CN1771585A - Base film for semiconductor wafer processing - Google Patents

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 DEG C for 10 minutes is not more than 1.00% in both the film-forming direction and the width direction.

Description

Base film for semiconductor wafer processing

Technical field

The present invention relates to base film for semiconductor wafer processing, this basement membrane uses to gather 2, and the 6-(ethylene naphthalate) is the biaxially oriented film of main component.More particularly, when the present invention relates in semiconductor wafer processing, particularly grinding back surface operation or scribing operation to use as grinding back surface adhesive band base or dicing tape base material, the grinding back surface adhesive tape with excellent size stability, flatness, mechanical strength with or the dicing tape basement membrane.

Background technology

During semiconductor was made, at the grinding step (grinding back surface operation) of chip back surface, become in the operation (scribing operation) of IC chip by the wafer cutting of finishing, the laminated adhesive tape that obtains of various bonding agents was used for fixing wafer.In the grinding back surface operation, the wafer that the surface has been formed circuit grinds the back side with the state that is fixed on the adhesive tape, by UV irradiation or heating etc. the cohesive force of bonding agent is reduced, and moves to the scribing operation then.In the scribing operation, be fixed on wafer on the adhesive tape and be cut into one by one IC chip unit, the same with the grinding back surface operation, by UV irradiation or heating etc. the cohesive force of bonding agent is reduced, take out one by one then.The IC chip that takes out is shifted into following welding sequence, plastic packaging operation.

In the past, plastic films such as the adhesive film of dicing tape and the base film of release film employing polyolefin and copolymer, polyvinyl chloride and copolymer thereof, polyester, Merlon, polyamide, polyimides, recently, consider from aspects such as mechanical strength, dimensional stability, thermal endurance, prices, for example shown in Japanese kokai publication hei 5-175332 communique, Japanese kokai publication hei 1-5838 communique, bring into use polyester film.Because the silicon wafer rate of finished products that contained impurity causes in polyester film and the organic siliconresin release layer is low, the someone discloses the method for use germanium compound as polymerization catalyst (Japanese kokai publication hei 10-214801 communique) in order to prevent.Consider that from the angle of same low contaminative Japanese kokai publication hei 11-20105 communique discloses the technology that release film is used in the tack coat protection that relates in grinding back surface adhesive tape or the dicing tape keeping process.

But, be accompanied by recently semi-conductive highly integratedly, the thickness of semiconductor wafer is at rapid attenuate, and people begin one's study and are fit to the novel semi-conductor Wafer Machining of wafer slimming.Particularly wafer thickness is extremely thin, and Ginding process in the past can cause the breakage of wafer, and grinding ratio is problem such as spended time in the past, as process technology, needs to consider to adopt the method for plasma etching for example etc.

But processing method newly developed is compared with processing method in the past, and processing temperature improves, and therefore is that the semiconductor wafer processing of base material becomes problem with thermal dimensional stability, the mechanical strength of film with the polyester film in the past.In the scribing operation, usually after when stripping tape, taking to shine the cohesive force that weakens bonding agent by heating or UV, stretch tape picks up the chip of cut-out, perhaps with chip from adhesive tape one side jack-up, between chip, open the slit, but the adhesive tape dimensional contraction is big during owing to heating, makes that picking up of chip is bad, produces the problem of the production efficiency variation of semiconductor wafer.

On the other hand, when using polyimides as base film, water absorption rate height, so the higher dimensional stability of demand.

In addition, in order to improve the productive rate of semiconductor wafer, in the industry always in the cleaningization of pursuing the operation process, the improvement of processability.

(patent documentation 1) Japanese kokai publication hei 5-175332 communique

(patent documentation 2) Japanese kokai publication hei 1-5838 communique

(patent documentation 3) Japanese kokai publication hei 10-214801 communique

(patent documentation 4) Japanese kokai publication hei 11-20105 communique

Summary of the invention

The objective of the invention is to solve the problem of above-mentioned conventional art, in semiconductor wafer processing, when particularly using as the base material of the base material of grinding back surface adhesive tape or dicing tape, the semiconductor machining basement membrane that can obtain at high temperature and all have excellent size stability, flatness, mechanical strength and the excellent suitable property of processing under the high humidity.

Other purpose of the present invention and advantage are as described below.

According to the present invention, the purpose of first aspect present invention and advantage can realize with basement membrane by following semiconductor machining, this basement membrane is with poly-2, the 6-(ethylene naphthalate) is the biaxially oriented film of main component, all is below 1.00% at the percent thermal shrinkage of 200 ℃ of heat treated film in the time of 10 minutes at the system film direction and the Width of film.

The purpose of second aspect present invention and advantage can realize that wherein base film for semiconductor wafer processing is used for grinding back surface adhesive tape or dicing tape by above-mentioned first base film for semiconductor wafer processing of the present invention.

The present invention's the 3rd purpose and advantage can realize that wherein the amount of the extraction oligomer of film is below 0.8% weight by the base film for semiconductor wafer processing of the present invention of above-mentioned first aspect, and the refractive index of film thickness direction is more than 1.501, below 1.515.

The purpose of fourth aspect present invention and advantage can realize by at least a following adhesive tape: above-mentioned first or the face of grinding back surface adhesive tape of the present invention with basement membrane of second aspect on contain the grinding back surface adhesive tape of bond layer; And above-mentioned first or the face of dicing tape of the present invention with basement membrane of second aspect on contain the dicing tape of bond layer.

The purpose of fifth aspect present invention and advantage can realize by at least a following adhesive tape compound: the grinding back surface adhesive tape compound that also contains release film on the bond layer of the grinding back surface adhesive tape of the present invention of above-mentioned fourth aspect; And the dicing tape that on the bond layer of the dicing tape of the present invention of above-mentioned fourth aspect, also contains release film.

Base film for semiconductor wafer processing of the present invention at high temperature with high humidity under dimensional stability, flatness and mechanical strength excellence.Be especially suitable for use as the dicing tape or the grinding back surface adhesive tape that in semiconductor wafer processing, use.

The best mode that carries out an invention

＜gather 2,6-(ethylene naphthalate) film 〉

Among the present invention, base film for semiconductor wafer processing is with poly-2, and 6-(ethylene naphthalate) (below be also referred to as PEN) is main component, can be that copolymer also can be a mixture.Should gather 2, dicarboxylic acids composition main in the 6-(ethylene naphthalate) is a naphthalenedicarboxylic acid, and main diol component is an ethylene glycol.Here, naphthalenedicarboxylic acid for example has 2,6-naphthalenedicarboxylic acid, 2, and 7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid etc., wherein preferred 2, the 6-naphthalenedicarboxylic acid." mainly " be meant in the constituent as the polymer of thin film composition of the present invention, and all at least 80% mole of repetitives for poly-2, and the 6-(ethylene naphthalate) is further preferred more than 90% mole, preferred especially more than 95% mole.That is, only otherwise can extremely lose of the present invention poly-ly 2, the script characteristic of 6-(ethylene naphthalate) film can guarantee when at high temperature using that dimensional stability, mechanical strength get final product.

During for copolymer, remove main component and gather 2, the copolymer composition of the formation copolymer beyond the 6-(ethylene naphthalate) can use has two compounds that become ester functional groups in the molecule.Described compound for example can preferably use as oxalic acid, adipic acid, phthalic acid, decanedioic acid, dodecyl dioctyl phthalate, M-phthalic acid, terephthalic acid (TPA), 1,4-cyclohexane cyclohexanedimethanodibasic, 4,4 '-diphenyl dioctyl phthalate, phenyl indan dioctyl phthalate, 2,7-naphthalenedicarboxylic acid, 1,2,3, the dioctyl phthalate of 4-tetrahydronaphthalene dioctyl phthalate, naphthalane dioctyl phthalate, diphenyl ether dioctyl phthalate etc.Also can preferably use as P-hydroxybenzoic acid, to the hydroxyl formic acid of '-hydroxyethoxy yl benzoic acid etc.Can also preferred use the di-alcohols etc. of the oxirane additive product, diethylene glycol (DEG), poly(ethylene oxide) glycol etc. of oxirane additive product as propylene glycol, trimethylene glycol, butylidene glycol, hexylidene glycol, cyclohexane methylene glycol, neopentyl glycol, bisphenol sulphone, bisphenol-A.

These compounds not only can use a kind, also can will use simultaneously more than 2 kinds.In these compounds, the preferred M-phthalic acid of acid composition, terephthalic acid (TPA), 4,4 '-diphenyl dioctyl phthalate, 2,7-naphthalenedicarboxylic acid, P-hydroxybenzoic acid, the oxirane additive product of the preferred trimethylene glycol of diol component, hexylidene glycol, neopentyl glycol, bisphenol sulphone.

That uses among the present invention is poly-2, and the 6-(ethylene naphthalate) can be for example by the compound of simple function compounds such as benzoic acid, methoxyl group PAG with part or all sealing of the hydroxyl of end and/or carboxyl.That uses among the present invention is poly-2, and the 6-(ethylene naphthalate) for example can be the copolymer in the scope of polymer of the chain basically that obtains of the one-tenth ester compounds as more than the trifunctional of glycerine, pentaerythrite etc. with minute quantity.

Film of the present invention can also be to remove main component to gather 2, also is mixed with other organic macromolecule mixture outside the 6-(ethylene naphthalate).Described organic macromolecule example has: PETG, polyethylene glycol isophthalate, polytrimethylene-terephthalate, poly-4,4 '-butylidene diphenyl dioctyl phthalate glycol ester, poly-2,7-(ethylene naphthalate), poly-2,6-naphthalenedicarboxylic acid propylidene ester, poly-2,6-naphthalenedicarboxylic acid DOPCP, poly-2, two (4-ethyleneoxy phenyl) sulfones of 6-naphthalenedicarboxylic acid etc.Wherein preferred polyethylene glycol isophthalate, polytrimethylene-terephthalate, poly-2,6-naphthalenedicarboxylic acid propylidene ester, poly-2, two (the 4-ethyleneoxy phenyl) sulfones of 6-naphthalenedicarboxylic acid.

The organic polymer that mixes with these PEN not only can also can will be used in combination more than 2 kinds with a kind.The organic macromolecule ratio of mixing with PEN is up to 20% mole according to the polymer repeat unit meter, and is preferred below 10% mole, the preferred especially scope below 5% mole.The preparation of described mixture can be implemented according to the preparation method of known usually polymer blend.

The polyester that uses among the present invention can obtain by well-known method.For example, directly obtain the method for the polyester of low polymerization degree by the reaction of dicarboxylic acids and glycol; Use well-known ester exchange catalyst, make the lower alkyl esters of dicarboxylic acids and the method that glycol carries out ester exchange reaction; Can in the presence of polymerization catalyst, carry out polymerization reaction more then.Catalyst for ester exchange reaction for example has the compound that contains sodium, potassium, magnesium, calcium, zinc, strontium, titanium, zirconium, manganese, cobalt, and they can be used in combination one or more.Polymerization catalyst for example has: antimonials such as antimony trioxide, four antimony oxides, antimony pentaoxide, trichloride antimony, antimonous bromide, Glycolic acid antimony, antimony acetate, with the germanium dioxide is the germanium compound of representative, tetraethyl titanate, metatitanic acid orthocarbonate, metatitanic acid tetraphenyl ester or their partial hydrolysate, titanium compounds such as titanium oxyoxalate two ammoniums, titanium oxyoxalate dipotassium, triacetyl acetate titanium.

In the above-mentioned polymerization catalyst, especially preferably use germanium compound.Be polycondensation catalyst preferably with described germanium compound, in the middle of the process after for example before finishing, just having begun to polymerization reaction from esterification or ester exchange reaction, it is added in the gained ester exchange reaction thing, and polycondensation reaction is carried out in heating while stirring under decompression state.Among the present invention, for example can preferably use fine crystallinity germanium oxide (3) germanium oxide of (1) amorphous oxidation germanium (2) to be dissolved in solution that water forms etc. as the germanium compound of polycondensation catalyst.In these germanium oxides, germanium compound be can preferably use, crystallinity germanium dioxide and amorphism germanium dioxide especially preferably used as crystallinity germanium dioxide, amorphism germanium dioxide, tetraethoxide germanium, four n-butanol germanium etc.

The amount of the germanium compound that uses in the polycondensation catalyst then can not obtain the facilitation effect of enough polymerization reactions very little; If extremely many, then the softening point of gained polyester may reduce, and the metallic element germanium that therefore remains in the polyester is preferably 10-1000ppm weight, more preferably 10-500ppm weight, further preferred 10-200ppm weight.The concentration value of germanium metallic element can followingly be measured: the sample of drying is arranged at scanning electron microscopy (SEM, the trade name that the instrumentation machine サ of Hitachi-PVC ス (strain) makes, " S570 type "), by connected energy dispersion type X-ray microanalyzer (XMA, (strain) pick trade name of making manufacturing, " EMAX-7000 ") carry out quantitative analysis.

When carrying out polymerization,, preferably contain phosphorus compound in order before polymerization reaction, to make the ester exchange catalyst inactivation via ester exchange reaction.Described phosphorus compound has phosphoric acid, phosphorous acid, phosphonic acids, phosphonate compound and their derivative etc.They can use separately also and can be used in combination two or more.Wherein, the phosphonate compound shown in the preferred following formula of phosphorus compound (I).

R ¹O-C(O)-X-P(O)-(OR ²) ₂ …(I)

Here, R1 in the formula and R2 are the alkyl of carbon number 1-4, and X is-CH ₂-or-CH (Y)-(Y represents phenyl), R ¹And R ²Can be identical or different.

Particularly preferred phosphorus compound is: dimethyl ester, diethylester, dipropyl and the dibutyl ester of carbomethoxy methane phosphonic acid, ethoxycarbonyl methane phosphonic acid, propyl ester base methane phosphonic acid, butyl ester base methane phosphonic acid, carbomethoxy-phosphono-phenylacetic acid, ethoxycarbonyl-phosphono-phenylacetic acid, propyl ester base-phosphono-phenylacetic acid and butyl ester base-phosphono-phenylacetic acid.

Among the present invention, the reason of preferred these phosphonate compounds is: compare with the phosphorus compound that uses as stabilizer usually, the reaction of metallizing thing is carried out more lentamente, so metallic compound catalytic activity longer duration in the polycondensation reaction, the result can reduce the addition of catalyst in polyester, with respect to catalyst,, also be difficult to damage the thermal stability of polyester even add the stabilizer of more amount.

Interpolation opportunity of these phosphorus compounds is as long as after ester exchange reaction essence finishes, and for example can add under the decompression under the atmospheric pressure before polycondensation reaction begins, after the beginning polycondensation reaction, after promptly obtaining polymer after latter stage of polycondensation reaction or the polycondensation reaction end.

Consider that from the thermal stability of polyester according to the P elements meter in the phosphorus compound, the preferred content of phosphorus compound is for gathering 2, the 20-100ppm weight in the 6-(ethylene naphthalate).

Poly-2 among the present invention, the 6-(ethylene naphthalate) can use 2, and 6-naphthalenedicarboxylic acid and ethylene glycol are raw material, also can use with 2, and 6-dimethyl naphthoic acid is 2 of representative, and the one-tenth ester derivant of 6-naphthalenedicarboxylic acid and ethylene glycol are raw material.In the preparation method via ester exchange reaction, ester exchange reaction is depressed enforcement in adding more than the 0.05MPa, below the 0.20MPa, can further reduce the addition of metallic compound like this.

The polyester that uses among the present invention can be made sheet behind melt polymerization, carry out solid polymerization under heating decompression or in the inert gas such as nitrogen.In order to reduce the extraction oligomer amount of film, also preferably carry out solid polymerization among the present invention.

With poly-2, the 6-(ethylene naphthalate) be the inherent viscosity of the polymer that obtains of main component be preferably 0.40dl/g above, below the 0.90dl/g.Inherent viscosity is to use o-chlorphenol as solvent, at 25 ℃ of value (units: dl/g) that measure down.

＜additive 〉

In order to make film have lubrification, contain inert particle with small scale in the preferred base film for semiconductor wafer processing of the present invention.Described inert particle is for example just like spherical silicon dioxide, porous silica, calcium carbonate, aluminium oxide, titanium dioxide, kaolin, barium sulfate, the such inorganic particle of zeolite, the perhaps organic granular as organic silicon resin particle, crosslinked polystyrene particle.About inorganic particle, because reason such as the particle diameter of composite is even, composite is more preferred than natural product.The crystal habit of inorganic particle, hardness, proportion, color etc. are not particularly limited, can decide according to application target.

The example of concrete inorganic particle has: calcium carbonate, porous silica, spherical silicon dioxide, kaolin, talcum powder, magnesium carbonate, brium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminium oxide, silica, titanium oxide, zirconia, lithium fluoride etc.

Wherein preferred especially calcium carbonate granule, spherical silicon dioxide particle, porous silica particle, tabular alumina silicate.

The example of organic granular is organic salt particle, cross-linked polymer particle etc.The example of described organic salt particle has: the terephthalate of calcium oxalate or calcium, barium, zinc, manganese, magnesium etc.In addition, the example of cross-linked polymer particle has the ethene base system monomer or the copolymer of divinylbenzene, styrene, acrylic or methacrylic acid.Organic granulars such as preferably polytetrafluoroethylene, organic siliconresin, benzoguanamine resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, thermosetting phenolic resin also.Preferred especially organic silicon resin particle, crosslinked polystyrene particle in the cross-linked polymer particle.

The particle diameter of the inert particle of adding in these films is more than the 0.05 μ m, below the 5 μ m for all preferred average grain diameter of various particles, more preferably 0.08 μ m above, below the 3.5 μ m, preferred especially 0.10 μ m is above, below the 3 μ m.In addition, more than preferred 0.08% weight of the total addition level of the inert particle that contains in the film, below 2.0% weight, more than preferred especially 0.1% weight, below 1.0% weight.

The inert particle of adding in the film can be the single component that is selected from the above-mentioned example, also can be to contain two kinds of compositions or three kinds of multicomponents that composition is above.During for single component, can contain the different particle more than 2 kinds of average grain diameter.

The trade name " the centrifugal particle size analyzer of CP-50 type " that the average grain diameter of inert particle uses (strain) Shimadzu Seisakusho Ltd. to make is measured, the centrifugal sedimentation curve that obtains with this mensuration is a benchmark, calculate the integral curve of each size particles and amount thereof, reading the pairing particle diameter of 50% weight thus, is average grain diameter value (with reference to the distribution of " granulometry technology " daily magazine industry news,, 242-247 page or leaf in 1975) with this value.

Film of the present invention especially preferably contains the particle that following ratio is formed: average grain diameter is that the calcium carbonate granule that 0.3 μ m is above, 0.8 μ m is following is more than 0.05% weight, below 0.4% weight, and/or average grain diameter be 0.1 μ m is above, 0.6 μ m is following spherical silicon dioxide particle be 0.03% weight above, below 0.5% weight, and/or average grain diameter be 0.1 μ m is above, 0.6 μ m is following organic silicon granule be 0.03% weight above, below 0.4% weight.And, can contain the inert particle of the different identical type of particle diameter simultaneously, at this moment, as long as the total content of the inert particle of identical type is in above-mentioned scope.

Film of the present invention can mix nucleus agent, antioxidant, heat stabilizer, lubricant, fire retardant, antistatic agent, polysiloxanes etc. according to purposes.

The interpolation opportunity of inert particle or other additive, the step before the 6-(ethylene naphthalate) system film got final product, and is not particularly limited, and for example can add at polymerization procedure, also can add when making film so long as poly-2.Consider from homodisperse angle, preferably inert particle or other additive are added in the ethylene glycol, when polymerization, add, make master slice, the master slice that obtains is not diluted with there being the sheet of interpolation with high concentration.

＜basement membrane 〉

Base film for semiconductor wafer processing of the present invention is to gather 2 with above-mentioned, and the 6-(ethylene naphthalate) is the biaxially oriented film that main component forms.Basement membrane among the present invention (can abbreviate film as) can be individual layer or the multilayer more than 2 layers, contains the multilayer more than 2 layers, preferably can realize the crimpiness with the flatness and the basement membrane of semiconductor wafer binding face simultaneously.The method that constitutes the multilayer more than 2 layers can use that coetrusion, extruding layer are legal, coating etc., this is not particularly limited, but consider from the angle of productive rate, preferred use above-mentioned poly-2, the 6-(ethylene naphthalate) constitutes multilayer by the coetrusion of being extruded each resin by many extruders.

Base film for semiconductor wafer processing of the present invention preferably uses as grinding back surface adhesive tape or dicing tape.

＜percent thermal shrinkage 〉

Film of the present invention all is below 1.00% at the percent thermal shrinkage of 200 ℃ of heat treated in the time of 10 minutes at the system film direction and the Width of film.Further the percent thermal shrinkage of preferred film of the present invention is more than-0.20%, below 0.80%, is preferably especially more than 0.10%, below 0.60%.Among the present invention, if no special instructions, system film direction is the direct of travel of film when making film continuously, is also referred to as length direction, makes film direction or MD direction vertically, continuously.In addition among the present invention, Width be meant along in the pellicular front with the vertical direction of system film direction, be also referred to as laterally or TD.

If surpass 1.00% with the percent thermal shrinkage of 200 ℃ of temperature heat treated in the time of 10 minutes, when then the temperature in the semiconductor wafer manufacturing procedure is high temperature, the dimensional contraction of basement membrane increases, and wafer thermal expansion, processing midway, wafer may come off from the bonding agent of adhesive tape, because the thin thickness of wafer is damaged sometimes.When percent thermal shrinkage was thermal expansion less than-0.20%, the thermal expansion of basement membrane was bigger than the thermal expansion of wafer, and the bonding agent of adhesive tape is extended the surface of wafer by the periphery of wafer.And the contraction or expansion of film all can must be stated from the semiconductor wafer warpage on the adhesive tape because of the expansion rate official post with wafer greatly to above scope of the present invention the time under two kinds of situations, thereby not preferred.In addition, when the expansion rate of film is bigger than the expansion rate of wafer, be inboard warpage with wafer side, become reason crowded between the chip, therefore need do one's utmost to suppress the expansion of film, promptly suppress percent thermal shrinkage as far as possible and develop to negative direction.

In order to obtain to have the film of required percent thermal shrinkage, more preferably in the manufacturing of film, carry out biaxial stretch-formed, thermal finalization, and then the thermal relaxation of carrying out film is handled.

＜extraction oligomer amount 〉

Using under 24 hours the condition of chloroform extraction, the oligomer extracted amount of film of the present invention is preferably below 0.8% weight.Further below preferred 0.6% weight, below preferred especially 0.5% weight.The oligomer extracted amount surpasses 0.8% weight, during then as base film for semiconductor wafer processing, under the processing temperature environment of in-process or in the bonding agent painting process, oligomer precipitate into membrane surface, causes the problems such as adhesion strength reduction between manufacturing procedure internal contamination or bond layer and the basement membrane.Separate out to film surface in order to suppress oligomer, effective method is the amount that reduces oligomer contained in the film, for this purposes, preferably reduces the extracted amount of oligomer.

In order to reduce the oligomer extracted amount, be desirable scope, preferably make and gather 2, the inherent viscosity of 6-(ethylene naphthalate) is that more preferably 0.48-0.85dl/g is preferably 0.50-0.80dl/g especially more than the 0.45dl/g, below the 0.90dl/g.Gather 2, the inherent viscosity of 6-(ethylene naphthalate) reaches down in limited time, and the extraction oligomer amount of film is not too much, and surpasses last prescribing a time limit, and needs the load of volume in polymerization and the film making process.

In order to make the oligomer extracted amount in desirable scope, the inherent viscosity of film is preferably 0.40-0.90dl/g.The measured value of inherent viscosity is to use chloroform as solvent, at 25 ℃ of value (units: dl/g) that measure down.

The refractive index of＜thickness direction 〉

Film of the present invention is preferably more than 1.501 in the refractive index on the thickness direction (nz), below 1.515.More preferably more than 1.503, below 1.513, preferred especially more than 1.504, below 1.512.The refractive index of thickness direction is less than 1.501, the anti-delamination variation of film then, and the cutting section of film produces burr, and the cutting dust can pollute operation sometimes.In addition, the refractive index of thickness direction surpasses 1.515, and then film becomes fragile, and when using as the basement membrane of grinding back surface adhesive tape or dicing tape, when stripping tape, breakage may take place film.

In order to obtain to have the film of desired refractive index on the thickness direction of film, the heat setting temperature in the time of can improving the basement membrane manufacturing perhaps reduces vertical or horizontal stretching ratio.

＜film gauge variation 〉

The deviation of film thickness of the present invention is below 15% with respect to the average thickness of film preferably, and is more preferably below 10%, preferred especially below 8%.The thickness deviation of film is more little, then the adhesion strength of the adhesive surface of grinding back surface adhesive tape and semiconductor wafer and dicing tape and semiconductor wafer is even, therefore can stablize bonding, can carry out more accurate grinding back surface and scribing, can provide that height becomes more meticulous, highdensity chip.

＜Young's modulus 〉

Film Young's modulus of the present invention is in the system film direction of film with more than all preferred 5400MPa of Width, below the 6900MPa, more preferably 5500MPa above, below the 6800MPa, preferred especially 5600MPa is above, below the 6700MPa.Below the preferred 1000MPa of Young's modulus difference of both direction.

Young's modulus is lower than 5400MPa, and then the rigidity deficiency of film is used and gathered 2, and the base film for semiconductor wafer processing of the high elastic modulus of 6-(ethylene naphthalate) film is difficult to filming.In addition, Young's modulus surpasses 6900MPa, and then film is easy to generate more dust when cutting, might pollute in the processing that requires under the cleanliness factor state.And, when picking up each chip of cutting, tape elongation or be difficult to by adhesive tape side jack-up chip, production efficiency is low.

＜surface roughness (Ra) 〉

The center line average surface rugosity (Ra) of at least one face of preferred film of the present invention be 3nm above, below the 80nm, more preferably 5nm above, below the 60nm, preferred especially 7nm is above, below the 50nm.Film is the multilayer more than 2 layers when constituting, and further the Ra sum on preferred film two sides is more than the 10nm, more preferably more than the 14nm.Here, center line average boldness (Ra) can be passed through talysurf (the accurate trade name of making " サ-Off コ system SE-3CK " in the trade name " サ-Off コ-ダ SE-30C " that (strain) little slope research institute makes or (strain) Tokyo), according to the method for JIS B-0601 regulation, be that 0.25mm, mensuration contact pilotage radius are that 3 μ m measure with the length of taking a sample.

Ra is lower than 3nm, then the sliding of film is poor, and the carrying during thin film fabrication, film surface was easy to generate cut when film batched, during with the state of film rolling rolling, the air of getting involved between film and the film is difficult to extract out, because of the flatness that gas hold-up diminishes film takes place.And Ra surpasses 80nm, and then film is sliding excessively, batches or is coated with after tack coat makes adhesive tape at film surface at film, might frequently batch skew when batching.

＜density of film 〉

Density of film of the present invention is preferably 1.356g/cm ³More than, 1.364g/cm ³Below.Further preferred 1.357g/cm ³More than, 1.362g/cm ³Below.Density is less than 1.356g/cm ³, then the crystallinity of film reduces, the dimensional stability deficiency in the semiconductor wafer manufacturing procedure.Density surpasses 1.364g/cm ³, then crystallinity is too high, and film loses toughness, when therefore making the base material of grinding back surface adhesive tape or dicing tape, breaks easily when stripping tape.The density value of film is in using the density gradient of calcium nitrate aqueous solution as solvent, 25 ℃ of values of measuring by the method for drifting along.

The average thickness of＜film 〉

The average thickness of preferred film of the present invention be 9 μ m above, below the 150 μ m, more preferably 9 μ m above, below the 125 μ m, preferred especially 12 μ m are above, below the 100 μ m.The average thickness of film is less than 9 μ m, and then the protection function as the mechanical strength of the supporter of wafer process, wafer surface may be not enough.The average thickness of film surpasses 150 μ m, and then the rigidity of film is strong excessively, and the adhesion strength of adhesive tape just may make the wafer breakage slightly by force when stripping tape, and the power that is used to extend film after the scribing is possible excessive.

＜the coefficient of kinetic friction 〉

The coefficient of kinetic friction between the film preferred film of the present invention (μ d) is below 0.5.The coefficient of kinetic friction (μ d) surpasses 0.5, and then in the film making process and the operability variation of bond layer coating processing, shortcoming appears or scratch etc. wrinkling in for example traveling or when batching on the roller of in-process.

＜percent thermal shrinkage poor 〉

About with film of the present invention at the film percent thermal shrinkage of 200 ℃ of following heat treatments in the time of 10 minutes, the absolute value of the difference of the percent thermal shrinkage (SMD) of the system film direction of film and the percent thermal shrinkage (STD) of Width (| SMD-STD|) be preferably below 0.60%, more preferably this value is below 0.50%, and is preferred especially below 0.40%.The absolute value of the difference of percent thermal shrinkage surpasses 0.60%, and when then using as the basement membrane of grinding back surface adhesive tape or dicing tape, the anisotropy of the change in size amount of film is big, and warpage may take place semiconductor wafer.

＜grinding back surface adhesive tape 〉

Grinding back surface adhesive tape of the present invention has bond layer on the face of above-mentioned grinding back surface adhesive tape with basement membrane.Grinding step at back surface of semiconductor wafer is in the grinding back surface operation, is used for the fixing of silicon wafer with grinding the grinding back surface adhesive tape of adhesive tape with laminated bond layer on the face of basement membrane overleaf, so just can silicon wafer be fixed with stable status.

＜dicing tape 〉

Dicing tape of the present invention has bond layer on the face of above-mentioned dicing tape with basement membrane.In the operation by semiconductor wafer cutting IC chip is in the scribing operation, will dicing tape with a face of basement membrane on the dicing tape of laminated bond layer be used for the fixing of silicon wafer, so just can silicon wafer be fixed with stable status.

＜coating layer 〉

In order to improve the easy viscosity with bonding agent, can grinding back surface adhesive tape of the present invention with or dicing tape at least one face with basement membrane on establish coating layer.Coating layer preferably contains at least a water-soluble or water dispersible macromolecule resin that is selected from mylar, polyurethane resin, acrylate, vinyl resin, especially preferably contains mylar and acrylate.The glass transition temperature of the mylar of preferred coating layer used in the present invention (Tg) is 0-100 ℃, more preferably 10-90 ℃.This mylar is preferably the polyester of water dissolvable or water dispersible, can contain some organic solvents.

Described mylar comprises polybase base acid as described below or it becomes ester derivant to become ester derivant with polyalcohol or its.Promptly, the example of polybase base acid composition has: terephthalic acid (TPA), M-phthalic acid, phthalic acid, biphenyl dicarboxylic acid acid anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexane cyclohexanedimethanodibasic, adipic acid, decanedioic acid, trimellitic acid, Pyromellitic Acid, dimeric dibasic acid, 5-sodium sulfo-phthalic acid etc.Use the synthetic copolymer polyester resin of these sour compositions more than 2 kinds.Can also use a spot of unsaturated polybase base acid composition, as hydroxycarboxylic acids such as maleic acid, itaconic acid etc. and P-hydroxybenzoic acid.The example of polyol component has ethylene glycol, 1,4-butanediol, diethylene glycol (DEG), dipropylene glycol, 1,6-hexylene glycol, 1, the oxirane of 4-cyclohexanedimethanol, Xylene glycol, dihydroxy methylpropane, poly-(oxirane) glycol, poly-(epoxy butane) glycol, bisphenol-A, bisphenol-A or expoxy propane addition compound product etc., but be not limited to these.

The glass transition temperature of the acrylate of coating layer used in the present invention (Tg) is-50 to 50 ℃, more preferably-50 to 25 ℃.This acrylate is preferably the acrylate of water dissolvable or water dispersible, can contain a small amount of organic solvent.

Described acrylate can be obtained by following acrylate monomer copolymerization.The example of this acrylate monomer has: alkyl acrylate, alkyl methacrylate (alkyl has: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, 2-ethylhexyl, cyclohexyl etc.); Acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, acrylic acid 2-hydroxy-propyl ester, methacrylic acid 2-hydroxy-propyl ester etc. contain the monomer of hydroxyl; Glycidyl acrylate, glycidyl methacrylate, glycidol ether etc. contain the epoxy radicals monomer; Acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and salt thereof (sodium salt, sylvite, ammonium salt, tertiary ammonium salt etc.) etc. contain the monomer of carboxyl or its salt; Acrylamide, Methacrylamide, the N-alkyl acrylamide, N-alkyl methyl acrylamide, N, N-dialkyl group acrylamide, methacrylic acid N, (alkyl has methyl to the N-dialkyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, the 2-ethylhexyl, cyclohexyl etc.), N-alkoxy propone acid amides, the N-alkoxy methyl acrylamide, N, N-dialkoxy acrylamide, N, (alkoxyl has methoxyl group to N-dialkoxy Methacrylamide, ethyoxyl, butoxy, isobutoxy etc.), acryloyl morpholine, N hydroxymethyl acrylamide, the N-methylol methacrylamide, N phenyl acrylamide, N-phenyl methyl acrylamide etc. contains the monomer of acylamino-; Anhydride monomers such as maleic anhydride, itaconic anhydride; Monomers such as vinyl isocyanate, pi-allyl isocyanates, styrene, AMS, vinyl methyl ether, EVE, vinyl trialkyl oxysilane, maleic acid mono alkyl ester, fumaric acid mono alkyl ester, itaconic acid mono alkyl ester, acrylonitrile, methacrylonitrile, vinylidene chloride, ethene, propylene, vinyl chloride, vinyl acetate, butadiene.The acrylate that uses as coating is not limited by this.

Film in order to form, above-mentioned composition used in the present invention preferably uses with the form of water-based masking liquids such as the aqueous solution, aqueous dispersions or emulsion.Film in order to form, can be as required, add other resin except that above-mentioned composition, for example have crosslinking agent, antistatic agent, colouring agent, surfactant, ultra-violet absorber, the lubricants (filler, wax) etc. such as polymer, melamine, epoxy compounds, aziridine of oxazoline group.Described lubricant is intended to improve the lubrification of film or improves anti-closure, can add lubricant as required.

The solid-state part concentration of water-based masking liquid is generally below 20% weight, more preferably 1-10% weight.If this ratio is less than 1% weight, then to the filming property deficiency of polyester film, and surpass 20% weight, then the stability of paint or coating outward appearance can variation.

Coating can followingly be provided with: at non-stretched film or carried out coating water-based masking liquid on the film of uniaxial tension, carry out then twin shaft to or uniaxial tension, thermal finalization, thus coating layer can be set on film securely.Coating process can be coated with rolling method, recessed method, the roller brush method, spraying process, air knife of being coated with method, infusion process, curtain coating method etc. and be used alone or in combination.

＜bonding agent 〉

The bonding agent that constitutes grinding back surface adhesive tape of the present invention or dicing tape can be extensive use of well-known bonding agent, and preferred acrylate is a bonding agent.The acrylic ester bonding agent specifically can use to be selected from acrylate and be the homopolymers of main composition unit and the acrylic ester polymer of copolymer, with and with other functional monomer's copolymer and these mixture of polymers.For example preferably use carbon number to be the methacrylate of the alkylol of 1-10, vinyl acetate base ester, acrylonitrile, vinyl alkyl ethers etc. as the acrylate of the alkylol of 1-10, carbon number.In addition, can or be used in combination more than 2 kinds independent a kind of aforesaid propylene acid esters based copolymer.

The functional monomer can use acrylic acid, methacrylic acid, maleic acid, acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester etc.Copolymer bonding agent with functional monomer can be set at value arbitrarily with cohesive force and cohesiveness by using crosslinking agent.Such crosslinking agent has: multicomponent isocyanate compound, polynary epoxy compounds, polynary nitrogen heterocycle propane compound, chelate compound etc.The multicomponent isocyanate compound specifically has toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, two isocyanic acids 1, the inferior own ester of 6-, different Buddhist and the compound of ketone vulcabond and their addition form.Polynary epoxy compounds specifically can use ethylene glycol diglycidylether, terephthalic acid diglycidyl ester acrylate etc.Polynary nitrogen heterocycle propane compound specifically can use three-2,4, and 6-(1-azacyclo-propyl group)-1,3,5-triazines, three [1-(2-methyl)-azacyclo-propyl group] phosphine oxide, six [1-(2-methyl)-azacyclo-propyl group] three phosphorus are for triazine etc.Chelate compound specifically can use ethyl acetoacetate chelating diisopropyl acid aluminium, three (ethyl acetoacetate) aluminium chelate etc.

The molecular weight of the acrylate based copolymer that these monomer polymerizations are obtained is 1.0 * 10 ⁵-10.0 * 10 ⁵, preferred 4.0 * 10 ⁵-8.0 * 10 ⁵Bond layer can use the bonding agent that can reduce cohesive force behind the irradiation radiation-curing when picking up, and concrete preferably the use with above-mentioned acrylic ester copolymer is host, wherein contains the bonding agent of radioactive ray polymerizable compound.Such radioactive ray polymerizable compound for example is extensive use of as Japanese kokai publication sho 60-196, No. 956 communiques and Japanese kokai publication sho 60-223, No. 139 communique is disclosed, by having the low molecular weight compound of 2 above optical polymerism carbon-to-carbon double bonds in the network molecule of rayed solid at least, specifically can use three acrylic acid trihydroxy methyl propyl ester, tetrapropylene acid tetra methylol methyl esters, pentaerythritol triacrylate, pentaerythritol tetracrylate, monohydroxy five acrylic acid pentaerythritol esters, six acrylic acid dipentaerythritol ester or diacrylate 1, the 4-butanediol ester, diacrylate 1,6-hexylene glycol ester, poly-ethylene glycol diacrylate, commercially available low polyester acrylate etc.

The radioactive ray polymerizable compound is except aforesaid propylene acid esters based compound, and can also adopt urethane acrylate is oligomer.Urethane acrylate is that oligomer passes through: with the polyol compound of polyester-type or polyether-type etc. and multicomponent isocyanate compound for example 2, the 4-toluene di-isocyanate(TDI), 2, the 6-toluene di-isocyanate(TDI), 1, the 3-XDI, 1, the 4-XDI, diphenyl methane 4, reactions such as 4-vulcabond, obtain the terminal isocyanate polyurethane prepolymer, make acrylate with hydroxyl or methacrylate for example acrylic acid 2-hydroxyethyl ester or methacrylic acid 2-hydroxyethyl ester again, acrylic acid 2-hydroxy-propyl ester, methacrylic acid 2-hydroxy-propyl ester, the polyacrylic acid glycol ester, polymethylacrylic acid glycol esters etc. obtain with its reaction.This urethane acrylate is that oligomer is the radioactive ray polymerizable compound that has the carbon-to-carbon double bond more than 1 at least.

As described urethane acrylate is oligomer, special adopt molecular weight be 3000-10000 3000-30000, preferred, the more preferably oligomer of 4000-8000, even then semiconductor wafer surface is thick, chip surface can not be attached with bonding agent yet when picking up wafer chip, thereby preferred.Use urethane acrylate be oligomer during as the radioactive ray polymerizable compound with use Japanese kokai publication sho 60-196, at least the situation that has the low molecular weight compound of 2 optical polymerism carbon-to-carbon double bonds in the disclosed molecule in No. 956 communiques is compared, and can obtain as the extremely excellent material of bonding sheet.That is, the cohesive force of bonding sheet before radiation exposure is enough big, and cohesive force fully reduces behind radiation exposure, thereby chip surface can residual bonding agent when picking up wafer chip.

Can also except that above-mentioned bonding agent and radioactive ray polymerizable compound, can also contain in the bond layer as required because of the painted compound of radiation exposure.By described radiation exposure, owing to contain painted compound in the bond layer, so behind the radiation exposure bonding sheet, this sheet is painted, by the light sensors wafer chip time, accuracy of detection is improved, and can not cause the misoperation when picking up wafer chip.In addition, also have and directly to judge whether radioactive ray have shone the effect of bonding sheet by visual.

Preferred object lesson adularescent (leuko) dyestuff of painted compound by radiation exposure.The dyestuff of the triphenyl methane system that the white dyestuff is preferably commonly used, fluorenes system, phenthazine system, aramine system, spiro-pyrans system.Preferably the example of the developer that uses simultaneously with these white dyestuffs has the electron acceptor such as initial stage polymer, aromatics carbon acid derivative, atlapulgite of employed phenol formaldehyde resin in the past, when changing tone, can also be used in combination various known developers.The above-mentioned compound painted by radiation exposure is included in the bond layer after can temporarily being dissolved in organic solvent etc. earlier again, also can make micronized and is included in the bond layer.This compound preferably uses in bond layer with 0.01-10% weight, preferred 0.5-5% weight.

＜grinding back surface adhesive tape compound 〉

Among the present invention, with the state keeping of grinding back surface adhesive tape compound, by release film protected usually by its bond layer surface for the grinding back surface adhesive tape.Divesting release film overleaf in the grinding step uses.That is, in the grinding back surface adhesive tape compound of the present invention, grind overleaf on the tack coat of adhesive tape and also have release film.

Laminated organosilicon release layer forms described release film on the face of polyester basement membrane containing, and the bonding aspect of organosilicon demoulding aspect and grinding back surface adhesive tape is fitted, as grinding back surface adhesive tape compound.Release film can also and contain between the basement membrane of polyester at the organosilicon release layer establishes prime coat.

＜dicing tape compound 〉

Among the present invention, with the state keeping of dicing tape compound, by release film protected usually by its bond layer surface for the dicing tape compound.Divesting release film in the scribing operation uses.That is, dicing tape compound of the present invention also is provided with release film on the tack coat of dicing tape.

Described release film is that laminated organosilicon release layer forms on the face of polyester basement membrane containing, and the bonding aspect of organosilicon demoulding aspect and dicing tape is fitted, and makes the dicing tape compound.Release film also can and contain between the basement membrane of polyester at the organosilicon release layer establishes prime coat.

The polyester basement membrane of＜formation release film 〉

Constitute the polyester basement membrane of release film of the present invention, can constitute, also can constitute by different polyester by the polyester identical with base film for semiconductor wafer processing of the present invention.Described polyester preferably exemplifies with PETG, gathers 2, and the 6-(ethylene naphthalate) is the polyester of main component.Here " mainly " be meant in the constituent of polymer, and all at least 80% mole of repetitives is ethylene glycol terephthalate or 2, the 6-(ethylene naphthalate), more preferably more than 90% mole, be preferably more than 95% mole especially.

The polyester basement membrane that constitutes release film is overleaf after attrition process and the scribing processing, and for irradiation ultraviolet radiation solidifies bonding agent and reduces cohesive force, preferably the light transmittance of this basement membrane is more than 85%.

＜organosilicon release layer 〉

The organosilicon release layer that constitutes release film of the present invention can followingly form: the masking liquid that for example will contain the curable organic siliconresin is coated on the face of polyester basement membrane, dry, curing.The curable organic siliconresin for example can be the organic siliconresin of any reaction system such as condensation reaction system, addition reaction system, ultraviolet ray or electron ray curing system, can use in the described curable organic siliconresin more than one.

＜preparation condition 〉

Below, the preparation method of basement membrane of the present invention is elaborated.Of the present invention poly-2,6-(ethylene naphthalate) film, for example can be that the following temperature of fusing point (following table is shown Tm) above (Tm+70 ℃) melt extrudes resin with common extrusion temperature, with of the surperficial quenching of gained film like fused mass, obtain the non-stretched film that inherent viscosity is 0.40-0.90dl/g at the rotation drum cooler.In this step, in order to improve film like fused mass and the stickiness of rotating drum cooler, the known charged static applying of the film like fused mass method that makes.Usually gather 2, therefore the resistance height of 6-(ethylene naphthalate) fused mass fits insufficient with above-mentioned drum cooler static sometimes.As solution, preferably contain the sulfonic acid quaternary phosphonium, wherein said sulfonic acid quaternary phosphonium is with respect to gathering 2, and whole difunctionality carboxylic acid compositions of 6-(ethylene naphthalate) have the ester forming functional group of 0.1-10mmol%.

The non-stretched film that obtains like this 120-170 ℃, more preferably under 130-160 ℃ temperature, with 2.8-3.5 stretching ratio longitudinal stretching doubly, under 120-150 ℃ temperature,, make biaxially oriented film then with 2.8-3.6 stretching ratio cross directional stretch doubly.The cross directional stretch multiplying power is preferably about 0.90-1.15 times multiplying power of longitudinal stretching multiplying power, and this can make the thickness deviation of film be limited in desirable scope.These stretchings can be to be divided into the multistage stretching that the multistage carries out.

The preferred biaxially oriented film that obtains like this is 235-255 ℃ of more preferably thermal finalization 0.3-20 second under 240-250 ℃ temperature.Then, in order to reduce percent thermal shrinkage, preferably further longitudinally and/or laterally, carry out thermal relaxation with the relaxation rate of 0.5-15% scope and handle.From the operation principle of stretching-machine, horizontal relaxation is carried out easily usually, and horizontal percent thermal shrinkage accomplishes to approach 0% easily.But be difficult to reduce percent thermal shrinkage longitudinally, particularly near the percent thermal shrinkage 200 ℃, therefore the stretching ratio and the draft temperature of above-mentioned vertical and horizontal are resultful.

Outside the preferably above-mentioned heat treatment of polyester film of the present invention, also after batching, heat-treat.Heat treatment method after batching is not specified, but preferred especially underslung relaxation heat treating process.But suspension type relaxation processing method preference hangs down downwards with deadweight via the roller that is arranged at the top as: the film that will handle, after the way heating therein, use the roller of below to cool off on one side, change into the direction of approximate horizontal on one side, cut off coiling tension with niproll, and batch.Sagging distance can be about 2-10m, and less than 2m, it is too small then to conduct oneself with dignity, and damages flatness easily, and heated perimeter is short in addition, is very difficult to obtain relaxation effect.On the other hand, if sagging distance surpasses 10m, then operability is poor, and it is heavy that deadweight becomes, and therefore has because of the different situations that can not obtain desirable percent thermal shrinkage in heating region position.

As long as the percent thermal shrinkage of gained Biaxially oriented polyester film under 200 ℃ is in desirable scope, heat treatment behind this film making process can (relaxation after the thermal finalization is handled) be carried out in the film making process of film, after also can and batching once, carry out relaxation and handle at the system film.Its processing method is not particularly limited.Consider that from heating film immediately preferred mode of heating is the infrared ray heating.In addition, preferred treatment temperature is that to be processed into the temperature that makes film be 200-240 ℃.If film temperature is lower than 200 ℃, the percent thermal shrinkage when then being difficult to reduce by 200 ℃, and film temperature surpasses 240 ℃, and then the easy variation of flatness has oligomer to separate out when serious, and film bleaches.Be stressed process domination of this albefaction, for example with the film portion of suspender belt frame in film roll, even below 200 ℃, with the part that band contacts also can albefaction.Film temperature can use contactless infra-red thermometer (for example バ Application-ズ formula radiation thermometer) to measure.In these heat treatment methods, suspension type relaxation heat treating process is than the easier percent thermal shrinkage of controlling the wide scope of film equably of the heat treatment in the film making process, thereby preferred.

On the other hand, the polyester basement membrane of formation release film is can be by method acquisition known or known in the art in the past.That is, the non-stretched film of the polyester that will melt extrude stretches along the single shaft direction, stretches along the direction vertical with above-mentioned draw direction then, carries out thermal finalization again and handles.Among the present invention, release layer can followingly be coated with: the masking liquid that for example will contain the release layer composition is coated on the polyester basement membrane, then heating and dry.The coating process of masking liquid can adopt known coating process, and for example rolling method, line are coated with method.Be attached on grinding back surface adhesive tape or the dicing tape by the release film that will obtain, can obtain each compound by above method.

Embodiment

Below provide embodiment, further describe the present invention.Each characteristic value among the embodiment is measured or is estimated by following method.If no special instructions, the part among the embodiment and ratio expression weight portion and weight ratio.

(1) percent thermal shrinkage

In temperature is set at 200 ℃ baking oven, under non-tense situation, film was kept 10 minutes, as percent thermal shrinkage S (%), calculate by following formula with the change in size before and after the heat treated.

S＝[(L ₀-L)/L ₀]×100 …(1)

In the formula, L ₀: distance between the punctuate before the expression heat treatment, L: distance between the punctuate after the expression heat treatment.Specimen width 20mm, length 200mm, distance is 150mm between the preceding punctuate of heat treatment.System film direction (MD) and Width (TD) both direction at film are measured, and obtain percent thermal shrinkage.

(2) oligomer extracted amount

Use the Soxhlet extractor, the 5g film sample is carried out extracting in 24 hours operation in chloroform.Measure the weight of dry rear film sample, by following formula (2), by weight W before extracting ₀(g) and extract the back weight W ₁(g) obtain oligomer extracted amount K (% weight).

K＝[(W ₀-W ₁)/W ₀]×100 …(2)

(3) eduction rate of the oligomer after the heating

Film is fixed on the wooden frame, in 160 ℃ hot air circulation (air) formula drier, kept 10 minutes then,, take the photo of film surface with the differential interference light microscope afterwards in the film surface AM aluminum metallization.Summation with the shared area of oligomer on this photo (leukasmus point-like) heats the oligomer eduction rate with respect to the percentage evaluation of the gross area.

Zero: the oligomer eduction rate is lower than 2.5%

▲: the oligomer eduction rate is 2.5-4.5%

*: the oligomer eduction rate is more than 4.5

(4) refractive index of film thickness direction (nz)

Use Abbe refractometer (manufacturing of the ア of Co., Ltd. go), 25 ℃ of refractive indexes of obtaining film thickness direction (z) with the Na-D line.

(5) Young's modulus

Cutting width is that 10mm, length are 150mm, and the clip spacing is that 10mm, draw speed are that 10mm/ minute, writing speed are 500mm/ minute, stretches with the omnipotent tensile test device of Insutoron type.System film direction (MD) and Width (TD) both direction at film are measured, and calculate Young's modulus by the tangent line of the riser portions of gained load elongation chart.

(6) center line average boldness (Ra)

By talysurf (the accurate trade name of making " サ-Off コ system SE-3CK " in (strain) Tokyo),, be that 0.25mm, mensuration contact pilotage radius are that 3 μ m measure with the length of taking a sample according to the method for JIS B-0601 regulation.

(7) film thickness

Use micrometer (trade name " K-402B type " that ア Application リ Star (strain) is made),, measure, measure 300 place's film thicknesses altogether with the interval of each 10cm at the system film direction (MD) and the Width (TD) of film.Calculate the mean value of gained 300 place's film thicknesses, obtain the average thickness t of film ₀(μ m).

Re-use electronic ga(u)ge (trade name " K-312A type " that ア Application リ Star (strain) is made), pin is pressed and is 30g, the speed of travel is 25mm/ second, measures in the length of continuous 2m respectively at the system film direction (MD) and the Width (TD) of film, obtains continuous thickness recording curve.Read maximum ga(u)ge t by this recording curve ₁(μ m) and minimum thickness t ₂(μ m).

By following formula (3), by the average thickness t of the film that obtains like this ₀(μ m) and maximum ga(u)ge t ₁(μ m) and minimum thickness t ₂(μ m) obtains thickness deviation D (%).

D＝[(t ₁-t ₂)/t ₀]×100 …(3)

(8) coefficient of kinetic friction (μ d)

The cutting film (sample) of 2 75mm (width) * 100mm (length) is stacked,, apply the counterweight that weight is 200g, the film of upside is slided with 150mm/ minute speed, the power F when sliding as load W (g) _d(g) calculate the coefficient of kinetic friction (μ d).Be determined under 23 ℃, 65%RH film is carried out carrying out after the humidity regulation in 24 hours.

The coefficient of kinetic friction=F _d/ W

(9) percent thermal shrinkage is poor

In temperature is set at 200 ℃ baking oven, under non-tense situation, film was kept 10 minutes, respectively for the system film direction (MD) and the Width (TD) of film, same with (1) percent thermal shrinkage, by following formula (1), calculate as percent thermal shrinkage S (%) by the change in size before and after each heat treated, calculate the absolute value of the thermal contraction rate variance of both direction.

S＝[(L ₀-L)/L ₀]×100 …(1)

In the formula, L ₀: distance between the punctuate before the expression heat treatment, L: distance between the punctuate after the expression heat treatment.

(10) density

According to JIS C2151, measure biaxial orientation and gather 2, the density of 6-(ethylene naphthalate) film.

(11) water absorption rate

According to JIS K7209, use the square basement membrane of the length of side as 50mm, immersion is 24 hours in 23 ℃ water, measures the water absorption rate of film then.

(12) dimensional stability

Use the basement membrane of 25 * 25cm, under 65 ℃, the atmosphere of 85%RH, placed 10 hours, measure the rolled state at 4 angles then, measure the mean value of amount of warpage (mm).Zero is qualified.

Zero: the amount of warpage that is lower than 10mm

*: the amount of warpage that 10mm is above

(13) processability of semiconductor wafer (grinding back surface and scribing)

Biaxial orientation at each embodiment and comparative example gathers 2, coating acrylic ester bonding agent (n-butyl acrylate and acrylic acid copolymer) on the 6-(ethylene naphthalate) film, and its thickness is 14 μ m, the preparation bonding sheet.Fit on the bond layer of resulting bonding sheet 8 inches silicon wafer carries out the grinding back surface and the scribing test of wafer respectively.After the scribing, carry out picking up of chip with on-expansible formula die Bonder.Scribing, the condition of picking up of this moment are as follows, the scribing cut channel degree of depth: 20 μ m under the tape surface; Thimble: 4; The diameter of absorption frame: 28mm ; Collet chuck: pyramid collet chuck; Jack-up distance: 2mm; Scribing size: 8mm * 8mm.

(14) processability of semiconductor wafer (grinding back surface and tape stripping)

Biaxial orientation at each embodiment and comparative example gathers 2, coating acrylic ester bonding agent (n-butyl acrylate and acrylic acid copolymer) on the 6-(ethylene naphthalate) film, and its thickness is 14 μ m, the preparation bonding sheet.Fit on the bond layer of gained bonding sheet 8 inches silicon wafer carries out the test of the grinding back surface and the tape stripping of wafer respectively.Test condition is: 150 ℃ of the heat treatment temperatures before 180 ℃ of the grinding back surface processing temperatures, tape stripping.

Embodiment 1

At 100 part 2, add 0.03 part of manganese acetate 4 hydrate in the mixture of 6-naphthalene diformic acid dimethyl ester and 60 parts of ethylene glycol, slowly intensification on one side is warming up to 240 ℃ by 150 ℃, Yi Bian carry out ester exchange reaction.In the reaction way, when reaction temperature reaches 170 ℃, add 0.024 part of antimony trioxide, the average grain diameter of adding 0.2% weight again is that 0.4 μ m, size ratio are 1.1 spherical silicon dioxide particle.When reaction temperature reaches 220 ℃, add 0.042 part of (being equivalent to 2mmol%) 3,5-dicarboxyl benzene sulfonic acid tetrabutyl phosphorus.Then carry out ester exchange reaction then, ester exchange reaction is added 0.023 part of trimethyl phosphate after stopping.Then product is transferred in the polymer reactor, be warming up to 290 ℃, under the high vacuum below the 0.2mmHg, carry out polycondensation reaction, the inherent viscosity that obtains measuring in 25 ℃ o-chlorphenol solution is the poly-2 of 0.62dl/g, 6-(ethylene naphthalate) polymer (being called " polymer C ").This polymer C 170 ℃ of dryings 6 hours, is supplied with extruder then,,, be expressed into surface smoothness and be 0.3S, surface temperature and be on 50 ℃ the going barrel, obtain non-stretched film by the slot-shaped mouthful of mould of opening degree 1mm with 305 ℃ of melting temperatures fusions.

The non-stretched film that obtains so vertically (is made the film direction) at 145 ℃ to stretch 3.3 times, then stretch 3.4 times at 140 ℃ horizontal (Width), handling 5 seconds and broad ways 243 ℃ of thermal finalizations again and shrink 5% (toe in), is that 16 μ m, inherent viscosity are that the biaxial orientation PEN film of 0.52dl/g is with the wide 3000m that batches of 1500mm with thickness.Then gained biaxial orientation PEN film is hung down downwards with deadweight via the niproll of being located at the top, heat by infrared heating device on the way therein, the temperature that makes film is 225 ℃, use the roller cooling at 4m place under the roller that is located at the top then on one side, change into the direction of approximate horizontal on one side, with batching behind the niproll partition coiling tension, carry out relaxation heat treatment.Relaxation is to make the niproll of top and the niproll of the blocking-up of coiling tension have speed difference.

With the biaxial orientation PEN film after the relaxation heat treatment that obtains like this as embodiment 1.

Evaluating characteristics result to the film of resulting embodiment 1 is as shown in table 1.About the wafer process of embodiment film, what can not take place that flatness etc. because of the hot change in size of film, film gauge variation or film causes that the misoperation of die Bonder device produces is bad, can carry out good pick-up operation.In addition, can not pollute in tack coat is coated with operation and semiconductor wafer manufacturing procedure, and film can be not damaged when stripping tape, the processability that semiconductor wafer is made is good.

Embodiment 2

The longitudinal stretching multiplying power is made as 2.9 times, and the cross directional stretch multiplying power changes to 3.1 times, does not carry out underslung relaxation heat treatment, in addition repeats operation similarly to Example 1, and obtaining thickness is the biaxial orientation PEN film of 75 μ m.

The film characteristics evaluation result of gained embodiment 2 is as shown in table 1.About the wafer process of embodiment film, what can not take place that flatness etc. because of the hot change in size of film, film gauge variation or film causes that the misoperation of die Bonder device produces is bad, can carry out good pick-up operation.In addition, can not pollute tack coat and be coated with operation and semiconductor wafer manufacturing procedure, and film can be not damaged when stripping tape, the processability that semiconductor wafer is made is good.

Embodiment 3

Among the embodiment 3, be prepared as follows the double-deck film that constitutes.At first, at 100 part 2, add 0.03 part of manganese acetate 4 hydrate in the mixture of 6-naphthalene diformic acid dimethyl ester and 60 parts of ethylene glycol, slowly intensification on one side is warming up to 240 ℃ by 150 ℃, Yi Bian carry out ester exchange reaction.In the reaction way, when reaction temperature reaches 170 ℃, add 0.024 part of antimony trioxide, the average grain diameter of adding 0.15% weight again is the calcium carbonate granule of 0.5 μ m.When reaction temperature reaches 220 ℃, add 0.042 part of (being equivalent to 2mmol%) 3,5-dicarboxyl benzene sulfonic acid tetrabutyl microcosmic salt.Then carry out ester exchange reaction then, ester exchange reaction is added 0.023 part of trimethyl phosphate after stopping.Then product is transferred in the polymer reactor, be warming up to 290 ℃, under the high vacuum below the 0.2mmHg, carry out polycondensation reaction, the inherent viscosity that obtains measuring in 25 ℃ o-chlorphenol solution is the poly-2 of 0.63dl/g, 6-(ethylene naphthalate) polymer (being called " polymer A ").

Similarly carry out ester exchange reaction with polymer A, add 0.02 part of amorphism germanium dioxide, the average grain diameter of adding 0.05% weight again is that 0.1 μ m, size ratio are 1.1 spherical silicon dioxide particle, in addition, similarly carry out polymerization with polymer A, the inherent viscosity that obtains measuring in 25 ℃ o-chlorphenol solution is the poly-2 of 0.63dl/g, 6-(ethylene naphthalate) polymer (being called " polymer B ").

With each polymer 170 ℃ of dryings 6 hours, supply with 2 extruders then respectively, melting temperature fusion with 300 ℃, being expressed into surface smoothness with the slot-shaped mouthful mould of coetrusion by opening degree 1mm is that 0.3S, surface temperature are on 50 ℃ the going barrel, obtains the non-stretched film of 2 layers of formation.Similarly to Example 1, this film is carried out biaxial stretch-formed step by step, carrying out thermal finalization, is that 16 μ m (the polymer A layer is that 10 μ m/ polymer B layers are 6 μ m), inherent viscosity are that the biaxial orientation PEN film of 0.54dl/g is with the wide 3000m that batches of 1500mm with film thickness.Then similarly to Example 1, use same suspension type relaxation annealing device, gained biaxial orientation PEN film is carried out relaxation heat treatment.With the biaxial orientation PEN film after the relaxation heat treatment that obtains like this as embodiment 3.

The film characteristics evaluation result of gained embodiment is as shown in table 1.Particularly about the wafer process of these embodiment films, flatness etc. because of the hot change in size of film, film gauge variation or film can not take place, and to cause the misoperation of die Bonder device to produce bad, can carry out good pick-up operation.In addition, can not pollute tack coat and be coated with operation and semiconductor wafer manufacturing procedure, and film can be not damaged when stripping tape, the processability that semiconductor wafer is made is good.

Comparative example 1

" the カ プ ト Application that uses Dong Li Du Pont to make; The H type " 50 μ m films.

The evaluating characteristics result of film is as shown in table 1.The hot change in size of film is very excellent, but water absorption rate height, the therefore poor dimensional stability under high humility.

Comparative example 2

Add 0.03 part of manganese acetate 4 hydrate in the mixture of 100 parts of dimethyl terephthalate (DMT)s and 60 parts of ethylene glycol, slowly intensification on one side is warming up to 240 ℃ by 150 ℃, Yi Bian carry out ester exchange reaction.In the reaction way, when reaction temperature reaches 170 ℃, add 0.024 part of antimony trioxide, the average grain diameter of adding 0.2% weight again is that 0.4 μ m, size ratio are 1.1 spherical silicon dioxide particle.When reaction temperature reaches 220 ℃, add 0.042 part of (being equivalent to 2mmol%) 3,5-dicarboxyl benzene sulfonic acid tetrabutyl microcosmic salt.Then carry out ester exchange reaction then, ester exchange reaction is added 0.023 part of trimethyl phosphate after stopping.Then product is transferred in the polymer reactor, be warming up to 290 ℃, carry out polycondensation reaction under the high vacuum below the 0.2mmHg, the inherent viscosity that obtains measuring in 25 ℃ o-chlorphenol solution is the polyethylene terephthalate polymer of 0.62dl/g.This polymer 170 ℃ of dryings 3 hours, is supplied with extruder then,,, be expressed into surface smoothness and be 0.3S, surface temperature and be on 25 ℃ the going barrel, obtain non-stretched film by the slot-shaped mouthful of mould of opening degree 1mm with 290 ℃ of melting temperatures fusions.

The non-stretched film that obtains so vertically (is made the film direction) at 90 ℃ to stretch 3.2 times, then stretch 3.8 times at 120 ℃ horizontal (Width), handling 5 seconds and broad ways 210 ℃ of thermal finalizations again and shrink 5% (toe in), is that 16 μ m, inherent viscosity are that biaxial orientation polyethylene glycol terephthalate's film of 0.55dl/g is with the wide 3000m that batches of 1500mm with thickness.Then gained biaxial orientation polyethylene glycol terephthalate film is hung down downwards with deadweight via the niproll that is arranged at the top, heat by infrared heating device on the way therein, make the temperature of film become 180 ℃, niproll with 4m place under the roller up cools off then, change into the direction of approximate horizontal on one side, with batching behind the niproll partition coiling tension, carry out relaxation heat treatment.Relaxation is to make the niproll of top and the niproll of blocking coiling tension have speed difference.

Biaxial orientation polyethylene glycol terephthalate's film after the relaxation heat treatment that obtains like this is made as comparative example 2.

The film characteristics evaluation result of gained comparative example 2 is as shown in table 1.Its wafer process is: because of the poor dimensional stability of film, chip position skew etc. takes place, because of the misoperation of die Bonder device produces bad.In addition, the amount of separating out of oligomer reaches tack coat is coated with the degree that operation and semiconductor wafer manufacturing procedure pollute.In addition, on the film surface after the heating, the oligomer eduction rate is also high.

Comparative example 3

In the comparative example 3, the longitudinal stretching multiplying power is made as 3.6 times, the cross directional stretch multiplying power changes to 3.7 times, in addition repeats operation similarly to Example 2, and obtaining thickness is the biaxial orientation PEN film of 50 μ m.

Evaluating characteristics result to the film of resulting comparative example 3 is as shown in table 1.The hot change in size of film has all surpassed 1.00% at the film vertical and horizontal, and the position deviation of chip takes place in the wafer process aspect, because of the misoperation of die Bonder device produces bad.

Comparative example 4

In the comparative example 4, the longitudinal stretching multiplying power is made as 3.6 times, the cross directional stretch multiplying power changes to 3.9 times, in addition repeats operation similarly to Example 1, carries out the heat treatment of suspension type relaxation, and obtaining thickness is the biaxial orientation PEN film of 20 μ m.

The film characteristics evaluation result of gained comparative example 4 is as shown in table 1.The hot change in size of film vertically surpasses 1.00% at film; The deviation of chip position takes place in the wafer process aspect, because of the misoperation of die Bonder device produces bad.

[table 1]

				Embodiment 1	Embodiment 2	Embodiment 3		Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4
												Layer constitutes				Individual layer	Individual layer	Double-deck		Individual layer	Individual layer	Individual layer	Individual layer
Polymer				Polymer C	Polymer C	Polymer A	Polymer B	-	-	Polymer C	Polymer C
												Add particle	Kind			Spherical silicon dioxide	Spherical silicon dioxide	Calcium carbonate	Spherical silicon dioxide	-	Spherical silicon dioxide	Spherical silicon dioxide	Spherical silicon dioxide
	Particle diameter		μm	0.4	0.4	0.5	0.1	-	0.4	0.4	0.4
													Addition		% weight	0.20	0.20	0.15	0.05	-	0.20	0.20	0.20
Longitudinal stretching	Multiplying power		Doubly	3.3	2.9	3.3		-	3.2	3.6	3.6
													Temperature		℃	145	145	145		-	90	145	145
Cross directional stretch	Multiplying power		Doubly	3.4	3.1	3.1		-	3.8	3.7	3.9
													Temperature		℃	140	140	140		-	120	140	140
Heat setting temperature			℃	243	243	243		-	210	243	243
												The suspension type The pre-heat treatment temperature of speeding			℃	225	Be untreated	225		-	180	Be untreated	225
Thin module feature viscosity			dl/g	0.52	0.52	0.54		-	0.55	0.52	0.52
												Film thickness			μm	16	75	16		50	16	50	20
Thickness deviation			％	8	11	8		-	8	6	4
												Percent thermal shrinkage		Vertical (MD)	％	0.50	0.80	0.50		0.20	0.60	1.40	1.10
		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
		Horizontal (TD)	MPa	6200	5800	6200		3700	5250	6600	7000
												Surface roughness			nm	15	16	19	4	-	18	16	15
Density			g/cm 3	1.360	1.362	1.360		-	-	1.357	1.358
												The oligomer extracted amount			% weight	0.4	0.5	0.5		-	1.3	-	-
Heating oligomer eduction rate			％	○	○	○		-	×	-	-
												Water absorption rate			％	0.3	0.3	0.3		1.3	0.4	-	-
Dimensional stability			-	○	○	○		×	×	-	-
												Semiconductor wafer processability (grinding back surface and scribing)				Very	Very	Very		Very	Bad	Bad	Bad
Semiconductor wafer processability (grinding back surface and tape stripping)				Very	Very	Very		Very	Bad	Bad	Bad

Embodiment 4

To 100 part 2, add 0.03 part of manganese acetate 4 hydrate in the mixture of 6-naphthalene diformic acid dimethyl ester and 60 parts of ethylene glycol, slowly intensification on one side is warming up to 240 ℃ by 150 ℃, Yi Bian carry out ester exchange reaction.In the reaction way, when reaction temperature reaches 170 ℃, add 0.024 part of antimony trioxide, the average grain diameter of adding 0.1% weight again is that 0.6 μ m, size ratio are 1.1 spherical silicon dioxide particle.When reaction temperature reaches 220 ℃, add 0.042 part of (being equivalent to 2mmol%) 3,5-dicarboxyl benzene sulfonic acid tetrabutyl microcosmic salt.Then carry out ester exchange reaction then, ester exchange reaction is added 0.023 part of trimethyl phosphate after stopping.Then product is transferred in the polymer reactor, be warming up to 290 ℃, under the high vacuum below the 0.2mmHg, carry out polycondensation reaction, the inherent viscosity that obtains measuring in 25 ℃ o-chlorphenol solution is poly-2 of 0.43dl/g, 6-(ethylene naphthalate) polymer (polymer D) and inherent viscosity are the poly-2 of 0.69dl/g, 6-(ethylene naphthalate) polymer (polymer E).With polymer E solid polymerization, make the polymer that inherent viscosity is 0.78dl/g (polymer F) again.

Polymer E 170 ℃ of dryings 6 hours, is supplied with extruder then,,, be expressed into surface smoothness and be 0.3S, surface temperature and be on 50 ℃ the going barrel, obtain non-stretched film by the slot-shaped mouthful of mould of opening degree 1mm with 305 ℃ of melting temperatures fusions.

The non-stretched film that obtains so vertically (is made the film direction) at 145 ℃ to stretch 3.0 times, then stretch 3.0 times at 140 ℃ horizontal (Width), handling for 5 seconds and shrink 4% (toe in) in broad ways 246 ℃ of thermal finalizations again, is that 30 μ m, inherent viscosity are that the biaxial orientation PEN film of 0.59dl/g is with the wide 3000m that batches of 1500mm with thickness.Then resulting biaxial orientation PEN film is hung down downwards with deadweight via the niproll that is arranged at the top, heat with infrared heating device on the way therein, make the temperature of film become 225 ℃, use the niproll cooling at 4m place under the roller up then on one side, change into the direction of approximate horizontal on one side, with batching behind the niproll partition coiling tension, carry out relaxation heat treatment.Relaxation is to make the niproll of top and the niproll of blocking coiling tension have speed difference.

With the biaxial orientation PEN film after the relaxation heat treatment that obtains like this as embodiment 4.

Evaluating characteristics result to the film of resulting embodiment 4 is as shown in table 2.The wafer process of this embodiment film is: flatness etc. because of the hot change in size of film, film gauge variation or film can not take place, and to cause the misoperation of die Bonder device to produce bad, can carry out good pick-up operation.In addition, be coated with in operation and the semiconductor wafer manufacturing procedure at tack coat and can not pollute, and film can be damaged when stripping tape, the processability during semiconductor wafer is made is good.

Embodiment 5

Use polymer F in embodiment 4, in addition repeat operation similarly to Example 4, obtaining thickness is the biaxial orientation PEN film of 50 μ m.With the biaxial orientation PEN film that obtains like this as embodiment 5.

Evaluating characteristics result to the film of resulting embodiment 5 is as shown in table 2.The wafer process of this embodiment film is: flatness etc. because of the hot change in size of film, film gauge variation or film can not take place, and to cause the misoperation of die Bonder device to produce bad, can carry out good pick-up operation.In addition, be coated with in operation and the semiconductor wafer manufacturing procedure at tack coat and can not pollute, and film can be damaged when stripping tape, the processability during semiconductor wafer is made is good.

Embodiment 6

Among the embodiment 4,3.3 times of 145 ℃ of longitudinal stretchings, then 3.3 times of 140 ℃ of cross directional stretch, in addition repeat operation similarly to Example 4, obtaining thickness is the biaxial orientation PEN film of 30 μ m.With the biaxial orientation PEN film that obtains like this as embodiment 6.

The film characteristics evaluation result of gained embodiment is as shown in table 2.The wafer process of this embodiment film is: flatness etc. because of the hot change in size of film, film gauge variation or film can not take place, and to cause the misoperation of die Bonder device to produce bad, can carry out good pick-up operation.In addition, be coated with in operation and the semiconductor wafer manufacturing procedure at tack coat and can not pollute, and film can be damaged when stripping tape, the processability during semiconductor wafer is made is good.

Embodiment 7

Use polymer D in embodiment 4, in addition repeat operation similarly to Example 4, obtaining thickness is the biaxial orientation PEN film of 50 μ m.With the biaxial orientation PEN film that obtains like this as embodiment 7.

Evaluating characteristics result to the film of resulting embodiment 7 is as shown in table 2.The wafer process of this embodiment film is: flatness etc. because of the hot change in size of film, film gauge variation or film can not take place, and to cause the misoperation of die Bonder device to produce bad, can carry out good pick-up operation.On the other hand, separate out to film surface because of oligomer the in-process pollution has taken place.

Embodiment 8

In embodiment 6, the amount that makes the inert particle that contains in the film is 0.01% weight, heat setting temperature is decided to be 233 ℃ again, in addition repeats operation similarly to Example 6, and obtaining thickness is the biaxial orientation PEN film of 30 μ m.With the biaxial orientation PEN film that obtains like this as embodiment 8.

Evaluating characteristics result to the film of resulting embodiment 8 is as shown in table 2.The wafer process of this embodiment film is: though the hot change in size of film reduces, the thermal contraction rate variance of vertical and horizontal exceeds desirable scope, has some stability problems in the semiconductor wafer manufacturing.

Embodiment 9

Among the embodiment 4,,, in addition repeat operation similarly to Example 4, obtain the biaxial orientation PEN film of thickness 30 μ m then 2.7 times of 140 ℃ of cross directional stretch 2.7 times of 145 ℃ of longitudinal stretchings.With the biaxial orientation PEN film that obtains like this as embodiment 9.

The film characteristics evaluation result of resulting embodiment is as shown in table 2.The processability of this wafer is: though the hot change in size of film reduces, the refractive index height of film thickness direction has taken place to cut powder etc. because of film and has caused in-process to pollute or breakage of thin film applied during tape stripping.

[table 2]

					Embodiment 4	Embodiment 5	Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9
											Polymer					E	F	E	D	E	E
Polymer property viscosity			dl/g		0.69	0.78	0.69	0.43	0.69	0.69
											Add particle	Kind				Spherical silicon dioxide	Spherical silicon dioxide	Spherical silicon dioxide	Spherical silicon dioxide	Spherical silicon dioxide	Spherical silicon dioxide
	Particle diameter		μm		0.6	0.6	0.6	0.6	0.6	0.6
												Addition		% weight		0.1	0.1	0.1	0.1	0.01	0.1
Longitudinal stretching	Multiplying power		Doubly		3.0	3.0	3.3	3.0	3.3	2.7
												Temperature		℃		145	145	145	145	145	145
Cross directional stretch	Multiplying power		Doubly		3.0	3.0	3.3	3.0	3.3	2.7
												Temperature		℃		140	140	140	140	140	140
Heat setting temperature			℃		246	246	246	246	233	246
											The suspension type The pre-heat treatment temperature of speeding			℃		225	225	225	225	225	225
Thin module feature viscosity			dl/g		0.59	0.64	0.59	0.39	0.59	0.59
											Film thickness			μm		30	50	30	50	30	30
Thickness deviation			％		10	9	7	12	6	17
											The extracted amount of oligomer			% weight		0.5	0.3	0.4	1.0	0.4	0.5
The refractive index of thickness direction (nz)					1.508	1.510	1.503	1.505	1.499	1.518
											Percent thermal shrinkage		SMD		％	0.35	0.37	0.40	0.30	0.85	0.20
		STD		％	0.03	0.02	0.03	0.01	0.10	0.00
													Difference		％	0.32	0.35	0.37	0.29	0.75	0.20
Coefficient of friction				μd	0.4	0.3	0.3	0.4	0.6	0.4
											Density				g/cm 3	1.360	1.362	1.362	1.357	1.358	-
Semiconductor wafer processability (grinding back surface and scribing)					Very	Very	Very	Very	Common	Common
											Semiconductor wafer processability (grinding back surface and tape stripping)					Very	Very	Very	Bad	Bad	Bad

Claims (15)

1. base film for semiconductor wafer processing, this basement membrane is with poly-2, the 6-(ethylene naphthalate) is the biaxially oriented film of main component, it is characterized in that: the percent thermal shrinkage at 10 minutes rear films of 200 ℃ of heat treated is below 1.00% at the system film direction and the Width of film.

2. the base film for semiconductor wafer processing of claim 1, described basement membrane is used for grinding back surface adhesive tape or dicing tape.

3. the base film for semiconductor wafer processing of claim 1, wherein the amount of the extraction oligomer of film is below 0.8% weight, the refractive index of film thickness direction is more than 1.501, below 1.515.

4. each base film for semiconductor wafer processing among the claim 1-3, wherein the thickness deviation of film is below 15%.

5. each base film for semiconductor wafer processing among the claim 1-3, wherein the Young's modulus of film be 5400MPa above, below the 6900MPa.

6. each base film for semiconductor wafer processing among the claim 1-3, wherein the center line average surface rugosity of at least one face of film be 3nm above, below the 80nm.

7. each base film for semiconductor wafer processing among the claim 1-3, wherein the density of film is 1.356g/cm ³More than, 1.364g/cm ³Below.

8. each base film for semiconductor wafer processing among the claim 1-3, wherein the average thickness of film be 9 μ m above, below the 150 μ m.

9. each base film for semiconductor wafer processing among the claim 1-3, wherein the coefficient of kinetic friction of film is below 0.5.

10. each base film for semiconductor wafer processing among the claim 1-3, described basement membrane is at the percent thermal shrinkage of 10 minutes rear films of 200 ℃ of heat treated, is below 0.60% at the absolute value of the difference of the percent thermal shrinkage of the percent thermal shrinkage of the system film direction of film and Width.

11. each base film for semiconductor wafer processing among the claim 1-3, wherein film comprises the multilayer more than 2 layers.

12. the grinding back surface adhesive tape described in the claim 2 contains bond layer on the one face.

13. grinding back surface adhesive tape compound further comprises release film on the grinding back surface adhesive tape of claim 12.

14. the dicing tape described in the claim 2 contains bond layer on the one face.

15. the dicing tape compound further comprises release film on the dicing tape of claim 14.