  (Patent Literature 3) Japanese Patent Application Laid-Open No. H10-102-148081
(特許文献 4 ) 特開平 1 1一 2 0 1 0 5号公報  (Patent Document 4) Japanese Patent Application Laid-Open No. H11-20110
発明の開示  Disclosure of the invention
本発明の目的は、 力、かる従来技術の を解決して、 半導体ウェハ加工、 特にバ ックグラインドテープの基材あるいはダイシングテープの基材として用いた際に、 高温下ならびに高湿下での優れた寸法安定性、 平滑性、 «強度、 およ！^れたカロ ェ適正を有する半導 ロェ用ベースフィルムを得ることを目的とする。 本発明のさらに他の目的おょぴ利点は以下の説明から明らかになろう。 The object of the present invention is to solve the problems of the prior art and to solve the problems of the prior art, and to use the semiconductor wafer at a high temperature and a high humidity when used as a substrate of a back grinding tape or a substrate of a dicing tape. Excellent dimensional stability, smoothness, «strength, and! The purpose is to obtain a semiconductor film base film with good caroet aptitude. Further objects and advantages of the present invention will become apparent from the following description.
本宪明によれば、 本発明の上記目的およひ利点は、 第 1に、  According to the present description, the above objects and advantages of the present invention are:
ポリエチレン一 2 , 6一ナフタレンジカルボキシレートを主たる成分としてなる二 軸配向フィルムであって、 2 0 0 °Cで 1 0分間熱処理した際のフィルムの熱収縮率 力 フィルムの製膜方向および幅方向のいずれも 1 . 0 0 %以下である半導体ゥェ ノヽ加工用ベースフィルムによつて達成される。 Polyethylene-1,2,6-biaxially oriented film containing naphthalenedicarboxylate as a main component, heat shrinkage of film when heat-treated at 200 ° C for 10 minutes Force Film forming direction and width direction Both are achieved by the base film for processing semiconductors having a content of 1.0% or less.
また、 本発明によれば、 本発明の上記目的およひ利点は、 第 2に、  According to the present invention, the above objects and advantages of the present invention are:
半導体ウェハ加工用ベースフィルムが、 パックグラインドテープ用またはダイシン グテープ用である上記第 1の本発明に記載の半導体ウエノ、加工用ベースフィルムに よっても達成される。 The present invention is also achieved by the semiconductor wafer and the base film for processing according to the first aspect of the present invention, wherein the base film for processing a semiconductor wafer is for a pack grinding tape or a dicing tape.
さらにまた、 本発明によれば、 本発明の上記目的およひ利点は、 第 3に、 フィルムの抽出ォリゴマー量が 0. 8重量％以下であり、 フィルムの厚み方向の屈 折率が 1 . 5 0 1以上 1 . 5 1 5以下である上記第 1の本発明に記載の半導体ゥェ ハ加ェ用ベースフィルムによっても達成される。  Furthermore, according to the present invention, the above objects and advantages of the present invention are: Third, the amount of extracted oligomer in the film is 0.8% by weight or less, and the refractive index in the thickness direction of the film is 1.8%. The present invention is also attained by the base film for semiconductor wafers according to the first aspect of the present invention, which has a value of not less than 501 and not more than 1.515.
本発明によれば、 本発明の上記目的およひ利点は、 第 4に、  According to the present invention, the above objects and advantages of the present invention are:
上記第 1または第 2の本発明のバックグラインドテープ用ベースフィルムの片面に 粘着剤層を有するバックグラインドテープ、 上記第 1または第 2の本発明のダイシ ングテープ用ベースフィルムの片面に粘着剤層を有するダイシングテープの少なく ともいずれか 1つによって達成される。 A back grinding tape having an adhesive layer on one surface of the base film for a back grinding tape of the first or second invention, and an adhesive layer on one surface of the base film for a dicing tape of the first or second invention. This is achieved by at least one of the dicing tapes.
さらに、 本発明によれば、 本発明の上記目的およひ利点は、 第 5に、  Further, according to the present invention, the above objects and advantages of the present invention are:
上記第 4の本発明のパックグラインドテープの粘着剤層の上にさらに離形フィルム を有するパックグラインドテ一^复合体、 上記第 4の本発明のダイシングテープの 粘着剤層の上にさらに離形フィルムを有するダイシングテー^复合体の少なくとも いずれか 1つによって達成される。 A pack grind tape composite further comprising a release film on the pressure-sensitive adhesive layer of the pack grind tape of the fourth present invention, and a release further on the pressure-sensitive adhesive layer of the dicing tape of the fourth present invention This is achieved by at least one of the dicing tabs having a film.
発明の効果  The invention's effect
本発明の半導体ゥェハ加工用ベースフィルムは、 高温下ならぴに高湿下での優れ た寸法安定性、 平滑性および機械強度に優れている。 特に、 半導体ウエノ、加工に使 用されるダイシングテープ用またはパッゥグラインドテープ用として好適である。  The base film for processing a semiconductor wafer of the present invention is excellent in dimensional stability, smoothness and mechanical strength under high temperature, especially under high humidity. In particular, it is suitable for semiconductor wafers, dicing tapes used for processing, or pad grinding tapes.
発明を実施するための最良の形態 くポリエチレン— 2， 6一ナフタレンジカルポキシレートフィルム > BEST MODE FOR CARRYING OUT THE INVENTION Polyethylene-2,61-naphthalenedicarboxylate film>
本発明において、 半導体ウエノヽ加ェ用ベースフィルムは、 ポリエチレン一 2 , 6 一ナフタレンジカルボキシレート （以下、 P E Nと称することがある。） を主たる成 分とし、 コポリマー又は混合体でもよい。 このポリエチレン一 2 , 6—ナフタレン ジカルボキシレートは、 主たるジカルボン酸成分は、 ナフタレンジカルボン酸であ り、 主たるグリコール成分は、 エチレングリコーノレである。 ここで、 ナフタレンジ カルボン酸としては、 たとえば 2 , 6—ナフタレンジカルボン酸、 2 , 7—ナフタ レンジカルボン酸、 1 , 5—ナフタレンジカルボン酸等を挙げることができ、 これ らの中で 2 , 6—ナフタレンジカルボン酸が好ましい。 また主たるとは、 本発明の フィルムの成分であるポリマーの構成成分にぉレ、て全橾返し単位の少なくとも 8 0 m o 1 %がエチレン一 2 , 6—ナフタレンジカルボキシレートであることを意味し、 更に好ましくは 9 0 m o 1 %以上、 特に好ましくは 9 5 m 0 1 %以上である。 すな わち、 本発明のポリエチレン一 2， 6—ナフタレンジカルボキシレートフィルム本 来の特性を極端に失うことがなく、 高温下の使用での寸法安定性、 «強度を確保 できればよい。  In the present invention, the base film for semiconductor wafers is mainly composed of polyethylene-12,61-naphthalenedicarboxylate (hereinafter sometimes referred to as PEN), and may be a copolymer or a mixture. In this polyethylene 1,2,6-naphthalene dicarboxylate, the main dicarboxylic acid component is naphthalenedicarboxylic acid, and the main glycol component is ethylene glycolone. Here, examples of the naphthalenedicarboxylic acid include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and the like. —Naphthalenedicarboxylic acid is preferred. Mainly means that at least 80 mo 1% of the total repeating units are ethylene-1,2,6-naphthalenedicarboxylate, which is a component of the polymer which is a component of the film of the present invention. It is more preferably at least 90% mo, particularly preferably at least 95% mo. In other words, it is sufficient that the polyethylene-1,2,6-naphthalenedicarboxylate film of the present invention does not extremely lose its original properties and that dimensional stability and high strength can be ensured when used under high temperatures.
コポリマーである ¾1ま、 主たる成分のエチレン一 2 , 6—ナフタレンジカノレボ キシレート以外のコポリマーを構成する共重合成分としては、 分子内に 2つのエス テノ1^成性官能基を有する化合物を用いることができる。 カゝかる化合物として例え ば、 シユウ酸、 アジピン酸、 フタル酸、 セパシン酸、 ドデカンジカルボン酸、 イソ フタル酸、 テレフタル酸、 1， 4ーシクロへキサンジカルボン酸、 4 , 4 ' —ジフ ェニルジカルボン酸、 フエニルインダンジカルボン酸、 2 , 7—ナフタレンジカル ボン酸、 テトラリンジカルボン酸、 デカリンジカルボン酸、 ジフエ-ルェーテルジ カルボン酸等の如きジカルボン酸を好ましく用いることができる。 また、 p—ォキ シ安息香酸、 P—ォキシェトキシ安息香酸等の如きォキシカルボン酸も好ましく用 いることができる。 さらにまた、プロピレングリコール、 トリメチレングリコール、 テトラメチレングリコール、 へキサメチレングリコール、 シクロへキサンメチレン グリコール、 ネオペンチルグリコール、 ビスフエノールスルホンのエチレンォキサ イド付加物、 ビスフエノール Aのエチレンオキサイド付加物、 ジエチレングリコー ル、 ポリエチレンォキシドグリコール等の如き 2価アルコール類等も好ましく用い ることができる。 As a copolymer, a compound having two esteno-1 ^ functional groups in the molecule is used as the copolymerization component of the copolymer other than the main component ethylene-1,2,6-naphthalenedicanoleboxylate. be able to. Examples of such compounds include oxalic acid, adipic acid, phthalic acid, sebacic acid, dodecanedicarboxylic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, Dicarboxylic acids such as phenylindanedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, tetralindicarboxylic acid, decalindicarboxylic acid and diphenyletherdicarboxylic acid can be preferably used. In addition, oxycarboxylic acids such as p-oxybenzoic acid and p-oxochetoxybenzoic acid can also be preferably used. Furthermore, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexanemethylene glycol, neopentyl glycol, ethylene oxide adduct of bisphenol sulfone, ethylene oxide adduct of bisphenol A, diethylene glycol And dihydric alcohols such as polyethylene oxide glycol are also preferably used. Can be
これらの化合物は 1種のみでなく 2種以上を同時に用いることができる。 またこ れらの化合物の中でも、 酸成分としてはイソフタル酸、 テレフタル酸、 4， 4 ' 一 ジフエ-ルジカルボン酸、 2 , 7—ナフタレンジカルボン酸、 p—ォキシ安息香酸 1S またグリコーノレ成分としてはトリメチレングリコーノレ、 へキサメチレングリコ ールネオペンチルグリコールおょぴビスフエノールスルホンのエチレンォキサイド 付加物が好ましい。  These compounds can be used alone or in combination of two or more. Among these compounds, isophthalic acid, terephthalic acid, 4,4'-diphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, p-oxybenzoic acid 1S are used as the acid component, and tris are used as the glycolone component. Methylene glycolone, hexamethylene glycol neopentyl glycol and bisphenol sulfone ethylene oxide adducts are preferred.
また、 本発明で使用するポリエチレン一 2 , 6—ナフタレンジカルボキシレート は例えば安息香酸、 メトキシポリアルキレングリコールなどの一官能性化合物によ つて末端の水酸基および/またはカルボキシル基の一部または全部を封鎖したもの であってもよい。 また本発明で使用するポリエチレン一 2， 6—ナフタレンジ力ノレ ボキシレートは、 例えば極く少量のグリセリン、 ペンタエリスリ トール等の如き三 官能以上のエステノ 成性化合物で実質的に線状のポリマーが得られる範囲内で共 重合したものであってもよい。  In addition, the polyethylene 1,2,6-naphthalenedicarboxylate used in the present invention may partially or entirely block terminal hydroxyl groups and / or carboxyl groups with a monofunctional compound such as benzoic acid or methoxypolyalkylene glycol. It may be what you did. The polyethylene-1,2,6-naphthalenediole reoxyxylate used in the present invention can be used to obtain a substantially linear polymer with an extremely small amount of a trifunctional or higher functional esteno-forming compound such as glycerin or pentaerythritol. It may be copolymerized within the range.
さらにまた本発明のフィルムは、 主たる成分のポリエチレン一 2， 6—ナフタレ ンジカルポキシレートのほ力 こ、他の有機高分子を混合した混合体であっても良い。 かかる有機高分子としては、 ポリエチレンテレフタレート、 ポリエチレンイソフタ レート、 ポリ トリメチレンテレフタレート、 ポリエチレン一 4， 4 ' ーテトラメチ レンジフエニルジカルポキシレート、 ポリエチレン一 2， 7 _ナフタレンジカルボ キシレート、 ポリ トリメチレン一 2， 6—ナフタレンジカルポキシレート、 ポリネ ォペンチレン一 2 , 6—ナフタレンジカルボキシレート、 ポリ （ビス （4ーェチレ ンォキシフエニル） スルホン） 一 2， 6—ナフタレンジカルボキシレート等を挙げ ることができる。 これらの中でも、 ポリエチレンイソフタレート、 ポリトリメチレ ンテレフタレート、 ポリ トリメチレン一 2， 6—ナフタレンジカルボキシレート、 ポリ （ビス （4一エチレンォキシフエ-ノレ） スノレホン） 一 2 , 6—ナフタレンジ力 ^^ボキシレートが好ましい。  Furthermore, the film of the present invention may be a mixture of polyethylene-1,2,6-naphthalene dicarboxylate as a main component and other organic polymers. Examples of such organic polymers include polyethylene terephthalate, polyethylene isophthalate, polytrimethylene terephthalate, polyethylene-1,4,4′-tetramethylenediphenyldicarboxylate, polyethylene-1,2,7-naphthalenedicarboxylate, polytrimethylene-1,2, Examples include 6-naphthalenedicarboxylate, polyneopentylene-1,2,6-naphthalenedicarboxylate, and poly (bis (4-ethylenoxyphenyl) sulfone) -1,2,6-naphthalenedicarboxylate. Among them, polyethylene isophthalate, polytrimethylene terephthalate, polytrimethylene-1,2,6-naphthalenedicarboxylate, poly (bis (4-ethyleneoxyphen-nore) sunolefon) 1,2,6-naphthalenedicarbonate ^^ boxylate Is preferred.
これらの P E Nと混合する有機高分子は 1種のみならず 2種以上を併用しても良 い。 P ENと混合する有機高分子の割合は、、 ポリマーの繰返し単位で、 高々 2 0 m o 1 %、 好ましくは 1 0 m o 1 %以下、 特に好ましくは 5 m o 1 %以下の範囲であ る。 カゝかる混合体の製造は一般に知られたポリエステノレ糸且成物の製造方法によって 実施できる。 The organic polymer mixed with these PENs may be used alone or in combination of two or more. The proportion of the organic polymer mixed with PEN is at most 20 mo 1%, preferably at most 10 mo 1%, particularly preferably at most 5 mo 1%, in the repeating unit of the polymer. You. The production of such a mixture can be carried out by a generally known method for producing a polyester fiber.
本発明で使用するポリエステルは従来公知の方法で得ることができる。 例えばジ カルボン酸とダリコールとの反応で、 直接、 低重合度ポリエステルを得る方法や、 ジカルボン酸の低級アルキルエステルとグリコールとを従 知のエステル交換触 媒を用いてエステル交換反応させる方法の後、 重 虫媒の存在下で重合反応を行え ばよい。 エステル交換反応触媒としては、 例えばナトリウム、 カリウム、 マグネシ ゥム、 カルシウム、 亜鈴、 ストロンチウム、 チタン、 ジルコニウム、 マンガン、 コ ノ レトを含む化合物が挙げられ、 これらは一種または二種以上併用してもよい。 重 ^虫媒としては、 三酸化アンチモン、 四酸化アンチモン、 五酸ィ匕アンチモン、 三塩 化アンチモン、 三臭化アンチモン、 アンチモングリコレート、 酢酸アンチモン等の アンチモン化合物、 二酸化ゲルマニウムで代表されるようなゲルマニウム化合物、 テトラェチノレチタネート、 テトラプロピルチタネート、 テトラフェニルチタネート またはこれらの部分加水 ^军物、 蓚酸チタ-ノレアンモニゥム、 蓚酸チタ二ルカリウ ム、 チタントリスァセチルァセトネートのようなチタン化合物が挙げられる。 上記の重合触媒のなかでも、 ゲルマニウムィ匕合物が特に好ましく用いられる。 か 力、るゲルマニウム化合物を重縮合反応触媒として、 例えばエステル化反応あるいは エステル交換^^完了前から重合反応開始直後の間に、 得られたエステル交換反応 物に添 >¾卩し、 ffi状態で^ しながらカロ熱して重縮合反応を行なわせることが好ま しい。 本発明において重縮合反応触媒に用いるゲルマニウム化合物としては、 例え ば （ィ） 無定形酸化ゲルマニウム （口） 微細な結晶性酸化ゲルマニウム （ハ） 酸化 ゲルマニウムを水に溶解した溶液等を好ましく用いることができる。 これらの酸化 ゲルマニウムのなかでも、結晶性二酸化ゲルマニウム、非晶性ニ酸化ゲルマニウム、 ゲルマ二ゥムテトラエトキシド、 ゲルマ二ゥムテトラー n—ブトキシド等の如きゲ ルマニウムィ匕合物を好ましく使用でき、 特に結晶性二酸化ゲルマニウムおよぴ非晶 性二酸化ゲルマ二ゥムを好ましく使用できる。  The polyester used in the present invention can be obtained by a conventionally known method. For example, after a method of directly obtaining a low-polymerization degree polyester by a reaction of dicarboxylic acid and dalicol, or a method of subjecting a lower alkyl ester of dicarboxylic acid and glycol to a transesterification reaction using a known transesterification catalyst, The polymerization reaction may be carried out in the presence of a heavy vehicle. Examples of the ester exchange reaction catalyst include compounds containing sodium, potassium, magnesium, calcium, dumbbell, strontium, titanium, zirconium, manganese, and konoleto, and these may be used alone or in combination of two or more. . Antimony trioxide, antimony tetroxide, antimony pentoxide, antimony trichloride, antimony tribromide, antimony glycolate, antimony acetate, antimony compounds such as antimony trioxide, antimony acetate, and germanium dioxide are typical examples of heavy insect media. Titanium compounds such as germanium compounds, tetraethino retitanate, tetrapropyl titanate, tetraphenyl titanate or partial hydrochloride thereof, titanium-noreammonium oxalate, titanium potassium oxalate, and titanium trisacetyl acetate Can be Among the above polymerization catalysts, germanium conjugates are particularly preferably used. As a catalyst for the polycondensation reaction, for example, between the completion of the esterification reaction or transesterification ^^ and immediately after the start of the polymerization reaction, the resulting transesterification product is added to the obtained transesterification reaction product in a ffi state. ^ It is preferable to carry out the polycondensation reaction by heating with calo. In the present invention, as the germanium compound used for the polycondensation reaction catalyst, for example, (a) amorphous germanium oxide (mouth) fine crystalline germanium oxide (c) a solution in which germanium oxide is dissolved in water can be preferably used. . Among these germanium oxides, germanium oxides such as crystalline germanium dioxide, amorphous germanium dioxide, germanium tetraethoxide, and germanium tetra-n-butoxide can be preferably used. Germanium dioxide and amorphous germanium dioxide can be preferably used.
重縮合反応触媒に用いるゲルマニウム化合物の量は、 あまり少ないと十分な重合 反応の促進効果が得られず、 また極端に多くすると得られるポリエステルの軟化点 力 S低下したりすることがあるので、 ポリエステル中に残存するゲルマニウムの金属 元素として好ましくは 1 0〜1 0 0 0重量 p p m、 より好ましくは 1 0〜5 0 0重 量 p p m、 さらに好ましくは 1 0〜2 0 0重量 p p mである。 なお、 ゲルマニウム の金属元素含有濃度は、 乾燥したサンプルを走査電子顕微鏡 （S EM, 日立計測機 器サービス （株） 製の商品名 「S 5 7 0型」） にセットし、 それに連結したエネルギ 一分散型 X線マイクロ一アナライザー (XMA, (株） 堀場製作所製の商品名 ΓΕΜ AX- 7 0 0 0」） にて定量分析を行った値である。 If the amount of the germanium compound used in the polycondensation reaction catalyst is too small, a sufficient effect of accelerating the polymerization reaction cannot be obtained, and if the amount is too large, the softening point force S of the obtained polyester may be reduced. Germanium metal remaining in the metal The element is preferably from 10 to 100 ppm by weight, more preferably from 10 to 500 ppm by weight, and still more preferably from 10 to 200 ppm by weight. The concentration of germanium in the metal element was determined by setting the dried sample on a scanning electron microscope (SEM, trade name “S570” manufactured by Hitachi Measuring Instruments Service Co., Ltd.) and connecting the energy to it. It is a value obtained by quantitative analysis using a dispersive X-ray microanalyzer (XMA, trade name: AX-700, manufactured by HORIBA, Ltd.).
エステル交換反応を経由して重合を行う：^は、 重合反応前にエステル交換触媒 を失活させる目的でリン化合物を含有することが好ましい。 かかるリン化合物とし ては、 リン酸、 亜リン酸、 ホスホン酸、 ホスホネート化合物及ぴそれらの誘導体等 があげられ、 これらは戦虫で使用しても二種以上を併用してもよい。 これらの中で も、 リン化合物として〖ま、下記式（ I )で表されるホスホネート化合物が好ましい。 Ri〇一 C (O) -X- P (O) 一 (O R2) 2 … （I ) Polymerization is carried out via a transesterification reaction: ^ preferably contains a phosphorus compound for the purpose of deactivating the transesterification catalyst before the polymerization reaction. Examples of such phosphorus compounds include phosphoric acid, phosphorous acid, phosphonic acid, phosphonate compounds and derivatives thereof, and these may be used in battle insects or in combination of two or more. Among these, a phosphonate compound represented by the following formula (I) is preferable as the phosphorus compound. Ri〇ichi C (O) -X- P (O) ichi (OR 2 ) 2 … (I)
ここで、 式中の、 R1および R2は炭素数原子数 1〜4のアルキル基、 Xは一 CH2— または一 CH (Y) - (Yは、 フエ二ル基を示す。） であり、 R1および R2はそれぞ れ同一でも異なっていても良い。 Here, in the formula, R 1 and R 2 are an alkyl group having 1 to 4 carbon atoms, X is one CH 2 — or one CH (Y) − (Y represents a phenyl group). R 1 and R 2 may be the same or different.
特に好ましいリン化合物は、 カルボメトキシメタンホスホン酸、 カルボエトキシ メタンホスホン酸、 カノレボプロポキシメタンホスホン酸、 力ノレボブトキシメタンホ スホン酸、 カルポメトキシーホスホノーフエ二ノレ酢酸、 カノレボエトキシーホスホノ ーフヱニル酢酸、 カルボプロポキシ一ホスホノーフエニル酢酸およびカルポプトキ シ一ホスホノーフエ二/レ醉酸のジメチ /レエステノレ、 ジェチ /レエステ /レ、 ジプロピノレ エステルおよびジブチルエステルである。  Particularly preferred phosphorus compounds are carbomethoxymethanephosphonic acid, carbethoxymethanephosphonic acid, canolevopropoxymethanephosphonic acid, phenolic olevobutoxymethanephosphonic acid, carpomethoxy-phosphonopheninoleacetic acid, and canolevoethoxyphosphono Dimethylacetate, carbopropoxy-phosphonophenylacetate, and carbopoxy-phosphonophene / lexanoic acid dimethyl / leestenole, jetty / leestene / le, dipropinole ester and dibutyl ester.
本発明において、 これらのホスホネート化合物の好ましい理由は、 通常安定剤と して使用されているリン化合物に比べ、 金属化合物との反応が比較的緩やかに進行 すること力 ら、 重縮合反応中の金属化合物の触 ¾性の持続時間が長 結果とし てポリェズテルへの触媒の添加量を少なくでき、 触媒に対して多量の安定剤を添加 してもポリエステルの熱安定性を損な!/、にくレ、ためである。  In the present invention, the reason why these phosphonate compounds are preferable is that the reaction with the metal compound proceeds relatively slowly as compared with the phosphorus compound which is usually used as a stabilizer. Long contact time of the compound As a result, the amount of catalyst added to the polyester can be reduced, and even if a large amount of stabilizer is added to the catalyst, the thermal stability of the polyester is impaired! / This is for you.
これらリン化合物の勸 P時期は、 エステル交換反応が実質的に終了した後であれ ばいつでもよく、 例えば、 重縮合反応を開始する以前の大気圧下、 重縮合反応を開 始した後の減圧下、 重縮合反応の末期または重縮合反応の終了後すなわちポリマー を得た後に添加してもよい。 The timing of the recommendation of these phosphorus compounds may be any time after the transesterification reaction is substantially completed, for example, under atmospheric pressure before the start of the polycondensation reaction, under reduced pressure after the start of the polycondensation reaction. At the end of polycondensation reaction or after completion of polycondensation reaction, ie polymer You may add after obtaining.
リン化合物の好ましい含有量は、 ポリエステルの熱安定性の点から、 リン化合物 中のリン元素としてポリエチレン一 2 , 6—ナフタレンジカルボキシレート中 2 0 〜： L 0 0重量 p p mであることが好ましい。  From the viewpoint of the thermal stability of the polyester, the content of the phosphorus compound is preferably 20 to: L 00 weight ppm in polyethylene mono 2,6-naphthalenedicarboxylate as the phosphorus element in the phosphorus compound.
本発明におけるポリエチレン一 2 , 6—ナフタレンジカルボキシレートは、 2 , 6一ナフタレンジカルボン酸とエチレングリコールを原料として用いたものでも、 2 , 6—ジメチルナフタレートに代表される 2 , 6一ナフタレンジカルボン酸のェ ステノ W ^成性誘導体とエチレンダリコールを原料として用いたものでもよい。 エス テル交換反応を経由する製造方法においては、 エステル交換反応を 0. 0 5 MP a 以上 0. 2 OMP a以下の加圧下にて実施することで、 金属化合物の添加量をさら に低減できる。  The polyethylene-1,2,6-naphthalenedicarboxylate used in the present invention may be prepared by using 2,6-naphthalenedicarboxylic acid and ethylene glycol as raw materials, and may be 2,6-naphthalenedicarboxylate represented by 2,6-dimethylnaphthalate. Esteno W ^ -forming derivatives of acid and ethylene dalicol may be used as raw materials. In the production method via the ester exchange reaction, the transesterification reaction is carried out under a pressure of not less than 0.05 MPa and not more than 0.2 OMPa, so that the amount of the metal compound added can be further reduced.
'なお、 本発明で使用されるポリエステルは、 溶融重合後これをチップ化し、 カロ熱 ffi下または窒素などの不活性気流中にぉ ヽて固相重合することもできる。 フィル ムの抽出オリゴマー量を低減させるために、 本発明において固相重合も好ましく行 われる。  It should be noted that the polyester used in the present invention can be formed into chips after melt polymerization, and then subjected to solid-phase polymerization under calorific heat or in an inert gas stream such as nitrogen. In order to reduce the amount of oligomer extracted from the film, solid-state polymerization is also preferably performed in the present invention.
なお、 ポリエチレン一 2， 6—ナフタレンジカルボキシレートを主たる成分とし てなるポリマーの固有粘度は 0. 4 0 (1 1 / §以上0. 9 0 d l Z g以下であるこ とが好ましレ、。また、固有粘度は o—クロロフエノールを溶媒として用!/、て、 2 5 °C で測定した値 （単位： d 1 / g ) である。 In addition, the intrinsic viscosity of the polymer containing polyethylene-1,6-naphthalenedicarboxylate as a main component is 0.40 (preferably not less than 1 1 / § and not more than 0.90 dl Zg). The intrinsic viscosity is a value (unit: d1 / g) measured at 25 ° C using o-chlorophenol as a solvent.
<添細>  <Addition>
' 本発明の半導体ウェハ加工用べ一スフイノレムには、 フィルムに滑り性を付与する ために不活性粒子を少割 有させることが好ましい。カゝかる不活性粒子としては、 例えば球状シリカ、 多孔質シリカ、 炭酸カルシウム、 アルミナ、 二酸化チタン、 力 ォリンクレー、 硫酸バリウム、 ゼォライトの如き無 »子、 或いはシリコーン樹脂 粒子、 架橋ポリスチレン粒子の如き有機粒子を挙げることができる。 無機粒子は粒 径が均一であること等の理由で、 天然品よりも合成品であることが好ましい。 « 粒子の結晶形態、 硬度、 比重、 色は特に制限されず、 目的に応じて使用することが できる。  It is preferable that the base particles for processing semiconductor wafers of the present invention have a small percentage of inert particles in order to impart slipperiness to the film. As the inert particles, for example, particles such as spherical silica, porous silica, calcium carbonate, alumina, titanium dioxide, potassium chloride, barium sulfate, zeolite, or organic particles such as silicone resin particles and cross-linked polystyrene particles Can be mentioned. It is preferable that the inorganic particles are synthetic products rather than natural products because the particle size is uniform. The crystal morphology, hardness, specific gravity, and color of the particles are not particularly limited, and can be used according to the purpose.
具体的な無«子としては、 炭酸カルシウム、 多孔質シリカ、 球状シリカ、 カオ リン、 タルク、炭酸マグネシウム、炭酸パリゥム、硫酸カルシウム、硫酸バリゥム、 リン酸リチウム、 リン酸カノレシゥム、 リン酸マグネシウム、 酸化アルミニウム、 酸 ィ匕'ケィ素、 酸化チタン、 酸化ジルコニウム、 フッ化リチウム等を挙げることができ る。 Specific examples of calcium carbonate include calcium carbonate, porous silica, spherical silica, and chao. Phosphorus, talc, magnesium carbonate, palladium carbonate, calcium sulfate, calcium sulfate, potassium sulfate, lithium phosphate, canolecum phosphate, magnesium phosphate, aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, lithium fluoride, etc. be able to.
これらの中でも、 炭酸カルシウム粒子、 球状シリカ粒子、 多孔質シリカ粒子、 板 状珪酸アルミニゥムが特に好ましレ、。  Among these, calcium carbonate particles, spherical silica particles, porous silica particles, and plate-like aluminum silicate are particularly preferred.
有鄉立子としては、 有 a¾粒子や架橋高分子粒子などが挙げられる。 かかる有機 塩粒子としては例えば摻酸カルシウムやカルシウム、 ノ リウム、 亜鉛、 マンガン、 マグネシウム等のテレフタル酸塩が挙げられる。 また、 架橋高分子粒子としては例 えば、 ジビエノレベンゼン、 スチレン、 ァクリノレ酸もしくはメタクリル酸のビ-ル系 モノマーの與虫体または共重合体が挙げられる。 さらにまた、 ポリテトラフルォロ エチレン、 シリコーン樹脂、 ベンゾグアナミン樹脂、 熱硬ィ匕エポキシ樹脂、 不飽和 ポリエステル樹脂、 «化性尿素樹脂、 «化性フエノール樹脂などの «粒子も 好ましく挙げられる。 架橋高分子粒子の中でもシリコーン樹脂粒子、 架橋ポリスチ レン粒子が特に好ましレ、。  Examples of the organic particles include organic particles and crosslinked polymer particles. Such organic salt particles include, for example, terephthalates such as calcium phosphate, calcium, norium, zinc, manganese, and magnesium. Examples of the crosslinked polymer particle include an insect or copolymer of a vinyl monomer such as dibienolebenzene, styrene, acryloleic acid or methacrylic acid. Furthermore, fine particles such as polytetrafluoroethylene, a silicone resin, a benzoguanamine resin, a thermosetting epoxy resin, an unsaturated polyester resin, a hydrophobizable urea resin, and a hydrophobizable phenol resin are also preferably exemplified. Among the crosslinked polymer particles, silicone resin particles and crosslinked polystyrene particles are particularly preferred.
これらフィルム中に添 []される不活性粒子の粒子径は、 各々の種類の粒子につい て、 平均粒径が 0. 05 以上 5 μπι以下であることが好ましく、 0. 08 μτη 以上 3. 5 ^am以下であることがさらに好ましく、 0. 1 0 m以上 3 m以下で あることが特に好ましレヽ。また、フィルム中に含まれる不活性粒子の全^)口量は 0. 05重量％以上 3重量％以下であること力好ましく、より好ましくは 0. 08重量％ 以上 2. 0重量％以下であり、 0. 1重量％以上 1. 0重量％以下であることが特 に好ましい。 ，  Regarding the particle size of the inert particles added to these films, the average particle size of each type of particles is preferably 0.05 to 5 μπι, and 0.08 μτη to 3.5. ^ am is more preferable, and it is particularly preferable that it is 0.10 m or more and 3 m or less. Further, the total amount of inert particles contained in the film is preferably 0.05% by weight or more and 3% by weight or less, more preferably 0.08% by weight or more and 2.0% by weight or less. It is particularly preferred that the content be 0.1% by weight or more and 1.0% by weight or less. ,
フィルムに添加する不活性粒子は上記に例示した中から選ばれた単一成分でもよ く、 二成分あるいは三成分以上を含む多成分でもよい。 また、 単一成分の:^には 平均粒径が異なる 2種類以上の粒子を含有しても良!/、。  The inert particles to be added to the film may be a single component selected from those exemplified above, or may be a multicomponent containing two or more components. In addition, a single component: ^ may contain two or more types of particles with different average particle sizes!
なお、 不活性粒子の平均雖は、 （株） 島津製作所製の商品名 「CP— 50型セン トリフューダルパーティクノレサイズアナライザー （C e n t r i f u g a l P a • r t i c l e S i z e Ann a 1 y z e r)j を用いて測定し、該測定から得ら れる遠心沈降曲線を基に算出した各粒径の粒子とその存在量との積算曲線から、 5 0重量％に相当する粒径を読み取った値である（「粒度測定技術」日刊工業新聞発行、 1 9 7 5年頁 2 4 2〜2 4 7参照）。 ' The average of inert particles is determined by using a CP-50 centrifugal particle size analyzer (Centrifugal P a • rticle Size Ann a 1 yzer) j manufactured by Shimadzu Corporation. From the integrated curve of particles of each particle size and their abundance calculated based on the centrifugal sedimentation curve obtained from the measurement. This is a value obtained by reading the particle size corresponding to 0% by weight (see “Particle Size Measurement Technology”, published by Nikkan Kogyo Shimbun, p. 1979, p. '
本発明のフィルムは、 平均粒径が 0 . 3 ^ 111以上0 . 8 z m以下である炭酸カル シゥム粒子を 0 . 0 5重量％以上 0 . 4重量％以下、および/または平均粒径が 0 . 1 μ m以上 0 . 6 m以下である球状シリ力粒子を 0 . 0 3重量％以上 0 . 5重量％ 以下、 および Zまたは平均丰立径が 0 . 1 Z m以上 0 . 6 μ m以下であるシリコーン 粒子を 0 · 0 3重量。 /。以上 0 . 4重量％以下の割合で 有することが特に好ましレ、。 さらに、 同じ種類の不活性粒子で粒径が異なる粒子が同時に含まれていても良く、 その場合は同じ種類の不活性粒子全体の含有量が上記の範囲内になってレ、ればよレ、。 本発明のフィルムは、 その用途に応じて結晶核剤、 酸化防止剤、熱安定化剤、 易 滑剤、 難燃剤、 帯電防止剤、 ポリシロキサン等を配合することができる。  In the film of the present invention, calcium carbonate particles having an average particle size of 0.3 to 111 or more and 0.8 zm or less are contained in an amount of 0.05 to 0.4% by weight and / or an average particle size of 0 to 0.4% by weight. Spherical particles having a particle size of 1 μm or more and 0.6 m or less are used in an amount of 0.3% by weight or more and 0.5% by weight or less, and the Z or average vertical diameter is 0.1 Zm or more and 0.6 μm. Below 0,03 weight of silicone particles. /. It is particularly preferred that the content be at least 0.4% by weight. Furthermore, particles of the same type of inert particles having different particle sizes may be simultaneously contained. In such a case, the content of the whole inert particles of the same type falls within the above-mentioned range. ,. The film of the present invention may contain a nucleating agent, an antioxidant, a heat stabilizer, a lubricant, a flame retardant, an antistatic agent, a polysiloxane, etc., depending on the use.
'不活性粒子やその他の添加剤の添加時期はポリエチレン一 2， 6一ナフタレンジ カルボキシレートを製膜するまでの段階であれば特に制限はなく、 ί列えば重合段階 で添加してもよく、 また製膜の際に添 してもよレヽ。 均一分散の見地からは、 不活 性粒子やその他の添加剤をエチレングリコール中に添加して重合時に高濃度添加し てマスターチップとし、 得られたマスターチップを無添加チップで希釈するのが好 ましい。  'The addition time of the inert particles and other additives is not particularly limited as long as it is a stage before the film formation of polyethylene 1,261-naphthalenedicarboxylate. It can also be added during film formation. From the viewpoint of uniform dispersion, it is preferable to add inactive particles and other additives to ethylene glycol and add them at a high concentration during polymerization to form a master chip, and dilute the obtained master chip with an additive-free chip. Good.
ぐべ一スフイノレム >  Gubei Sufuinorem>
本発明の半導体ウエノ、加工用ベースフィルムは、 上述したポリエチレン一 2 , 6 一ナフタレンジカルボキシレートを主たる成分としてなる二軸配向フィルムである。 本発明におけるベースフィルム （フィルムと略記することがある） は、 単層または 2層以上の複数層のいずれであってもよく、 2層以上の複数層からなることが、 半 導体ウェハとの密着面の平坦性およびベースフィルムの卷取り性を両立する上で好 ましい。 2層以上の複数層を構成する'手段としては、 共押出し法、 押出しラミネー ト法、 コーティング法等を用いることができ、 特に限定はされないが、 生産性の観 点から上述したポリエチレン一 2， 6—ナフタレンジカノレポキシレートを使用して 複数台の押出し機から各々榭脂を押し出す共押出し法で複数層を構成すること力 S好 ましい。  The semiconductor wafer and the base film for processing according to the present invention are biaxially oriented films containing the above-mentioned polyethylene-12,61-naphthalenedicarboxylate as a main component. The base film (which may be abbreviated as a film) in the present invention may be a single layer or a plurality of layers of two or more layers. It is preferable for achieving both flatness of the surface and winding property of the base film. As means for forming two or more layers, a co-extrusion method, an extrusion laminating method, a coating method, and the like can be used, and are not particularly limited. It is preferable to form a plurality of layers by a co-extrusion method in which each resin is extruded from a plurality of extruders using 6-naphthalene dicanolepoxylate.
また本発明の半導体ウェハ加工用ベースフィルムは、 バックグラインドテープ用 またはダイシングテープ用であることが好まし！/、。 Further, the base film for processing a semiconductor wafer of the present invention is used for back grinding tape. Or preferably for dicing tape! / ,.
ぐ熱収縮率 >  Heat shrinkage>
本発明のフィルムは、 2 0 0 で 1 0分間加熱処理したときの熱収縮率が、 フィ ルムの製膜方向および幅方向のいずれも 1 . 0 0 %以下である。 本発明のフィルム の熱収縮率は、 _ 0. 2 0 %以上 0. 8 0 %以下であることがさらに好ましく、 一 0. 1 0 %以上 0. 6 0 %以下であることが特に好ましい。 本発明では、 特に断ら ない限り、 製膜方向とはフィルムが連 膜されるときの進行方向であり、 フィル ムの長手方向、 縦方向、 連; ¾膜方向または MD方向と称することがある。 また、 本発明では、幅方向とはフィルム面内方向における製膜方向に直交する方向であり、 横方向または TDと称することもある。  The film of the present invention has a heat shrinkage of not more than 1.0% in both the film forming direction and the width direction when subjected to heat treatment at 200 for 10 minutes. The heat shrinkage of the film of the present invention is more preferably from −0.20% to 0.80%, particularly preferably from 0.10% to 0.60%. In the present invention, unless otherwise specified, the film forming direction is a traveling direction when a film is formed, and may be referred to as a longitudinal direction, a longitudinal direction, a continuous direction, a film direction or an MD direction of the film. Further, in the present invention, the width direction is a direction orthogonal to the film forming direction in the in-plane direction of the film, and may be referred to as a lateral direction or TD.
2 0 0 °Cの で 1 0分間加熱処理したときの熱机縮率が 1 . 0 0 %を超えると、 半導体ウェハ加工工程における が高温となった場合に、 ベースフィルムの寸法 収縮が大きくなる一方で、 ウェハは熱膨張するため、 加工工程の途中でウェハがテ ープの粘着剤から脱落したり、 場合によってはゥェハの厚みが薄!/ヽために する ことがある。 熱収縮率が一 0. 2 0 %未満の:^、 すなわち熱膨張する:^にはゥ ェハの熱膨張よりもベースフィルムの熱膨張が大きくなり、 テープの粘着剤がゥェ ハの周辺部からウェハの表面に回り むことがある。 さらに、 フィルムの収縮また は膨張が本発明の範囲を超えて大きい^ 8\ いずれの^^もウェハの膨張率との差 によって、 テープ上に載っている半導体ウェハが反るため好ましくない。 また、 フ イルムの膨張率が半導体ウェハの膨張率よりも大きい^^は、 ウェハ側を内側にし て反り、 チップ同士のせりあいの原因となるため、 フィルムの膨張、 すなわち熱収 縮率がマイナスになる方向は極力抑制する必要がある。  If the heat shrinkage ratio after heat treatment at 200 ° C for 10 minutes exceeds 1.0%, the dimensional shrinkage of the base film will increase when the temperature rises in the semiconductor wafer processing process. On the other hand, since the wafer thermally expands, the wafer may fall off the adhesive of the tape during the processing process, or in some cases, the thickness of the wafer may be too thin. When the heat shrinkage is less than 0.20%: ^, that is, when the thermal expansion occurs, the thermal expansion of the base film becomes larger than the thermal expansion of the wafer. May move to the wafer surface from the part. Further, any of the 8 8 が in which the shrinkage or expansion of the film is large beyond the scope of the present invention is not preferable because the semiconductor wafer mounted on the tape warps due to the difference from the expansion coefficient of the wafer. Also, if the expansion coefficient of the film is larger than the expansion coefficient of the semiconductor wafer, it warps with the wafer side inward and causes chips to stick together, so that the expansion of the film, that is, the heat shrinkage rate becomes negative. Direction must be suppressed as much as possible.
なお、 所望の熱収縮率を有するフィルムを得るために、 フィルムの製造において 二軸延伸し、 熱固定を行った後、 さらに、 フィルムの熱弛緩処理を行うことがより 好ましい。  In order to obtain a film having a desired heat shrinkage rate, it is more preferable to perform biaxial stretching and heat setting in the production of the film, and then perform a heat relaxation treatment on the film.
<抽出オリゴマー量〉  <Amount of extracted oligomer>
本発明のフィルムのオリゴマー抽出量は、 クロロホルムを用いて 2 4時間抽出す る条件において 0. 8重量％以下であることが好ましい。 さらに好ましくは 0. 6 重量％以下、 特に好ましくは 0 . 5重量。 /0以下である。 ォリゴマー抽出量が 0 . 8 重量0 /0を超えると半導体ウエノ、加工用ベースフィルムとして用いた:^に、 工程内 の加工温度環境下や粘着剤層塗設工程にお！/ヽてォリゴマーがベースフィルム表面に 析出し、 加工工程内の汚染や粘着剤層とベースフィルム間の接着強度が低下する等 の問題を引き起こすことがある。 フィルム表面へのオリゴマーの析出を抑制するに は、 フィルム中に含まれるオリゴマー量を^させることが最も効果的であり、 本 用途向けにはォリゴマー抽出量を少なくすることが好ましい。 The oligomer extraction amount of the film of the present invention is preferably 0.8% by weight or less under the condition of extracting with chloroform for 24 hours. It is more preferably 0.6% by weight or less, particularly preferably 0.5% by weight. / 0 or less. Oligomer extraction is 0.8 It exceeds weight 0/0 when the semiconductor Ueno, was used as a working base film: ^ a, your a processing temperature environment or a pressure-sensitive adhesive layer Coating process in step! / Polyolomer may precipitate on the surface of the base film, causing problems such as contamination in the processing step and a decrease in the adhesive strength between the pressure-sensitive adhesive layer and the base film. The most effective way to suppress the precipitation of oligomers on the film surface is to reduce the amount of oligomers contained in the film, and it is preferable to reduce the amount of oligomer extracted for this application.
なお、 オリゴマー抽出量を少なくし、 所望の範囲とするためには、 ポリエチレン -2, 6—ナフタレンジカルボキシレートの固有粘度を 0. 45 d l/g以上 0. 90 d lZg以下にすることが好ましく、 さらに好ましくは 0. 48〜0. 85 d 1/g、 特に好ましくは 0. 50〜0. 80 d 1/gである。 ポリエチレン一 2, 6一ナフタレンジカノレポキシレートの固有粘度が下限に満たない場合は、 フイノレム の抽出オリゴマー量が多くなりすぎ、 一方上限を超える； ^は、 重合および製膜ェ 程で過剰な負荷を要することがある。  In addition, in order to reduce the amount of oligomers extracted and to maintain the desired range, it is preferable that the intrinsic viscosity of polyethylene-2,6-naphthalenedicarboxylate be 0.45 dl / g or more and 0.90 dlZg or less. It is more preferably from 0.48 to 0.85 d1 / g, particularly preferably from 0.50 to 0.80 d1 / g. If the intrinsic viscosity of poly (1,6-naphthalenedicanolepoxylate) is less than the lower limit, the amount of finolem extracted oligomer will be too large, but will exceed the upper limit; ^ indicates excessive load in the polymerization and film forming process May be required.
また、オリゴマー抽出量を所望の範囲とするためには、フィルムの固有粘度は 0. 40-0. 90 d 1/gであることが好ましい。 なお、 固有粘度は o—クロ口フエ ノールを溶媒として用いて、 25 °Cで測定した値 （単位： d 1/g) である。 く厚み方向の屈折率 >  Further, in order to keep the oligomer extraction amount in a desired range, the intrinsic viscosity of the film is preferably 0.40 to 0.90 d1 / g. The intrinsic viscosity is a value (unit: d1 / g) measured at 25 ° C using o-chlorophenol as a solvent. Refractive index in the thickness direction>
本発明のフィルムの厚み方向の屈折率 (n z) は 1. 501以上 1. 515以下 であることが好ましい。 より好ましくは 1. 503以上 1. 513以下であり、 特 に好ましくは 1. 504以上 1. 512以下である。 厚み方向の屈折率が 1. 50 1未満であるとフィルムの而^ "ラミ性が^ ί匕するため、 フィルムの切断端面にバリ が発生するようになり、 ^^によっては切粉が工程内を汚染することがある。また、 厚み方向の屈折率が 1. 515を超えるとフィルムが脆くなり、 パックグラインド テープやダイシングテープのベースフィルムとして用いられた場合のテープ剥離の 際にフィルム破れが発生することがある。  The refractive index (nz) in the thickness direction of the film of the present invention is preferably from 1.501 to 1.515. It is more preferably 1.503 or more and 1.513 or less, particularly preferably 1.504 or more and 1.52 or less. When the refractive index in the thickness direction is less than 1.501, the laminating property of the film is degraded, so that burrs are generated on the cut end surface of the film. When the refractive index in the thickness direction exceeds 1.515, the film becomes brittle, and when the tape is used as a base film for pack grind tape or dicing tape, the film tears when peeling. Sometimes.
なお、 フィルムの厚み方向におレ、て所望の屈折率を有するフィルムを得るために は、 ベースフィルム製造時の熱固定? を上げる、 もしくは »向または横方向の 延伸倍率を下げることで可能である。  In order to obtain a film having a desired refractive index in the thickness direction of the film, it is possible to increase the heat setting during the production of the base film or to reduce the stretching ratio in the »direction or in the transverse direction. is there.
<フイノレムの厚みのバラツキ > 本発明のフィルムの厚みのパラツキは、 フィルムの平均厚みに対して 15%以下 であること力好ましく、 10%以下であることがより好ましく、 8%以下であるこ とが特に好ましい。 フィルムの厚みのパラツキが小さい程、 バックグラインドテー プと半導体ゥェハぉよびダイシングチープと半導体ウエノヽとの接着面の接着強度が 均一ィ匕し、 安定したテーピングが可能となるため、 .より精密なバックグラインドぉ よびダイシングが可能となり、高精細化、高密度化に好ましいチップを供給できる。 <Variation in the thickness of Huinorem> The variation in the thickness of the film of the present invention is preferably 15% or less, more preferably 10% or less, and particularly preferably 8% or less based on the average thickness of the film. The smaller the variation in film thickness, the more uniform the bonding strength between the back grinding tape and the semiconductor wafer and the bonding surface between the dicing chip and the semiconductor wafer, and stable taping becomes possible. Back grinding and dicing can be performed, and a chip suitable for high definition and high density can be supplied.
<ヤング率〉  <Young's modulus>
本発明のフィルムのヤング率は、 フィルムの製膜方向と幅方向のいずれにお!/、て も、 540 OMP a以上 690 OMP a以下であること力 S好ましく、 より好ましく は 550 OMP a以上 680 OMP a以下であり、 特に好ましくは 560 OMP a 以上 670 OMP a以下である。 また両方向のヤング率の差は、 100 OMP a以 下であることが好ましい。  The Young's modulus of the film of the present invention is preferably 540 OMPa or more and 690 OMPa or less in both the film forming direction and the width direction of the film. OMPa or less, particularly preferably 560 OMPa or more and 670 OMPa or less. The difference between the Young's moduli in both directions is preferably 100 OMPa or less.
ヤング率が 540 OMP a未満であるとフィルムの剛性が不足し、 ポリエチレン -2, 6一ナフタレンジカルボキシレートフィルムの高弾性率を活用した半導体ゥ ェハ加工用ベースフィルムの薄膜化が困難になることがある。 また、 ヤング率が 6 90 OMP aを超えるとフィルムの裁断時に切粉が多く発生し易くなり、 クリーン 状態での加工を汚染する可能性がある。 さらに、 切断した各チップのピックアップ 時にテープのエキスパンドゃテープ側からのチップの突上げが困難になり、 生産効 率が低下する。  If the Young's modulus is less than 540 OMPa, the rigidity of the film will be insufficient, and it will be difficult to reduce the thickness of the base film for semiconductor wafer processing utilizing the high elastic modulus of polyethylene-2,61-naphthalenedicarboxylate film. Sometimes. On the other hand, if the Young's modulus exceeds 690 OMPa, a large amount of chips tend to be generated when cutting the film, which may contaminate processing in a clean state. Furthermore, when picking up each cut chip, it is difficult to push up the chip from the expanding tape side of the tape, which reduces production efficiency.
く表面粗さ （Ra) > ί  Surface roughness (Ra)> ί
本発明のフィルムの少なくとも片面における中心線平均表面粗さ （Ra) は 3n m以上 80n m以下であることが好ましく、 より好ましくは 5 n m以上 60 n m以 下、 特に好ましくは 7 nm以上 5 Onm以下である。 さらに、 フィルムが 2層以上 の複数層構成の^^、 フィルム両面の R aの和が 10 n m以上であることが好まし く、 14 n m以上であることがより好ましい。 ここで、 中心線平均粗さ （R a ) は J I S B— 0601に規定する方法により、 カットオフは 0. 25 mm、 測定触 針は 3^πιのものを用いて表面粗さ計（(株） 小坂研究戸製の商品名 「サーフコ ーダ SE—30CJあるいは（株）東京精密製の商品名「サーフコム SE—3CKJ) にて測定される。 . R aが 3 n m未満であるとフィルムの滑りが悪く、 フィルム製造時の搬送や、 フ ィルムの卷取りにおレ、てフィルム表面に擦り傷が発生しゃすくなつたり、 フィルム を口ール状態に卷き取った場合にフイルムとフィルムの間に巻込まれた空気が抜け にくく、 発生したエアだまりによってフィルムの平面十生力《損なわれることがある。 一方、 R aが 80 nmを超えるとフィルムが滑り過ぎるため、 フィルムの卷取り、 またはフィルム表面に粘着層を塗設してテープとした後の卷取りにおいて巻ズレが 頻繁に発生する可能†生がある。 The center line average surface roughness (Ra) on at least one side of the film of the present invention is preferably 3 nm or more and 80 nm or less, more preferably 5 nm or more and 60 nm or less, and particularly preferably 7 nm or more and 5 Onm or less. It is. Further, the film is preferably composed of two or more layers, and the sum of Ra on both surfaces of the film is preferably 10 nm or more, and more preferably 14 nm or more. Here, the center line average roughness (R a) is determined by the method specified in JISB-0601, the cutoff is 0.25 mm, and the measurement probe is 3 ^ πι. Measured under the trade name “Surf Coder SE-30CJ” manufactured by Kosaka Kento or “Surfcom SE-3CKJ” manufactured by Tokyo Seimitsu Co., Ltd. If Ra is less than 3 nm, the film will not slide easily, and the film surface will be abraded when transported during film production or when the film is wound, or the film will be in a whirl state. When the film is wound, it is difficult for air trapped between the film and the film to escape, and the air traps generated may impair the flatness of the film. On the other hand, if Ra exceeds 80 nm, the film slips too much, so that misalignment may frequently occur when winding the film or winding it after applying an adhesive layer on the film surface to form a tape. There is.
<フィルム密度 >  <Film density>
本発明のフィルムの密度は 1. 356 gZcm3以上 1. 364 gZcm3以下で あることが好ましい。 さらに好ましくは 1. 35 7 § 。1113以上1. 36 2 gZc m3以下である。 密度が 1. 3 56 gZ cm3未満であると、 フィルムの結晶性;^低 く半導体ウエノ、加工工程における寸法安定性が不十分となることがある。 また、 密 度が 1. 364 gZ cm3を超えると結晶性が高くなり過ぎてフィルムの靭性が失わ れるため、 バックグラインドテープやダイシングテープの基材とした場合のテープ 剥離に際に破断しやすくなる。 なお、 フィルムの密度は硝酸カルシウム水溶液を溶 媒として用いた密度勾配間中、 25 °Cで浮沈法により測定された値である。 The density of the film of the present invention is preferably 1.356 gZcm 3 or more and 1.364 gZcm 3 or less. More preferably, 1.357 §. It is not less than 111 3 and not more than 1.36 2 gZcm 3 . If the density is less than 1.356 gZ cm 3 , the crystallinity of the film is low; the semiconductor wafer may have insufficient dimensional stability in the processing step. If the density exceeds 1.364 gZ cm 3 , the crystallinity will be too high and the toughness of the film will be lost. Become. The density of the film is a value measured by the floatation method at 25 ° C during a density gradient using an aqueous solution of calcium nitrate as a solvent.
くフィルムの平均厚み >  Average film thickness>
本発明のフィルムの平均厚みは 9 in以上 1 5 0 πι以下であることカ好ましく、 さらに好ましくは 9 m以上 1 25 m以下、 特に好ましくは 1 2 μ m以上 1 00 ; m以下である。 フィルムの平均厚みが 9 m未満であると、 ウエノヽ加ェにおける 支持体としての灘強度やウエノ、表面の保謙能が不足する齢がある。 一方、 フ イルムの平均厚みが 1 50 μπιを超えると非常にフィルムのスティフネスが強くな りすぎ、 テープの粘着強度が若干でも強い：^には、 テープ剥離の際にウェハが破 損したり、 ダイシング後にフィルムをエキスパンドするための力が大きくなりすぎ る可能性がある。  The average thickness of the film of the invention is preferably from 9 in to 150 πι, more preferably from 9 m to 125 m, and particularly preferably from 12 μm to 100; If the average thickness of the film is less than 9 m, there will be an age at which the strength of Nada, Ueno, and surface humidification as a support in Uenoka will be insufficient. On the other hand, if the average thickness of the film exceeds 150 μπι, the stiffness of the film becomes extremely strong, and even if the adhesive strength of the tape is slightly strong: In the case of ^, the wafer may be damaged when the tape is peeled off, or dicing may occur. Later, the force to expand the film may be too great.
<動摩聽数 >  <Number of listening>
本発明のフィルムは、 フィルム同士の動摩擦係数 (μ d) が 0. 5以下であるこ とが好ましい。 動摩 罕、数 (μ d) が 0. 5を超えると、 製膜工程中および粘着剤 層塗布加工中でのハンドリング性が悪くなり、 例えば工程内のロール上での走行中 またはロール状に卷取る際にしゎゃスクラツチ等の欠点を生じる。 The film of the present invention preferably has a coefficient of dynamic friction (μd) between the films of 0.5 or less. If the number of friction (μd) exceeds 0.5, the handleability during the film forming process and during the application of the adhesive layer will deteriorate, for example, when running on a roll in the process. Or, when wound up in a roll, drawbacks such as scratches may occur.
く熱収縮率の差 >  Difference in heat shrinkage>
本発明のフィルムを 2 0 0 °Cで 1 0分間熱処理した際のフィルムの熱収縮率は、 フィルムの製膜方向の熱収縮率 (SMD) と幅方向の熱 TO率 (S TD) との差の 絶対値 （ | SMD— S T D l ) が 0 . 6 0 %以下であることが好まし!/、。 この値は さらに好ましくは 0 . 5 0 %以下、 特に好ましくは 0 . 4 0 %以下である。 熱収縮 率の差の絶対値が 0 . 6 0 %を超えると、 バックグラインドテープやダイシングテ ープのベースフィルムとして使用した場合にフィルムの寸法変化量の異方性が大き く、 半導体ウェハの反りが発生する^がある。  When the film of the present invention was heat-treated at 200 ° C. for 10 minutes, the heat shrinkage of the film was determined by calculating the heat shrinkage (SMD) in the film forming direction and the thermal TO ratio (S TD) in the width direction. It is preferable that the absolute value of the difference (| SMD— STD l) is 0.60% or less! / ,. This value is more preferably 0.50% or less, particularly preferably 0.40% or less. If the absolute value of the difference in the heat shrinkage exceeds 0.6%, the dimensional change of the film becomes large when used as a base film for a back grinding tape or a dicing tape, and the semiconductor wafer warps. There is a ^ that occurs.
くパックグラインドテープ >  Ku Pack Grinding Tape>
本発明におけるバックグラインドテープは上述のバックグラインドテープ用べ一 -スフィルムの片面-に粘着剤層を有する。 半導体ウエノ、裏面の-研磨工程であるバック グラインドエ程において、 パックグラインドテープ用ベースフィルムの片面に粘着 剤層が積層されたバックグラインドテープをシリコンゥェハの固定用に用いること によって、 シリコンウェハを安定した状態で固定することが可能となる。  The back grinding tape in the present invention has an adhesive layer on the above-mentioned base for back grinding tape-one side of the film. In the back grinding process, which is a polishing process for semiconductor wafers and the back surface, a silicon wafer is stabilized by using a back grinding tape in which an adhesive layer is laminated on one side of a base film for a pack grinding tape for fixing the silicon wafer. It can be fixed in a state.
<ダイシングテープ >  <Dicing tape>
本発明におけるダイシングテープは上述のダイシングテープ用ベースフィルムの 片画こ粘着剤層を有する。 半導体ウェハから I Cチップを切断する工程であるダイ シング工程にぉレ、て、 ダイシングテープ用ベースフィルムの片面に粘着剤層が積層 されたダイシングテープをシリコンウェハの固定用に用いることによって、 シリコ ンウェハを安定した状態で固定することが可能となる。  The dicing tape in the present invention has the single-sided pressure-sensitive adhesive layer of the above-mentioned base film for dicing tape. In the dicing process, which is the process of cutting IC chips from semiconductor wafers, a dicing tape in which an adhesive layer is laminated on one surface of a base film for dicing tape is used for fixing silicon wafers, and silicon wafers are fixed. Can be fixed in a stable state.
ぐ塗布層 >  Coating layer>
本発明のバックグラインドテープ用またはダイシングテープ用ベースフィルムに は、 粘着剤との易接着性を向上させる目的でその少なくとも片面に塗布層を設ける ことができる。 塗布層はポリエステル樹脂、 ゥレタン樹脂、 ァクリル樹脂、 ビュル 系樹脂から選ばれる少なくとも 1種の水溶性または水分散性高分子樹脂からなるこ とが好ましく、 特にポリエステル樹脂とアタリル榭脂の両方を含むの力 S好ましレ、。 本発明で用いる塗布層のポリエステル樹脂は、ガラス転移点（T g )が 0〜： L 0 0 °C、 更に好ましくは 1 0〜 9 0 °Cのものである。 該ポリエステル樹脂は、 水に可溶性ま たは分散性のポリエステ/レが好ましレ、が、 多少の有機溶剤を含有しても良レ、。 The base film for a back grinding tape or a dicing tape of the present invention may be provided with a coating layer on at least one surface thereof for the purpose of improving the adhesiveness with an adhesive. The coating layer is preferably made of at least one water-soluble or water-dispersible polymer resin selected from a polyester resin, a urethane resin, an acryl resin, and a butyl resin, and particularly contains both a polyester resin and an attaryl resin. Power S preferred ,. The polyester resin of the coating layer used in the present invention has a glass transition point (T g) of 0 to: L 00 ° C, more preferably 10 to 90 ° C. The polyester resin is soluble in water. Or, a dispersible polyester / resin is preferred, but it may contain some organic solvent.
力かるポリエステノレ樹脂としては、 以下のような多塩基酸またはそのエステ/ 成誘導体とポリオールまたはそのエステノ 導体から成る。 すなわち、 多塩基 酸成分としてはテレフタノレ酸、 イソフタノレ酸、 フタノレ酸、 無水フタル酸、 2， 6— ナフタレンジカルボン酸、 1， 4ーシクロへキサンジカルボン酸、 アジピン酸、 セ パシン酸、 トリメリット酸、 ピロメリット酸、 ダイマー酸、 5—ナトリゥムスルホ ィソフタル酸等が挙げられる。 これら酸成分を 2種以上用いて共重合ポリエステル 樹脂を合成する。 また、 若干量ながら不飽和多:^ ¾酸成分のマレイン酸、 ィタコン 酸等及び p -ヒドロキシ安息香酸等の如きヒドロキシカルボン酸を用いることがで きる。 また、 ポリオール成分としては、 エチレングリコール、 1 , 4一ブタンジォ ール、 ジエチレングリコール、 ジプロピレングリコーノレ、 1 , 6—へキサンジォー ノレ、 1， 4—シクロへキサンジメタノーノレ、 キシレングリコーノレ、 ジメチローノレプ 口パン、 ポリ （エチレンォキシド） グリコーノレ、 ポリ （テトラメチレンォキシド） グリコール、 ビスフエノール A、 ビスフエノール Aのエチレンオキサイドまたはプ ロピレンォキサイド付加体等が挙げられるがこれらに限定されるものではない。 本発明で用いる塗布層のァクリル樹脂は、ガラス転移点（T g )が一 5 0〜 5 0 °C、 更に好ましくは一 5 0〜 2 5 °Cのものである。 該ァクリル樹脂は、 水に可溶性また は分散性のァクリルが好ましレ、が、 多少の有機溶剤を含有しても良い。  The powerful polyester resin includes a polybasic acid or an ester / ester derivative thereof and a polyol or an estero conductor thereof as described below. That is, polybasic acid components include terephthalenic acid, isophthalenic acid, phthalenic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sepasic acid, trimellitic acid, Examples include melitic acid, dimer acid, and 5-sodium sulfonic acid. A copolymerized polyester resin is synthesized using two or more of these acid components. Also, it is possible to use a small amount of an unsaturated polycarboxylic acid such as maleic acid, itaconic acid and the like, and hydroxycarboxylic acids such as p-hydroxybenzoic acid. The polyol components include ethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylene glycolone, and dimethylolone. Bread, poly (ethylene oxide) glycolone, poly (tetramethylene oxide) glycol, bisphenol A, ethylene oxide of bisphenol A or propylene oxide adduct, etc., but are not limited thereto. . The acryl resin of the coating layer used in the present invention has a glass transition point (Tg) of 150 to 50 ° C, more preferably 150 to 25 ° C. The acryl resin is preferably water-soluble or dispersible acryl, but may contain some organic solvent.
かかるァクリル樹脂としては以下のようなアクリルモノマーから共重合できる。 このアクリルモノマーとしては、 アルキルアタリレート、 アルキルメタクリレート (アルキル基としては、 メチル基、 ェチル基、 n—プロピル基、 イソプロピル基、 n—ブチノレ基、 イソブチル基、 t—ブチノレ基、 2—ェチルへキシル基、 シクロへキ シル基等）； 2—ヒドロキシェチルァクリレート、 2—ヒドロキシェチノレメタクリレ ート、 2—ヒドロキシプロピノレアタリレート、 2—ヒドロキシプロピ^/メタクリレ 一ト等のヒドロキシ含有モノマー；グリシジノレァクリレート、 グリシジルメタクリ レート、 ァリルグリシジルエーテノ! ^のエポキシ基含有モノマー；アタリル酸、 メ タクリル酸、 ィタコン酸、 マレイン酸、 フマール酸、 クロトン酸、 スチレンスノレホ ン酸及ぴその塩 （ナトリウム塩、 カリウム塩、 アンモユウム塩、 第三級ァミン塩等） 等のカルボキシ基またはその塩を含有するモノマー；アクリルアミド、 メタクリル アミド、 N—アルキルアクリルアミド、 N—アルキルメタクリルアミド、 N, N— ジアルキルァクリルアミド、 N, N—ジアルキノレメタタリレート （アルキル基とし ては、 メチノレ基、 ェチノレ基、 n—プロピル基、 イソプロピル基、 n—プチノレ基、 ィ ソプチノレ基、 t—プチノレ基、 2—ェチルへキ、ンル基、 シクロへキシル基等）、 N—ァ ルコキシアクリルアミド、 N—アルコキシメタクリルアミド、 N, N—ジアルコキ シアクリルアミド、 N， N—ジアルコキシメタクリルアミド （ァノレコキシ基として は、 メトキシ基、 エトキシ基、 ブトキシ基、 イソブトキシ基等)、 アタリロイルモル ホリン、 N—メチロールァクリノレアミド、 N—メチロールメタクリルアミド、 N— フエニルアクリルアミド、 N—フエニルメタクリルアミド等のアミ ド基を含有する モノマー；無水マレイン酸、 無水ィタコン酸等の酸無水物のモノマー；ビニノレイソ シァネート、 ァリノレイソシァネート、 スチレン、 ひーメチノレスチレン、 ビニ/レメチ ノレエーテノレ、 ビ-ノレエチノレエ一テル、 ビニノレトリアノレコキシシラン、 ァノレキ 'ノレマレ ィン酸モノエステル、 アルキルフマール酸モノエステル、 アルキルィタコン酸モノ エステル、 アクリロニトリル、 メタタリロニトリル、 塩化ビニリデン、 エチレン、 プロピレン、 塩化ビュル、 酢酸ビニル、 ブタジエン等のモノマーが挙げられる。 塗 布層として用いられるァクリル樹脂は、 これらに限定されるものではない。 Such an acryl resin can be copolymerized from the following acrylic monomers. Examples of the acrylic monomer include alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butynole, isobutyl, t-butynole, and 2-ethylhexyl). Group, cyclohexyl group, etc.); hydroxy such as 2-hydroxyethyl acrylate, 2-hydroxyethynolemethacrylate, 2-hydroxypropinolate tallate, 2-hydroxypropyl / methacrylate, etc. Monomer containing: Glycidino acrylate, glycidyl methacrylate, epoxy group-containing monomer of aryl glycidyl etheno! ^; Atalilic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene snorenoic acid and Its salts (sodium salt, potassium salt, ammoyu Unsalted, monomer containing a carboxy group or a salt thereof of the tertiary Amin salt, etc.) and the like; acrylamide, methacrylamide Amide, N-alkyl acrylamide, N-alkyl methacrylamide, N, N-dialkyl acrylamide, N, N-dialkynolemethalylate Group, n-butylinole group, isoptinole group, t-butylinole group, 2-ethylhexyl, methyl group, cyclohexyl group, etc.), N-alkoxyacrylamide, N-alkoxymethacrylamide, N, N-dialkoxy Cyacrylamide, N, N-dialkoxymethacrylamide (an anolexoxy group is methoxy, ethoxy, butoxy, isobutoxy, etc.), atalyloylmorpholine, N-methylol acrylolamide, N-methylol methacrylamide, Examples of N-phenylacrylamide and N-phenylmethacrylamide Monomer-containing monomers; acid anhydride monomers such as maleic anhydride and itaconic anhydride; vinylinoleic isocyanate, arlinoleic isocyanate, styrene, hymethinolestyrene, vinyl / lemethinoleate tenolé, and vinyloletinolate Ter, vinylinoletrianorekoxysilane, anoreki 'olemaleic acid monoester, alkyl fumaric acid monoester, alkyl itaconic acid monoester, acrylonitrile, methacrylonitrile, vinylidene chloride, ethylene, propylene, vinyl chloride, vinyl acetate, And monomers such as butadiene. The acryl resin used as the coating layer is not limited to these.
本発明で用いられる上記組成物は、 劃莫を形成させるために、 水激夜、 水分散液 或いは乳化液等の水†生塗液の形態で使用されるのが好ましい。 を形成するため に、 必要に応じて、 前記組成物以外の他の樹脂、 例えばォキサゾリン基を有する重 合体、 メラミン、 エポキシ、 アジリジン等の架橋剤、 帯電防止剤、 着色剤、 界面活 性剤、 紫外線吸収剤、 滑剤 （フイラ一、 ワックス） などを^]口することができる。 力かる滑剤はフィルムの滑り性の向上あるいは耐プロッキング性の向上を目的とし て、 必要に応じて滑剤を添加することができる。  The composition used in the present invention is preferably used in the form of a water-based coating solution such as a watery night, an aqueous dispersion, or an emulsion in order to form a fine grain. If necessary, other resins other than the above composition, for example, a polymer having an oxazoline group, a crosslinking agent such as melamine, epoxy, and aziridine, an antistatic agent, a coloring agent, a surfactant, ^] You can use UV absorbers, lubricants (filament, wax) etc. A strong lubricant may be added as necessary for the purpose of improving the slipperiness or blocking resistance of the film.
水性塗液の固形分濃度は、 通常 2 0重量％以下であり、 更には 1〜： 1 0重量％で あることが好ましレ、。 この割合が 1重量％未満であると、 ポリエステルフィルムへ の塗れ性が不足し、 一方、 2 0重量％を越えると塗剤の安定性や塗布舰が謝匕す ることがある。  The solid content concentration of the aqueous coating solution is usually 20% by weight or less, and preferably 1 to 10% by weight. If the proportion is less than 1% by weight, the coatability on the polyester film will be insufficient, while if it exceeds 20% by weight, the stability of the coating and the coating property may be degraded.
塗布層は、 未延伸フィルムまたは一軸延伸が終了したフィルムに水性塗液を塗布 し、 その後、 2方向または 1方向に延伸し熱固定することでフィルム上に強固に設 けることができる。 塗工方法としてはロールコート法、 グラビアコート法、 ロール ブラッシュ法、 スプレー法、 エアーナイフコート法、 含浸法、 カーテンコート法等 を稱虫または組み合わせて用いることが出来る。 The coating layer is applied firmly to the unstretched film or uniaxially stretched film by applying the aqueous coating solution, and then stretched in two or one direction and thermally fixed. Can be opened. As a coating method, a roll coat method, a gravure coat method, a roll brush method, a spray method, an air knife coat method, an impregnation method, a curtain coat method, or the like can be used or in combination.
<粘着剤 >  <Adhesive>
本発明のバックグラインドテープやダイシングテープを構成する粘着剤としては 従 知のものが広く用いられうるが、 アタリル系粘着剤が好ましレヽ。 アタリル系 粘着剤としては、 具体的には、 アクリル酸エステルを主たる構成単位とする戦虫重 合体およぴ共重合体から選ばれたァクリル系重合体その他の官能性単量体との共重 合体およびこれら重合体の混合物が用いられる。 たとえば、 炭素数 1〜 1 0のアル キルアルコールのァクリル酸エステル、 炭素数 1 ~ 1 0のアルキルアルコールのメ タクリノレ酸エステル、 酉乍酸ビニルエステル、 アクリロニトリル、 ビュルアルキルェ 一テルなどを好ましく使用できる。 また上記アクリル系共重合体は、 1種単独また は 2種以上を組み合わせて用！/、ることができる。  As the pressure-sensitive adhesive constituting the back-grinding tape and the dicing tape of the present invention, known pressure-sensitive adhesives can be widely used, but an ataryl-based pressure-sensitive adhesive is preferred. As the ataryl adhesive, specifically, copolymers with acryl-based polymers and other functional monomers selected from combat insect polymers and copolymers having an acrylic acid ester as a main structural unit. Combinations and mixtures of these polymers are used. For example, acrylic acid esters of alkyl alcohols having 1 to 10 carbon atoms, methacryloleic acid esters of alkyl alcohols having 1 to 10 carbon atoms, vinyl esters of acetic acid, acrylonitrile, and butyl alkyl ether can be preferably used. . The above acrylic copolymers can be used alone or in combination of two or more! / You can.
また、 官能†生単量体としては、 アタリル酸、 メタタリル酸、 マレイン酸、 2—ヒ ドロキシェチノレアタリレート、 2—ヒドロキシェチルメタタリレート等が用いられ る。 官能性単量体を有する共重合体粘着剤は、 架橋剤を使用することにより接着力 と纖力とを任意の値に設定することができる。 このような架橋剤としては、 多価 イソシァネート化合物、 多価エポキシ化合物、 多価アジリジン化合物、 キレート化 合物等がある。 多価イソシァネート化合物としては、 具体的にはトルイレンジイソ シァネート、 ジフエ二/レメタンジイソシァネート、 へキサメチレンジイソシァネー ト、 イソホロンジイソシァネートおょぴこれらのァダクトタイプのもの等が用いら れる。 多価エポキシ化合物としては、 具体的にはエチレングリコールジグリシジル エーテル、 テレフタル酸ジグリシジルエステルアタリレート等が用いられる。 多価 アジリジン化合物としては、 具体的にはトリスー 2 , 4 , 6— ( 1一アジリジニノレ) - 1 , 3 , 5—トリアジン、 トリス 〔1一 （2—メチノレ） 一アジリジニノレ〕 ホスフ インォキシド、 へキサ 〔1一 （2—メチノレ） 一アジリジニノレ〕 トリホスファトリア ジン等が用いられる。 またキレート化合物としては、 具体的にはェチルァセトァセ テートアルミニウムジイソプロピレート、 アルミニウムトリス （ェチルァセトァセ テート） 等が用いられる。 これらのモノマーを重合して得られるアクリル系共重合体の分子量は、 1 . 0 X 1 05〜： 1 0 . 0 X 1 05であり、 好ましくは 4 . 0 X 1 05〜8 . 0 X 1 05である。 さらに、 粘着剤層として、 ¾l線を照射することにより硬ィ匕して、 ピックアップ時 の接着力を低下できるものも用いることができる。 具体的には、 上記ァクリノレ系共 重合体を主剤として、 これに放射線重合性化合物を含ませた粘着剤を用いることが 好ましい。このような放射線重合性化合物としては、たとえば特開昭 6 0—1 9 6 , 9 5 6号公報およぴ特開昭 6 0— 2 2 3 , 1 3 9号公報に開示されているような、 光照射によって三次元網状化しうる分子内に光重合性炭素一炭素二重結合を少なく とも 2個以上有する低分子量化合物が広く用いられ、 具体的には、 トリメチロール プロパントリアタリレート、 テトラメチロールメタンテトラアタリレート、 ペンタ エリスリ トーノレトリアタリレート、 ペンタエリスリ トールテトラアタリレート、 ジ ペンタエリスリ トールモノヒドロキシペンタアタリレート、 ジペンタエリスリ トー ルへキサアタリレ トあるいは 1 , 4—プチレングリコールジァクリレート、 1， 6—へキサンジォーノレジァクリレート、 ポリエチレングリコ一/レジァクリレート、 市販のオリゴエステルァクリレートなどが用いられる。 Further, as the functional monomer, for example, atalylic acid, methacrylic acid, maleic acid, 2-hydroxyxethynoleate tallate, 2-hydroxyethyl methacrylate, and the like are used. By using a cross-linking agent, the adhesive force and the fiber force of a copolymer adhesive having a functional monomer can be set to arbitrary values. Examples of such a crosslinking agent include a polyvalent isocyanate compound, a polyvalent epoxy compound, a polyvalent aziridine compound, and a chelate compound. Specific examples of polyvalent isocyanate compounds include toluylene diisocyanate, diphene / lemethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Etc. are used. Specific examples of the polyepoxy compound include ethylene glycol diglycidyl ether, terephthalic acid diglycidyl ester atalylate, and the like. As the polyvalent aziridine compound, specifically, tris-2,4,6-((1-aziridinole)-1,3,5-triazine, tris [1-1 (2-methinole) -aziridininole] phosphinoxide, hexa [ 11- (2-Methinole) -aziridininole] Triphosphatriazine or the like is used. Specific examples of the chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), and the like. The molecular weight of the acrylic copolymer obtained by polymerizing these monomers is 1.0 X 10 5 to: 10.0 X 10 5 , preferably 4.0 X 10 5 to 8.5. 0 X 1 0 5. Further, as the pressure-sensitive adhesive layer, a pressure-sensitive adhesive layer which can be hardened by irradiating a UV ray to reduce the adhesive force at the time of pickup can be used. Specifically, it is preferable to use a pressure-sensitive adhesive containing the above acrylonitrile-based copolymer as a main component and a radiation-polymerizable compound. Such radiation-polymerizable compounds are disclosed, for example, in JP-A-60-196,956 and JP-A-60-223,139. In addition, low molecular weight compounds having at least two or more photopolymerizable carbon-carbon double bonds in a molecule that can be three-dimensionally reticulated by light irradiation are widely used, specifically, trimethylol propane triatalylate, and tetramethylol. Methylol methanetetraaphthalate, pentaerythritol tonoretriatalate, pentaerythritol tetraatalylate, dipentaerythritol monohydroxypentaatalylate, dipentaerythritolhexaatalylate or 1,4-butylene glycol diacrylate, 1,6 —Hexane diono resin acrylate, polyethylene glycol / resin acrylate, commercially available Such as Gore-ester § chestnuts rate is used.
さらに脑線重合性化合物として、上記のようなアタリレート系化合物のほかに、 ゥレタンァクリレート系オリゴマーを用いることもできる。 ウレタンアタリレート 系ォリゴマ一は、ポリエステル型またはポリエーテノレ型などのポリ才ール化合物と、 多価ィソシァネート化合物たとえば 2， 4 _トリレンジィソシァネート、 2 , 6— トリレンジイソシァネート、 1， 3—キシリレンジイソシァネート、 1 , 4—キシ リレンジィソシァネート、 ジフエエルメタン 4 , 4ージイソシァネートなどを反応 させて得られる末端ィソシァネートウレタンプレポリマーに、 ヒドロキシル基を有 するァクリレートあるいはメタタリレートたとえば 2—ヒドロキシェチ Λ ^アタリレ ートまたは 2—ヒドロキシェチルメタタリレート、 2—ヒドロキシプロピルアタリ レート、 2—ヒドロキシプロピルメタタリレート、 ポリエチレングリコールアタリ レート、 ポリエチレングリコールメタクリレートなどを反応させて得られる。 この ゥレタンァクリレート系オリゴマ一は、 炭素一炭素二重結合を少なくとも 1個以上 有する放射線重合性化合物である。  Further, as the X-ray polymerizable compound, a polyurethane acrylate oligomer can be used in addition to the above-mentioned atalylate compound. The urethane atalylate-based oligomer is composed of a polyester compound such as a polyester type or a polyethenolate type, and a polyvalent isocyanate compound such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, Hydroxyl groups are present in the terminal isocyanate urethane prepolymer obtained by reacting 3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane 4,4-diisocyanate, etc. Acrylates or methacrylates such as 2-hydroxyethyl Λ ^ arytalate or 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, etc. Obtained by. This urethane acrylate oligomer is a radiation polymerizable compound having at least one carbon-carbon double bond.
このようなウレタンアタリレート系オリゴマーとして、 特に分子量が 3 0 0 0〜 3 0 0 0 0、 好ましくは 3 0 0 0〜1 0 0 0 0、 さらに好ましくは 4 0 0 0〜8 0 0 0であるものを用いると、 半導体ウエノ、表面が粗い^にも、 ウェハチップのピ ックアツプ時にチップ表面に粘着剤が付着することがなレヽため好ましい。 またウレ タンァクリレート系オリゴマーを放射線重合性化合物として用いる には、 特開 昭 6 0— 1 9 6， 9 5 6号公報に開示されたような分子内に光重合隨素一炭素二 重結合を少なくとも 2個以上有する低分子量化合物を用いた と比較して、 粘着 シートとして極めて優れたものが得られる。 すなわち粘着シートのお谢線照射前の 接着力は充分に大きく、 また放射線照射後には接着力が充分に低下してウェハチッ プのピックァップ時にチップ表面に粘着剤が残存することはなレ、。 Such a urethane acrylate copolymer has a molecular weight of 300 to If a wafer having a size of 300,000, preferably 300,000 to 100,000, and more preferably 400,000 to 800, is used, the wafer chip can be used even for semiconductor wafers and rough surfaces. This is preferable because the adhesive does not adhere to the chip surface during the pick-up. Further, in order to use a urethane acrylate oligomer as a radiation polymerizable compound, at least a photopolymerizable single-carbon double bond must be included in the molecule as disclosed in JP-A-60-196,956. As compared with the case where a low molecular weight compound having two or more compounds is used, an extremely excellent pressure-sensitive adhesive sheet can be obtained. In other words, the adhesive force of the adhesive sheet before irradiation with the ultraviolet ray is sufficiently large, and the adhesive force after irradiation is sufficiently reduced so that the adhesive does not remain on the chip surface when picking up the wafer chip.
また必要に応じて、 粘着剤層中に、 上記のような粘着剤と藤線重合性化合物と に加えて、 放射線照射により着色する化合物を含有させることもできる。 このよう な灘線照射により、 着色する化合物を粘着剤層に含ませることによって、 粘着シ 一トに放射線が照射された後には該シートは着色され、 したがって光センサーによ つてウェハチップを検出する際に検出精度が高まり、 ウェハチップのピックアップ 時に誤動作が生ずることがない。 また粘着シートに放射線が照射されたカ否かが目 視により直ちに判明するという効果が得られる。  If necessary, the pressure-sensitive adhesive layer may contain, in addition to the pressure-sensitive adhesive and the crosslinkable polymerizable compound as described above, a compound that is colored by irradiation with radiation. By applying a compound to be colored to the adhesive layer by such Nada line irradiation, the sheet is colored after the adhesive sheet is irradiated with radiation, and therefore, the wafer sensor is detected by an optical sensor. In this case, the detection accuracy is improved, and no malfunction occurs when picking up a wafer chip. Further, an effect is obtained that whether or not radiation has been applied to the pressure-sensitive adhesive sheet can be immediately determined visually.
腿線照射により着色する化合物の好ましい具体例としてはロイコ染料が挙げら れる。 ロイコ染料としては、 'I貧用のトリフエ二ノレメタン系、 フノレオラン系、 フヱノ チアジン系、 オーラミン系、 スピロピラン系のものが好ましく用いられる。 これら ロイコ染料とともに好ましく用いられる顕色剤としては、 従来から用いられている フエノールホルマリン樹脂の初期重合体、 芳香族カルボン酸誘導体、 活性白土など の電子受容体が挙げられ、 さらに、 色調を変ィ匕させる は種々公知の発色剤を組 て用いることもできる。 このような ¾†線照射によって着色する化合物は、一 且有機溶媒などに溶解された後に粘着剤層中に含ませてもよく、 また微粉末状にし て粘着剤層中に含ませてもよい。この化合物は、粘着剤層中に 0. 0 1〜1 0重量％ 好ましくは 0. 5〜 5重量。 /0の量で用 ヽられることが望ましレ、。 Preferable specific examples of the compound colored by irradiation with the thigh line include leuco dye. As the leuco dye, triphenylenomethane type, phenololean type, phenothiazine type, auramine type and spiropyran type dyes for poor use are preferably used. Developers preferably used with these leuco dyes include conventionally used electron acceptors such as phenol formalin resin prepolymers, aromatic carboxylic acid derivatives, and activated clay, and the like. Various known color formers can be used in combination. Such a compound that is colored by irradiation with X-rays may be included in the adhesive layer after being dissolved in an organic solvent or the like, or may be included in the adhesive layer in the form of fine powder. . This compound is present in the pressure-sensitive adhesive layer in an amount of 0.01 to 10% by weight, preferably 0.5 to 5% by weight. Desirable, used in an amount of / 0 .
<パックグラインドテーフ ¾合体 >  <Pack grind toe combination>
本発明において、 バックグラインドテープは通常、 粘着剤層の表面を離形フィル ムにより保護されたバックグライシドテ一: 复合体の状態で保管され、 バックダラ インド工程で離形フィルムを剥離除去して使用される。 すなわち、 本発明のバック グラインドテープ複合体は、 バックグラインドテープの粘着層の上にさらに離形フ イルムを有する。 In the present invention, the back-grinding tape is usually stored in the form of a back-grid tape in which the surface of the pressure-sensitive adhesive layer is protected by a release film; The release film is peeled off and used in the Indian process. That is, the back grinding tape composite of the present invention further has a release film on the adhesive layer of the back grinding tape.
かかる離形フィルムは、 ポリエステノレよりなるベースフィルムの片面にシリコー ン離形層を積層させてなるものであり、 シリコーン離形層面とパックグラインドテ ープの粘着層面とを貼りあわせ、 バックグラインドテ一:^复合体とする。 離形フィ ルムは、 シリコーン離形層とポリエステルよりなるベースフィルムの間にさらにプ. ライマー層を有していてもよい。  Such a release film is obtained by laminating a silicone release layer on one side of a base film made of polyester, and bonding the silicone release layer surface to the adhesive layer surface of the pack grind tape to form a back grind tape. One: ^ 复 Merge. The release film may further have a primer layer between the silicone release layer and the base film made of polyester.
<ダイシングテープ複合体 > '  <Dicing tape composite> ''
本発明において、 ダイシングテープは通常、 粘着剤層の表面を離形フィルムによ り保護されたダイシングテープ複合体の状態で保管され、 ダイシングェ程で離形フ イルムを剥離除去して使用される。すなわち、本発明のダイシングテ一 复合体は、 ダイシングテープの粘着層の上にさらに離形フィルムを有する。  In the present invention, the dicing tape is usually stored in the state of a dicing tape composite in which the surface of the pressure-sensitive adhesive layer is protected by a release film, and the release film is peeled and removed in the dicing process. That is, the dicing tape composite of the present invention further has a release film on the adhesive layer of the dicing tape.
力かる離形フィルムは、 ポリエステルよりなるベースフィルムの片面にシリコー ン離形層を積層させてなるものであり、 シリコーン離形層面とダイシングテープの 粘着層面とを貼りあわせ、 ダイシングテ一: 7¾合体とする。 離形フィルムは、 シリ コーン離形層とポリエステルよりなるベースフィルムの間にさらにプライマー層を 有していてもよい。  A strong release film is made by laminating a silicone release layer on one side of a base film made of polyester.The silicone release layer surface and the adhesive layer surface of the dicing tape are bonded together to form a dicing tape: I do. The release film may further have a primer layer between the silicone release layer and the base film made of polyester.
く離形フィルムを構成するポリエステルベースフィルム >  Polyester base film constituting release film>
本発明の離形フィルムを構成するポリエステルベースフィルムは、 本発明の半導 体ウェハ加工用ベースフイノレムと同一のポリエステノレで構成してもよいが、 異なる ポリエステノレで構成してもよい。 かかるポリエステノレとして、 ポリエチレンテレフ タレート、 ポリエチレン _ 2， 6—ナフタレンジカルボキシレートを主たる成分と するポリエステルが好ましく例示される。 ここで主たるとは、 ポリマーの構成成分 において^!桑返し単位の少なくとも 8 O m o 1 %がエチレンテレフタレートまたは エチレン一 2， 6—ナフタレンジカルポキシレートであることを意味し、 より好ま しくは 9 0 m o 1 %以上、 特に好ましくは 9 5 m o 1 %以上である。  The polyester base film constituting the release film of the present invention may be composed of the same polyester as the base finolem for processing a semiconductor wafer of the present invention, or may be composed of a different polyester. Preferable examples of such polyesters include polyesters containing polyethylene terephthalate and polyethylene_2,6-naphthalenedicarboxylate as main components. Here, “mainly” means that at least 8% of Omo 1% of the repeating unit in the polymer component is ethylene terephthalate or ethylene-1,6-naphthalenedicarboxylate, and more preferably 90%. mo 1% or more, particularly preferably 95 mo 1% or more.
なお、 離形フィルムを構成するポリエステルベースフィルムは、 パ、ンクグライン ド加工およびダイシング加工後、 紫外線照射して粘着剤を硬化させ、 粘着力を低下 させるために、該ベースフィルムの光^ ¾i率が 8 5 %以上であることが好ましい。 くシリコーン离無層> The polyester base film, which constitutes the release film, is hardened by UV irradiation after curing, dicing, and curing. In order to achieve this, the light transmittance of the base film is preferably 85% or more. Silicone-free layer>
本発明の離形フィルムを構成するシリコーン離形層は、 Uえば硬化性シリコーン 樹脂を含む塗液をポリエステルベースフィルムの片面に塗布し、 乾燥、 硬化させる ことにより形成できる。硬化性シリコーン樹脂としては、縮合反応系、付加反応系、 紫外線もしくは電子線硬化系などレ、ずれの反応系のものが例示され、 かかる硬化性 シリコーン樹脂の中から 1種以上用いることができる。  The silicone release layer constituting the release film of the present invention can be formed by applying a coating liquid containing, for example, a curable silicone resin to one surface of a polyester base film, followed by drying and curing. Examples of the curable silicone resin include a condensation reaction system, an addition reaction system, an ultraviolet or electron beam curing system, and a reaction system with a deviation, and one or more of such curable silicone resins can be used.
ぐ製造条件 > '  Manufacturing conditions> ''
本発明のベースフィルムの製造方法について、 詳述する。 本発明のポリエチレン —2， 6—ナフタレンジカルボキシレートフィルムは、 例えば通常の押出温度、 す なわち融点 （以下 Tmと表わす） 以上 （Tm+ 7 0°C) 以下の? で、 樹脂を溶融 押出して得られたフィルム状溶融物を、 回転冷却ドラムの表面で急冷し、 固有粘度 が 0 . 4 0〜0. 9 0 d l Z gの未延伸フィルムを得る。 この工程でフィルム状溶 融物と回転冷却ドラムとの密着性を高める目的で、 フィルム状溶融物に静電荷を付 与する静^着法が知られている。 一般にポリエチレン一 2 , 6—ナフタレンジ力 ルポキシレートは溶融物の電気抵抗が高 、ため、 上記の冷却ドラムとの静電密着が 不十分になる がある。 この対策としては、 ポリエチレン一 2， 6—ナフタレン ジカノレボキシレートの全 2官能性カルボン酸成分に対し、 0. 1〜 1 0 mm o 1 % のエステノ 成性官能基を有するスルホン酸 4級ホスホニゥムを含有させるのが好 ましい。  The method for producing the base film of the present invention will be described in detail. The polyethylene-2,6-naphthalenedicarboxylate film of the present invention can be obtained by, for example, melt-extruding a resin at a normal extrusion temperature, that is, at a temperature not lower than the melting point (hereinafter referred to as Tm) (Tm + 70 ° C). The obtained film-like melt is quenched on the surface of a rotary cooling drum to obtain an unstretched film having an intrinsic viscosity of 0.40 to 0.90 dl Zg. In order to increase the adhesion between the film-like melt and the rotary cooling drum in this step, a static adhesion method of applying an electrostatic charge to the film-like melt is known. In general, polyethylene 1,2,6-naphthalenedioxy propyloxylate has a high electrical resistance of a molten material, so that the above-mentioned electrostatic adhesion to the cooling drum may be insufficient. As a countermeasure, quaternary sulfonic acid with 0.1 to 10 mmo 1% of esteno-forming functional group based on all bifunctional carboxylic acid components of polyethylene 1,2,6-naphthalene dicanoleboxylate It is preferred to include phosphonium.
このようにして得られた未延伸フィルムは、 1 2 0〜1 7 0 ° (、 より好ましくは 1 3 0〜1 6 0°Cの で、 縦方向に 2. 8〜3. 5倍の延伸倍率で延伸され、 次 V、で横方向に 1 2 0〜 1 5 0 °Cの で 2. 8〜 3. 6倍の延伸倍率で延伸され、 二軸酉己向フィルムとなる。 なお、 概伸倍率は縦延伸倍率の 0. 9 0〜1 . 1 5倍 程度の倍率にすることがフィルムの厚みのパラツキを所望の範囲にする上で好まし い。また、これらの延伸は複数段階に分割して行なわれる多段延伸であってもよい。 このようにして得られた二軸配向フィルムは、 2 3 5〜2 5 5 °C、 より好ましく は 2 4 0 °C〜 2 5 0。(：の温度で 0. 3〜 2 0秒間熱固定するのが好まし 、。その後、 熱収縮率を低下させる目的で、 »向および Zまたは^"向に、 弛緩率 0. 5〜1 5 %の範囲で熱弛緩処理を行うのがさらに好ましい。 なお、 延伸機の機構から、 一 般に横方向の弛緩がやり易く、 横方向の熱«率は 0 %に近づけることが容易であ る。 一方、 縦方向の熱収縮率、 特に 2 0 0°C近辺の熱収縮率を小さくすることは難 しいため、前述のような縦方向と横方向の延伸倍率および延伸 カ効果的である。 また、 本発明のポリエステノレフイノレムは、 前記のような熱処理のほかに、 巻き取 つた後に熱処理することがより好ましい。 巻き取った後の熱処理の方法は特定され ないが、 懸垂式の弛縫処理法が特に好ましい。 懸垂式の弛纖処理法とは、 処理 するフィルムを上方に設置した口一ラーを経て下方に自重で垂下させ、 その途中で カロ熱した後、 下方のローラーで冷却しながらほぼ水平方向に向きを変え、 エップ口 一ラーで巻取り張力を遮断した上で卷き取るものが好ましく挙げられる。 垂下距離 は 2〜1 0 m程度がよく、 2 m未満では自重が小さすぎて平面性が損われ易く、 ま た、 カロ熱範囲が短いので弛緩効果を得ることが非常に難しい。 他方、 垂下距離が 1 0 mを超えると、 作業性が悪く、 自重が重くなるので、 加熱域の位置によっては所 望の熱収縮率が得られないことがある。 The unstretched film thus obtained is stretched in the longitudinal direction by a factor of 2.8 to 3.5 times at a temperature of 120 to 170 ° (more preferably, a temperature of 130 to 160 ° C). The film is stretched at a draw ratio of 2.8 to 3.6 times at 120 to 150 ° C in the transverse direction at the next V, and becomes a biaxial film. The elongation ratio is preferably in the range of 0.90 to 1.15 times the longitudinal stretching ratio in order to keep the thickness variation of the film within a desired range. The biaxially oriented film thus obtained may have a biaxially oriented film of from 235 to 255 ° C, more preferably from 240 to 250 ° C. : It is preferable to heat set at a temperature of 0.3 to 20 seconds, and then to reduce the heat shrinkage, in the »direction and in the Z or ^" direction, in the relaxation rate of 0.5 to 1 It is more preferable to perform the thermal relaxation treatment in the range of 5%. Note that, in general, relaxation in the horizontal direction is easy due to the mechanism of the stretching machine, and the heat coefficient in the horizontal direction can be easily approached to 0%. On the other hand, since it is difficult to reduce the heat shrinkage in the vertical direction, particularly in the vicinity of 200 ° C., the stretching ratio and the stretching in the vertical and horizontal directions as described above are effective. In addition to the heat treatment as described above, it is more preferable that the polyester refinolem of the present invention is heat-treated after winding. The method of heat treatment after winding is not specified, but a hanging-type loosening treatment method is particularly preferable. The suspended fiber treatment method is as follows: the film to be processed is dropped downward by its own weight through a mouthpiece installed above, heated by calories in the middle, and then turned almost horizontally while being cooled by rollers below. Preferably, winding is performed after the winding tension is cut off by an ep-mouth. The hanging distance is preferably about 2 to 10 m. If it is less than 2 m, its own weight is so small that its flatness tends to be impaired, and its caloric heat range is so short that it is very difficult to obtain a relaxing effect. On the other hand, if the drooping distance exceeds 10 m, workability is poor and the weight becomes heavy, so that the desired heat shrinkage may not be obtained depending on the location of the heating zone.
この製膜工程後の熱処理は、 得られる二軸配向ポリエステルフィルムの 2 0 0 °C における熱収縮率が所望の範囲になるものなら、 フィルムの製膜工程内 （熱固定後 の弛緩処理） で行われてもフィルムを製膜し一度卷き取つた後の弛緩熱処理で行わ れても特にその処 法は限定されない。 好ましい加熱方式は、 即時にフィルムを カロ熱できることから赤外 口熱である。 また、 好ましい弛緩熱処理 ½は、 フィル ム温度が 2 0 0〜 2 4 0 °Cとなるように処理するものである。 フィルム温度が 2 0 0 °C未満では 2 0 0 °Cでの熱収縮率を小さくすること力 S難しく、 他方、 フィルム温 度が 2 4 0 °Cを超えると平面性が謝ヒし易く、 ひどレ、^^はォリゴマーが析出して フィルムが白くなることがある。 この白化は圧力履歴に左右され、 例えば吊りベル トをフィルムロールのフィルム部分に架けて運搬すると、 2 0 0。C以下であっても、 ベルトと翻虫した部分が白化する:^がある。 なお、 フィルム fi¾は、 非翻虫の赤 外線式?破計 （例えばバーンズ^ n射 計） を用いて測定できる。 これらの熱処 理方法の中、ブイ /レムの広範囲な範囲の熱収縮率をより均一に抑えやすレ、ことから、 製膜工程での熱処理よりも懸垂式弛緩熱処理法が好ましい。  The heat treatment after the film forming step is performed in the film forming step (relaxation treatment after heat setting) if the heat shrinkage at 200 ° C. of the obtained biaxially oriented polyester film is within a desired range. Even if it is performed, even if it is performed by a relaxation heat treatment after the film is formed and once wound up, the processing method is not particularly limited. A preferred heating method is infrared heat because the film can be immediately calo-heated. In addition, a preferred relaxation heat treatment is a treatment in which the film temperature is set to 200 to 240 ° C. If the film temperature is lower than 200 ° C, it is difficult to reduce the heat shrinkage at 200 ° C. On the other hand, if the film temperature exceeds 240 ° C, the flatness tends to be worse. In the case of terrible, ^^, the oligomer may precipitate and the film may become white. This whitening depends on the pressure history. For example, if a hanging belt is transported over the film part of a film roll, it will be 200. Even if it is less than C, the belt and the infested part are whitened: ^. The film fi¾ can be measured using a non-inverting infrared spectrometer (eg, a Burns ^ n radiometer). Among these heat treatment methods, the suspension relaxation heat treatment method is preferable to the heat treatment in the film forming process because the heat shrinkage in a wide range of buoy / REM can be suppressed more uniformly.
—方、 離形フィルムを構成するポリエステルベースフィルムは、 従来から知られ. ている、 あるいは当業界に蓄積されている方法で得ることができる。 すなわち、 溶 融 ·押出されたポリエステルの未延伸フィルムを一軸方向に延伸し、 次いで上記延 伸方向と直角方向に延伸し、 さらに熱固定処理を行なう。 本発明において、 离 ΙΜϋ は、 '例えば離型層の成分を含む塗液をポリエステルベースフィルムに塗布し、 加熱 乾燥させることにより塗設することができる。 '塗液の'塗布方法としては公知の塗工 方法が適用することができ、 例えばロー^/コーター法、 ブレードコーター法を用い ることができる。 以上の方法により得られた離形フィルムをパックグラインドテー プゃダイシングテープに張り合わせることで、 各複合体が得られる。 実施例 -On the other hand, polyester base films that make up release films have been known for some time. Or can be obtained by methods that are accumulated in the art. That is, the unstretched polyester film that has been melted and extruded is uniaxially stretched, then stretched in a direction perpendicular to the stretching direction, and further subjected to a heat setting treatment. In the present invention, 离 can be applied, for example, by applying a coating liquid containing a component of a release layer to a polyester base film and drying by heating. A known coating method can be applied as a 'coating liquid' coating method, and for example, a low / coater method or a blade coater method can be used. Each composite is obtained by laminating the release film obtained by the above method on a pack grind tape dicing tape. Example
以下、 実施例を挙げて本発明を更に詳細に説明する。 なお、 実施例中の各特性値 は以下の方法により測定または評価したものである。 また、 実施例中の部および比 は、 特に断らない限り、 重量部および重量比を示す。 (1) 熱収縮率  Hereinafter, the present invention will be described in more detail with reference to examples. Each characteristic value in the examples was measured or evaluated by the following method. Parts and ratios in the examples are parts by weight and weight ratios unless otherwise specified. (1) Heat shrinkage
200°Cに温度設定されたオーブンの中に無緊張状態で 10分間フィルムを保持 し、 加熱処理前後での寸法変ィ匕を熱収縮率 S (%) として下式 (1) により算出す る。 ·  The film is held in an oven set at a temperature of 200 ° C without tension for 10 minutes, and the dimensional change before and after the heat treatment is calculated as the heat shrinkage S (%) by the following equation (1). . ·
S= [(L0-L) /L0] X 100 … (1) S = [(L 0 -L) / L 0 ] X 100… (1)
ただし、 L。：熱処理前の標点間距離、 L：熱処理後の標点間距離をそれぞれ表す。 なお、 試料幅 20mm、 長さ 200mmであり、 熱処理前の標点間距離は 150m mである。 フィルムの製^^向 （MD) と幅方向 （TD) の両方向で測定を行い、 熱収縮率を求めた。 However, L. : Distance between gauges before heat treatment, L: distance between gauges after heat treatment. The sample width is 20 mm and length is 200 mm, and the distance between gauge points before heat treatment is 150 mm. The heat shrinkage was determined by measuring in both the machine direction (MD) and width direction (TD) of the film.
(2) オリゴマー抽出量  (2) Oligomer extraction amount
フィルムサンプル 5 gをソクスレー抽出器を用！/、てクロ口ホルム内で 24時間抽 出操作を行った。 乾燥後のフィルムサンプルの重量を測定し、 抽出前重量 W。 (g) と抽出後重量 (g) とからオリゴマー抽出量 K (重量％) を下式'（2) により求 めた。  Use 5 g of film sample with Soxhlet extractor! / The extraction operation was performed for 24 hours in the black hole Holm. The weight of the film sample after drying is measured, and the weight before extraction W. (g) and the weight (g) after extraction, the oligomer extraction amount K (% by weight) was determined by the following equation (2).
K= [(Wo-W,) /W0] X I 00 … (2) (3) カロ熱後のオリゴマー析出率 K = [(Wo-W,) / W 0 ] XI 00… (2) (3) Oligomer precipitation rate after calorific heat
フィルムを木枠に固定した後 1 6 0°Cの熱風循環 （空気） 式乾燥器内に 1 0分間 保持した後、 フィルム表面にアルミニウムを蒸着し、 微分干涉 光学顕微鏡でフィ ルム表面の写真を ¾ ^する。 この写真上でオリゴマー （白い斑点状に写る） の占め る面積の総和の写真全面積に対する百分率で加熱オリゴマー析出率を評価する。 After fixing the film to the wooden frame, holding it in a hot air circulating (air) dryer at 160 ° C for 10 minutes, depositing aluminum on the film surface, and using a differential drying optical microscope to photograph the film surface ¾ ^ On this photograph, the oligomer deposition rate as a percentage of the total area occupied by oligomers (appearing as white spots) with respect to the total area of the photograph is evaluated.
〇： オリゴマー析出率 2. 5%未満 〇: oligomer precipitation rate less than 2.5%
Δ： オリゴマー析出率 2. 5〜4. 5%  Δ: oligomer deposition rate 2.5 to 4.5%
X ： オリゴマー析出率 4. 5 %以上  X: oligomer precipitation rate 4.5% or more
(4) フィルムの厚み方向の屈折率 (n z)  (4) Refractive index in the thickness direction of the film (nz)
ァッベの屈折率計 （株式会社ァタゴ製） を使用して、 2 5 °Cにて N a一 D線を用 いてフィルムの厚み方向 （z) の屈折率を求めた。  Using an Abbe refractometer (manufactured by Atago Co., Ltd.), the refractive index in the thickness direction (z) of the film was determined at 25 ° C using a Na-D line.
(5) ヤング率  (5) Young's modulus
試料幅 1 Omm、 長さ 1 5 Ommに切り、 チャック間 1 00mmにして引張速度 1 0 mm/分、 チヤ一ト速度 5 00 mm/分でィンストロンタイプの万能引張試験 装置で引張る。 フイノレムの製膜方向 （MD) と幅方向 （TD) の両方向で測定を行 レ、、 得られた荷重一伸び曲線の立上部の接線よりヤング率を算出する。  Cut the sample to a width of 1 Omm and a length of 15 Omm, set the distance between the chucks to 100 mm, and pull at a tensile speed of 10 mm / min and a chart speed of 500 mm / min using an universal type tensile tester of Instron type. The measurement is performed in both the film forming direction (MD) and the width direction (TD) of the finolem, and the Young's modulus is calculated from the tangent at the top of the obtained load-elongation curve.
(6) 中心線平均粗さ （Ra)  (6) Center line average roughness (Ra)
J I S B— 060 1に規定する方法により、 カツトオフは 0. 25 mm, 測定 触針は 3 μπιのものを用いて表面粗さ計（(株）東京精密製の商品名 「サーフコ ム SE— 3 CK」） にて測定する。  According to the method specified in JISB-0601, the cut-off is 0.25 mm, the measuring probe is 3 μπι. A surface roughness meter (trade name “Surfcom SE-3CK” manufactured by Tokyo Seimitsu Co., Ltd.) ) Measure at.
(7) フィルム厚み ' マイクロメーター （アンリツ （株） 製の商品名 「K一 402 B型」） を用いて、 フ イルムの製膜方向 （MD) および幅方向 （TD) において各々 1 0 c m間隔で測定 を行い、 全部で 300ケ所のフィルム厚みを測定する。 得られた 300ケ所のフィ ルム厚みの平均値を算出してフィルム平均厚み t。 (μια) を得る。  (7) Film thickness 厚 み Using a micrometer (trade name “K-402B” manufactured by Anritsu Corporation), the film thickness is 10 cm in each of the film forming direction (MD) and width direction (TD). The film thickness is measured at a total of 300 locations. The average value of the film thickness at 300 locations was calculated and the average film thickness t was calculated. (μια).
さらに電子マイクロメーター （アンリツ （株） 製の商品名 「K— 3 1 2A型」） を 用いて、 針圧 30 g、 走行速度 25 mm 秒でフィルムの製 J ^向 （MD) および 幅方向 （TD) それぞれ 2mの長さにわたって測定し、 連^?:みチャートを得る。 このチャートから最大厚み t (βτα) と最小厚み t 2 (μΐη) を読み取る。 こうして得られたフィルム平均厚み t。 （μπι) および最大厚み (μτη と最 小厚み t 2 (^m) と力ら、 下式 （3) により厚みのパラツキ D (%) を求める。 D= t 2) /t。] X 1 00 … (3) Furthermore, using an electronic micrometer (trade name “K-31A type” manufactured by Anritsu Corporation), the film was made in the J ^ direction (MD) and the width direction (MD) at a needle pressure of 30 g and a running speed of 25 mmsec. TD) Measure over a length of 2m each, and get a chart. The maximum thickness t (βτα) and the minimum thickness t 2 (μΐη) are read from this chart. Average thickness t of the film thus obtained. (Μπι) and the maximum thickness (μτη, the minimum thickness t 2 (^ m), and force), and calculate the thickness variation D (%) using the following equation (3): D = t 2 ) / t. ] X 1 00… (3)
(8) 動摩聽数 (μ d)  (8) Number of movements (μd)
75mm (幅） X 1 0 Omm (長さ） のカツトフイノレム （サンプノレ） を 2枚重ね た上に重量 200 gのおもりを荷重 W (g) として乗せ、 上側のフィルムを 1 50 mmZ分の速度で滑らせ、 滑らせている時の力 Fd (g) から動摩^罕、数 を 計算する。 なおフィルムは 23 °C、 6 5%R Η·で 24時間調湿した後に測定する。 動摩聽数 =Fd,W A stack of two 75mm (width) x 10 Omm (length) cut huinolems (sampnoles), a weight of 200 g is placed as a load W (g), and the upper film is slid at a speed of 150 mmZ. Calculate the number of moving and shaking from the force F d (g) when sliding. The film is measured after conditioning for 24 hours at 23 ° C and 65% RΗ. Number of dynamics = F d , W
(9) 熱収縮率の差 - (9) Difference in heat shrinkage-
20 0°Cに温度設定されたオーブンの中に無緊張状態で 1 0分間フィルムを保持 し、 フィルムの製膜方向 （MD) および幅方向 （TD) のそれぞれにおいて、 各々 の加熱処理前後での寸法変化から (1) 熱収縮率と同様、 熱収縮率 S (%) を下式 (1) により算出し、 両方向の熱収縮率の差の絶対値を算出する。 The film was held for 10 minutes in an oven set at a temperature of 200 ° C without tension, and before and after each heat treatment in the film forming direction (MD) and width direction (TD). From the dimensional change, (1) The heat shrinkage S (%) is calculated by the following equation (1), as in the case of the heat shrinkage, and the absolute value of the difference in the heat shrinkage in both directions is calculated.
S= [(L0-L) /L0] X 1 00 … (1) S = [(L 0 -L) / L 0 ] X 1 00… (1)
ただし、 L 0：熱処理前の標点間距離、 L：熱処理後の標点間距離をそれぞれ表す。 Here, L0: distance between gauge points before heat treatment, and L: distance between gauge points after heat treatment.
(1 0) 密度  (1 0) Density
J I S C 2 1 5 1に準じて二軸配向ポリエチレン一 2， 6—ナフタレンジカル ボキシレートフィルムの密度を測定した。  The density of the biaxially oriented polyethylene-1,6-naphthalenedicarboxylate film was measured according to JIS C2151.
(1 1) 吸水率  (1 1) Water absorption
J I S K 7209に準じて、一辺が 50 mmの正方形のベースフィルムを用!/、、 23 °Cの水に 24時間浸水させた後、 フィルムの吸水率を測定した。  In accordance with JIS K 7209, a square base film having a side of 50 mm was used! /, Immersed in water at 23 ° C for 24 hours, and the water absorption of the film was measured.
(1 2) 寸法安定性  (1 2) Dimensional stability
25 X 25 cmのベースフィルムを用レヽ、 6 5°C、 8 5%RHの雰囲気下で 1 0 0時間放置後、 4隅のカール状態を測定し、 反り量 （mm) の平均値を測定した。 〇が合格である。  After leaving a 25 x 25 cm base film for 100 hours in an atmosphere of 65 ° C and 85% RH, measure the curl state of the four corners and measure the average value of the amount of warpage (mm) did. 〇 is passed.
〇； 1 0 mm未満の反り量  〇; Warpage less than 10 mm
X ； 1 0 mm以上の反り量  X: Warpage of 10 mm or more
(1 3) 半導体ウェハの加工性 （パックグラインドおよびダイシング） 各実施例および比較例の二軸配向ポリエチレン一 2 , 6—ナフタレンジカノレポキ シレートフィルムにアクリル系粘着剤 （n—プチルァクリレートとァクリル酸との 共重合体） を厚さ 14 μπιとなるように塗布し、 粘着シートをィ燥した。 得られた 粘着シートの粘着剤層上に 8ィンチのシリコンゥエノ、を貝據してゥェハのバックグ ラインドおよびダイシングのテストをそれぞれ行なった。 なお、 ダイシングを行つ た後に非拡張型ダイボンダ一でチップのピックァップを行つた。 この際のダイシン グ、 ピックアップの条件は、 ダイシング切込み深さ ：テープ表面から 20μιη、 突 き上げピン： 4本、 吸着ホルダーの径： 28ιηηιφ、 コレット ：角錐コレツト、 突 き上げ距離： 2mm、 ダイシングサイズ： 8111111 8111111でぁる。 (1 3) Processability of semiconductor wafer (pack grinding and dicing) An acrylic adhesive (copolymer of n-butyl acrylate and acrylic acid) was applied to the biaxially oriented polyethylene mono-, 2,6-naphthalenedicanolepoxylate film of each of Examples and Comparative Examples to a thickness of 14 μπι. And the adhesive sheet was dried. An 8-inch silicon wafer was placed on the pressure-sensitive adhesive layer of the obtained pressure-sensitive adhesive sheet, and a back grinding test and a dicing test were performed on the wafer. After dicing, chips were picked up using a non-expandable die bonder. The conditions for dicing and picking up were as follows: dicing depth: 20μιη from tape surface, four push-up pins, diameter of suction holder: 28ιηηιφ, collet: pyramid collet, throw-up distance: 2mm, dicing size : 8111111 It is 8111111.
(14) 半導体ウェハの加工性 （バックグラインドおよびテープ剥離） 各実施例および比較例の二軸配向ポリエチレン一 2 , 6—ナフタレンジカノレボキ シレートフィルムにアタリノレ系粘着斉 (J (n—プチルアタリレートとアタリノレ酸との 共重合体） を厚さ 14μπιとなるように塗布し、 粘着シートをィ懷した。 得られた 粘着シートの粘着剤層上に 8ィンチのシリコンウェハを貼着してゥェハのバックグ ラインドおょぴテープ剥離のテストをそれぞれ行なった。 なお、 テスト条件は、 バ ックグラインド加工温度： 180°C、テープ剥離前の熱処理温度： 150°Cである。  (14) Processability of semiconductor wafers (back grinding and tape peeling) Atarinole-based adhesive properties (J (n-butyl atari) were applied to the biaxially oriented polyethylene mono 2,6-naphthalenedicanoleboxylate films of Examples and Comparative Examples. (A copolymer of acrylate and atalinoleic acid) was applied to a thickness of 14 μπι, and an adhesive sheet was placed on the adhesive layer of the obtained adhesive sheet. The test conditions were as follows: back grinding temperature: 180 ° C, heat treatment temperature before tape peeling: 150 ° C.
実施例 1  Example 1
2, 6 _ナフタレンジカルボン酸ジメチノレ 100部とエチレングリコーノレ 60部 の混合物に、 酢酸マンガン · 4zR塩 0. 03部を添加し、 150°Cから 240°Cに 徐々に昇温しながらエステル交換反応を行った。 途中、 反応 が 170°Cに達し た時点で三酸化ァンチモン 0. 024部を添加し、 さらに平均粒径 0. 4 /Z m、 粒 径比 1. 1の球状シリ力粒子を 0. 2重量％添加した。そして、反応、 が 220 °C に達した時点で 3， 5ージカルボキシベンゼンスルホン酸テトラブチルホスホ-ゥ ム塩 0. 042部 （2mmo l%に相当） を添加した。 その後、 引き続いてエステ ル交換反応を行！/ヽ、 エステル交換反応終了後、 燐酸トリメチノレ 0. 023部を添加 した。 ついで、 反応生成物を重合反応器に移し、 290°Cまで昇温し、 0. 2mm H g以下の高真空下にて重縮合反応を行 \ 25 °Cの o—クロロフエノール激夜で 測定した固有粘度が 0. 62 d lZg、 のポリエチレン一 2, 6—ナフタレンジ力 ルボキシレートポリマー（「ポリマー C」と呼ぶ）を得た。このポリマー Cを 170°C で 6時間乾燥させた後、 押出機に供給し、 溶融 3 0 5°Cで溶融し、 開度 l mm のスリット状ダイを通して、 表面仕上げ 0. 3 S、 表面温度 5 0°Cの回転ドラム上 に押出し、 未延伸フィルムを得た。 To a mixture of 100 parts of 2,6-_naphthalenedicarboxylic acid dimethinole and 60 parts of ethylene glycolone, 0.03 parts of manganese acetate / 4zR salt was added, and transesterification was performed while gradually raising the temperature from 150 ° C to 240 ° C. Was done. During the reaction, when the reaction reached 170 ° C, 0.024 parts of antimony trioxide was added, and 0.2 weight of spherical silica particles having an average particle diameter of 0.4 / Zm and a particle diameter ratio of 1.1 were added. % Was added. Then, when the temperature of the reaction reached 220 ° C., 0.042 parts (corresponding to 2 mmol%) of 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt was added. After that, continue the ester exchange reaction! / ヽ, After the transesterification reaction, 0.023 parts of trimethynole phosphate was added. Next, the reaction product was transferred to a polymerization reactor, heated to 290 ° C, and subjected to polycondensation under a high vacuum of 0.2 mmHg or less. As a result, a polyethylene-1,6-naphthalenediene ruboxylate polymer having an intrinsic viscosity of 0.62 dlZg (referred to as “Polymer C”) was obtained. 170 ° C of this polymer C After being dried for 6 hours in the extruder, it is melted at a temperature of 30 ° C and melted through a slit die with an opening of l mm. The surface finish is 0.3 S, and the rotating drum has a surface temperature of 50 ° C. This was extruded to obtain an unstretched film.
こうして得られた未延伸フィルムを、 1 4 5 で,»向 （製 向） に 3 . 3倍 に延伸し、 次いで 1 4 0 °Cで横方向 （幅方向） に 3 . 4倍延伸し、 さらに 2 4 3 °C で 5秒間熱固定処 ¾¾ぴ幅方向に 5 %収縮させ （トウイン)、厚み 1 6 μ m、 固有粘 度 0. 5 2 d 1 / gの二軸配向 P E Nフィルムを 1 5 0 O mm幅で 3 0 0 O mの口 ール状に卷き取った。 その後、 得られた二軸配向 P E Nフィルムを、 上方に設置さ れたニップローラーを経て下方に自重で垂下させながら、 その途中でフィノレム^ J が 2 2 5 °Cとなるように赤外勵ロ熱装置で加熱した後、 上方に設置されたローラー より 4 m下方にある-ップローラーで冷却しながらほぼ水平方向に向きを変え、 二 ップローラーで卷取り張力を遮断した後に卷き取り、 弛緩熱処理を行った。 弛緩は 上方のニップローラーと卷取り張力の遮断を行うニップローラーとの速度の差をつ けて行った。  The unstretched film thus obtained is stretched 3.3 times in the direction (orientation) at 144, and then stretched 3.4 times in the transverse direction (width direction) at 140 ° C. Further heat-setting at 243 ° C for 5 seconds さ せ Shrink 5% in the width direction (tow-in) and apply a biaxially oriented PEN film with a thickness of 16 μm and an intrinsic viscosity of 0.5 2 d 1 / g to 1 It was wound up into a 300-Om width in a 50-Omm width. After that, the obtained biaxially oriented PEN film is dripped downward by its own weight via the nip roller installed above, and the infrared excitation filter is set so that the finolem ^ J becomes 2225 ° C on the way. After heating with a heating device, the roller is turned almost horizontally while cooling with a roll roller located 4 m below the roller installed above, winding off the winding tension with a nip roller, and winding and relaxing heat treatment. went. Relaxation was performed by using the difference in speed between the upper nip roller and the nip roller that shuts off the winding tension.
こうして得られた弛緩熱処理後の二軸配向 P E Nフィルムを実施例 1とした。 得られた実施例 1のフィルムの特性評価結果を表 1に示す。 実施例フィルムのゥ エノ、加工性については、 フィルムの熱寸法変化、 フィルムの厚みパラツキやフィル ムの平面性等によるダイポンダー装置の誤動作による不良も起きず、 良好なピック アップ操作ができた。 また、 粘着層塗設工程内おょぴ半導体ゥヱノ、加工工程内を汚 染することなく、 さらに、 テープ剥離ではフィルム破れがなく、 半導体ウェハの製 造における加: L†生は良好であった。  The thus obtained biaxially oriented PEN film after the relaxation heat treatment was used as Example 1. Table 1 shows the property evaluation results of the obtained film of Example 1. With respect to the heat and workability of the film of the example, a good pick-up operation could be performed without causing a malfunction due to a malfunction of the diponder device due to a change in the thermal dimension of the film, a variation in the thickness of the film or the flatness of the film. In addition, the semiconductor layer in the adhesive layer coating process was not contaminated, and the processing process was not contaminated.Further, the film was not broken by peeling off the tape, and the processing performance in manufacturing semiconductor wafers was good. .
実施例 2  Example 2
»向の延伸倍率を 2. 9倍とし、 横方向の延伸倍率を 3. 1倍に変更し、 懸垂 式の弛緩熱処理を行わなかつた以外は、 実施例 1と同様な操作を繰り返し、 厚み 7 5 μ mの二軸配向 P E Nフィルムを得た。  The same operation as in Example 1 was repeated except that the stretching ratio in the direction of »was changed to 2.9 times, the stretching ratio in the horizontal direction was changed to 3.1 times, and the suspension relaxation heat treatment was not performed. A 5 μm biaxially oriented PEN film was obtained.
得られた実施例 2のフィルムの特性評価結果を表 1に示す。 実施例フィルムのゥ エノ、加工性については、 フィルムの熱寸法変化、 フィルムの厚みパラツキやフィル ' ムの平面性等によるダイボンダ一装置の誤動作による不良も起きず、 良好なピック , アップ操作ができた。 また、 粘着層塗設工程内および半導体ウエノ、加工工程内を汚 染することなく、 さらに、 テープ剥離ではフィルム破れがなく、 半導体ウェハの製 造における加工性は良好であった。 Table 1 shows the property evaluation results of the obtained film of Example 2. Regarding the film thickness and workability of the example film, there was no failure due to the malfunction of the die bonder device due to the change in the thermal dimension of the film, the thickness variation of the film, the flatness of the film, etc. Was. In addition, the inside of the adhesive layer coating process and the semiconductor No dyeing was observed, and no film was broken by tape peeling, and the workability in the production of semiconductor wafers was good.
実施例 3  Example 3
実施例 3としては、 次のようにして 2層構成のフィルムを作成した。 まず、 2， 6—ナフタレンジカルボン酸ジメチル 1 00部とエチレングリコール 60部の混合 物に、 酢酸マンガン · 4水塩 0. 03部を添 し、 1 50°Cから 240°Cに徐々に 昇温しながらエステル交換反応を行った。 途中、 反応 が 1 70°Cに達した時点 で三酸化アンチモン 0. 024部を添加し、 さらに平均立径 0. 5 μπιの炭酸カル シゥム粒子を 0. 1 5重量0 /。添加した。 そして、 反応温度が 220。Cに達した時点 で 3, 5—ジカルボキシベンゼンスルホン酸テトラブチルホスホニゥム塩 0. 04 2部 （2mmo l %に相当） を添加した。 その後、 引き続いてエステル交換反応を 行レヽ、エステル交換反応終了後、燐酸トリメチル 0. 023部を添加した。ついで、 反応生成物を重合反応器に移し、 290°Cまで昇温し、 0. 2mmHg以下の高真 空下にて重縮合反応を行レヽ、 25 °Cの o—クロロフエノール激夜で測定した固有粘 度が 0· 6 3 d 1 /g、 のポリエチレン一 2, 6—ナフタレンジカルボキシレート ポリマー （「ポリマー A」 と呼ぶ） を得た。 In Example 3, a two-layer film was formed as follows. First, add 0.03 parts of manganese acetate tetrahydrate to a mixture of 100 parts of dimethyl 2,6-naphthalenedicarboxylate and 60 parts of ethylene glycol, and gradually raise the temperature from 150 ° C to 240 ° C. The transesterification was carried out while performing the reaction. Way, the reaction of antimony trioxide was added 0.024 parts at which point 1 70 ° C, further average elevation diameter 0.5 0.1 5 wt carbonate Cal Shiumu particles μπι 0 /. Was added. And the reaction temperature is 220. When the temperature reached C, 0.04 parts of 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt (corresponding to 2 mmol%) was added. Thereafter, a transesterification reaction was subsequently performed, and after the transesterification reaction was completed, 0.023 parts of trimethyl phosphate was added. Then, the reaction product was transferred to a polymerization reactor, heated to 290 ° C, and subjected to polycondensation under a high vacuum of 0.2 mmHg or less, and measured at 25 ° C o-chlorophenol intensely at night. As a result, a polyethylene-1,6-naphthalenedicarboxylate polymer having a specific viscosity of 0.63 d 1 / g (referred to as “Polymer A”) was obtained.
また、 ポリマー Aと同様にしてエステル交換反応を行い、 重 虫媒として非晶性ニ 酸化ゲルマニゥム 0. 02部を添口し、 さらに平均粒径 0. 1 μΐη, 粒径比 1. 1 の球状シリ力粒子を 0. 05重量％添 Πした以外はポリマー Αと同様にして重合を 行レヽ、 25 °Cの o—クロロフエノ一ノレ激夜で測定した固有釆占度が 0. 6 3 d 1 Z g、 のポリエチレン一 2， 6—ナフタレンジカルボキシレートポリマー （「ポリマー BJ と呼ぶ） を得た。 In addition, transesterification was carried out in the same manner as in Polymer A, and 0.02 parts of amorphous germanium oxide was added as a heavy carrier, and a spherical particle having an average particle diameter of 0.1 μΐη and a particle diameter ratio of 1.1 was also added. Polymerization was carried out in the same manner as for polymer except that 0.05% by weight of silicic acid particles were added, and the intrinsic occupancy measured at 0 ° C o-chlorophenone night at 0.6 ° C was 0.63 d1. Z g of polyethylene-1,6-naphthalenedicarboxylate polymer (referred to as “Polymer BJ”) was obtained.
これらの各ポリマーを各々 1 70 °Cで 6時間乾燥させた後、 2台の別々の押出機 に供給し、 各々溶融 300°Cで溶融し、 共押出し法により開度 1 mmのスリッ ト状ダイを通して、表面仕上げ 0. 3 S、表面 ^J 50 °Cの回転ドラム上に押出し、 2層構成の未延伸フィルムを得た。 この未延伸フィルムを、 実施例 1と同様に逐次 に二軸延伸し、 熱固定を行って、 フィルム厚み 1 6〃 m (ポリマー A層側 1 0 μ m ポリマー B層側 6 ^πι)、 固有粘度 0. 54 d 1/gの二軸配向 PENフィルムを 1 50 Omm幅で 300 Omのロ^ "ル状に卷き取った。 その後、 実施例 1と同様に 得られた二軸配向 P E Nフィルムを同じ懸垂式の弛緩熱処3¾置を使って、 弛 処理を行つた。 こうして得られた弛«処理後の二軸配向 P E Nフィルムを実施例 3とした。 After drying each of these polymers at 170 ° C for 6 hours, they are fed to two separate extruders, each melted at 300 ° C, and co-extruded to form slits with an opening of 1 mm. The mixture was extruded through a die onto a rotating drum having a surface finish of 0.3 S and a surface of ^ J at 50 ° C to obtain a two-layer unstretched film. This unstretched film was successively biaxially stretched in the same manner as in Example 1 and heat-set to obtain a film thickness of 16 μm (polymer A layer side: 10 μm, polymer B layer side: 6 ^ πι). A biaxially oriented PEN film having a viscosity of 0.54 d 1 / g was wound up in a roll shape of 300 Om with a width of 150 Omm. The obtained biaxially oriented PEN film was subjected to a relaxation treatment using the same suspension-type relaxation heat treatment apparatus. The biaxially oriented PEN film after the relaxation treatment thus obtained was used as Example 3.
得られた実施例のフィルムの特性評価結果を表 1に示す。 特にこれら実施例フィ ルムのウエノ、加工性については、 フィルムの熱寸法変化、 フィルムの厚みバラツキ ゃフィルムの平面性等によるダイボンダ一装置の誤動作による不良も起きず、 良好 なピックアップ操作ができた。 また、 粘着層塗設工程内および半導体ウエノ、加工ェ 程内を汚染することなく、 さらに、 テープ剥離ではフィルム破れがなく、 半導体ゥ ェハの製造における加工性は良好であった。  Table 1 shows the property evaluation results of the obtained films of the examples. In particular, as for the film and workability of these films, there was no failure due to a malfunction of the die bonder unit due to a change in the thermal dimension of the film, a variation in the thickness of the film, or the flatness of the film, and a good pick-up operation was performed. Further, the inside of the adhesive layer coating step, the semiconductor wafer, and the processing step were not contaminated, and further, the film was not broken by tape peeling, and the workability in the production of the semiconductor wafer was good.
比較例 1  Comparative Example 1
東レ'デュポン製 「カプトン；タイプ H」 の 5 0 mフィルムを用いた。  A 50m film of "Kapton; Type H" manufactured by Toray DuPont was used.
フィルムの特性言 面結果を表 1に示す。 フィルムの熱寸法変ィ匕は非常に優れて ヽ るが、 吸水率が高いため、 高湿度下では寸法安定性に劣るものであった。  Table 1 shows the characteristics of the film. Although the thermal dimensional change of the film was excellent, the dimensional stability under high humidity was poor due to the high water absorption.
比較例 2  Comparative Example 2
テレフタル酸ジメチル 1 0 0部とェチレングリコール 6 0部の混合物に、 酢酸マ ンガン · 4水塩 0 . 0 3部を添加し、 1 5 0 から 2 4 0 °Cに徐々に昇温しながら エステル交換反応を行った。 途中、 反応 が 1 7 0 °Cに達した時点で三酸化アン チモン 0 . 0 2 4部を添 し、 さらに平均粒径 0 . 4〃 m、 粒径比 1 . 1の球状シ リ力粒子を 0 . 2重量。 /0添 した。そして、反応 が 2 2 0 °Cに達した時点で 3 , 5—ジカルボキシベンゼンスルホン酸テトラブチルホスホニゥム塩 0 . 0 4 2部（2 mm o 1 %に相当） を添口した。 その後、 弓 Iき続いてエステル交換反応を行い、 ェ ステノレ交換反応終了後、 燐酸トリメチル 0 . 0 2 3部を添カロした。 ついで、 反応生 成物を重合反応器に移し、 2 9 0 °Cまで昇温し、 0. 2 mmH g以下の高真空下に て重縮合反応を行 、、 2 5 °Cの o—クロ口フエノール溶液で測定した固有粘度が 0 . 6 2 d 1 / g , のポリエチレンテレフタレートポリマーを得た。 このポリマーを 1 7 0 °Cで 3時間乾燥させた後、 押出機に供給し、 溶融 2 9 0°Cで溶融し、 開度 1 mmのスリット状ダイを通して、 表面仕上げ 0 . 3 S、 表面温 2 5 °Cの回転ドラ ム上に押出し、 未延伸フィルムを得た。 To a mixture of 100 parts of dimethyl terephthalate and 60 parts of ethylene glycol was added 0.03 parts of manganese acetate tetrahydrate, and the temperature was gradually raised from 150 to 240 ° C. A transesterification reaction was performed. On the way, when the reaction reached 170 ° C, 0.024 parts of antimony trioxide was added, and spherical particles having an average particle diameter of 0.4 μm and a particle diameter ratio of 1.1 were added. The 0.2 weight. / 0 added. Then, when the reaction reached 220 ° C., 0.042 parts (corresponding to 2% of 1%) of 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt was added. Thereafter, transesterification was carried out following the bow I. After the esterification exchange reaction was completed, 0.023 parts of trimethyl phosphate was added. Then, the reaction product was transferred to a polymerization reactor, heated to 290 ° C, and subjected to a polycondensation reaction under a high vacuum of 0.2 mmHg or less. A polyethylene terephthalate polymer having an intrinsic viscosity of 0.62 d 1 / g as measured with a phenol solution in the mouth was obtained. This polymer was dried at 170 ° C for 3 hours, fed to an extruder, melted at 290 ° C, passed through a slit die with an opening of 1 mm, surface finish 0.3 S, surface It was extruded on a rotating drum at a temperature of 25 ° C to obtain an unstretched film.
こうして得られた未延伸フィルムを、 9 0 °Cで縦方向 （製膜方向） に 3 . 2倍に 延伸し、 次いで 1 2 0°Cで横方向 （幅方向） に 3 . 8倍延伸し、 さらに 2 1 0 °Cで 5秒間熱固定処 ¾¾ぴ幅方向に 5 %収縮させ（トウイン)、厚み 1 6 ,α πι, 固有粘度 0 . 5 5 d l Zgの二軸配向ポリエチレンテレフタレートフィルムを 1 5 0 0 mm 幅で 3 0 0 0 mのロール状に卷き取った。 その後、 得られた二軸配向ポリエチレン テレフタレートフィルムを、 上方に設置されたニップローラーを経て下方に自重で 垂下させながら、 その途中でフィルム が 1 8 0 °Cとなるように赤外勵口熱装置 で加熱した後、 上方に設置されたローラーより 4 m下方にあるニップローラ一で冷 却しながらほぼ水平方向に向きを変え、 二ップローラーで卷取り張力を遮断した後 に卷き取り、 弛 処理を行つた。 弛緩は上方の二ップローラーと巻取り張力の遮 断を行う-ップローラーとの速度の差をつけて行つた。 The unstretched film obtained in this way is increased 3.2 times in the longitudinal direction (film forming direction) at 90 ° C. Stretched, then stretched 3.8 times in the transverse direction (width direction) at 120 ° C, and heat-set at 210 ° C for 5 seconds. A biaxially oriented polyethylene terephthalate film having 16, α πι and an intrinsic viscosity of 0.55 dl Zg was wound into a roll of 3500 m in width of 1500 mm. After that, the obtained biaxially oriented polyethylene terephthalate film is suspended downward by its own weight through a nip roller installed above, and the infrared heating device is set so that the film temperature becomes 180 ° C in the middle. After cooling in the nip roller, which is 4 m below the roller installed above, change the direction substantially horizontally while cooling with a nip roller. I went. Relaxation was performed with a difference in speed between the upper nip roller and the winding roller, which shuts off the winding tension.
こうして得られた弛, β処理後の二軸配向ポリエチレンテレフタレートフイノレム を比較例 2とした。  The thus obtained biaxially oriented polyethylene terephthalate finolem after the relaxation and β treatment was used as Comparative Example 2.
得られた比較例 2のフィルムの特性評価結果を表 1に示す。 ウエノ、加工性につい ては、 フィルムの寸法安定性の悪さにより、 チップの位置ズレ等が発生し、 ダイポ ンダー装置の誤動作による不良が生じた。 また、 粘着層塗設工程内および半導体ゥ ェハ加工工程内を汚染する a のオリゴマー析出量であった。 また加熱後のフィル ム表面へのオリゴマー析出率も高かった。  Table 1 shows the property evaluation results of the obtained film of Comparative Example 2. Regarding the stencil and processability, the chip was misaligned due to the poor dimensional stability of the film, and malfunctions occurred due to malfunction of the diponder device. In addition, the amount of oligomer “a” contaminating the inside of the adhesive layer coating step and the inside of the semiconductor wafer processing step was found. Also, the oligomer precipitation rate on the film surface after heating was high.
比較例 3  Comparative Example 3
比較例 3としては、 縦方向の延伸倍率を 3 . 6倍とし、 横方向の延伸倍率を 3 . 7倍に変更した以外は実施例 2と同様な操作を繰り返し、 厚み 5 0 μ mの二軸配向 P E Nフィルムを得た。  As Comparative Example 3, the same operation as in Example 2 was repeated except that the stretching ratio in the longitudinal direction was changed to 3.6 times and the stretching ratio in the transverse direction was changed to 3.7 times. An axially oriented PEN film was obtained.
得られた比較例 3のフィ /レムの特性評価結果を表 1に示す。 フイルムの熱寸法変 化がフィルム縦方向および横方向のいずれも 1 . 0 0 %を超え、 ウェハ加工性につ レ、ては、 チップの位置ズレ等が発生し、 ダイポンダー装置の誤動作による不良が生 じた。  Table 1 shows the results of evaluating the characteristics of the fi / rem of Comparative Example 3 obtained. The thermal dimensional change of the film exceeds 1.0% in both the vertical and horizontal directions of the film, resulting in wafer processability, chip displacement, etc., and failure due to malfunction of the diponder device. occured.
比較例 4  Comparative Example 4
比較例 4としては、 向の延伸倍率を 3 . 6倍とし、 横方向の延伸倍率を 3 . 9倍変更した以外は実施例 1と同様な操作を繰り返し、 懸垂式の弛纖処理を行つ て、 厚み 2 0 mの二軸配向 P E Nフィルムを得た。 得られた比較例 4のフィルムの †生評価結果を表 1に示す。 フィルムの熱寸法変 化がフィルム縦方向において 1 . 0 0 %を超え、 ウエノ、加工性については、 チップ の位置ズレ等が発生し、 ダイボンダー装置の誤動作による不良が生じた。 In Comparative Example 4, the same operation as in Example 1 was repeated except that the stretching ratio in the horizontal direction was changed to 3.6 times and the stretching ratio in the horizontal direction was changed to 3.9 times, and the suspension-type relaxation fiber treatment was performed. Thus, a biaxially oriented PEN film having a thickness of 20 m was obtained. Table 1 shows the results of the regeneration evaluation of the obtained film of Comparative Example 4. The change in the thermal dimension of the film exceeded 1.0% in the longitudinal direction of the film, and in the case of the wafer and the workability, the chip was misaligned and the die bonder device failed due to malfunction.
【表 1】 【table 1】
実施例 1 実施例 2 実施例 3 比較例 1 比較例 2 比較例 3 比較例 4 層構成 単層 単層 2層 単層 単層 単層 単層 ポリマー ポリマー C ポリマー C ポリマー A Iボリマ一 B ― 一 ポリマー C ポリマー C 添加粒子 種類 球状シリカ球状シリカ炭酸カルシウム I球状シリカ ― 球状シリカ球状シリカ球状シリカ 粒径 U m 0.4 0.4 0.5 0.1 ― 0.4 0.4 0.4 添加量 重量％ 0.20 0.20 0.15 0.05 一 0.20 0.20 0.20 縦延伸 倍率 倍 3.3 2.9 3.3 ― 3.2 3.6 3.6 imJ¾. 145 145 145 一 90 145 145 横延伸 倍率 倍 3.4 3.1 3.1 ― 3.8 3.7 3.9  Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Layer Configuration Single Layer Single Layer Two Layer Single Layer Single Layer Single Layer Single Layer Polymer Polymer C Polymer C Polymer AI Bolima B-One Polymer C Polymer C Added particles Type Spherical silica Spherical silica Calcium carbonate I Spherical silica-Spherical silica Spherical silica Spherical silica Particle size U m 0.4 0.4 0.5 0.1-0.4 0.4 0.4 Amount added% by weight 0.20 0.20 0.15 0.05 1 0.20 0.20 0.20 Longitudinal stretching magnification 3.3 2.9 3.3 ― 3.2 3.6 3.6 imJ¾. 145 145 145 1 90 145 145 Lateral stretching magnification × 3.4 3.1 3.1 ― 3.8 3.7 3.9
。c 140 140 140 一 120 140 140 熱固定温度 。c 243 243 243 一 210 243 243 懸垂式弛緩熱処理温度 °c 225 処理なし 225 ― 180 処理なし 225 フィルム固有粘度 dl/g 0.52 0.52 0.54 ― 0.55 0.52 0.52 フィルム厚み p. m 16 75 16 50 16 50 20 厚みのまらつき % 8 11 8 ― 8 6 4 熱収縮率 縦 (MD) % 0.50 0.80 0.50 0.20 0.60 1.40 1.10  . c 140 140 140 1 120 140 140 Heat setting temperature. c 243 243 243 1 210 243 243 Hanging relaxation heat treatment temperature ° c 225 No treatment 225 ― 180 No treatment 225 Film intrinsic viscosity dl / g 0.52 0.52 0.54 ― 0.55 0.52 0.52 Film thickness p.m 16 75 16 50 16 50 20 Thickness Fluctuation% 8 11 8 ― 8 6 4 Thermal shrinkage ratio Vertical (MD)% 0.50 0.80 0.50 0.20 0.60 1.40 1.10
横 (TD) % 0.05 0.30 0.05 0.10 0.10 1.20 0.30 ヤング率 縦 (MD) MPa 6100 5600 6100 3700 5300 6500 6400  Horizontal (TD)% 0.05 0.30 0.05 0.10 0.10 1.20 0.30 Young's modulus Vertical (MD) MPa 6100 5600 6100 3700 5300 6500 6400
横 (TD) MPa 6200 5800 6200 3700 5250 6600 7000 表面粗さ nm 15 16 19 4 ― . 18 16 15 密度 gZcm 1.360 1.362 1.360 ― 一 1.357 1.358 オリゴマ抽出量 重量％ 0.4 0.5 0.5 一 1.3 ― ― 加熱オリゴマ析出率 % 〇 〇 〇 ― X ― ― 吸水率 % 0.3 0.3 0.3 1.3 0.4 ― 一 寸法安定性 一 〇 〇 〇 X X ― 一 半導体ウェハの加工性 (ハ'ツクク 'ライ  Lateral (TD) MPa 6200 5800 6200 3700 5250 6600 7000 Surface roughness nm 15 16 19 4-. % 〇 〇 〇 ― X ― ― Water absorption% 0.3 0.3 0.3 1.3 0.4 ― Dimensional stability 〇 〇 〇 XX ― Workability of semiconductor wafers
ンド及びダイシンゲ） 良 良 良 良 不良 不良 不良 半導体ウェハの加工性 (ハ'ックク 'ライ  Good Good Good Good Good Bad Bad Bad Bad Workability of semiconductor wafers
ンドおよびテープ剥離） 良 良 良 良 不良 不良 不良 Good Good Good Good Good Bad Bad Bad
[実施例 4] [Example 4]
2, 6—ナフタレンジ力ルポン酸ジメチル 1 00部とエチレングリコール 60部 の混合物に、 酢酸マンガン · 4水塩 0. 03部を添カロし、 1 50°Cから 240°Cに 徐々に昇温しながらエステノレ交換反応を行つた。 途中、 反応温度が 1 70 °Cに達し た時点で三酸化ァンチモン 0. 024部を添加し、 さらに平均粒径 0..6 μ m、 粒 径比 1. 1の球状シリ力粒子を 0. 1重量％添加した。そして、反応温度が 220 °C に達した時点で 3 , 5ージカルボキシベンゼンスルホン酸テトラプチルホスホニゥ ム塩 0. 042部 （2mmo l %に相当） を添加した。 その後、 引き続いてエステ ル交換反応を行レヽ、エステル交換反応終了後、 燐酸トリメチノレ 0. 023部を添加 した。 ついで、 反応生成物を重合反応器に移し、 29 0°Cまで昇温し、 0. 2mm H g以下の高真空下にて重縮合反応を行レ、、 25 °Cの o—クロロフエノール激夜で 測定した固有粘度が 0. 43 d 1/gのポリエチレン一 2， 6—ナフタレンジ力ノレ ボキシレートポリマー （ポリマー D) および固有粘度が 0. 6 9 d lZgのポリエ チレン一 2， 6—ナフタレンジカルボキシレートポリマー （ポリマー E) を得た。 さらにポリマー Eを固相重合し、 固有粘度が 0. 78 d lZg (ポリマー F) とし た。  2,6-Naphthalenediphenyl dimethyl sulfonate (100 parts) and ethylene glycol (60 parts) are mixed with 0.03 parts of manganese acetate tetrahydrate, and the temperature is gradually raised from 150 ° C to 240 ° C. While performing an estenole exchange reaction. During the reaction, when the reaction temperature reached 170 ° C, 0.024 parts of antimony trioxide was added, and spherical silica particles having an average particle diameter of 0.6 μm and a particle diameter ratio of 1.1 were added. 1% by weight was added. Then, when the reaction temperature reached 220 ° C., 0.042 parts (corresponding to 2 mmol%) of 3,5-dicarboxybenzenesulfonic acid tetrabutylphosphonium salt was added. Thereafter, an ester exchange reaction was subsequently carried out, and after the transesterification reaction was completed, 0.023 parts of trimethinol phosphate was added. Then, the reaction product was transferred to a polymerization reactor, heated to 290 ° C, and subjected to a polycondensation reaction under a high vacuum of 0.2 mmHg or less. Polyethylene-1,2,6-naphthalene di- ore-boxylate polymer (polymer D) with an intrinsic viscosity of 0.43 d1 / g measured at night and polyethylene-1,2,6 with an intrinsic viscosity of 0.69 dlZg —A naphthalenedicarboxylate polymer (Polymer E) was obtained. Polymer E was further solid-phase polymerized to have an intrinsic viscosity of 0.78 dlZg (Polymer F).
ポリマー Eを 1 70。Cで 6時間乾燥させた後、押出機に供給し、溶融温度 305 °C で溶融し、 開度 lmmのスリット状ダイを通して、 表面仕上げ 0. 3 S、 表面 50°Cの回転ドラム上に押出し、 未延伸フィルムを得た。  Polymer E 170. After drying at C for 6 hours, it is fed to an extruder, melted at a melting temperature of 305 ° C, extruded through a slit die with an opening of lmm, onto a rotating drum with a surface finish of 0.3 S and a surface of 50 ° C. An unstretched film was obtained.
こうして得られた未延伸フィルムを、 1 45°Cで縦方向 （製膜方向） に 3. 0倍 に延伸し、 次 ヽで 140 °Cで横方向 （Φ畐方向） に 3. 0倍延伸し、 さらに 246 °C で 5秒間熱固定処 @¾ぴ幅方向に 4 %収縮させ（トウイン)、厚み 30 μ m、 固有粘 度 0. 5 9 d 1/gの二軸配向 PENフィルムを 1 50 Omm幅で 300 Omの口 ール状に卷き取った。 その後、 得られた二軸配向 PENフィルムを、 上方に設置さ れた-ップローラーを経て下方に自重で垂下させながら、 その途中でフィルム? が 225 °Cとなるように赤外!^口熱装置で加熱した後、 上方に設置されたローラー より 4m下方にあるニップローラーで冷却しながらほぼ水平方向に向きを変え、 二 ップローラーで卷取り張力を遮断した後に卷き取り、 弛緩熱処理を行った。 弛緩は 上方の二ップローラーと卷取り張力の遮断を行ぅニップロ一ラーとの速度の差をつ けて行った。 The unstretched film thus obtained is stretched 3.0 times in the longitudinal direction (film forming direction) at 145 ° C, and then stretched 3.0 times in the transverse direction (Φ 畐 direction) at 140 ° C in the next step. Then heat-set at 246 ° C for 5 seconds. @ ¾ ぴ Shrink 4% in the width direction (tow-in) and apply a 30 μm thick, 0.59 d 1 / g biaxially oriented PEN film to the 1 It was wound up in a 50 Omm width and 300 Om mouth shape. After that, the obtained biaxially oriented PEN film is dripped downward by its own weight via a roll-up roller installed at the top, and the infrared temperature is adjusted so that the film temperature becomes 225 ° C on the way. After heating in, the nip roller was placed 4 m below the roller placed above, and the direction was changed almost horizontally while cooling with a nip roller. Winding tension was cut off by a nip roller, and then the film was wound and subjected to relaxation heat treatment. Relaxation cuts off the winding tension with the upper nip roller. I went there.
こうして得られた弛«処理後の二軸配向 P E Nフィルムを実施例 4とした。 得られた実施例 4のフィルムの特性評価結果を表 2に示す。 実施例フィルムのゥ エノ、加工性については、 フィルムの熱寸法変化、 フィルムの厚みバラツキやフィル ムの平面性等によるダイボンダ一装置の誤動作による不良も起きず、 良好なピック アップ操作ができた。 また、 粘着層塗設工程内おょぴ半導体ウエノ、加工工程内を污 染することなく、 さらに、 テープ剥離ではフィルム破れがなく、 半導体ウェハの製 造における加工性は良好であった。  The biaxially oriented PAN film thus obtained after the relaxation treatment was used as Example 4. Table 2 shows the property evaluation results of the obtained film of Example 4. Regarding the heat and workability of the film of the example, a good pick-up operation could be performed without a failure due to a malfunction of the die bonder device due to a change in the thermal dimension of the film, a variation in the thickness of the film or the flatness of the film. In addition, the semiconductor wafer and the processing step were not contaminated in the adhesive layer coating step, the film was not broken by tape peeling, and the workability in the production of the semiconductor wafer was good.
[実施例 5 ]  [Example 5]
実施例 4にお!/ヽてポリマー Fを使用した以外は、 実施例 4と同様な操作を繰り返 し、 厚み 5 0 ^ mの二軸配向 P E Nフィルムを得た。 このようにして得られた二軸 配向 P E Nフィルムを実施例 5とした。  The same operation as in Example 4 was repeated except that polymer F was used in Example 4, to obtain a 50-μm-thick biaxially oriented PAN film. The biaxially oriented PEN film thus obtained was used as Example 5.
得られた実施例 5のフィルムの特性評価結果を表 2に示す。 実施例フィルムのゥ エノ、加工性については、 フィルムの熱寸法変化、 フィルムの厚みパラツキやフィル ムの平面性等によるダイポンダー装置の誤動作による不良も起きず、 良好なピック ァップ操作ができた。 また、 粘着層塗設工程内およぴ半導体ゥエノ、加工工程内を汚 染することなく、 さらに、 テープ剥離ではフィルム破れがなく、 半導体ウェハの製 造における加工性は良好であった。  Table 2 shows the property evaluation results of the obtained film of Example 5. With respect to the heat and workability of the film of the example, there was no failure due to the malfunction of the diponder device due to the change in the thermal dimension of the film, the variation in the thickness of the film, the flatness of the film, and the like, and a good pick-up operation was performed. In addition, the inside of the adhesive layer coating process, the semiconductor coating, and the inside of the processing process were not contaminated, and further, the film was not broken by tape peeling, and the workability in the production of semiconductor wafers was good.
[実施例 6]  [Example 6]
実施例 4にお!/、て 1 4 5 °Cで縦方向に 3. 3倍に延伸し、 次いで 1 4 0 °Cで 向に 3 · 3倍延伸した以外は、 実施例 4と同様な操作を繰り返し、 厚み 3 0 μ の 二軸配向 Ρ Ε Νフィルムを得た。 このようにして得られたニ軸配向 Ρ Ε Νフィルム を実施例 6とした。  In Example 4, the same as Example 4, except that the film was stretched 3.3 times in the machine direction at 145 ° C, and then stretched 3.3 times in the direction at 140 ° C. The operation was repeated to obtain a biaxially oriented Ρ Ε Ρ film having a thickness of 30 μm. The biaxially-oriented film obtained in this manner was used as Example 6.
得られた実施例のフィルムの特性評価結果を表 2に示す。 実施例フィルムのゥェ ノ、加工性については、 フィルムの熱寸法変化、 フィルムの厚みパラツキやフィルム の平面性等によるダイポンダー装置の誤動作による不良も起きず、 良好なピックァ ップ操作ができた。 また、 粘着層塗設工程内および半導体ウエノ、加工工程内を汚染 することなく、 さらに、 テープ剥離ではフィルム破れがなく、 半導体ウェハの製造 における力 ΡΙ性は良好であった。 [実施例 7 ] Table 2 shows the property evaluation results of the obtained films of the examples. Regarding the lithography and processability of the film of the example, a good pick-up operation could be performed without causing a failure due to a malfunction of the diponder device due to a change in the thermal dimension of the film, a variation in the thickness of the film or the flatness of the film. In addition, the inside of the adhesive layer coating step, the semiconductor wafer, and the processing step were not contaminated, and the tape was not broken by peeling off the tape. Thus, the flexibility in the production of semiconductor wafers was good. [Example 7]
実施例 4にお ヽてポリマー Dを使用した以外は、 実施例 4と同様な操作を,操り返 し、 厚み 5 0 u mの二軸配向 P E Nフィルムを得た。 このようにして得られた二軸 配向 P E Nフィノレムを実施例 7とした。  The same operation as in Example 4 was repeated except that Polymer D was used in Example 4, to obtain a biaxially oriented PAN film having a thickness of 50 μm. The biaxially oriented PEN finolem thus obtained was used as Example 7.
得られた実施例 7のフィルムの特性評価結果を表 2に示す。 ゥエノ、加工性にっレヽ ては、 フィルムの熱寸法変化、 フィルムの厚みバラツキやフィルムの平面性等によ るダイボンダー装置の誤動作による不良も起きず、 良好なピックァップ操作ができ た。 一方、 フィルム表面へのオリゴマー析出による工程内汚染が発生した。  Table 2 shows the property evaluation results of the obtained film of Example 7. With regard to the eno and processability, a good pick-up operation was performed without any failure due to malfunction of the die bonder due to changes in the thermal dimensions of the film, variations in the thickness of the film, and flatness of the film. On the other hand, contamination in the process due to oligomer precipitation on the film surface occurred.
[実施例 8 ]  [Example 8]
実施例 6において、フィルム中に含まれる不活性粒子の量を 0 . 0 1重量％とし、 さらに熱固定 を 2 3 3 °Cにした以外は、 実施例 6と同様な操作を繰り返し、 厚 み 3 0 μ mの二軸配向 P E Nフィルムを得た。 このようにして得られた二軸配向 P E Nフィ /レムを実施例 8とした。  In Example 6, the same operation as in Example 6 was repeated except that the amount of the inert particles contained in the film was set to 0.01% by weight and the heat setting was set to 233 ° C. A 30 μm biaxially oriented PEN film was obtained. The biaxially oriented PEN film / rem obtained in this manner was used as Example 8.
得られた実施例 8のフィルムの特性評価結果を表 2に示す。 ゥヱハ加工性にっレヽ ては、 フィルムの熱寸法変ィ匕は小さいものの、 縦方向および横方向の熱収縮率の差 が所望の範囲を超えるため、 半導体ウェハの製造における安定性に若干問題があつ た。  Table 2 shows the property evaluation results of the obtained film of Example 8. Regarding the workability, although the thermal dimensional change of the film is small, the difference in the thermal shrinkage in the vertical and horizontal directions exceeds the desired range, so that there is a slight problem in the stability in the production of semiconductor wafers. It was hot.
[実施例 9 ]  [Example 9]
実施例 4にお!/ヽて 1 4 5 °Cで ifc^向に 2 . 7倍に延伸し、 レヽで 1 4 0 °Cで横方 向に 2 . 7倍延伸した以外は、 実施例 4と同様な操作を繰り返し、 厚み 3 0 μ ιηの 二軸配向 Ρ Ε Νフィルムを得た。 このようにして得られたニ軸配向 Ρ Ε Νフィルム を実施 ί列 9とした。  In Example 4, except that the film was stretched 2.7 times in the ifc direction at 145 ° C, and stretched 2.7 times in the horizontal direction at 140 ° C in Example 4. The same operation as in 4 was repeated to obtain a biaxially oriented Ρ Ρ Ε film having a thickness of 30 μιη. The biaxially-oriented film obtained in this manner was referred to as Run # 9.
得られた実施例のフィルムの特性評価結果を表 2に示す。 ゥェハ加工性にっレ、て は、 フィルムの熱寸法変ィ匕は小さいものの、 フィルム厚み方向の屈折率が高く、 フ ィルムの切粉等による工程内汚染やテープ剥離の際のフィルム破れが発生した。 【表 2】 Table 2 shows the property evaluation results of the obtained films of the examples. Deterioration of the film process, although the thermal dimensional change of the film is small, the refractive index in the film thickness direction is high, causing contamination in the process due to film chips, etc., and film tearing at the time of tape peeling. did. [Table 2]
Figure imgf000038_0001
Figure imgf000038_0001

Claims

請求の範囲 The scope of the claims
1 . ポリエチレン一 2 , 6—ナフタレンジカルボキシレートを主たる成分として なる二軸配向フィルムであって、 2 0 0 °Cで 1 0·分間熱処理した際のフィルムの熱 収縮率が、 フィルムの製膜方向および幅方向のいずれも 1. 0 0 %以下であること を特徴とする半導体ウエノ、加工用ベースフィルム。 1. A biaxially oriented film containing polyethylene 1,2,6-naphthalenedicarboxylate as a main component, and the heat shrinkage of the film after heat treatment at 200 ° C for 10 minutes A semiconductor wafer and a base film for processing, characterized in that the content in both the width direction and the width direction is 1.0% or less.
2. 半導体ウエノ、加工用ベースフィルムが、 バックグラインドテープ用またはダ ィシングテープ用である請求項 1記載の半導体ウエノ、加工用ベースフィルム。 2. The semiconductor wafer and the base film for processing according to claim 1, wherein the semiconductor wafer and the base film for processing are for back grinding tape or dicing tape.
3. フィルムの抽出オリゴマー量が 0. 8重量0 /0以下であり、 フィルムの厚み方 向の屈折率が 1 . 5 0 1以上 1 . 5 1 5以下である請求項 1記載の半導体ゥヱハカ口 工用ベースフィルム。 3. Film and the extraction oligomer amount 0.8 wt 0/0 less, the refractive index in the thickness Direction of the film 1.5 0 1 to 1.5 1 5 or less semiconductor Uwehaka port of claim 1, wherein Base film for construction.
4. フィルムの厚みのバラツキが 1 5 %以下である請求項 1〜3のいずれかに記 載の半導体ウェハ加工用ベースフィルム。 4. The base film for processing a semiconductor wafer according to claim 1, wherein a variation in the thickness of the film is 15% or less.
5. フィルムのヤング率が 5 4 0 OMP a以上 6 9 0 OMP a以下である請求項 1〜 3のレ、ずれかに記載の半導体ウエノヽ加ェ用ベースフィルム。 5. The base film for semiconductor wafer processing according to any one of claims 1 to 3, wherein the Young's modulus of the film is not less than 540 OMPa and not more than 690 OMPa.
6 . フィルムの少なくとも'片面における中心線平均表面粗さが 3 n m以上 8 0 η m以下である請求項 1〜 3のいずれかに記載の半導体ウェハ加工用ベースブイルム。 6. The base film for processing a semiconductor wafer according to claim 1, wherein a center line average surface roughness on at least one side of the film is 3 nm or more and 80 ηm or less.
7. フィルムの密度が 1 . 3 5 6 8 /。1113以上1 . 3 6 4 g Z c m3以下である 請求項 1〜 3のレ、ずれ力に記載の半導体ウェハ加工用ベースフィルム。 7. The density of the film is 1.3 5 6 8 /. 4. The base film for processing a semiconductor wafer according to any one of claims 1 to 3, wherein the base film is at least 111 3 and at most 1.36 4 g Z cm 3 .
8. フィルムの平均厚みが 9 m以上 1 5 0 m以下である請求項 1〜 3のいず れかに記載の半導体ウェハ加工用ベースフィルム。 8. The base film for processing a semiconductor wafer according to claim 1, wherein the film has an average thickness of 9 m or more and 150 m or less.
9. フィルムの動摩聽数が 0. 5以下である請求項 1〜 3のいずれ力に記載の 半導体ゥェハ加工用ベースフィルム。 9. The base film for processing a semiconductor wafer according to any one of claims 1 to 3, wherein the number of dynamic sounds of the film is 0.5 or less.
1 0. 2 0 0°Cで 1 0分間熱処理した際のフィルムの熱収縮率は、 フィルムの製 膜方向の熱収縮率と Ψ畐方向の熱収縮率との差の絶対値が 0. 6 0 %以下である請求 項 1〜 3のレ、ずれかに記載の半導体ウエノ、加工用ベースフィルム。 The heat shrinkage of the film when heat-treated at 10.000 ° C. for 10 minutes is the absolute value of the difference between the heat shrinkage in the film forming direction and the heat shrinkage in the Ψ 畐 direction of 0.6. The semiconductor wafer according to any one of claims 1 to 3, which is 0% or less, and the base film for processing.
1 1 . フィルムが 2層以上の複数層からなる請求項 1〜 3のいずれかに記載の半 導体ウエノ、加工用ベースフィルム。 11. The semiconductor wafer and the base film for processing according to claim 1, wherein the film comprises two or more layers.
1 2. バックグラインドテープ用ベースフィルムの片面に粘着剤層を有する請求 項 2に記載のバックグラインドテープ。 1 2. The back grinding tape according to claim 2, having an adhesive layer on one surface of the base film for the back grinding tape.
Ί 3. 請求項 1 2記載のバックグラインドテープの粘着剤層の上にさらに离膨フ ィルムを有するパックグラインドテ一: ^合体。 Ί 3. A pack grind te which further has a swelling film on the pressure-sensitive adhesive layer of the back grind tape according to claim 12.
1 4. ダイシングテープ用ベースフィルムの片面に粘着剤層を有する請求項 2に 記載のダイシングテープ。 1 4. The dicing tape according to claim 2, wherein the dicing tape has an adhesive layer on one surface of a base film for the dicing tape.
1 5. 請求項 1 4記載のダイシングテープの粘着剤層の上にさらに離形ブイルム を有するダイシングテープ複合体。 15. A dicing tape composite further comprising a release film on the pressure-sensitive adhesive layer of the dicing tape according to claim 14.
PCT/JP2004/004943 2003-04-08 2004-04-06 Base film for semiconductor wafer processing WO2004090962A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005505286A JPWO2004090962A1 (en) 2003-04-08 2004-04-06 Base film for semiconductor wafer processing

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003103908 2003-04-08
JP2003-103908 2003-04-08

Publications (1)

Publication Number Publication Date
WO2004090962A1 true WO2004090962A1 (en) 2004-10-21

Family

ID=33156837

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/004943 WO2004090962A1 (en) 2003-04-08 2004-04-06 Base film for semiconductor wafer processing

Country Status (5)

Country Link
JP (1) JPWO2004090962A1 (en)
KR (1) KR20050118302A (en)
CN (1) CN1771585A (en)
TW (1) TW200426934A (en)
WO (1) WO2004090962A1 (en)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005116652A (en) * 2003-10-06 2005-04-28 Nitto Denko Corp Protective sheet for processing semiconductor wafer and method for grinding back surface of semiconductor wafer
JP2006035503A (en) * 2004-07-23 2006-02-09 Toray Ind Inc Laminated polyester film
JP2006316218A (en) * 2005-05-16 2006-11-24 Teijin Dupont Films Japan Ltd Biaxially oriented polyester film
JP2007149856A (en) * 2005-11-25 2007-06-14 Hamamatsu Photonics Kk Laser processing method
WO2007116856A1 (en) * 2006-04-03 2007-10-18 Gunze Limited Surface protective tape used for back grinding of semiconductor wafer and base film for the surface protective tape
JP2007280976A (en) * 2006-04-03 2007-10-25 Gunze Ltd Base film for surface protection tape used for grinding rear face of semiconductor wafer
JP2008045082A (en) * 2006-08-21 2008-02-28 Teijin Dupont Films Japan Ltd Biaxially oriented polyester film for automobile drive motors
JP2009028914A (en) * 2007-07-24 2009-02-12 Lintec Corp Printing laminated sheet
JP2010165986A (en) * 2009-01-19 2010-07-29 Teijin Dupont Films Japan Ltd Film for reinforcing flexible printed circuit board, flexible printed circuit board reinforcement plate, and flexible printed circuit board laminate
EP1887061A3 (en) * 2006-08-10 2011-01-19 Nitto Denko Corporation Pressure-sensitive adhesive sheets for wafer grinding
JP2015189960A (en) * 2014-03-29 2015-11-02 三菱樹脂株式会社 polyester film
JP2015211081A (en) * 2014-04-24 2015-11-24 日東電工株式会社 Dicing/die-bonding film
JP2016047933A (en) * 2008-04-21 2016-04-07 エルジー・ケム・リミテッド Pressure-sensitive adhesive film and back-grinding method using the same
WO2016152957A1 (en) * 2015-03-24 2016-09-29 古河電気工業株式会社 Semiconductor processing tape
JP2017005072A (en) * 2015-06-09 2017-01-05 日東電工株式会社 Semiconductor wafer protection adhesive sheet
JP1574161S (en) * 2016-08-31 2017-04-17
JP2017087709A (en) * 2015-11-07 2017-05-25 三菱樹脂株式会社 Laminated polyester film
JP2017110216A (en) * 2015-12-15 2017-06-22 積水化学工業株式会社 Semiconductor protective tape
JP2020036007A (en) * 2018-08-23 2020-03-05 東レ株式会社 Film, and method of manufacturing film

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5008999B2 (en) * 2007-02-06 2012-08-22 リンテック株式会社 Dicing tape and method for manufacturing semiconductor device
KR100944274B1 (en) * 2008-11-28 2010-02-25 스템코 주식회사 Flexible circuit board and method for fabricating the board, semiconductor package comprising the board and method for fabricating the package
TWI418604B (en) * 2010-11-17 2013-12-11 Furukawa Electric Co Ltd Semiconductor wafer processing tape
SG11201906507PA (en) * 2018-03-28 2019-11-28 Furukawa Electric Co Ltd Tape for semiconductor processing

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05175127A (en) * 1991-12-24 1993-07-13 Mitsui Toatsu Chem Inc Vapor deposition method of metal on semiconductor wafer rear face
JPH10214801A (en) * 1997-01-31 1998-08-11 Teijin Ltd Dicing tape
JP2002270560A (en) * 2001-03-07 2002-09-20 Lintec Corp Method for working wafer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05175127A (en) * 1991-12-24 1993-07-13 Mitsui Toatsu Chem Inc Vapor deposition method of metal on semiconductor wafer rear face
JPH10214801A (en) * 1997-01-31 1998-08-11 Teijin Ltd Dicing tape
JP2002270560A (en) * 2001-03-07 2002-09-20 Lintec Corp Method for working wafer

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4666565B2 (en) * 2003-10-06 2011-04-06 日東電工株式会社 Protective sheet for processing semiconductor wafer and method for grinding back surface of semiconductor wafer
JP2005116652A (en) * 2003-10-06 2005-04-28 Nitto Denko Corp Protective sheet for processing semiconductor wafer and method for grinding back surface of semiconductor wafer
JP2006035503A (en) * 2004-07-23 2006-02-09 Toray Ind Inc Laminated polyester film
JP4622360B2 (en) * 2004-07-23 2011-02-02 東レ株式会社 Laminated polyester film
JP2006316218A (en) * 2005-05-16 2006-11-24 Teijin Dupont Films Japan Ltd Biaxially oriented polyester film
JP2007149856A (en) * 2005-11-25 2007-06-14 Hamamatsu Photonics Kk Laser processing method
US9102005B2 (en) 2005-11-25 2015-08-11 Hamamatsu Photonics K.K. Laser processing method
WO2007116856A1 (en) * 2006-04-03 2007-10-18 Gunze Limited Surface protective tape used for back grinding of semiconductor wafer and base film for the surface protective tape
JP2007280976A (en) * 2006-04-03 2007-10-25 Gunze Ltd Base film for surface protection tape used for grinding rear face of semiconductor wafer
JP5258556B2 (en) * 2006-04-03 2013-08-07 グンゼ株式会社 Surface protective tape used for back surface grinding of semiconductor wafer and base film for the surface protective tape
EP1887061A3 (en) * 2006-08-10 2011-01-19 Nitto Denko Corporation Pressure-sensitive adhesive sheets for wafer grinding
JP2008045082A (en) * 2006-08-21 2008-02-28 Teijin Dupont Films Japan Ltd Biaxially oriented polyester film for automobile drive motors
JP2009028914A (en) * 2007-07-24 2009-02-12 Lintec Corp Printing laminated sheet
JP2016047933A (en) * 2008-04-21 2016-04-07 エルジー・ケム・リミテッド Pressure-sensitive adhesive film and back-grinding method using the same
JP2010165986A (en) * 2009-01-19 2010-07-29 Teijin Dupont Films Japan Ltd Film for reinforcing flexible printed circuit board, flexible printed circuit board reinforcement plate, and flexible printed circuit board laminate
JP2015189960A (en) * 2014-03-29 2015-11-02 三菱樹脂株式会社 polyester film
JP2015211081A (en) * 2014-04-24 2015-11-24 日東電工株式会社 Dicing/die-bonding film
JPWO2016152957A1 (en) * 2015-03-24 2017-05-25 古河電気工業株式会社 Semiconductor processing tape
WO2016152957A1 (en) * 2015-03-24 2016-09-29 古河電気工業株式会社 Semiconductor processing tape
JP2017005072A (en) * 2015-06-09 2017-01-05 日東電工株式会社 Semiconductor wafer protection adhesive sheet
JP2017087709A (en) * 2015-11-07 2017-05-25 三菱樹脂株式会社 Laminated polyester film
JP2017110216A (en) * 2015-12-15 2017-06-22 積水化学工業株式会社 Semiconductor protective tape
JP7100957B2 (en) 2015-12-15 2022-07-14 積水化学工業株式会社 Semiconductor protective tape
JP1574161S (en) * 2016-08-31 2017-04-17
JP2020036007A (en) * 2018-08-23 2020-03-05 東レ株式会社 Film, and method of manufacturing film
JP7400263B2 (en) 2018-08-23 2023-12-19 東レ株式会社 Film and film manufacturing method

Also Published As

Publication number Publication date
CN1771585A (en) 2006-05-10
TWI294646B (en) 2008-03-11
TW200426934A (en) 2004-12-01
JPWO2004090962A1 (en) 2006-07-06
KR20050118302A (en) 2005-12-16

Similar Documents

Publication Publication Date Title
WO2004090962A1 (en) Base film for semiconductor wafer processing
JP4971703B2 (en) Polyester film for organic EL display substrate and gas barrier laminated polyester film for organic EL display substrate comprising the same
JP4052021B2 (en) Oriented polyester film and laminated film using the same
JPWO2005110718A1 (en) Oriented polyester film
JP5837411B2 (en) Polyester film for in-mold transfer
JP2004311750A (en) Base film for semiconductor wafer processing
JP3909268B2 (en) Highly transparent and easily adhesive polyester film
WO2000021752A1 (en) Release film
JP2006051661A (en) Mold release film
JP2010225434A (en) Flexible electronics device substrate and manufacturing method thereof
JP2003334912A (en) Highly transparent and easily adhesive polyester film
JP5108675B2 (en) Composite film
JP2006152072A (en) Antistatic film for semiconductor production and method for producing the same
JP5420454B2 (en) Release film for polarizing plate
JP2019166656A (en) Release film for ceramic green sheet production
JP4169546B2 (en) Laminated polyester film
JP2006051681A (en) Mold release film
JP4734694B2 (en) Biaxially stretched polyester film for molding process and molded laminate
JP2011245739A (en) Mold release film for double-sided adhesive sheet without substrate
JP2003049011A (en) Easy adhesion polyester film for optical
JP2008279669A (en) Mold release film
JP2022146445A (en) polyester film roll
JP4817729B2 (en) Flame retardant stretched polyester film
JP2006007423A (en) Polyester film for back-grinding tape
JP4401933B2 (en) Biaxially oriented laminated polyester film for electrical insulation

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2005505286

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 1020057018820

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 20048094427

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 1020057018820

Country of ref document: KR

122 Ep: pct application non-entry in european phase