WO2014126096A1 - Pressure-sensitive adhesive tape for use in semiconductor processing - Google Patents
Pressure-sensitive adhesive tape for use in semiconductor processing Download PDFInfo
- Publication number
- WO2014126096A1 WO2014126096A1 PCT/JP2014/053181 JP2014053181W WO2014126096A1 WO 2014126096 A1 WO2014126096 A1 WO 2014126096A1 JP 2014053181 W JP2014053181 W JP 2014053181W WO 2014126096 A1 WO2014126096 A1 WO 2014126096A1
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- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive layer
- adhesive tape
- semiconductor processing
- Prior art date
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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 an adhesive tape for semiconductor processing used for dicing a semiconductor wafer in a process of manufacturing a semiconductor device. More specifically, the present invention relates to an adhesive tape for semiconductor processing used for manufacturing a semiconductor element including a step of cleaning the surface of the semiconductor element using a chemical.
- a protective sheet a sheet obtained by applying an acrylic adhesive or the like on a base material made of a plastic film is generally used.
- the thickness of the semiconductor chip has been required to be 50 ⁇ m or less.
- the semiconductor wafer is formed only with the protective tape. The wafer cannot be supported, and the semiconductor wafer is warped after grinding, or is bent when stored in a wafer cassette, making it difficult to handle the semiconductor wafer and making handling and conveyance automated.
- a method has been proposed in which a glass substrate, a ceramic substrate, a silicon wafer substrate, or the like is bonded to a semiconductor wafer via an adhesive to provide support to the semiconductor wafer (see, for example, Patent Document 1). .
- a support member such as a glass substrate, a ceramic substrate, or a silicon wafer substrate instead of the protective sheet, the handling property of the semiconductor wafer is greatly improved, and the conveyance can be automated.
- the support member is peeled by (1) dissolving or decomposing the adhesive between the support member and the semiconductor wafer with chemicals, and (2) irradiating the adhesive between the support member and the semiconductor wafer with laser light. In general, it is carried out by a method such as photolysis.
- the method (1) requires a long time for diffusing chemicals in the adhesive
- the method (2) requires a long time for laser scanning. There was a problem.
- each method has a problem that it is necessary to prepare a special substrate as a support member.
- the semiconductor wafer whose back surface has been ground is then transferred to a dicing process and cut into individual chips.
- the semiconductor wafer alone is the one after grinding. Since the semiconductor wafer becomes extremely difficult to handle due to warpage of the semiconductor wafer and bending when stored in the wafer cassette, the ground surface of the semiconductor wafer immediately before the back surface grinding of the semiconductor wafer prior to peeling of the support member.
- a dicing tape is bonded to the ring frame and supported and fixed to the ring frame. Therefore, the cleaning of the adhesive residue on the semiconductor wafer caused by the peeling of the support member with the chemical is performed in a state where the semiconductor wafer is adhered to the dicing tape, and the dicing tape has high solvent resistance. Desired.
- the pressure-sensitive adhesive layer contains an energy ray-curable acrylic resin composition and has a gel fraction of 70% or more (see, for example, Patent Document 4). .
- the present invention is a dicing tape having adhesive strength that can suppress chip jumping at the time of dicing and easy peeling at the time of pick-up, and in the manufacturing process of a semiconductor element using the support member, the support member To provide an adhesive tape for semiconductor processing in which the adhesive does not dissolve and contaminate the semiconductor element even when the cleaning liquid for cleaning the adhesive residue bonded to the semiconductor wafer is applied to the adhesive. With the goal.
- the inventors of the present invention are pressure-sensitive adhesive tapes for semiconductor processing having a pressure-sensitive adhesive layer on a base resin film, and methyl isobutyl ketone for the pressure-sensitive adhesive layer. It was found that by setting the contact angle to a specific value, the adhesive does not dissolve and contaminate the semiconductor element even when the cleaning liquid is applied to the adhesive. The present invention has been made based on this finding.
- the semiconductor processing pressure-sensitive adhesive tape according to the present invention is a pressure-sensitive adhesive tape for semiconductor processing in which a radiation-curable pressure-sensitive adhesive layer is formed on at least one surface of a base resin film, and before the pressure-sensitive adhesive layer is irradiated with ultraviolet rays.
- the contact angle with respect to methyl isobutyl ketone is 25.1 ° to 60 °.
- the pressure-sensitive adhesive layer contains silicon acrylate or a fluorine-containing oligomer, and the content of the silicon acrylate or fluorine-containing oligomer is more than 0% by mass and more than 5% by mass with respect to the total solid content of the pressure-sensitive adhesive layer. Less is preferred.
- the above-mentioned pressure-sensitive adhesive tape for semiconductor processing preferably has a gel fraction of 65% or more and 100% or less with respect to the methyl isobutyl ketone before irradiation of the pressure-sensitive adhesive layer.
- the above-mentioned pressure-sensitive adhesive tape for semiconductor processing preferably has a peak value in a probe tack test of 200 to 600 kPa before the radiation-curable pressure-sensitive adhesive layer is irradiated with ultraviolet rays.
- the pressure-sensitive adhesive tape for semiconductor processing is a pressure-sensitive adhesive tape for semiconductor processing in which a radiation-curable pressure-sensitive adhesive layer is formed on at least one surface of a base resin film, and provides support to a semiconductor wafer. UV irradiation of the pressure-sensitive adhesive layer with respect to chemicals used for cleaning the adhesive residue on the semiconductor wafer generated when the support member bonded to the semiconductor wafer via an adhesive is peeled
- the front contact angle is preferably 25 ° or more and smaller than 180 °.
- the support member can be used as a semiconductor wafer in the manufacturing process of a semiconductor element that has an adhesive strength that can suppress chip jumping during dicing and an easy peelability during pick-up. Even when the cleaning liquid for cleaning the adhesive residue bonded to the adhesive is applied to the adhesive, the adhesive does not dissolve and contaminates the semiconductor element.
- At least one adhesive layer is formed on at least one side of the base resin film.
- the contact angle of the pressure-sensitive adhesive layer with respect to methyl isobutyl ketone is 25 ° or more, preferably 28 ° or more, more preferably 30 ° or more. More preferably, the contact angle of the pressure-sensitive adhesive layer with respect to methyl isobutyl ketone is 25.1 ° to 60 °, and more preferably 25.1 ° to 54 °.
- the cleaning of the adhesive residue on the semiconductor wafer caused by the peeling of the support member with chemicals is performed from above the semiconductor wafer while spinning the semiconductor wafer attached to the ring frame via the dicing tape.
- the chemical is sprayed in a shower-like manner, and the chemical droplets are discharged radially from the central portion of the rotating semiconductor wafer by centrifugal force.
- the contact angle of the pressure-sensitive adhesive layer to methyl isobutyl ketone is 25 ° or more, the wettability of methyl isobutyl ketone to the pressure-sensitive adhesive layer is low, and the contact area between the pressure-sensitive adhesive layer and methyl isobutyl ketone is reduced. Since the chemical droplets can be discharged efficiently, the adhesive layer has less dissolving action from methyl isobutyl ketone, and the adhesive tape for semiconductor processing may be exposed to chemicals such as methyl isobutyl ketone and its derivatives.
- the adhesive does not melt and the semiconductor chip is not contaminated by the chemical.
- the contact angle is smaller than 25 °, the wettability of methyl isobutyl ketone to the pressure-sensitive adhesive layer is high, the contact area between the pressure-sensitive adhesive layer and methyl isobutyl ketone is increased, and the pressure-sensitive adhesive layer has a dissolving action received from methyl isobutyl ketone.
- the adhesive melted by the chemicals contaminates the semiconductor chip.
- the contact angle with respect to the methyl isobutyl ketone of the adhesive layer surface means the contact angle immediately after the contact of the adhesive layer surface and methyl isobutyl ketone.
- This contact angle is a value measured at a temperature of 23 ° C. and a humidity of 50%. The measurement can be performed using a commercially available contact angle measuring device.
- the contact angle with respect to the methyl isobutyl ketone of the adhesive layer surface in this invention shall be measured about the adhesive layer before radiation irradiation.
- the gel fraction of methyl isobutyl ketone before irradiation of the pressure-sensitive adhesive layer is preferably 65% or more and 100% or less.
- the contact angle of the pressure-sensitive adhesive layer with respect to methyl isobutyl ketone is 25 ° or more and the gel fraction is 65% or more and 100% or less, adhesive residue on the semiconductor wafer generated when the support member is peeled off
- the adhesive melts due to the above chemicals.
- the semiconductor chip is not contaminated.
- the gel fraction means the ratio of the crosslinked pressure-sensitive adhesive component excluding the cross-linked component in the pressure-sensitive adhesive layer. The method described below was used for calculation of the gel fraction.
- the gel fraction is a state where the pressure-sensitive adhesive layer surface is protected by a separator or the like immediately after the pressure-sensitive adhesive layer is formed, and is measured for the pressure-sensitive adhesive layer before irradiation with energy rays.
- the peak value of the probe tack test before the irradiation of the adhesive layer is 200 to 600 kPa. If the peak value of the probe tack test is too small, the adhesion of the pressure-sensitive adhesive layer to the adherend is insufficient, and the support member is bonded to the semiconductor wafer via an adhesive in order to provide support to the semiconductor wafer. When peeling off, it peels between a semiconductor wafer and an adhesive tape, and it becomes difficult to peel a support member from a semiconductor wafer. If the peak value of the probe tack test is too large, glue residue that adheres to the adhesive layer residue on the chips picked up by dividing the semiconductor wafer, or chipping due to contact between the chips when picking up the chips may occur. It becomes easy. The method described below is used for the probe tack measurement.
- the probe tack is measured by using, for example, a tacking tester TAC-II manufactured by Resuka Corporation.
- Constant Load is used in which the probe is pushed down to the set pressurization value and controlled to hold the pressurization value until the set time elapses.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape is turned up, and a probe made of SUS304 having a diameter of 3.0 mm is brought into contact with the upper side.
- the speed at which the probe is brought into contact with the measurement sample is 30 mm / min, the contact load is 100 gf, and the contact time is 1 second.
- the probe is peeled upward at a peeling speed of 600 mm / min, and the force required for peeling is measured.
- the probe temperature is 23 ° C.
- the plate temperature is 23 ° C.
- Base resin film As the base resin film, when UV is used as the radiation for curing the pressure-sensitive adhesive layer, the base resin film needs to be light transmissive, but when using an electron beam as the radiation, the base resin The film does not necessarily have to be light transmissive.
- Materials constituting the base resin film include polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, and polybutene, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, and ethylene- (Meth) acrylic acid ester copolymer such as ethylene copolymer, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polymethyl methacrylate engineering plastics, soft polyvinyl chloride, semi-rigid polyvinyl chloride, polyester, polyurethane, Polymer materials such as polyamide, polyimide natural rubber and synthetic rubber are preferred.
- polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, and polybutene
- ethylene-vinyl acetate copolymer ethylene- (meth) acrylic acid copolymer
- ethylene- (Meth) acrylic acid ester copolymer such as
- the base resin film is a film using an ionomer of an ethylene-acrylic acid copolymer.
- the thickness of the base resin film is not particularly limited, but is preferably 10 to 500 ⁇ m, more preferably 40 to 400 ⁇ m, and particularly preferably 70 to 250 ⁇ m.
- the surface of the base resin film that contacts the pressure-sensitive adhesive layer may be subjected to corona treatment or treatment with a primer or the like in order to improve adhesion.
- the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is an ultraviolet curable pressure-sensitive adhesive, and there is no particular limitation as long as the contact angle with respect to methyl isobutyl ketone before ultraviolet irradiation on the surface of the pressure-sensitive adhesive layer is 25 ° or more and is smaller than 180 °. And can be appropriately selected from conventionally known pressure-sensitive adhesives.
- rubber adhesive using natural rubber or synthetic rubber acrylic adhesive using poly (meth) acrylic acid alkyl ester or copolymer of (meth) acrylic acid alkyl ester and other monomers, etc.
- General pressure-sensitive adhesives such as polyurethane pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, and polycarbonate-based pressure-sensitive adhesives can be used, and UV curable resins such as UV-curable monomer components and oligomer components are blended with these general pressure-sensitive adhesives.
- the UV-curable monomer component When a carbon-carbon double bond-introduced acrylic polymer having a carbon-carbon double bond in the polymer side chain or in the main chain or at the end of the main chain is used as the base polymer, the UV-curable monomer component or It is not necessary to add an ultraviolet curable resin such as an oligomer component.
- acrylic using poly (meth) acrylic acid ester or a copolymer of (meth) acrylic acid ester and other monomers (hereinafter collectively referred to as acrylic polymer). System adhesives are preferred.
- examples of the (meth) acrylic acid ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) Butyl acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate
- the method for producing the acrylic polymer is not particularly limited, but may be used to increase the weight average molecular weight with a crosslinking agent or introduce an ultraviolet curable carbon-carbon double bond by a condensation reaction or an addition reaction. It preferably has a functional group such as a carboxyl group or a glycidyl group.
- an ultraviolet curable carbon-carbon double bond into an acrylic polymer is carried out by copolymerizing an acrylic polymer component and a monomer having a functional group to prepare an acrylic polymer having a functional group.
- a compound having a functional group capable of reacting with a functional group in an acrylic polymer having a carbon-carbon double bond is converted into an acrylic polymer having a functional group by ultraviolet curing of the carbon-carbon double bond (ultraviolet polymerizable). It can be prepared by carrying out a condensation reaction or an addition reaction while maintaining the above.
- the acrylic polymer having a functional group can be copolymerized with a constituent (meth) acrylic acid ester, and a monomer having a functional group such as a hydroxyl group, a carboxyl group, or a glycidyl group (copolymerizable monomer) is copolymerized. It can be obtained by polymerization.
- Monomers that can be copolymerized with (meth) acrylic acid esters and have a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (methacrylate).
- Acrylate 6-hydroxyhexyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate and the like.
- a monomer that can be copolymerized with (meth) acrylic acid ester and has a carboxyl group (meth) acrylic acid (acrylic acid, methacrylic acid), itaconic acid, maleic acid, fumaric acid, crotonic acid, And isocrotonic acid.
- Examples of the monomer that can be copolymerized with (meth) acrylic acid ester and have a glycidyl group include glycidyl (meth) acrylate.
- the compound having a functional group capable of reacting with a functional group and a carbon-carbon double bond includes 2-isocyanatoethyl (meth) acrylate when the functional group to be subjected to condensation reaction or addition reaction is a hydroxyl group. 1,1- (bisacryloyloxymethyl) ethyl isocyanate and the like.
- the functional group to be subjected to the condensation reaction or addition reaction is a carboxyl group
- glycidyl methacrylate, allyl glycidyl ether and the like can be mentioned.
- unsaturated carboxylic acids such as (meth) acrylic acid and the like can be mentioned.
- the acrylic polymer preferably has a low content of low molecular weight substances from the viewpoint of preventing contamination of workpieces such as semiconductor devices.
- the weight average molecular weight of the acrylic polymer is preferably 100,000 or more, and more preferably 200,000 to 2,000,000. If the weight average molecular weight of the acrylic polymer is too small, the anti-contamination property to the workpiece such as a semiconductor device is lowered, and if too large, the viscosity of the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 5 becomes extremely high, Production of the adhesive tape 1 becomes difficult.
- the acrylic polymer preferably has a glass transition point of ⁇ 70 ° C. to 0 ° C., more preferably ⁇ 65 ° C. to ⁇ 20 ° C., from the viewpoint of developing adhesiveness. If the glass transition point is too low, the viscosity of the polymer becomes low and it becomes difficult to form a stable coating film. If the glass transition point is too high, the pressure-sensitive adhesive becomes hard and the wettability to the adherend deteriorates.
- the acrylic polymer may be used alone or in combination of two or more acrylic polymers as long as compatibility is allowed.
- the ultraviolet curable resin used in the pressure-sensitive adhesive layer by blending with a general pressure-sensitive adhesive is not particularly limited, but examples include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, poly Examples thereof include oligomers having a functional group such as a hydroxyl group or a carboxyl group such as ether (meth) acrylate, (meth) acrylic acid oligomer and itaconic acid oligomer.
- a photopolymerization initiator can be blended in the pressure-sensitive adhesive used in the present invention.
- the photopolymerization initiator include isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthioxanthone, diethylthioxanthone, benzyldimethylketanol, ⁇ -hydroxycyclohexyl phenyl ketone, 2-hydroxymethylphenol.
- Examples include enilpropane.
- the addition amount of the photopolymerization initiator is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the ultraviolet curable resin.
- the carbon-carbon double bond-introduced acrylic The amount is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer.
- the pressure-sensitive adhesive used in the present invention can be blended with a tackifier, a pressure-adjusting agent, a surfactant, or other modifiers as necessary.
- the tackiness of the pressure-sensitive adhesive layer 5 can be appropriately controlled by controlling the crosslinking density of the pressure-sensitive adhesive material.
- Control of the cross-linking density of the adhesive material can be achieved through an appropriate cross-linking agent such as a polyfunctional isocyanate compound, epoxy compound, melamine compound, metal salt compound, metal chelate compound, amino resin compound or peroxide.
- an appropriate method such as a method of crosslinking treatment or a method of mixing a compound having two or more carbon-carbon double bonds and crosslinking treatment by irradiation with energy rays.
- the contact angle of the pressure-sensitive adhesive layer 5 with respect to methyl isobutyl ketone on the surface of the pressure-sensitive adhesive layer 5 before irradiation with ultraviolet light can be adjusted by adjusting the comonomer ratio of the acrylic polymer and adding a silicone resin, a fluororesin or the like as an additive. is there. It is also possible to combine these with adjustment based on the number average molecular weight of the ultraviolet curable resin.
- a (meth) acrylic acid alkyl ester having an alkyl chain having 4 or more carbon atoms more preferably a (meth) acrylic acid alkyl ester having an alkyl chain having 8 or more carbon atoms is used.
- the (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl chain, more preferably 8 or more carbon atoms in the alkyl chain is contained in an amount of 50% by mass or more based on the entire comonomer.
- a silicon-modified acrylate can be used, and as the fluororesin, a fluorine-containing oligomer can be used.
- a silicon-modified acrylate can be preferably used.
- the thickness of the pressure-sensitive adhesive layer is preferably 5 ⁇ m or more and 70 ⁇ m or less, more preferably 8 ⁇ m or more and 50 ⁇ m or less, and further preferably 10 ⁇ m or more and 30 ⁇ m or less. If the pressure-sensitive adhesive layer is too thin, it will not be able to follow the unevenness of the electrode, causing the problem that cutting water and cutting waste will enter during dicing, and conversely if it is too thick, chipping will increase during dicing. The quality of the element deteriorates.
- the energy ray for curing the pressure-sensitive adhesive layer is preferably radiation, and examples of the radiation include light rays such as ultraviolet rays (UV), electron beams, and the like.
- UV ultraviolet rays
- electron beams and the like.
- the method for forming the pressure-sensitive adhesive layer on the base resin film is not particularly limited.
- the above-mentioned acrylic resin composition can be formed by applying and drying the base resin film on a base resin film by a commonly used coating method. It can produce by sticking the adhesive layer apply
- a synthetic resin film that is usually used as a separator for protecting the pressure-sensitive adhesive layer may be attached to the pressure-sensitive adhesive layer side until it is put to practical use.
- the constituent material of the synthetic resin film include synthetic resin films such as polyethylene, polypropylene, and polyethylene terephthalate, and paper.
- the surface of the synthetic resin film may be subjected to release treatment such as silicone treatment, long-chain alkyl treatment, fluorine treatment, etc., as necessary, in order to enhance the peelability from the pressure-sensitive adhesive layer 3.
- the thickness of the synthetic resin film is usually about 10 to 100 ⁇ m, preferably about 25 to 50 ⁇ m.
- the support member is made of a material selected from the group consisting of silicon, sapphire, crystal, metal (eg, aluminum, copper, steel), various glasses and ceramics.
- the surface of the support member to which the adhesive is applied can also include other deposited materials. For example, it is possible to deposit silicon nitride on a silicon wafer, thereby changing the bonding characteristics.
- the support member may be separated between the circuit formation surface of the semiconductor wafer and the plasma polymer separation layer.
- a bead portion that is raised one step at the periphery may be formed. In this case, it is preferable to remove the bead portion with a solvent before the adhesive liquid is pre-dried.
- Adhesive As the adhesive, a commercially available adhesive can be used in the present invention.
- WaferBONDTM material WaferBONDTM HT 10.10 for slide bonding process, WaferBONDTM CR200 for chemical bonding process
- Brewer Sciences Roller, Missouri
- ELASTOSIL LR a Berghausen material made by WACKER. 3070 etc.
- resins or polymers that exhibit high adhesion to semiconductor materials, glass or metals, and particularly preferred are, for example, (a) UV curable resins such as reactive epoxies and acrylics at high solids, (B) Thermosetting resins of the same family such as two-part epoxy or silicone adhesives, (c) Thermoplastic acrylic resins, styrene resins, vinyl halide (fluorine-free) resins or vinyl ester polymers And the copolymers are coated with polyamides, polyimides, polysulfones, polyethersulfones, or polyurethanes in a molten state or as a solution coating, and dried by baking after coating to form the support member and the semiconductor wafer. Further, (d) cyclic olefins and polyolefin rubbers (for example, polyisobutylene) Or (e) tackifying resins which is based on hydrocarbons.
- UV curable resins such as reactive epoxie
- the adhesive water is used at the time of polishing, so a water-insoluble polymer compound is preferable, and a high softening point is desirable.
- a high molecular compound a novolac resin, an epoxy resin, an amide resin, a silicon resin, an acrylic resin, a urethane resin, polystyrene, polyvinyl ether, polyvinyl acetate, a modified product thereof, or a mixture thereof is dissolved in a solvent.
- the acrylic resin material is preferable because it has a heat resistance of 200 ° C. or higher, generates less gas, and hardly generates cracks.
- novolak resin has no scum and is inferior to acrylic resin material in terms of heat resistance, amount of generated gas, and generation of cracks, but is preferable in terms of high softening point and easy peeling of the solvent after bonding.
- a plasticizer may be mixed to prevent cracks during film formation.
- the solvent is preferably one that can dissolve the above resin and can form a film uniformly on the wafer, such as ketones (for example, acetone, methyl ethyl ketone, cyclohexane, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, etc.), many Monohydric alcohols or derivatives thereof (for example, ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate or their monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether) Etc.), cyclic ethers (eg, dioxane), esters (eg, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, Methyl bottles, ethyl pyruvate, methyl meth
- an activator may be added thereto.
- a cleaning liquid for removing the adhesive residue remaining on the semiconductor wafer 1 after peeling the adhesive and the support member from the semiconductor wafer in addition to the organic solvent used for the adhesive, monohydric alcohols (for example, , Methanol, ethanol, propanol, isopropanol, butanol, etc.), lactones (eg, ⁇ -butyrolactone, etc.), lactams (eg, ⁇ -butyrolactam, etc.), ethers (eg, diethyl ether, anisole, etc.), aldehydes ( For example, dimethylformaldehyde, dimethylacetaldehyde, etc.) may be used. Of these, the aforementioned ketones or derivatives thereof are particularly preferable.
- monohydric alcohols for example, , Methanol, ethanol, propanol, isopropanol, butanol, etc.
- lactones eg, ⁇ -butyrolactone, etc.
- lactams
- Example 1 Methyl acrylate, 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate were copolymerized at a ratio of 5: 14: 1 in ethyl acetate by a conventional method to obtain a solution containing an acrylic polymer.
- an ultraviolet curable oligomer obtained by reacting a solution containing the acrylic polymer with pentaerythritol triacrylate and diisocyanate as an ultraviolet curable compound, and Irgacure 651 (trade name, BASF) 2.5 parts by weight, 1.0 parts by weight of trimethylolpropane-modified tolylene diisocyanate as a polyisocyanate compound, and 0.15 parts by weight of silicon-modified acrylate are added to form a radiation curable adhesive.
- a resin composition was prepared.
- This resin composition was applied onto a release treatment surface of a polyethylene terephthalate separator that had been subjected to a release treatment in advance so that the thickness of the pressure-sensitive adhesive layer after drying was 10 ⁇ m, and was dried at 80 ° C. for 10 minutes. Then, the adhesive tape for semiconductor processing was produced by pasting together with the corona treatment surface of the low density polyethylene by which the surface was previously corona-treated, and transferring an adhesive to a base resin film.
- Example 2 A semiconductor processing pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that 0.77 parts by mass of silicon-modified acrylate was blended.
- Example 3 A semiconductor processing adhesive tape was prepared in the same manner as in Example 1 except that 8.08 parts by mass of silicon-modified acrylate was blended.
- Example 4 The photopolymerizable carbon-carbon duplex is bonded to the 3-hydroxypropyl acrylate side chain terminal OH group of a copolymer of 2-ethylhexyl acrylate (70 mol%), methacrylic acid (1 mol%), and 2-hydroxypropyl acrylate (29 mol%).
- a compound having a bond and a functional group an acrylic compound (A1: molecular weight 700000) having a photopolymerizable carbon-carbon double bond obtained by addition reaction of the NCO group of 2-methacryloyloxyethyl isocyanate was obtained.
- this compound (A1) 1 part by mass of trimethylolpropane-modified hexamethylene diisocyanate as polyisocyanate and 5.0 parts by mass of Irgacure 184 (trade name, manufactured by BASF) as a photopolymerization initiator were added.
- a resin composition that was a radiation-curable adhesive was prepared. This resin composition was applied onto a release treatment surface of a polyethylene terephthalate separator that had been subjected to a release treatment in advance so that the thickness of the pressure-sensitive adhesive layer after drying was 10 ⁇ m, and was dried at 80 ° C. for 10 minutes. Then, the adhesive tape for semiconductor processing was produced by pasting together with the corona treatment surface of the low density polyethylene by which the surface was previously corona-treated, and transferring an adhesive to a base resin film.
- Example 5 An adhesive tape for semiconductor processing was produced in the same manner as in Example 4 except that 0.11 part by mass of silicon-modified acrylate was blended.
- Example 6 A semiconductor processing pressure-sensitive adhesive tape was produced in the same manner as in Example 4 except that 0.53 parts by mass of silicon-modified acrylate was blended.
- Example 7 A semiconductor processing pressure-sensitive adhesive tape was produced in the same manner as in Example 4 except that 5.58 parts by mass of silicon-modified acrylate was blended.
- Example 8 A semiconductor processing pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that 0.15 parts by mass of the fluorine-containing oligomer was blended.
- Example 9 Ethyl acrylate, butyl acrylate, and 2-hydroxyethyl acrylate were copolymerized at a ratio of 10: 9: 1 by an ordinary method in ethyl acetate to obtain a solution containing an acrylic polymer.
- an ultraviolet curable oligomer obtained by reacting a solution containing the acrylic polymer with pentaerythritol triacrylate and diisocyanate as an ultraviolet curable compound, and Irgacure 651 (trade name, BASF) 2.5 parts by mass, 1.0 parts by mass of trimethylolpropane-modified tolylene diisocyanate as a polyisocyanate compound, and 0.31 parts by mass of silicon-modified acrylate are added to form a radiation curable adhesive.
- a resin composition was prepared.
- This resin composition was applied onto a release treatment surface of a polyethylene terephthalate separator that had been subjected to a release treatment in advance so that the thickness of the pressure-sensitive adhesive layer after drying was 10 ⁇ m, and was dried at 80 ° C. for 10 minutes. Then, the adhesive tape for semiconductor processing was produced by pasting together with the corona treatment surface of the low density polyethylene by which the surface was previously corona-treated, and transferring an adhesive to a base resin film.
- Example 10 A semiconductor processing pressure-sensitive adhesive tape was produced in the same manner as in Example 9, except that 0.77 parts by mass of silicon-modified acrylate was blended.
- Example 11 A pressure-sensitive adhesive tape for semiconductor processing was prepared in the same manner as in Example 4 except that 0.1 part by mass of trimethylolpropane-modified hexamethylene diisocyanate was added as a polyisocyanate.
- Example 1 A semiconductor processing adhesive tape was prepared in the same manner as in Example 1 except that the silicon-modified acrylate was not blended.
- Example 2 A semiconductor processing pressure-sensitive adhesive tape was produced in the same manner as in Example 9 except that 0.15 parts by mass of silicon-modified acrylate was blended.
- ⁇ Probe tack> This was carried out using a TAC-II tacking tester manufactured by Leska.
- Constant Load was used in which the probe was pushed down to the set pressure value and kept controlled until the set time passed.
- the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape for semiconductor processing was turned up, and a probe made of SUS304 having a diameter of 3.0 mm was brought into contact from above.
- the speed at which the probe is brought into contact with the measurement sample is 30 mm / min
- the contact load is 100 gf
- the contact time is 1 second.
- the probe was peeled upward at a peeling speed of 600 mm / min, the force required for peeling was measured, and the peak value was read.
- the probe temperature was 23 ° C. and the plate temperature was 23 ° C.
- ⁇ Gel fraction> The separator was removed from the semiconductor processing adhesive tape cut to a size of 50 mm ⁇ 50 mm, and its mass A was weighed. Next, this weighed sample of the dicing tape for semiconductor processing was left for 48 hours in a state immersed in 100 g of methyl isobutyl ketone (MIBK), and then dried in a constant temperature layer at 50 ° C., and its mass B was weighed. Further, the pressure-sensitive adhesive layer of the sample was wiped off using 100 g of ethyl acetate, and then the mass C of the sample was weighed, and the gel fraction was calculated by the following formula (1).
- MIBK methyl isobutyl ketone
- ⁇ Solvent resistance 1> After bonding the adhesive tape for semiconductor processing obtained in Examples and Comparative Examples to an 8-inch semiconductor wafer and fixing it to the ring frame, while spraying methyl isobutyl ketone (MIBK) as an organic solvent from the semiconductor wafer side, Spin cleaning was performed by rotating at 20 rpm. After cleaning and drying, observe the adhesive layer in the area where the semiconductor wafer of the dicing tape for semiconductor processing is not affixed. If the adhesive was not dissolved or swollen, ⁇ , and some adhesives were swollen.
- MIBK methyl isobutyl ketone
- a plasma polymer separation layer, a silicone rubber adhesive layer, and a support member are formed on a 6-inch silicon wafer having a thickness of about 700 ⁇ m.
- a structure 1 in which 2.5 mm glass plates were sequentially laminated was obtained.
- the adhesive tape for semiconductor processing obtained in Examples and Comparative Examples is bonded to the rear surface of the wafer (the surface on which the plasma polymer separation layer or the like is not laminated) of the structure 1 obtained as described above, and is placed on the ring frame. After fixing, the support member was evaluated for peelability by use of Des-Bonder DB12T manufactured by Suss.
- the support member can be removed from the surface of the wafer, and a material acceptable for practical use is marked as ⁇ , and it is determined to be acceptable, and the wafer back surface and the adhesive tape for semiconductor processing are not peeled off between the plasma polymer separation layer of the support member and the wafer surface. And the support member could not be removed from the wafer surface was evaluated as x.
- Examples 1 to 11 in which the contact angle of the pressure-sensitive adhesive layer with respect to methyl isobutyl ketone before ultraviolet irradiation was 25.1 ° or more and smaller than 180 ° (60 ° or less) It is a pass judgment in the evaluation item of the solvent resistance, and can be used practically without any problem in the production of a semiconductor element including a step of cleaning the surface of the semiconductor element using a chemical.
- the pressure-sensitive adhesive layer was able to improve solvent resistance by containing silicon acrylate or a fluorine-containing oligomer.
Abstract
Description
50mm×50mmの大きさにカットした半導体加工用粘着テープから、セパレータを除去し、その質量Aを秤量した。次にこの秤量した半導体加工用粘着テープのサンプルを例えばメチルイソブチルケトン(MIBK)100g中に浸漬した状態で48時間放置した後、50℃の恒温層で乾燥し、その質量Bを秤量した。更に100gの酢酸エチルを用いてサンプルの粘着剤層を拭き取り除去した後、サンプルの質量Cを秤量し、下記式(1)によりゲル分率を算出した。
(Calculation of gel fraction)
The separator was removed from the semiconductor processing adhesive tape cut to a size of 50 mm × 50 mm, and its mass A was weighed. Next, this weighed sample of the adhesive tape for semiconductor processing was allowed to stand for 48 hours in a state immersed in, for example, 100 g of methyl isobutyl ketone (MIBK), and then dried in a constant temperature layer at 50 ° C., and its mass B was weighed. Further, the pressure-sensitive adhesive layer of the sample was wiped off using 100 g of ethyl acetate, and then the mass C of the sample was weighed, and the gel fraction was calculated by the following formula (1).
プローブタックの測定は、例えば株式会社レスカのタッキング試験機TAC-IIを用いて行う。測定モードは、設定した加圧値までプローブを押し込み、設定した時間が経過するまで加圧値を保持するようにコントロールし続けるConstant Loadを用いる。セパレータを剥離した後、粘着テープの粘着剤層を上にし、上側より直径3.0mmのSUS304製のプローブを接触させる。プローブを測定試料に接触させる時のスピードは30mm/minであり、接触荷重は100gfであり、接触時間は1秒である。その後、プローブを600mm/minの剥離速度で上方に引き剥がし、引き剥がすのに要する力を測定する。プローブ温度は23℃であり、プレート温度は23℃とする。 (Measurement of probe tack)
The probe tack is measured by using, for example, a tacking tester TAC-II manufactured by Resuka Corporation. In the measurement mode, Constant Load is used in which the probe is pushed down to the set pressurization value and controlled to hold the pressurization value until the set time elapses. After peeling the separator, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape is turned up, and a probe made of SUS304 having a diameter of 3.0 mm is brought into contact with the upper side. The speed at which the probe is brought into contact with the measurement sample is 30 mm / min, the contact load is 100 gf, and the contact time is 1 second. Thereafter, the probe is peeled upward at a peeling speed of 600 mm / min, and the force required for peeling is measured. The probe temperature is 23 ° C., and the plate temperature is 23 ° C.
基材樹脂フィルムとしては、粘着剤層を硬化させる放射線としてUVを用いる場合には基材樹脂フィルムは光透過性であることが必要であるが、放射線として電子線を用いる場合には基材樹脂フィルムは必ずしも光透過性である必要はない。基材樹脂フィルムを構成する材料としては、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、およびポリブテンのようなポリオレフィン、エチレン-酢酸ビニル共重合体、エチレン-(メタ)アクリル酸共重合体およびエチレン-(メタ)アクリル酸エステル共重合体のようなエチレン共重合体、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート、ポリメタクリル酸メチル等のエンジニアリングプラスチック、軟質ポリ塩化ビニル、半硬質ポリ塩化ビニル、ポリエステル、ポリウレタン、ポリアミド、ポリイミド天然ゴムならびに合成ゴムなどの高分子材料が好ましい。またこれらの群から選ばれる2種以上が混合されたものもしくは複層化されたものでもよく、粘着剤層との接着性によって任意に選択することができる。基材樹脂フィルムとしては、エチレン-アクリル酸共重合体のアイオノマーを用いてなるフィルムであることがさらに好ましい。 (Base resin film)
As the base resin film, when UV is used as the radiation for curing the pressure-sensitive adhesive layer, the base resin film needs to be light transmissive, but when using an electron beam as the radiation, the base resin The film does not necessarily have to be light transmissive. Materials constituting the base resin film include polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, and polybutene, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, and ethylene- (Meth) acrylic acid ester copolymer such as ethylene copolymer, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polymethyl methacrylate engineering plastics, soft polyvinyl chloride, semi-rigid polyvinyl chloride, polyester, polyurethane, Polymer materials such as polyamide, polyimide natural rubber and synthetic rubber are preferred. Moreover, what mixed 2 or more types chosen from these groups, or what was multilayered may be sufficient, and it can select arbitrarily by adhesiveness with an adhesive layer. More preferably, the base resin film is a film using an ionomer of an ethylene-acrylic acid copolymer.
粘着剤層を構成する粘着剤は、紫外線硬化型粘着剤であり、粘着剤層表面の紫外線照射前におけるメチルイソブチルケトンに対する接触角が25°以上であり、180°よりも小さい限りは特に制限はなく、従来公知の粘着剤の中から適宜選択して用いることができる。例えば天然ゴムや合成ゴム等を用いたゴム系粘着剤、ポリ(メタ)アクリル酸アルキルエステルや(メタ)アクリル酸アルキルエステルと他のモノマーとの共重合体等を用いたアクリル系粘着剤、その他ポリウレタン系粘着剤やポリエステル系粘着剤やポリカーボネート系粘着剤などの一般的な粘着剤を用いることができ、これら一般的な粘着剤に紫外線硬化性のモノマー成分やオリゴマー成分等の紫外線硬化樹脂を配合した紫外線硬化型粘着剤の他、ベースポリマーとして、炭素-炭素二重結合をポリマー側鎖または主鎖中もしくは主鎖末端に有する炭素-炭素二重結合導入型アクリル系ポリマーを用いる紫外線硬化型粘着剤が例示できる。ベースポリマーとして、炭素-炭素二重結合をポリマー側鎖または主鎖中もしくは主鎖末端に有する炭素-炭素二重結合導入型アクリル系ポリマーを用いた場合は、必ずしも、紫外線硬化性のモノマー成分やオリゴマー成分等の紫外線硬化樹脂を配合する必要はない。 (Adhesive layer)
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is an ultraviolet curable pressure-sensitive adhesive, and there is no particular limitation as long as the contact angle with respect to methyl isobutyl ketone before ultraviolet irradiation on the surface of the pressure-sensitive adhesive layer is 25 ° or more and is smaller than 180 °. And can be appropriately selected from conventionally known pressure-sensitive adhesives. For example, rubber adhesive using natural rubber or synthetic rubber, acrylic adhesive using poly (meth) acrylic acid alkyl ester or copolymer of (meth) acrylic acid alkyl ester and other monomers, etc. General pressure-sensitive adhesives such as polyurethane pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, and polycarbonate-based pressure-sensitive adhesives can be used, and UV curable resins such as UV-curable monomer components and oligomer components are blended with these general pressure-sensitive adhesives. UV curable adhesive using carbon-carbon double bond-introduced acrylic polymer having carbon-carbon double bond in polymer side chain or main chain or main chain terminal as base polymer An agent can be illustrated. When a carbon-carbon double bond-introduced acrylic polymer having a carbon-carbon double bond in the polymer side chain or in the main chain or at the end of the main chain is used as the base polymer, the UV-curable monomer component or It is not necessary to add an ultraviolet curable resin such as an oligomer component.
サポート部材は、ケイ素、サファイヤ、水晶、金属(例えば、アルミニウム、銅、鋼)、種々のガラスおよびセラミックスから成る群から選択された素材から構成される。このサポート部材の接着剤を貼り付ける面には堆積された他の素材を含むこともできる。例えば、シリコンウエハ上に窒化ケイ素を蒸着することも可能で、これにより接合特性を変えることができる。 (Support material)
The support member is made of a material selected from the group consisting of silicon, sapphire, crystal, metal (eg, aluminum, copper, steel), various glasses and ceramics. The surface of the support member to which the adhesive is applied can also include other deposited materials. For example, it is possible to deposit silicon nitride on a silicon wafer, thereby changing the bonding characteristics.
前記サポート部材を貼り付けるにあたっては、半導体ウエハの回路形成面に後述する接着剤の接着剤液を塗布した後、塗布した接着剤をオーブンまたはホットプレートで乾燥させる。また、接着剤(接着剤層)の必要な厚さを得るために、接着剤液の塗布と予備乾燥を複数回繰り返してもよい。 (Paste of support member)
When affixing the support member, an adhesive solution of an adhesive described later is applied to the circuit forming surface of the semiconductor wafer, and then the applied adhesive is dried in an oven or a hot plate. Moreover, in order to obtain the required thickness of the adhesive (adhesive layer), the application of the adhesive liquid and the preliminary drying may be repeated a plurality of times.
接着剤としては、本発明においては市販のものを使用することができる。例えば、ブリューワーサイエンス社(ミズーリ州ローラ)から販売されているWaferBONDTM材料(スライドボンディングプロセス用のWaferBONDTM HT 10.10、ケミカルボンディングプロセス用のWaferBONDTM CR200)や、WACKER製のバーグハウゼンの材料であるELASTOSIL LR 3070等が挙げられる。 (adhesive)
As the adhesive, a commercially available adhesive can be used in the present invention. For example, WaferBONDTM material (WaferBONDTM HT 10.10 for slide bonding process, WaferBONDTM CR200 for chemical bonding process) sold by Brewer Sciences (Roller, Missouri) or ELASTOSIL LR, a Berghausen material made by WACKER. 3070 etc. are mentioned.
半導体ウエハから接着剤とサポート部材を剥離した後に、半導体ウエハ1上に残存する接着剤残渣を取り除くための洗浄液としては、上記の接着剤に使用される有機溶剤に加え、一価アルコール類(例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール等)、ラクトン類(例えば、γ-ブチロラクトン等)、ラクタム類(例えば、γ-ブチロラクタム等)、エーテル類(例えば、ジエチルエーテルやアニソール等)、アルデヒド類(例えば、ジメチルホルムアルデヒド、ジメチルアセトアルデヒド等)を使用してもよい。これらのなかでも、特に前述のケトン類もしくはその誘導体が好ましい。 (Cleaning solution for adhesive residue)
As a cleaning liquid for removing the adhesive residue remaining on the semiconductor wafer 1 after peeling the adhesive and the support member from the semiconductor wafer, in addition to the organic solvent used for the adhesive, monohydric alcohols (for example, , Methanol, ethanol, propanol, isopropanol, butanol, etc.), lactones (eg, γ-butyrolactone, etc.), lactams (eg, γ-butyrolactam, etc.), ethers (eg, diethyl ether, anisole, etc.), aldehydes ( For example, dimethylformaldehyde, dimethylacetaldehyde, etc.) may be used. Of these, the aforementioned ketones or derivatives thereof are particularly preferable.
アクリル酸メチル、アクリル酸2-エチルヘキシルおよび2-ヒドロキシエチルアクリレートを5:14:1の割合で、酢酸エチル中で常法により共重合させて、アクリル系ポリマーを含む溶液を得た。続いて、前記アクリル系ポリマーを含む溶液に、紫外線硬化性化合物として、ペンタエリスリトールトリアクリレートおよびジイソシアネートを反応させて得た紫外線硬化性オリゴマー50質量部と、光重合開始剤としてイルガキュア651(商品名、BASF社製)2.5質量部と、ポリイソシアネート系化合物としてトリメチロールプロパン変性トリレンジイソシアネートを1.0質量部、更にシリコン変性アクリレートを0.15質量部加えて、放射線硬化性粘着剤である樹脂組成物を調製した。この樹脂組成物を、予め離型処理の施されたポリエチレンテレフタレートセパレータの離型処理面上に、乾燥後の粘着層の厚みが10μmとなるように塗工し、80℃で10分間乾燥させた後、予め表面にコロナ処理が施された低密度ポリエチレンのコロナ処理面と貼り合わせて基材樹脂フィルムに粘着剤を転写させることで半導体加工用粘着テープを作製した。 (Example 1)
Methyl acrylate, 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate were copolymerized at a ratio of 5: 14: 1 in ethyl acetate by a conventional method to obtain a solution containing an acrylic polymer. Subsequently, 50 parts by mass of an ultraviolet curable oligomer obtained by reacting a solution containing the acrylic polymer with pentaerythritol triacrylate and diisocyanate as an ultraviolet curable compound, and Irgacure 651 (trade name, BASF) 2.5 parts by weight, 1.0 parts by weight of trimethylolpropane-modified tolylene diisocyanate as a polyisocyanate compound, and 0.15 parts by weight of silicon-modified acrylate are added to form a radiation curable adhesive. A resin composition was prepared. This resin composition was applied onto a release treatment surface of a polyethylene terephthalate separator that had been subjected to a release treatment in advance so that the thickness of the pressure-sensitive adhesive layer after drying was 10 μm, and was dried at 80 ° C. for 10 minutes. Then, the adhesive tape for semiconductor processing was produced by pasting together with the corona treatment surface of the low density polyethylene by which the surface was previously corona-treated, and transferring an adhesive to a base resin film.
シリコン変性アクリレートを0.77質量部配合した以外は、実施例1と同様にして、半導体加工用粘着テープを作製した。 (Example 2)
A semiconductor processing pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that 0.77 parts by mass of silicon-modified acrylate was blended.
シリコン変性アクリレートを8.08質量部配合した以外は、実施例1と同様にして、半導体加工用粘着テープを作製した。 (Example 3)
A semiconductor processing adhesive tape was prepared in the same manner as in Example 1 except that 8.08 parts by mass of silicon-modified acrylate was blended.
2-エチルヘキシルアクリレート(70mol%)、メタクリル酸(1mol%)、2-ヒドロキシプロピルアクリレート(29mol%)の共重合体の3-ヒドロキシプロピルアクリレート側鎖末端OH基に、光重合性炭素-炭素二重結合および官能基を有する化合物として、2-メタクリロイルオキシエチルイソシアネートのNCO基を付加反応させた光重合性炭素-炭素二重結合を有するアクリル系化合物(A1:分子量700000)を得た。この化合物(A1)100質量部に対して、ポリイソシアネートとしてトリメチロールプロパン変性ヘキサメチレンジイソシアネートを1質量部、光重合開始剤としてイルガキュア184(商品名、BASF社製)を5.0質量部加えて、放射線硬化性粘着剤である樹脂組成物を調製した。この樹脂組成物を、予め離型処理の施されたポリエチレンテレフタレートセパレータの離型処理面上に、乾燥後の粘着層の厚みが10μmとなるように塗工し、80℃で10分間乾燥させた後、予め表面にコロナ処理が施された低密度ポリエチレンのコロナ処理面と貼り合わせて基材樹脂フィルムに粘着剤を転写させることで半導体加工用粘着テープを作製した。 Example 4
The photopolymerizable carbon-carbon duplex is bonded to the 3-hydroxypropyl acrylate side chain terminal OH group of a copolymer of 2-ethylhexyl acrylate (70 mol%), methacrylic acid (1 mol%), and 2-hydroxypropyl acrylate (29 mol%). As a compound having a bond and a functional group, an acrylic compound (A1: molecular weight 700000) having a photopolymerizable carbon-carbon double bond obtained by addition reaction of the NCO group of 2-methacryloyloxyethyl isocyanate was obtained. To 100 parts by mass of this compound (A1), 1 part by mass of trimethylolpropane-modified hexamethylene diisocyanate as polyisocyanate and 5.0 parts by mass of Irgacure 184 (trade name, manufactured by BASF) as a photopolymerization initiator were added. A resin composition that was a radiation-curable adhesive was prepared. This resin composition was applied onto a release treatment surface of a polyethylene terephthalate separator that had been subjected to a release treatment in advance so that the thickness of the pressure-sensitive adhesive layer after drying was 10 μm, and was dried at 80 ° C. for 10 minutes. Then, the adhesive tape for semiconductor processing was produced by pasting together with the corona treatment surface of the low density polyethylene by which the surface was previously corona-treated, and transferring an adhesive to a base resin film.
シリコン変性アクリレートを0.11質量部配合した以外は、実施例4と同様にして、半導体加工用粘着テープを作製した。 (Example 5)
An adhesive tape for semiconductor processing was produced in the same manner as in Example 4 except that 0.11 part by mass of silicon-modified acrylate was blended.
シリコン変性アクリレートを0.53質量部配合した以外は、実施例4と同様にして、半導体加工用粘着テープを作製した。 (Example 6)
A semiconductor processing pressure-sensitive adhesive tape was produced in the same manner as in Example 4 except that 0.53 parts by mass of silicon-modified acrylate was blended.
シリコン変性アクリレートを5.58質量部配合した以外は、実施例4と同様にして、半導体加工用粘着テープを作製した。 (Example 7)
A semiconductor processing pressure-sensitive adhesive tape was produced in the same manner as in Example 4 except that 5.58 parts by mass of silicon-modified acrylate was blended.
含フッ素オリゴマーを0.15質量部配合した以外は、実施例1と同様にして、半導体加工用粘着テープを作製した。 (Example 8)
A semiconductor processing pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that 0.15 parts by mass of the fluorine-containing oligomer was blended.
アクリル酸エチル、アクリル酸ブチルおよび2-ヒドロキシエチルアクリレートを10:9:1の割合で、酢酸エチル中で常法により共重合させて、アクリル系ポリマーを含む溶液を得た。続いて、前記アクリル系ポリマーを含む溶液に、紫外線硬化性化合物として、ペンタエリスリトールトリアクリレートおよびジイソシアネートを反応させて得た紫外線硬化性オリゴマー50質量部と、光重合開始剤としてイルガキュア651(商品名、BASF社製)2.5質量部と、ポリイソシアネート系化合物としてトリメチロールプロパン変性トリレンジイソシアネートを1.0質量部、更にシリコン変性アクリレートを0.31質量部加えて、放射線硬化性粘着剤である樹脂組成物を調製した。この樹脂組成物を、予め離型処理の施されたポリエチレンテレフタレートセパレータの離型処理面上に、乾燥後の粘着層の厚みが10μmとなるように塗工し、80℃で10分間乾燥させた後、予め表面にコロナ処理が施された低密度ポリエチレンのコロナ処理面と貼り合わせて基材樹脂フィルムに粘着剤を転写させることで半導体加工用粘着テープを作製した。 Example 9
Ethyl acrylate, butyl acrylate, and 2-hydroxyethyl acrylate were copolymerized at a ratio of 10: 9: 1 by an ordinary method in ethyl acetate to obtain a solution containing an acrylic polymer. Subsequently, 50 parts by mass of an ultraviolet curable oligomer obtained by reacting a solution containing the acrylic polymer with pentaerythritol triacrylate and diisocyanate as an ultraviolet curable compound, and Irgacure 651 (trade name, BASF) 2.5 parts by mass, 1.0 parts by mass of trimethylolpropane-modified tolylene diisocyanate as a polyisocyanate compound, and 0.31 parts by mass of silicon-modified acrylate are added to form a radiation curable adhesive. A resin composition was prepared. This resin composition was applied onto a release treatment surface of a polyethylene terephthalate separator that had been subjected to a release treatment in advance so that the thickness of the pressure-sensitive adhesive layer after drying was 10 μm, and was dried at 80 ° C. for 10 minutes. Then, the adhesive tape for semiconductor processing was produced by pasting together with the corona treatment surface of the low density polyethylene by which the surface was previously corona-treated, and transferring an adhesive to a base resin film.
シリコン変性アクリレートを0.77質量部配合した以外は、実施例9と同様にして、半導体加工用粘着テープを作製した。 (Example 10)
A semiconductor processing pressure-sensitive adhesive tape was produced in the same manner as in Example 9, except that 0.77 parts by mass of silicon-modified acrylate was blended.
ポリイソシアネートとしてトリメチロールプロパン変性ヘキサメチレンジイソシアネートを0.1質量部配合した以外は、実施例4と同様にして、半導体加工用粘着テープを作製した。 (Example 11)
A pressure-sensitive adhesive tape for semiconductor processing was prepared in the same manner as in Example 4 except that 0.1 part by mass of trimethylolpropane-modified hexamethylene diisocyanate was added as a polyisocyanate.
シリコン変性アクリレートを配合しなかった以外は、実施例1と同様にして、半導体加工用粘着テープを作製した。 (Comparative Example 1)
A semiconductor processing adhesive tape was prepared in the same manner as in Example 1 except that the silicon-modified acrylate was not blended.
シリコン変性アクリレートを0.15質量部配合した以外は、実施例9と同様にして、半導体加工用粘着テープを作製した。 (Comparative Example 2)
A semiconductor processing pressure-sensitive adhesive tape was produced in the same manner as in Example 9 except that 0.15 parts by mass of silicon-modified acrylate was blended.
平らな面で測定を行う必要があるため、基材フィルムの粘着剤層が設けられていない方の面を、両面テープを用いて表面が平らのガラス板に固定した。セパレータを剥離した後、メチルエチルケトンを滴下し、接触角θを協和化学株式会社製FACE接触角計CA-S150型を用いて測定した。測定温度は23℃、測定湿度は50%である。粘着剤層表面の接触角の測定は粘着テープへの紫外線照射を行う前の状態で行った。 <Contact angle of the adhesive layer surface>
Since it is necessary to perform measurement on a flat surface, the surface of the base film not provided with the adhesive layer was fixed to a glass plate having a flat surface using a double-sided tape. After the separator was peeled off, methyl ethyl ketone was added dropwise, and the contact angle θ was measured using a FACE contact angle meter CA-S150 manufactured by Kyowa Chemical Co., Ltd. The measurement temperature is 23 ° C. and the measurement humidity is 50%. The measurement of the contact angle on the surface of the pressure-sensitive adhesive layer was carried out in a state before performing ultraviolet irradiation on the pressure-sensitive adhesive tape.
株式会社レスカのタッキング試験機TAC-IIを用いて行った。測定モードは、設定した加圧値までプローブを押し込み、設定した時間が経過するまで加圧値を保持するようにコントロールし続けるConstant Loadを用いた。セパレータを剥離した後、半導体加工用粘着テープの粘着剤層を上にし、上側より直径3.0mmのSUS304製のプローブを接触させた。プローブを測定試料に接触させる時のスピードは30mm/minであり、接触荷重は100gfであり、接触時間は1秒である。その後、プローブを600mm/minの剥離速度で上方に引き剥がし、引き剥がすのに要する力を測定し、そのピーク値を読み取った。プローブ温度は23℃であり、プレート温度は23℃とした。 <Probe tack>
This was carried out using a TAC-II tacking tester manufactured by Leska. As the measurement mode, Constant Load was used in which the probe was pushed down to the set pressure value and kept controlled until the set time passed. After the separator was peeled off, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape for semiconductor processing was turned up, and a probe made of SUS304 having a diameter of 3.0 mm was brought into contact from above. The speed at which the probe is brought into contact with the measurement sample is 30 mm / min, the contact load is 100 gf, and the contact time is 1 second. Thereafter, the probe was peeled upward at a peeling speed of 600 mm / min, the force required for peeling was measured, and the peak value was read. The probe temperature was 23 ° C. and the plate temperature was 23 ° C.
50mm×50mmの大きさにカットした半導体加工用粘着テープから、セパレータを除去し、その質量Aを秤量した。次にこの秤量した半導体加工用ダイシングテープのサンプルを100gのメチルイソブチルケトン(MIBK)中に浸漬した状態で48時間放置した後、50℃の恒温層で乾燥し、その質量Bを秤量した。更に100gの酢酸エチルを用いてサンプルの粘着剤層を拭き取り除去した後、サンプルの質量Cを秤量し、下記式(1)によりゲル分率を算出した。
<Gel fraction>
The separator was removed from the semiconductor processing adhesive tape cut to a size of 50 mm × 50 mm, and its mass A was weighed. Next, this weighed sample of the dicing tape for semiconductor processing was left for 48 hours in a state immersed in 100 g of methyl isobutyl ketone (MIBK), and then dried in a constant temperature layer at 50 ° C., and its mass B was weighed. Further, the pressure-sensitive adhesive layer of the sample was wiped off using 100 g of ethyl acetate, and then the mass C of the sample was weighed, and the gel fraction was calculated by the following formula (1).
8インチの半導体ウエハに、実施例、比較例で得られた半導体加工用粘着テープを貼り合せ、リングフレームに固定した後、半導体ウエハ側から有機溶剤としてメチルイソブチルケトン(MIBK)を吹きつけながら、20rpmで回転させスピン洗浄を施した。洗浄・乾燥終了後に半導体加工用ダイシングテープの半導体ウエハが貼られていない領域の粘着剤層を観察し、粘着剤の溶解または膨潤が見られなかったものを○、一部粘着剤の膨潤が見られたものの実用上問題のない軽微なものを△とし合格と判定、粘着剤の溶解が見られたもの、実用上問題となるレベルの重度の膨潤が見られたものを×とし不合格とした。
<耐溶剤性2>
8インチの半導体ウエハに、実施例、比較例で得られた半導体加工用粘着テープを貼り合せ、リングフレームに固定した後、メチルイソブチルケトン(MIBK)中に1時間浸漬した。その後、20rpmで回転させスピン乾燥を施した後に半導体加工用ダイシングテープの半導体ウエハが貼られていない領域の粘着剤層を観察し、粘着剤の溶解または膨潤が見られなかったものを○、一部粘着剤の膨潤が見られたものの実用上問題のない軽微なものを△とし合格と判定、粘着剤の溶解が見られたもの、実用上問題となるレベルの重度の膨潤が見られたものを×とし不合格とした。 <Solvent resistance 1>
After bonding the adhesive tape for semiconductor processing obtained in Examples and Comparative Examples to an 8-inch semiconductor wafer and fixing it to the ring frame, while spraying methyl isobutyl ketone (MIBK) as an organic solvent from the semiconductor wafer side, Spin cleaning was performed by rotating at 20 rpm. After cleaning and drying, observe the adhesive layer in the area where the semiconductor wafer of the dicing tape for semiconductor processing is not affixed. If the adhesive was not dissolved or swollen, ○, and some adhesives were swollen. Although it was judged that the minor one that had no practical problem was marked as △, it was judged as acceptable, the one that the adhesive was dissolved, and the one that showed severe swelling at a level that would cause a practical problem was marked as × .
<Solvent resistance 2>
The adhesive tape for semiconductor processing obtained in Examples and Comparative Examples was bonded to an 8-inch semiconductor wafer, fixed to a ring frame, and then immersed in methyl isobutyl ketone (MIBK) for 1 hour. Then, after rotating at 20 rpm and spin drying, the adhesive layer in the region where the semiconductor wafer was not pasted of the dicing tape for semiconductor processing was observed. Slight swelling of the adhesive was observed, but a minor one that had no practical problems was marked as △, and it was judged as acceptable, the adhesive was dissolved, and severe swelling was observed at a level causing practical problems X was rejected.
米国特許出願公開第2011/0272092号明細書に開示される方法を用いることにより、厚さ約700μmの6インチのシリコンウエハ上に、プラズマポリマー分離層、シリコーンゴム接着剤層、サポート部材として厚さ2.5mmのガラス板が、順に積層された構造体1を得た。上記のようにして得られた構造体1のウエハ背面(プラズマポリマー分離層等が積層されていない面)に実施例、比較例で得られた半導体加工用粘着テープを貼り合せ、リングフレーム上に固定した後、Suss社製De-Bonder DB12Tに供することにより、サポート部材の剥離性を評価した。サポート部材のプラズマポリマー分離層とウエハ表面の間で剥離し、サポート部材をウエハ表面から除去できたものを○、一部でウエハ背面と半導体加工用粘着テープの間での剥離が発生したものの、サポート部材をウエハ表面から除去することができ、実用上許容できるものを△とし、合格と判定、サポート部材のプラズマポリマー分離層とウエハ表面の間で剥離せず、ウエハ背面と半導体加工用粘着テープの間で剥離し、サポート部材をウエハ表面から除去できなかったものを×とし不合格とした。 <Support member peelability>
By using the method disclosed in US Patent Application Publication No. 2011/0272092, a plasma polymer separation layer, a silicone rubber adhesive layer, and a support member are formed on a 6-inch silicon wafer having a thickness of about 700 μm. A structure 1 in which 2.5 mm glass plates were sequentially laminated was obtained. The adhesive tape for semiconductor processing obtained in Examples and Comparative Examples is bonded to the rear surface of the wafer (the surface on which the plasma polymer separation layer or the like is not laminated) of the structure 1 obtained as described above, and is placed on the ring frame. After fixing, the support member was evaluated for peelability by use of Des-Bonder DB12T manufactured by Suss. Peeling between the plasma polymer separation layer of the support member and the wafer surface, and the support member could be removed from the wafer surface ○, partly peeled between the wafer back and the semiconductor processing adhesive tape, The support member can be removed from the surface of the wafer, and a material acceptable for practical use is marked as △, and it is determined to be acceptable, and the wafer back surface and the adhesive tape for semiconductor processing are not peeled off between the plasma polymer separation layer of the support member and the wafer surface. And the support member could not be removed from the wafer surface was evaluated as x.
Claims (4)
- 基材樹脂フィルムの少なくとも一方の面に放射線硬化性の粘着剤層が形成された半導体加工用粘着テープであって、
前記粘着剤層の放射線照射前におけるメチルイソブチルケトンに対する接触角が25.1°~60°であることを特徴とする半導体加工用粘着テープ。 A pressure-sensitive adhesive tape for semiconductor processing in which a radiation-curable pressure-sensitive adhesive layer is formed on at least one surface of a base resin film,
A pressure-sensitive adhesive tape for semiconductor processing, wherein the pressure-sensitive adhesive layer has a contact angle with respect to methyl isobutyl ketone before irradiation of radiation of 25.1 ° to 60 °. - 前記粘着剤層が、シリコンアクリレートまたは含フッ素オリゴマーを含有し、前記シリコンアクリレートまたは含フッ素オリゴマーの含有量が、前記粘着剤層の全固形分に対して0質量%よりも多く5質量%よりも少ないことを特徴とする請求項1に記載の半導体加工用粘着テープ。 The pressure-sensitive adhesive layer contains silicon acrylate or a fluorine-containing oligomer, and the content of the silicon acrylate or fluorine-containing oligomer is more than 0% by mass and more than 5% by mass with respect to the total solid content of the pressure-sensitive adhesive layer. The pressure-sensitive adhesive tape for semiconductor processing according to claim 1, wherein the pressure-sensitive adhesive tape is small.
- 前記粘着剤層の放射線照射前における前記メチルイソブチルケトンに対するゲル分率が、65%以上100%以下であることを特徴とする請求項1または請求項2に記載の半導体加工用粘着テープ。 The pressure-sensitive adhesive tape for semiconductor processing according to claim 1 or 2, wherein the pressure-sensitive adhesive layer has a gel fraction with respect to the methyl isobutyl ketone before irradiation with radiation of 65% or more and 100% or less.
- 前記粘着剤層の放射線照射前におけるプローブタック試験のピーク値が、200~600kPaであることを特徴とする請求項1から請求項3のいずれか一項に記載の半導体加工用粘着テープ。 The pressure-sensitive adhesive tape for semiconductor processing according to any one of claims 1 to 3, wherein a peak value of a probe tack test before irradiation of the pressure-sensitive adhesive layer is 200 to 600 kPa.
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WO2016056269A1 (en) * | 2014-01-23 | 2016-04-14 | 古河電気工業株式会社 | Adhesive tape for protecting semiconductor wafer surface and method for processing semiconductor wafer |
WO2019235487A1 (en) * | 2018-06-05 | 2019-12-12 | 積水化学工業株式会社 | Pressure-sensitive adhesive tape |
CN115011274A (en) * | 2022-06-24 | 2022-09-06 | 浙江权威胶粘制品有限公司 | Modified acrylate high-temperature-resistant adhesive tape and preparation method thereof |
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JP5607847B1 (en) * | 2013-11-29 | 2014-10-15 | 古河電気工業株式会社 | Adhesive tape for semiconductor processing |
WO2015132852A1 (en) * | 2014-03-03 | 2015-09-11 | 古河電気工業株式会社 | Adhesive tape for semiconductor processing |
KR102143801B1 (en) * | 2016-09-23 | 2020-08-12 | 동우 화인켐 주식회사 | Optically Clear Adhesive Composition, and Optically Clear Adhesive Film comprising the Same, and Flat Panel Display |
JP7031141B2 (en) * | 2017-06-01 | 2022-03-08 | 昭和電工マテリアルズ株式会社 | Semiconductor processing tape |
JP7060547B2 (en) * | 2019-05-29 | 2022-04-26 | 古河電気工業株式会社 | Glass processing tape |
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JP5019657B1 (en) * | 2011-10-27 | 2012-09-05 | 古河電気工業株式会社 | Adhesive tape for semiconductor device processing |
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