CN107075322B - The processing method of semiconductor wafer surface protection adhesive tape and semiconductor wafer - Google Patents
The processing method of semiconductor wafer surface protection adhesive tape and semiconductor wafer Download PDFInfo
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- CN107075322B CN107075322B CN201580056130.XA CN201580056130A CN107075322B CN 107075322 B CN107075322 B CN 107075322B CN 201580056130 A CN201580056130 A CN 201580056130A CN 107075322 B CN107075322 B CN 107075322B
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- Prior art keywords
- semiconductor wafer
- convex block
- adhesive tape
- adhesive
- polymer
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 127
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 123
- 238000003672 processing method Methods 0.000 title claims abstract description 23
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- 239000012790 adhesive layer Substances 0.000 claims abstract description 45
- 239000002253 acid Substances 0.000 claims abstract description 42
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 32
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- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 3
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- LCJHLOJKAAQLQW-UHFFFAOYSA-N acetic acid;ethane Chemical compound CC.CC(O)=O LCJHLOJKAAQLQW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000002998 adhesive polymer Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QDHUQRBYCVAWEN-UHFFFAOYSA-N amino prop-2-enoate Chemical class NOC(=O)C=C QDHUQRBYCVAWEN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- AJKZIPCWVAURSI-UHFFFAOYSA-N carbamic acid;2-methylprop-2-enoic acid Chemical compound NC(O)=O.CC(=C)C(O)=O AJKZIPCWVAURSI-UHFFFAOYSA-N 0.000 description 1
- NYVPYOCCTPDTKV-UHFFFAOYSA-N carbamic acid;isocyanic acid Chemical group N=C=O.NC(O)=O NYVPYOCCTPDTKV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical class ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- XRXDLBRJHUCCHH-UHFFFAOYSA-N diiodomethane Chemical compound ICI.ICI XRXDLBRJHUCCHH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 229940048102 triphosphoric acid Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—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
-
- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Landscapes
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Adhesive Tapes (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A kind of processing method with convex block semiconductor wafer surface protection adhesive tape and with convex block semiconductor wafer,This is the band convex block semiconductor wafer surface protection adhesive tape with ultra-violet solidified adhesive phase on base material film with adhesive tape with the protection of convex block semiconductor wafer surface,Wherein,It is 10,000 or more 200 ten thousand or less and the group with the carbon-carbon double bond of type containing radiation-curing that the adhesive phase, which contains weight average molecular weight,,(methyl) acrylate copolymer of hydroxyl and carboxyl,The surface free energy of the adhesive layer surface of ultraviolet light pre-irradiation is 25.5mN/m less than 35mN/m,The surface of the adhesive phase after the solidification of ultraviolet light irradiation high 5mN/m or more of surface free energy compared with the surface of the adhesive phase of ultraviolet light pre-irradiation,And it is small to the contact angle of diiodomethane,The hydroxyl value for constituting the polymer of above-mentioned adhesive layer surface is 30mgKOH/g~100mgKOH/g,The acid value for constituting the polymer of above-mentioned adhesive layer surface is 5mgKOH/g~65mgKOH/g.
Description
Technical field
The present invention relates to the processing methods of semiconductor wafer surface protection adhesive tape and semiconductor wafer.More specifically,
It is related to the surface protection adhesive tape and semiconductor wafer of the semiconductor wafer used whens by grinding semiconductor wafer at film etc.
Processing method.
Background technology
Semiconductor package part manufactures to obtain by following methods：Semiconductor die is being made in the slice such as high purity silicon monocrystalline
After piece, integrated circuit is formed in the wafer surface by ion implanting, etching etc., thus manufactures semiconductor package part.By right
The back side for being formed with the semiconductor wafer of integrated circuit is ground, is ground, and it is desired so that semiconductor wafer is processed into
Thickness.At this point, in order to protect the integrated circuit for being formed in semiconductor wafer surface, semiconductor wafer surface protection adhesive tape is used
(being hereinafter also referred to as " surface protection band ").
It is accommodated in wafer case after the semiconductor wafer of back side grinding overleaf grinding terminates, is carried to cutting action,
It is processed into semiconductor chip.
In the past, it needs to make the thickness of semiconductor wafer be 200 μm~400 μm or so by back side grinding etc..But with
The progress of high-density installation technology in recent years needs that semiconductor chip is made to minimize, and the filming of semiconductor wafer continues to develop.
According to the difference of the type of semiconductor chip, need that semiconductor wafer is made to be as thin as 100 μm or so.Moreover, can pass through to increase
The quantity of the disposable manufactured semiconductor chip of processing, it is intended to use large-scale chip.A diameter of 5 inches or 6 English before this
Very little chip is mainstream, in contrast, the semiconductor wafer of 8 inches~12 inches of diameter is processed into semiconductor chip in recent years
Become mainstream.
The filming of semiconductor wafer and the trend of enlargement are there are the flash memory field of NAND type or NOR type or conducts
It is particularly significant in the fields such as the DRAM of volatile memory.For example, by the grinding semiconductor wafer of 12 inches of diameter to thickness 150
μm or less situation be also not uncommon for.
In general, semiconductor wafer is taken out by mechanical arm from the special box referred to as wafer case piecewise, using positioned at
Semiconductor wafer fixation in equipment for grinding is kept with fixture, carries out back side grinding.The semiconductor wafer being ground through the back side
It is contained to wafer case by mechanical arm and is delivered to subsequent processing.At this point, if the warpage of semiconductor wafer is big, suction will produce
It is attached bad or generate chip in the worst cases and be detached from and the problems such as fall from absorption arm during transport.But due to being referred to as
The appearance of the film grinding special machine of system (in-line system) or the exploitation of special adhesive tape, the problem are obtaining in line
To solution (for example, see patent document 1 and 2).It is therefore contemplated that the trend that chip changes to filming can increasingly accelerate from now on.
Chip after grinding, which is mounted to, to be cut crystal zone or cuts on brilliant viscous epitaxial, removes surface protection band later.To large size
In the case that the back side of semiconductor wafer is ground and makes wafer film, if not inhibiting the surface side for being attached at the chip
The peeling force of the surface protection band on surface, then the load that chip is applied to when removing surface protection band is excessive, and chip is easy broken
It splits.
In addition, for discrete chip, in order to improve performance, also in iterative method filming.Due to the discrete
Chip implements the difference in height different sizes on special surface treatment or surface, therefore is easy when removing surface protection band residual
The raising of glue, fissility becomes one of important topic.
For surface protection band, high chip retentivity is needed in the grinding process of chip back surface, in stripping
It is required that low adhesion power.Therefore, it is widely used for the adhesive tape for the adhesive phase for having ultra-violet solidified in the past as surface protection
Band.Surface protection band with ultra-violet solidified adhesive phase can be fitted in the state of with high adhesion and partly be led
Body chip, therefore excellent adhesion, show high chip retentivity.On the other hand, consolidated by irradiating ultraviolet light before stripping
Change, bonding force can be made to reduce, therefore further improve fissility.(for example, see patent document 3).
But the reactivity of ultra-violet solidified adhesive phase is high, if thus wafer surface be modified, bond sometimes
Oxidant layer reacts with the wafer surface at branch and generates and remove bad or wafer breakage.In addition, wafer surface is equipped with sometimes
Include the insulating resin layer and conductor wirings pattern of polyimides etc., if in wafer surface there are insulating resin layer, surface is protected
The bonding force of protecting band increases, and fissility reduces.
In this condition, as improving method of the surface protection band from the fissility of semiconductor surface, in patent document 4
It describes and the character of adhesive layer surface is adjusted as index using to the contact angle of diiodomethane (diiodomethane).
In addition, as method of the surface protection band from the fissility of semiconductor surface is improved, under having been recorded in patent document 5
State content：Also the surface free energy of adhesive phase will not only be made to the contact angle of diiodomethane (diiodomethane) as index
For index, the character of adhesive layer surface is adjusted.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-151355 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2003-261842 bulletins
Patent document 3：Japanese Unexamined Patent Publication 9-298173 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2009-242776 bulletins
Patent document 5：No. 2013/122060 pamphlet of International Publication No.
Invention content
Problems to be solved by the invention
But as described in above patent document 4, it is specific property to make the adhesive layer surface of surface protection band
Shape and improve in the case of the fissility of semiconductor wafer, when conveying operation or storage are to wafer case, semiconductor wafer
Peripheral part (edge) is sometimes prone to remove (i.e. it is easy to marginal swell occurs) from adhesive tape.If marginal swell occurs, in cutting later
When crystal zone is bonded, edge break or wafer breakage are likely to occur due to pressurizeing caused by roller.In addition, being protected by the surface
In the case that protecting band is applied to band convex block (electrode) semiconductor wafer, it is unable to get sometimes abundant with the wafer surface with convex block
Adaptation, be easy to be mixed into air (air) between surface protection band and wafer surface.
On the other hand, the surface protection band described in patent document 5 shines since the ultraviolet light of process management complexity is omitted
Process is penetrated, thus adhesive used in adhesive phase is pressure sensitive.Therefore, in patent document 5, it is not conceived to adhesive
Adhesive used in layer is the improvement of the surface protection bands of radiation-curings type such as ultraviolet light.
The issue of the present invention is to provide a kind of semiconductor wafer surface protection adhesive tape and use the half of the adhesive tape
The processing method of conductor chip, even if the semiconductor wafer surface protection adhesive tape is applied to the recessed of convex block semiconductor wafer
Adaptation is also excellent in the case of nonreentrant surface, and is less susceptible to that marginal swell occurs, in turn, even if on the surface of semiconductor wafer
Protection band binding face there are insulating layer or conductor wirings pattern in the case of also can easily be shelled in the case of not damage wafers
From the residue glue of the wafer surface after stripping is also few, and adhesive used in adhesive phase is radiation-curing type.
Solution for solving the problem
The present inventor has made intensive studies in view of the above subject.As a result, it has been found that making ultra-violet solidified adhesive
When irradiating the character that rear surface free energy increases and the contact angle of diiodomethane becomes smaller for ultraviolet light, even with convex block semiconductor
The convex-concave surface of chip etc., is also sufficiently carried out closely sealed, nor marginal swell easily occurs, in turn, even if in semiconductor die
There are insulating layer or conductor wirings patterns for the surface protection band binding face of piece, also can easily be shelled from semiconductor wafer by the adhesive tape
From may also suppress the residue glue of the wafer surface after stripping.The present invention be further studied repeatedly based on these technological thoughts and
It completes.
That is, the main points of the present invention are as described below.
(1) a kind of band convex block semiconductor wafer surface protection adhesive tape, it is ultra-violet solidified to have on base material film
Adhesive phase band convex block semiconductor wafer surface protection adhesive tape, which is characterized in that
It is 10,000 or more 200 ten thousand or less and with the carbon-to-carbon pair of type containing radiation-curing that the adhesive phase, which contains weight average molecular weight,
The group of key, (methyl) acrylate copolymer of hydroxyl and carboxyl,
The surface free energy of the adhesive layer surface of ultraviolet light pre-irradiation is 25.5mN/m less than 35mN/m,
The table on the surface of the adhesive phase after the solidification of ultraviolet light irradiation and the adhesive phase of ultraviolet light pre-irradiation
The high 5mN/m or more of surface free energy is compared in face,
The table on the surface of the adhesive phase after the solidification of ultraviolet light irradiation and the adhesive phase of ultraviolet light pre-irradiation
Face is compared, small to the contact angle of diiodomethane,
Above-mentioned (methyl) acrylate copolymer is the importing radiation-curing type carbon-to-carbon double bond base for making to have hydroxyl and carboxyl
Polymer obtained from polymer before group is reacted with the compound with radiation-curing type carbon-to-carbon double bond group, is forming
In whole monomer components of polymer before the importing radiation-curing type carbon-to-carbon double bond group, including (methyl) acrylic acid
1mol%~10mol%,
The hydroxyl value for constituting the polymer of above-mentioned adhesive layer surface is 30mgKOH/g~100mgKOH/g,
The acid value for constituting the polymer of above-mentioned adhesive layer surface is 5mgKOH/g~65mgKOH/g.
(2) the band convex block semiconductor wafer surface protection adhesive tape as described in (1), which is characterized in that above-mentioned that there is radiation
The compound of line curing type carbon-to-carbon double bond group is isocyanic acid 2- (methyl) acryloyloxyethyl ester.
(3) the band convex block semiconductor wafer surface protection adhesive tape as described in (2), which is characterized in that relative to above-mentioned (first
Base) 100 mass parts of acrylate copolymer, the blend amount of above-mentioned isocyanic acid 2- (methyl) acryloyloxyethyl ester be 1 mass parts~
20 mass parts.
(4) the band convex block semiconductor wafer surface protection adhesive tape as described in any one of (1)~(3), which is characterized in that
Relative to above-mentioned 100 mass parts of (methyl) acrylate copolymer, the mass parts of 0.1 mass parts of mixture crosslinking agent~5.
(5) the band convex block semiconductor wafer surface protection adhesive tape as described in any one of (1)~(4), which is characterized in that
The acid value for constituting the polymer of above-mentioned adhesive layer surface is 10mgKOH/g~35mgKOH/g.
(6) a kind of processing method with convex block semiconductor wafer, to use the band described in any one of (1)~(5) convex
The processing method with convex block semiconductor wafer of block semiconductor wafer surface protection adhesive tape, which is characterized in that the processing method
Including following processes (A)~(D).
Process (A) has the surface of convex block to be bonded above-mentioned band convex block semiconductor wafer in the formation with convex block semiconductor wafer
The process of surface protection adhesive tape；
Process (B), to above-mentioned with convex block semiconductor wafer and above-mentioned band convex block semiconductor wafer surface protection adhesive tape
Binding face opposite side the process that is ground of surface；
Process (C) irradiates ultraviolet light to above-mentioned band convex block semiconductor wafer surface protection adhesive tape and makes above-mentioned band convex block
The cured process of semiconductor wafer surface protection adhesive tape；And
Process (D) removes above-mentioned band convex block semiconductor wafer surface protection adhesive tape from above-mentioned band convex block semiconductor wafer
Process.
(7) processing method with convex block semiconductor wafer as described in (6), which is characterized in that above-mentioned band convex block semiconductor
Chip has insulating layer with the above-mentioned binding face with convex block semiconductor wafer surface protection adhesive tape.
(8) processing method with convex block semiconductor wafer as described in (6) or (7), which is characterized in that the height of above-mentioned convex block
Degree is 15 μm or more.
When in this specification, referring to " surface of adhesive phase " or " adhesive layer surface ", as long as not special declaration, then be
Refer to the surface with the binding face opposite side of base material film.
In this specification, refer in semiconductor wafer laminated semiconductor wafer surface protection adhesive tape, towards semiconductor die
Piece surface is bonded adhesive layer surface.
In this specification, term " (methyl) acrylic acid " is with any one of acrylic acid and methacrylic acid or includes the two
Meaning use.This is also identical in the case of term " (methyl) acryloyl group ", " (methyl) acrylamide ".
The effect of invention
Even if the semiconductor wafer surface protection adhesive tape of the present invention is applied to the convex blocks such as band solder projection or golden convex block
Semiconductor wafer convex-concave surface when be not easy to be mixed into air, excellent adhesion is not easy to that marginal swell occurs.In addition, this
The fissility of the semiconductor wafer surface protection adhesive tape of invention is also excellent, even if fitting in large-scale semiconductor wafer surface simultaneously
It, also can be in the feelings of not damage wafers in the case of being ground to the chip back surface and being processed into 100 μm of thin film wafers below
It is easy to carry out stripping under condition, may also suppress the residue glue of the wafer surface after stripping.Even if in addition, to semiconductor wafer surface
Protection similarly to show good fissility with there are the case where insulating layer or conductor wirings pattern in adhesive tape gluing face.
Therefore, semiconductor wafer surface protection of the invention uses adhesive tape suitable for as apparent height as discrete chip
The bigger semiconductor wafer of difference, is used the semiconductor wafer with the salient pole being made of insulating layer and conductor wirings pattern
In the surface protection adhesive tape applied to semiconductor wafer of the flip-chip mounting means with solder projection or golden convex block etc..
In addition, the processing method of semiconductor wafer according to the present invention, it is brilliant can to obtain thin film semiconductor with high finished product rate
Piece.That is, the processing method of the semiconductor wafer of the present invention is suitable for the manufacturing method as thin film semiconductor's chip.
It is further clear by following contents that the above and other feature and advantage of the present invention can suitably refer to attached drawing.
Description of the drawings
Fig. 1 is the sectional view for an embodiment for showing the semiconductor wafer surface protection adhesive tape of the present invention.
Specific implementation mode
<<Semiconductor wafer surface protection adhesive tape>>
With reference to attached drawing, to the preferred semiconductor wafer surface protection adhesive tape (hereinafter referred to as " present invention of the present invention
Adhesive tape ") illustrate.As shown in schematical sectional view in Fig. 1, adhesive tape 10 of the invention base material film 11 at least
Single side is formed with adhesive phase 12, keeps adhesive phase 12 Nian Jie with semiconductor wafer 13 and uses.
In the following, the embodiment that the present invention will be described in detail.
<Adhesive phase>
The adhesive phase of the adhesive tape of the present invention can be single layer, or form different two or more adhesive phases
Multilayered structure made of lamination.Adhesive phase at least its surface of the adhesive tape of the present invention is ultra-violet solidified, preferred adhesive
Layer is generally ultra-violet solidified.The present invention adhesive tape in, through ultraviolet light irradiation solidification after adhesive layer surface with it is ultraviolet
The adhesive layer surface of line pre-irradiation compare the high 5mN/m or more of surface free energy, and with the adhesive phase of ultraviolet light pre-irradiation
It compares to diiodomethane (CH on surface2I2) contact angle it is small.
(surface free energy of adhesive layer surface)
In the present invention, the surface free energy of adhesive layer surface is the value obtained using Owens and Wendt methods, to viscous
The contact angle to pure water and diiodomethane of mixture layer surface is measured (drop volume：2 μ L of pure water, it 3 μ L of diiodomethane, reads
Take the time：After being added dropwise 30 seconds, measure atmosphere：23 DEG C of temperature, relative humidity 50%), the simultaneous equations of following formula 1 is solved, by
This finds out the surface free energy of adhesive layer surface.It should be noted that in this specification, following " surface of solids " refers to gluing
Mixture layer surface.
【Number 1】
<Formula 1>
rs=γs p+γs d (1)
72.8(1+cosθ1 H(51.0 γ of)=2s p)1/2+2(21.8γs d)1/2 (2a)
50.8(1+cosθ1 I(2.3 γ of)=2s p)1/2+2(48.5rs d)1/2 (2b)
γs：Surface free energy
γs p：The polar component of surface free energy
γs d：The dispersive component of surface free energy
θ1 H：Contact angle of the pure water to the surface of solids
θl I：Diiodomethane (CH2I2) to the contact angle of the surface of solids
Herein, formula (1) is Fowkes-Owens formulas, distinguishes the component of surface free energy, it is believed that surface free energy γsIt is
The polar component γ of surface free energys pThe dispersive component γ of (being only London (London) power) with surface free energys d(include moral
The sum of visit (Debye) power or hydrogen bond force).Above-mentioned formula (2a) and (2b) are the interface that will be directed to solid s and interface as liquid 1
Tension γs 1Spread F owkes models relational expression combined with Young formulas obtained from relational expression, wherein formula (2a) be pure water
In the case of relational expression, formula (2b) be diiodomethane in the case of relational expression.
The surface tension γ of pure water1, surface tension polar component γ1 p, surface tension dispersive component γ1 dIt is followed successively by respectively
72.8mN/m, 51.0mN/m, 21.8mN/m, the surface tension γ of diiodomethane1, surface tension polar component γ1 p, surface tension
Dispersive component γ1 dBe followed successively by 50.8mN/m, 2.3mN/m, 48.5mN/m respectively, thus plug these values into above-mentioned formula (2a) and
In (2b).
It should be noted that pure water is different from the polar component of diiodomethane and dispersive component, thus surface as described above
Tension is different.This is because pure water and diiodomethane are different in terms of whether there is or not the difference of hydrogen bond, electronegativity, accompanying this pole
Property is substantially different.In particular, in the case of water, the hydrogen bonds such as-OH and-O- are strong, the ratio of polar component is big.
In adhesive, by assigning hydroxyl or carboxyl into polymer, thus it is possible to vary polar component.As a result, to water
Contact angle changes, thus can change surface free energy.In stripping tape, thus it is speculated that leading to residue glue because agglomerating deficiency
In the case of generation, dispersive component is top dog, and residue glue has occurred on the surface for implementing special activation process
In the case of, polar component is top dog.Therefore, in order to solve the problems, such as the residue glue on the surface to various characters, control pair
The contact angle of water or diiodomethane, the i.e. surface free energy of adhesive layer surface are critically important.
Ultra-violet solidified adhesive by ultraviolet light irradiates bonding force reduce, as a result, with the stripping of semiconductor wafer
It is improved from property.In this way, ultra-violet solidified adhesive phase is different from the adhesive phase of pressure sensitive, the meeting after ultraviolet light pre-irradiation
The physical property or structure change of adhesive phase occurs.
Ultra-violet solidified adhesive phase generally comprises Photoepolymerizationinitiater initiater, even if thus also can before ultraviolet curing
It reacts and occurs be bonded with such as wafer surface because of the influence of heat or light.When the bonding becomes stripping the reason of residue glue.This
Inventor has found, relatively low by the way that the surface free energy of the adhesive layer surface before ultraviolet curing to be suppressed to a certain extent,
The reaction that can inhibit above-mentioned ultraviolet light pre-irradiation while maintaining adhesiveness, can prevent through when chip and adhesive tape it is viscous
It connects.
On the other hand, according to the research of the present inventor it is found that after uv irradiation, even if the surface of adhesive layer surface
Free energy height to a certain degree, is not easy to peeling-off bad.Think that its reason is：In addition to making bonding because ultraviolet light irradiates
Other than agent solidification, bonding force reduce, above-mentioned Photoepolymerizationinitiater initiater is set to be disappeared by the caused curing reaction of ultraviolet light irradiation
Consumption, to be reduced with the reactivity of wafer surface.In turn, the inventors discovered that, pass through the adhesive phase after irradiating ultraviolet light
The surface free energy on surface improves to a certain extent, and it is grand that conveying or box in the device can be effectively prevented edge when storing
It rises.If occur marginal swell, as described above, be easy because cut crystal zone fitting when roller generate pressure due to edge break occurs, most
Bad situation can cause wafer breakage.
In the adhesive tape of the present invention, the surface free energy and ultraviolet light of the adhesive layer surface after the solidification of ultraviolet light irradiation
The surface free energy of the adhesive layer surface of pre-irradiation is compared, preferably high 6mN/m or more, more preferably high 7mN/m or more.In addition,
In the adhesive tape of the present invention, surface free energy and the ultraviolet light pre-irradiation of the adhesive layer surface after the solidification of ultraviolet light irradiation
The difference of the surface free energy of adhesive phase is usually 15mN/m hereinafter, also preferably 12mN/m or less.
In addition, for the adhesive tape of the present invention, the surface free energy of the adhesive layer surface of ultraviolet light pre-irradiation is
25.5mN/m is less than 35mN/m, more preferably 28mN/m~33mN/m.
(to the contact angle of diiodomethane)
If being conceived to the contact angle to diiodomethane, adhesive layer surface meaning coloring big to the contact angle of diiodomethane
Scattered component is big, in this case, the molecular separating force for constituting the polymer of adhesive becomes strong and is difficult to extend.After uv irradiation,
The crosslink density of adhesive is substantially increased, if therefore constitute adhesive polymer molecular separating force it is too strong, can become it is hard and
It is crisp, it is easy to cause residue glue because glue ruptures in the stripping of adhesive tape.Conversely, adhesive layer surface is small to the contact angle of diiodomethane
In the case of, the molecular separating force for constituting the polymer of adhesive is weak, so even also having after the solidification that ultraviolet light irradiates
For the flexibility of stretching, glue is not easily broken, when being removed from protrusions such as convex blocks, glue be also not secured to the protrusions such as convex block and
It is easy to fall off.Therefore, after the solidification of the adhesive phase irradiated through ultraviolet light, contact angle of the adhesive layer surface to diiodomethane
Preferably as low as to a certain degree.
On the other hand, surface protection band is being fitted in into chip of the surface with big protrusions or high difference of height such as convex blocks
When, if the adaptation of the chip and adhesive phase is insufficient, it is likely that be involved in air and be bonded.If being involved in air,
It is hindered due to curing caused by the oxygen in air, even if irradiation ultraviolet light is also possible to not be cured.In this case, it constitutes
Crosslinking between the polymer molecule of adhesive becomes inadequate, if therefore the polymer of ultraviolet light pre-irradiation molecular separating force not
Height is then easy to happen cohesion and destroys.That is, before the curing reaction irradiated through ultraviolet light, adhesive layer surface is to diiodomethane
Contact angle is preferably greatly to a certain degree.
In the adhesive tape of the present invention, preferably the adhesive layer surface of ultraviolet light pre-irradiation to the contact angle (I) of diiodomethane with
Adhesive layer surface after the solidification of ultraviolet light irradiation meets (I) to the contact angle (II) of diiodomethane>(II) relationship, and
Its poor (I-II) is 5 degree~20 degree.
In addition, in the adhesive tape of the present invention, the adhesive layer surface of ultraviolet light pre-irradiation is preferred to the contact angle of diiodomethane
It is 50 degree~80 degree, more preferably 55 degree~75 degree, particularly preferably 55 degree~66.5 degree.
In the present invention, in order to measure the surface free energy of the adhesive phase after solidification and to the contact angle of diiodomethane and into
It is capable for make adhesive phase cured " ultraviolet light irradiation " refer to be 500mJ/cm according to accumulative exposure2Mode to viscous
Mixture layer overall exposure ultraviolet light.High-pressure sodium lamp can be used for example in ultraviolet light irradiation.
The case where composition of adhesive phase about the present invention is first single layer structure to adhesive phase illustrates.
The present invention adhesive tape in, adhesive phase by can by ultraviolet light irradiates cured form is constituted.The adhesive phase
Containing polymer, Photoepolymerizationinitiater initiater and crosslinking agent are preferably comprised.The adhesive phase can also contain as needed to be useful for preventing
Additive or the plasticizer etc. for only soaking or improving sliding.
(adhesive)
In the adhesive tape of the present invention, adhesive used in adhesive phase as long as because ultraviolet light irradiate cure as long as do not have it is special
Do not limit, at least containing a kind at least one can by ultraviolet light irradiates carry out polymerisation reactive group polymerization
Object (hereinafter referred to " ultra-violet solidified polymer ").
Above-mentioned adhesive is preferably using ultra-violet solidified polymer as main component.More specifically, purple is preferably comprised
50 mass % of outside line curable polymer or more, further preferably 80 mass % or more, further preferably 90 mass % with
On.
The reactive group of polymerisation can be carried out by the way that ultraviolet light irradiates, preferably ethylenic bond is unsaturated as above-mentioned
Group, the i.e. group with carbon-to-carbon double bond, for example, vinyl, allyl, styryl, (methyl) acryloyl-oxy
Base, (methyl) Acryloyl amino etc..
Above-mentioned ultra-violet solidified polymer is not particularly limited, for example, (methyl) acrylate copolymer,
Polyester, ethylene or styrol copolymer, polyurethane.It should be noted that in the present invention, these ultra-violet solidified polymer can
One kind is used alone, can also be used in combination of two or more.
It is 10,000 or more 200 that adhesive phase in the present invention, which contains as the weight average molecular weight of ultra-violet solidified polymer,
For ten thousand (methyl) acrylate copolymers below as neccessary composition, being somebody's turn to do (methyl) acrylate copolymer has radiation-curing type
Carbon-to-carbon double bond, hydroxyl and carboxyl.
In the present invention, above-mentioned weight average molecular weight, which is 10,000 or more 200 ten thousand (methyl) acrylate copolymers below, to be used
Commercially available substance can also use the substance synthesized by conventional method.In the case where being synthesized, (methyl) acrylic acid is poly-
It is preferably to make to have the polymer before the importing radiation-curing type carbon-to-carbon double bond group of hydroxyl and carboxyl and have radiation to close object
Polymer obtained from the compound reaction of line curing type carbon-to-carbon double bond group.In this case, radioactive ray are imported in formation to consolidate
In whole monomer components of polymer before change type carbon-to-carbon double bond group, preferably comprise (methyl) acrylic acid 1mol%~
10mol%.
In the present invention, as the compound with radiation-curing type carbon-to-carbon double bond group, preferably make aftermentioned isocyanide
Substance obtained from sour 2- (methyl) acryloyloxyethyl esters are reacted with aftermentioned hydroxyl polymer-containing.
It should be noted that in the present invention, relative to 100 mass parts of (methyl) acrylate copolymer, isocyanic acid 2- (first
Base) blend amount of acryloyloxyethyl ester is preferably the mass parts of 1 mass parts~20, the mass parts of more preferably 6 mass parts~20.
As the synthetic method of above-mentioned ultra-violet solidified polymer, such as following methods are because easy and easy and preferred：
(a) for polymer with ethylenically unsaturated groups, make to have the compounds of ethylenically unsaturated groups with
Polymer is reacted, the method for obtaining the polymer for being imported with ethylenically unsaturated groups；(b) using with ethylenic bond insatiable hunger
With the method for the oligomer [for example, a kind of carbamate (methyl) acrylic acid oligomer etc. as crosslinking agent] of group,
The method of wherein preferred above-mentioned (a).
In the method for above-mentioned (a), as the compound with ethylenically unsaturated groups, using unsaturated with the ethylenic bond
Group has a compound of the structure of different reactive group (being known as reactive group α), and as being imported with ethylenic bond
The polymer of unsaturated group is carried out using with the reactive group α with the compound with ethylenically unsaturated groups
The polymer (hereinafter referred to " polymer with reactive group β ") of the structure of the reactive group β of reaction, makes reactivity
Group α is reacted with β.
Such for example preferred one of reactive group α, β is to carry out the group of nucleophillic attack, and another one is to bear nucleophilic
The group of attack or the group for bearing addition reaction.As such reactive group, for example, hydroxyl, amino, mercapto
Base, carboxyl, epoxy group, oxetanyl, isocyanate group, group, halogen atom, alkoxy or the virtue for forming cricoid acid anhydrides
Epoxide carbonyl etc..
Herein, in the case where any one of reactive group α and β are hydroxyl, amino, sulfydryl, carboxyl, another reaction
Property group can be epoxy group, oxetanyl, isocyanate group, group, halogen atom, the alkoxy for forming cricoid acid anhydrides
Or aryloxycarbonyl.
Reactive group α possessed by compound with ethylenically unsaturated groups is preferably the base for bearing nucleophillic attack
Group or the group for bearing addition reaction, such as preferably epoxy group, oxetanyl, isocyanate group, the cricoid acid of formation
Group, halogen atom, alkoxy or the aryloxycarbonyl of acid anhydride, more preferably epoxy group, oxetanyl, isocyanate group or
The group of cricoid acid anhydrides, further preferably epoxy group, oxetanyl or isocyanate group are formed, further preferably
For isocyanate group.
On the other hand, reactive group β possessed by the polymer of ethylenically unsaturated groups is imported with preferably to carry out
The group of nucleophillic attack, such as preferably hydroxyl, amino, sulfydryl or carboxyl, more preferably hydroxyl, amino or sulfydryl, into one
Step is preferably hydroxyl, amino or carboxyl, further preferably hydroxyl or carboxyl, wherein preferably hydroxyl.
As with ethylenically unsaturated groups and reactive group α compound or for synthesize have it is reactive
The monomer with reactive group β of the polymer of group β, can enumerate compound below.
Reactive group is the compound-of carboxyl
(methyl) acrylic acid, cinnamic acid, itaconic acid, fumaric acid etc.
Reactive group is the compound-of hydroxyl
Have (methyl) acrylic acid hydroxy alkyl ester of hydroxyl [for example, (methyl) acrylic acid -2- hydroxyl ethyl esters, (first in alcohol portion
Base) 2-hydroxypropyl acrylate, trimethylolpropane list (methyl) acrylate, ethylene glycol list (methyl) acrylate, diethyl two
Alcohol list (methyl) acrylate], amine portion have hydroxyl alkylamine N- (hydroxyalkyl) alkyl (methyl) acrylamide [example
Such as, N- methylols (methyl) acrylamide, N, the bis- methylols of N- (methyl) acrylamide], allyl alcohol etc.
Reactive group is the compound-of amino
Have (methyl) acrylate of amino [for example, (methyl) acrylic acid 2- (alkyl amino) in alcohol portion
Ethyl ester, (methyl) acrylic acid 3- (alkyl amino) propyl ester], (methyl) acrylamide etc.
Reactive group is the compound-of cricoid acid anhydrides
Maleic anhydride, itaconic anhydride, fumaric acid anhydride, phthalic anhydride etc.
Reactive group is epoxy group or the compound-of oxetanyl
(methyl) glycidyl acrylate, allyl glycidyl ether, 3- ethyl -3- hydroxymethyl-oxetanes etc.
Reactive group is the compound-of isocyanate group
Isocyanic acid (methyl) acryloyloxyalkyl is [for example, isocyanic acid 2- (methyl) acryloyloxyethyl ester, isocyanic acid
2- (methyl) acryloxies propyl ester], will be polynary different using the compound with hydroxyl or carboxyl and ethylenically unsaturated groups
Compound made of the part progress urethane of the isocyanate group of cyanate esters [for example, 2~10 functions
The urethane acrylate oligomer of (methyl) acrylic acid] etc.
It should be noted that as above-mentioned urethane acrylate oligomer, such as preferably make (methyl) propylene
The alcohol portions such as acid -2- hydroxyl ethyl esters, (methyl) 2-hydroxypropyl acrylate, pentaerythrite three (methyl) acrylate have the (first of hydroxyl
Base) acrylic acid hydroxy alkyl ester and toluene di-isocyanate(TDI), methylenediphenyl diisocyanate, hexamethylene diisocyanate, naphthalene
It is more than the diisocyanate such as diisocyanate, methylene bis cyclohexyl isocyanates, isophorone diisocyanate or 3 functions
Oligomer at least one isocyanate group obtained from isocyanates is reacted.Alternatively, it is also possible to for except (methyl) third
Outside olefin(e) acid hydroxy alkyl ester and multicomponent isocyanate also with polyol compound, polyetherdiol compound or polyester-diol compound into
Oligomer obtained from row reaction.
Reactive group is the compound-of halogen atom
Halogenations triazines such as tri- chloro- 1,3,5- triazines of 2,4,6-, bis- chloro- 6- methoxyl groups -1,3,5- triazines of 2,4- etc.
As the above-mentioned compound with ethylenically unsaturated groups and reactive group α, preferably above-mentioned reactive base
Group is the compound of isocyanate group, on the other hand, as the monomer of the synthesis for the polymer with reactive group β,
It is preferred that above-mentioned reactive group is the compound of carboxyl or the compound that reactive group is hydroxyl, more preferable reactive group is
The compound of hydroxyl.
The method of above-mentioned (b) uses above-mentioned carbamate (methyl) acrylate oligomer (as described later, oligomer
Also it is one kind of crosslinking agent), (methyl) acrylic copolymer and carbamate (methyl) acrylate oligomer can be made total
It deposits and constitutes ultra-violet solidified adhesive phase.As (methyl) acrylic copolymer, preferably make (methyl) acrylic acid with
Substance obtained from (methyl) acrylic ester polymerization.Constitute the excellent of (methyl) acrylate component of (methyl) acrylic copolymer
Form slection state is identical as the substance illustrated by the aftermentioned copolymer composition as in the polymer with reactive group β.
The above-mentioned monomer component with reactive group β accounts for the whole for constituting the above-mentioned polymer with reactive group β
The ratio of monomer component is preferably 5 moles of %~50 mole %, more preferably 20 moles of %~40 mole %.
In addition, making that there is ethylenically unsaturated groups and the compound of reactive group α and having reactive group β's
When polymer is reacted and imports ethylenically unsaturated groups to the polymer with reactive group β, preferably with respect to tool
There are 100 mass parts of polymer of reactive group β to make to have the compound of reactive group α to react the mass parts of 1 mass parts~40,
The more preferably reaction mass parts of 1 mass parts~30 further preferably react the mass parts of 1 mass parts~20, particularly preferably react 1 mass
Part~10 mass parts.
By the reactive group β of the remained unreacted after the reacting of above-mentioned reactive group α and β, can utilize aftermentioned
Crosslinking agent etc. adjust resin properties.
The above-mentioned polymer with reactive group β preferably monomer component and work with reactive group β with above-mentioned
For copolymer composition (methyl) acrylate component as its constituent.
As (methyl) acrylate, preferably one kind or two or more (methyl) alkyl acrylate.It is somebody's turn to do (methyl)
The alcohol portion of acrylate does not have above-mentioned reactive group β.It is preferred that the alcohol portion of above-mentioned (methyl) acrylate is unsubstituted.
As such (methyl) acrylate, the carbon atom number in alcohol portion is preferably 1~12.The carbon atom number in alcohol portion is more excellent
1~10, further preferably 4~10 are selected as, wherein preferred alcohols portion is the substance of branched alkyl, particularly preferred (methyl) propylene
Acid -2- ethylhexyl esters.
In addition, including that two or more (methyl) acrylate components is used as composition in above-mentioned ultraviolet polymerizing polymer
In the case of ingredient, (methyl) acrylic acid that the carbon atom number in alcohol portion is 1~8 should be preferably comprised in (methyl) acrylate component
Ester ingredient, wherein preferably comprising (methyl) ethyl acrylate ingredient.
In the following, enumerating the concrete example for being introduced to the monomer in polymer as above-mentioned copolymer composition.
The Arrcostab-of (methyl) acrylic acid
As the Arrcostab of (methyl) acrylic acid, the substance that the carbon atom number in preferred alcohols portion is 1~12, for example,
(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) third
Olefin(e) acid isobutyl ester, (methyl) isoamyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl caproite, (methyl)
Isooctyl acrylate monomer, the different nonyl ester of (methyl) acrylic acid, (methyl) isodecyl acrylate etc..They can be used alone, can also
Two or more is used in mixed way.By sharing two or more, the various functions as adhesive can be played, and then can be simultaneous
Care for the tracing ability to the difference in height of semiconductor wafer surface and the non-polluting including preventing residue glue.
Monomer-other than the Arrcostab of (methyl) acrylic acid
As the monomer other than the Arrcostab of (methyl) acrylic acid, vinyl acetate, styrene or (methyl) can be enumerated
Acrylamide, such as N, N- acrylamides, N, N- acrylamides, n-isopropyl acrylamide, N- acryloyls
Morpholine etc..They may be used alone, can also be 2 or more kinds in combination.
The ratio that above-mentioned copolymer composition accounts for the whole monomer components for constituting the above-mentioned polymer with reactive group β is preferred
For 5 moles of %~50 mole %, more preferably 20 moles of %~40 mole %.
Above-mentioned surface free energy or adhesive layer surface in the present invention can pass through the contact angle of diiodomethane or water
It adjusts the type and content of ultra-violet solidified polymer and the polymer shared with the polymer and freely controls.
Wherein, preferably by adjusting constitute ultra-violet solidified polymer the monomer component with reactive group β,
The type and content ratio of copolymer composition, (methyl) acrylic component of (methyl) alkyl acrylate ingredient etc etc. carries out
Control.
For example, being that hydroxyl, carboxyl or amino (contain in the reactive group β of the polymer with reactive group β
Amide groups) in the case of, reactive group β can be reacted with the compound with reactive group α and ethylenically unsaturated groups,
But make unreacted hydroxyl, carboxyl or amino remaining.Furthermore it is possible to by existing in the polymer with reactive group β
2 kinds of reactivity group base β (for example, carboxyl and hydroxyl), and only make the part part of hydroxyl (such as only) of one of which with
Reactive group α is reacted, to make one reactive group (hydroxyl) a part and another one reactive group
(carboxyl) remains, so as to according to remaining reactive group type or amount and control surface free energy or adhesive phase table
In face of the contact angle of water.
In this case, the polarity of such as carboxyl is higher than hydroxyl or amino, surface free energy or contact angle can significantly changes.
In addition, for example by also including by carboxyl, association caused by amino (amide-containing) mutual hydrogen bond
Puppet is crosslinked and cohesiveness is made also to improve, thus can also adjust the contact angle to diiodomethane.
Conversely, in the case where the reactive group β of remaining is mainly hydroxyl, the polarity not up to degree of carboxyl, thus
The influence of surface free energy or adhesive layer surface to the contact angle of water to adhesive layer surface is small, but due to being hardly formed
By hydroxyl each other caused by pseudo- crosslinking, thus can in the case where having little influence on the contact angle to diiodomethane adjustment table
Face free energy.
Have it should be noted that the amount of the reactive group β remained in ultra-violet solidified polymer also depends on
The blend amount of the compound of reactive group α can also be adjusted according to the type and blend amount of aftermentioned crosslinking agent.That is,
The surface free energy of adhesive layer surface can be adjusted by crosslinking agent.
In the present invention, relative to above-mentioned 100 mass parts of (methyl) acrylate copolymer, preferably 0.1 mass of mixture crosslinking agent
Part~5 mass parts.
In order to control adhesive phase surface free energy polar component, contained by the preferred adhesive phase of adhesive tape of the invention
Ultra-violet solidified polymer include hydroxyl, hydroxyl and carboxyl or hydroxyl and amino (amide-containing).Wherein, it preferably comprises
Hydroxyl and carboxyl.
The hydroxyl value for constituting the polymer of adhesive layer surface is preferably 5mgKOH/g~100mgKOH/g, is more preferably
10mgKOH/g~100mgKOH/g, further preferably 20mgKOH/g~100mgKOH/g, particularly preferably 30mgKOH/g~
100mgKOH/g.By being set as within the scope of this, cohesiveness can be controlled by crosslinking agent or by being not involved in crosslinked residual hydroxyl
Base carrys out control surface free energy.In addition, constitute adhesive layer surface polymer acid value be preferably 0mgKOH/g~
70mgKOH/g, more preferably 5mgKOH/g~65mgKOH/g, further preferably 10mgKOH/g~65mgKOH/g or
5mgKOH/g~35mgKOH/g, particularly preferably 10mgKOH/g~35mgKOH/g, most preferably 15mgKOH/g~
35mgKOH/g.Wherein, the hydroxyl value for preferably comprising the polymer of adhesive layer surface is 10mgKOH/g~100mgKOH/g and acid
Value is 5mgKOH/g~65mgKOH/g, and the hydroxyl value of more preferable polymer is 20mgKOH/g~100mgKOH/g and acid value is
The hydroxyl value of 10mgKOH/g~65mgKOH/g, further preferred polymer are 30mgKOH/g~100mgKOH/g and acid value is
The hydroxyl value of 10mgKOH/g~35mgKOH/g, particularly preferred polymer are 30mgKOH/g~100mgKOH/g and acid value is
15mgKOH/g~35mgKOH/g.It should be noted that in the present invention, the hydroxyl value of polymer be 30mgKOH/g~
In the case of 100mgKOH/g, the acid value of polymer is 5mgKOH/g~65mgKOH/g (preferably 5mgKOH/g~35mgKOH/
G) it is also preferred mode.In addition, the acidic group mainly having in the polymer of composition adhesive layer surface is preferably carboxyl.
Above-mentioned acid value is the polymer using ultraviolet light pre-irradiation (before solidification) as sample and according to JIS K5601-2-1:
1999 acid values measured.In addition, hydroxyl value is the hydroxyl value measured according to JIS K 0070.
It should be noted that in this specification, " hydroxyl value " be the polymer of ultraviolet light pre-irradiation (before solidification) solid at
The hydroxyl value divided is found out using KOH and is acylated the required obtained hydroxyl value of hydroxyl；" acid value " be ultraviolet light pre-irradiation (Gu
Before change) polymer solid constituent acid value, i.e., using as required by the KOH for neutralizing the required alkali of acidic-groups such as carboxyl
The acid value gone out.
The weight average molecular weight of ultra-violet solidified polymer used in above-mentioned adhesive phase be 10000~2000000, it is excellent
50000~2000000 are selected as, in addition, in the case where the polymer and other polymer are shared, the polymerization that is preferably shared
The weight average molecular weight of object is also within the above range.
If the weight average molecular weight of polymer used in above-mentioned adhesive phase is excessive, it polymerize difficult, abbe number and gets higher,
To the polymer containing low molecular weight, thus cohesiveness is possible to be lower.On the other hand, if molecular weight is too small, polymer
The cohesiveness of itself can be lower, thus easily become residue glue Producing reason.In the adhesive tape of the present invention, used in adhesive phase
The weight average molecular weight of polymer is preferably 200000~800000.
Weight average molecular weight calculates as follows：Pass through gel permeation chromatography (manufacture of Waters societies, the name of an article：150-C ALC/
GPC) 1% solution obtained from being dissolved in tetrahydrofuran is measured, the value measured is converted as polystyrene
Weight average molecular weight and calculate.
(Photoepolymerizationinitiater initiater)
The adhesive phase of the present invention particularly preferably contains Photoepolymerizationinitiater initiater.Cause by adjusting the photopolymerization of adhesive phase
The blend amount of agent can control the bonding force after crosslinking.As such Photoepolymerizationinitiater initiater, specifically, benzene can be enumerated
Acyloin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzyldiphenyl thioether, tetramethylthiuram monosulfide, idol
Nitrogen bis-isobutyronitrile, two benzils, diacetyl, β-chloroanthraquinone etc..Photoepolymerizationinitiater initiater is usually with relative to ethylenic bond insatiable hunger
With the polymer of group and 100 mass parts of total amount of the compound with ethylenically unsaturated groups are the matter of 0.1 mass parts~10
The ratio for measuring part uses.By irradiating ultraviolet light to the ultra-violet solidified adhesive phase being thusly-formed, can be greatly reduced
Bonding force can easily remove the adhesive tape from clung body.
(crosslinking agent)
In the present invention, crosslinking agent is preferably comprised in adhesive phase.The reactive group of crosslinkable groups as crosslinking agent
The crosslinking agent preferably to react with the reactive group β of the polymer with reactive group β.
For example, in the case where the reactive group β of the resin with reactive group β is carboxyl or hydroxyl, as friendship
The reactive group for joining the crosslinkable groups of agent is preferably cricoid acid anhydrides, isocyanate group, epoxy group, halogen atom, more preferably
For isocyanate group or epoxy group.
By using such crosslinking agent, the anti-of the polymer with reactive group β can be adjusted according to its blend amount
The remaining quantity of answering property group β can control surface free energy in desired range.
In addition, by using crosslinking agent, the cohesiveness of adhesive phase can also be controlled.
As the crosslinking agent for being preferred for above-mentioned adhesive phase, polyhydric isocyanate compound, polynary epoxy can be enumerated
Compound, polynary nitrogen heterocycle propane compound, chelate compound etc..As polyhydric isocyanate compound, specifically, can be with
Enumerate toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate
With their addition product type etc..
As polynary epoxide, ethylene glycol diglycidylether, terephthalic acid diglycidyl ester can be enumerated
Acrylate etc..Polynary nitrogen heterocycle propane compound can enumerate three -2,4,6- (1- '-aziridinos) -1,3,5- triazines, three [1-
(2- methyl)-'-aziridino] phosphine oxide, six [1- (2- methyl)-'-aziridino] triphosphoric acid triazines etc..In addition, as sequestration
Object is closed, ethyl acetoacetate aluminum-diisopropoxide, three (ethyl acetoacetate) aluminium etc. can be enumerated.
Alternatively, it is also possible to use intramolecular that there is the above ethylenic bond of at least two not in adhesive used in the present invention
The crosslinking agent of saturated group, it is preferable to use the crosslinking agents of oligomer or polymer, crosslinking agent are itself served as ultra-violet solidified
Resin.
There is the low molecular compound of the above ethylenically unsaturated groups of at least two as intramolecular, for example,
Trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, pentaerythrite 4 third
Olefin(e) acid ester, dipentaerythritol monohydroxypentaacryande, dipentaerythritol hexaacrylate, 1,4 butanediol diacrylate,
1,6 hexanediyl esters, polyethyleneglycol diacrylate, oligoester acrylate etc..
In addition to this, urethane acrylate oligomer can also be used, specifically, can be extensively using making tool
There is (methyl) acrylate of hydroxyl (for example, (methyl) acrylic acid -2- hydroxyl ethyl esters, (methyl) 2-hydroxypropyl acrylate, poly- second
Glycol (methyl) acrylate) reacted with terminal isocyanate carbamate prepolymer obtained from substance, the terminal isocyanate
Acid esters carbamate prepolymer is the polyol compound and polyhydric isocyanate compound (example for making polyester-type or polyether-type etc.
Such as, 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene di-isocyanate(TDI)s, 1,3- benzene dimethylene diisocyanate, Isosorbide-5-Nitrae-benzene two are sub-
Methyl diisocyanate, diphenyl methane 4,4- diisocyanate etc.) reaction obtained from.
Relative to 100 mass parts of polymer for constituting adhesive phase, the content of crosslinking agent is preferably 0.1 mass parts~5.0
Mass parts, the more preferably mass parts of 0.5 mass parts~4.0.
(additive)
In the present invention, in addition to those specified above, adhesive phase can also contain additive.
As such additive, such as the additive for preventing from soaking or improving sliding, can enumerate poly-
Silicone acrylate (for example, silicone diacrylate, six acrylate of polysiloxanes), ultraviolet curing accelerating agent.
Can also include the amino acrylates as water-proofing agent in addition, as the additive.In addition, as the additive, it can also
Including plasticizer.The surfactant used when alternatively, it is also possible to included in the polymerization of polymer.
(storage modulus)
The storage modulus of adhesive or adhesive phase to the present invention is not particularly limited, if in view of residue glue or to bumps
The tracing ability of shape, then the storage modulus of preferred ultraviolet light pre-irradiation be 30000Pa~75000Pa, more preferably 35000Pa~
60000Pa.(it is 500mJ/cm according to accumulative exposure after the solidification of ultraviolet light irradiation2Mode to adhesive phase integrally according to
Penetrate ultraviolet light and after so that it is cured) the storage modulus of adhesive be preferably 100000Pa or more.
In the adhesive tape of the present invention, as described above, adhesive phase can be to form two or more different adhesive laminations to form
Multilayered structure.In the case where adhesive phase is multilayered structure, the composition of the layer on the surface of composition adhesive phase is at least set to be
The composition (mode illustrated by composition i.e. as the adhesive phase of single layer structure) of above-mentioned adhesive phase.Additionally, it is preferred that multilayer
All adhesive phases of structure are the composition of above-mentioned adhesive phase (illustrated by the composition i.e. as the adhesive phase of single layer structure
Mode).
(thickness of adhesive phase)
The thickness of adhesive phase is not particularly limited, preferably 10 μm~300 μm, more preferably 30 μm~200 μm, into
One step is preferably 40 μm~200 μm.
In addition, adhesive phase can be arranged according to purpose on the two sides of base material film.
In order to form adhesive phase on base material film, as set forth above, it is possible to by conventional method in at least single of base material film
At least one adhesive of face coating.
(other layers)
In the present invention, the middle layers such as priming coat can be arranged as required between base material film and adhesive phase.
<Release liner>
The adhesive tape of the present invention can have release liner over the binder layer.As release liner, demoulded using through silicone
The polyethylene terephthalate film etc. of processing.Alternatively, it is also possible to use poly- third without silicone demoulding processing as needed
Alkene film etc..
<Base material film>
As the material of base material film used in the present invention, to protect semiconductor wafer from carrying out grinding to the back side
When impacted as the main purpose, it is especially important to retentivities with water resistance and with processing component such as water cleanings.As
Such base material film, for example, the base material film described in Japanese Unexamined Patent Publication 2004-186429 bulletins.
It should be noted that the base material film used in the present invention can use the usually base material film used in adhesive tape, example
Polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, vinyl-vinyl acetate copolymer, ethylene-the third can such as be enumerated
The homopolymer or copolymer of the alpha-olefins such as olefin(e) acid ester copolymer, ionomer, makrolon, gather polyethylene terephthalate
The thermoplastic elastomer (TPE)s such as the engineering plastics such as methyl methacrylate, polyurethane, styrene-ethylene-butadiene or amylene based copolymer,
Or base material film made of two or more base material film mixed in these group or multiple stratification.
Among these, optimal ethylene-vinyl acetate copolymer, vinyl-acrylate copolymer, amino first in the present invention
The copolymer of acid esters acrylate oligomer and isobornyl acrylate.It should be noted that urethane acrylate is low
The copolymer of polymers and isobornyl acrylate can be using the Photoepolymerizationinitiater initiater illustrated within the adhesive layer come to amino first
Acid esters acrylate oligomer and isobornyl acrylate are manufactured.
In addition, the base material film of the preferred visible light permeability of base material film, the base material film of further preferred ultraviolet light permeability.Separately
Outside, the thickness of base material film is not particularly limited, preferably 50 μm~500 μm.If base material film thickness be 50 μm hereinafter, if into
Thickness and precision is easy to be deteriorated when row manufacture, and rigidity is low, thus the retentivity shortcoming of chip, causes to convey mistake sometimes.
Conversely, if the thickness of base material film is more than 500 μm, cause to convey mistake because warpage after grinding becomes larger, or because rigidity is too strong
And adhesive tape can not be made.The thickness of base material film is more preferably 80 μm~300 μm, further preferably 100 μm~300 μm.
In turn, as base material film, can also make adhesive carry out ultraviolet curing and membranization at base material film.Such as
The base material film manufactured by the method by Japanese Unexamined Patent Publication 11-343469 bulletins etc. can be used.
<<The processing method of semiconductor wafer and semiconductor wafer>>
The semiconductor wafer of the adhesive tape of the application present invention is not particularly limited, the semiconductor of all modes is can be applied to
Chip.
Processing method (hereinafter referred to " the processing side of the invention of the semiconductor wafer of the adhesive tape of the present invention is used
Method ") include at least following processes (A)~(D).
(A) in the process of the adhesive tape of the surface of the semiconductor wafer fitting present invention；
(B) to the surface (back side of chip) with the binding face opposite side of the adhesive tape of the present invention of above-mentioned semiconductor wafer
The process being ground；
(C) the adhesive tape irradiation radioactive ray of the present invention are made with the cured process of adhesive tape of the present invention；
(D) from the process of the adhesive tape of the above-mentioned semiconductor wafer stripping present invention.
The radioactive ray irradiated in above-mentioned operation (C) refer to the ionization of the light or electron ray etc of ultraviolet light etc
Radioactive ray.The radioactive ray irradiated in above-mentioned operation (C) are preferably ultraviolet light.The accumulative irradiation of radioactive ray in above-mentioned operation (C)
Amount is preferably 300mJ/cm2~1000mJ/cm2Left and right.
The adhesive tape of the present invention is also suitable for the surface for the semiconductor wafer for having insulating layer as the binding face in the adhesive tape
Protection band.Even if that is, there is the insulating layer for including polyimide resin etc. in semiconductor wafer surface, can also take into account good
Adaptation and good fissility.
In addition, even if the binding face in adhesive tape has the convex blocks such as electrode, good adaptation and good can also be taken into account
Fissility.For example, even if the height of the convex blocks such as electrode is 15 μm or more and then is 50 μm or more, can also take into account good close
Conjunction property and good fissility.From practicality, the height of above-mentioned convex block is 300 μm or less.
In addition, processing method through the invention and the thickness that has carried out thin film semiconductor's chip of back side grinding is preferably
20 μm~500 μm, more preferably 50 μm~200 μm.
By using the processing method of the present invention, thin film semiconductor's chip can be obtained with high finished product rate.That is, the present invention
The processing method of semiconductor wafer is suitable for the manufacturing method as thin film semiconductor's chip.
Embodiment
Hereinafter, based on embodiment, the present invention will be described in more detail, and however, the present invention is not limited to these examples.
Embodiment 1
The urethane acrylate system oligomer (villages the Xin Zhong chemical industry strain formula meeting that mixture weight average molecular weight is 3500
Society manufacture) 50 mass parts, 50 mass parts of isobornyl acrylate, Irgacure184 (the BASF societies systems as Photoepolymerizationinitiater initiater
Make) 5.0 mass parts, obtain ultraviolet-curing resin composition.It, will be obtained by pond mould (fountain die) mode
Ultraviolet-curing resin composition is using 270 μm of PET film (Dongli Ltd.s being applied to as cast donor sheets of thickness
Manufacture：38 μm of thickness) on, form resin composition layer.Just after coating, further lamination is identical on resin composition layer
PET film uses high-pressure sodium lamp (160W/cm, height 10cm) with light quantity 500mJ/cm later2Condition carry out ultraviolet light irradiation,
Thus make resin composition layer crosslinked/cured, obtain the base material film that thickness is 270 μm.
Mixture methacrylic acid 1.5mol%, acrylic acid-2-ethyl caproite 64mol%, acrylic acid -2- hydroxyl ethyl esters
34.5mol% is polymerize in the solution, to obtain polymer solution.In the solution, relative to 100 mass of polymer
18 mass parts of part mixing isocyanic acid 2- methacryloyloxyethyls (Showa Denko K. K's manufacture, Karenz MOI), to
Hydroxyl imports ethylenically unsaturated groups, thus synthesizes the acrylic copolymer polymer (weight containing ethylenically unsaturated groups
Average molecular weight：400000；Hydroxyl value 99.1mgKOH/g；Acid value 10.5mgKOH/g).
CORONET L of the mixture as crosslinking agent in the acrylic copolymer polymer containing ethylenically unsaturated groups
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 2.5 mass parts, (the BASF societies systems of Irgacure 184 as Photoepolymerizationinitiater initiater
Make) 5.0 mass parts, obtain adhesive composition.
In such a way that the thickness of adhesive is 40 μm, adhesive composition is applied to by lamination in above-mentioned two sides
On the above-mentioned base material film of PET film stripping, it is bonded with transparent release liner (50 μm of thickness), to obtain the glue of 310 μm of thickness
Band.
<Embodiment 2>
Mixture methacrylic acid 2.0mol%, acrylic acid-2-ethyl caproite 70mol%, acrylic acid -2- hydroxyl ethyl esters
28mol% is polymerize in the solution, to obtain polymer solution.In the solution, mixed relative to 100 mass parts of polymer
10 mass parts of isocyanic acid 2- methacryloyloxyethyls (Showa Denko K. K's manufacture, Karenz MOI) are closed, to hydroxyl
Ethylenically unsaturated groups are imported, the acrylic copolymer polymer containing ethylenically unsaturated groups is thus synthesized and (divides equally again
Son amount：500000, hydroxyl value 50.8mgKOH/g, acid value 10.5mgKOH/g).
CORONET L of the mixture as crosslinking agent in the acrylic copolymer polymer containing ethylenically unsaturated groups
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 0.5 mass parts, (the BASF societies systems of Irgacure 184 as Photoepolymerizationinitiater initiater
Make) 5.0 mass parts, obtain adhesive composition.
In such a way that the thickness of adhesive is 130 μm, obtained adhesive composition is applied to transparent stripping
It pads on (50 μm of thickness), is bonded with 100 μm ethane-acetic acid ethyenyl ester (EVA) film of thickness, to obtain 230 μm of thickness
Adhesive tape.
<Embodiment 3>
Mixture methacrylic acid 4.0mol%, acrylic acid-2-ethyl caproite 76mol%, acrylic acid -2- hydroxyl ethyl esters
20mol% is polymerize in the solution, to obtain polymer solution.In the solution, relative to 100 mass parts of polymer
10 mass parts of isocyanic acid 2- acryloyloxyethyl esters (Showa Denko K. K's manufacture, Karenz AOI) are mixed, are led to hydroxyl
Enter ethylenically unsaturated groups, thus synthesizes the acrylic copolymer polymer (Weight-average molecular containing ethylenically unsaturated groups
Amount：350000, hydroxyl value 33.8mgKOH/g, acid value 19.9mgKOH/g).
CORONET L of the mixture as crosslinking agent in the acrylic copolymer polymer containing ethylenically unsaturated groups
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 1.5 mass parts and TETRAD-X (Mitsubishi Gas Chemical Co., Ltd's manufacture) 0.3
Mass parts, Irgacure 651 (manufacture of BASF societies) 5.0 mass parts as Photoepolymerizationinitiater initiater, obtain adhesive composition.
In such a way that the thickness of adhesive is 130 μm, obtained adhesive composition is applied to transparent stripping
On liner, low density polyethylene (LDPE) (LDPE) film for being formed by 100 μm of adhesive phase and thickness is bonded, to obtain thickness
230 μm of adhesive tape.
<Embodiment 4>
Mixture methacrylic acid 6.0mol%, ethyl acrylate 74mol%, acrylic acid -2- hydroxyl ethyl ester 20mol%, molten
It is polymerize in liquid, to obtain polymer solution.In the solution, relative to 100 mass parts of polymer mixing isocyanic acid 2-
10 mass parts of methacryloyloxyethyl (Showa Denko K. K's manufacture, Karenz MOI), ethylenic bond is imported to hydroxyl
Thus unsaturated group synthesizes the acrylic copolymer polymer (weight average molecular weight containing ethylenically unsaturated groups：700000,
Hydroxyl value 33.7mgKOH/g, acid value 33.1mgKOH/g).
CORONETL of the mixture as crosslinking agent in the acrylic copolymer polymer containing ethylenically unsaturated groups
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 0.9 mass parts, the EsacureKIP-150 as Photoepolymerizationinitiater initiater
(manufacture of Lamberte societies) 5.0 mass parts, obtain adhesive composition.
In such a way that the thickness of adhesive is 130 μm, obtained adhesive composition is applied to transparent stripping
It pads on (50 μm of thickness), is bonded with 100 μm of EVA film of thickness, to obtain the adhesive tape of 230 μm of thickness.
<Embodiment 5>
Mixture methacrylic acid 1.0mol%, acrylic acid-2-ethyl caproite 78mol%, acrylic acid -2- hydroxyl ethyl esters
21mol% is polymerize in the solution, to obtain polymer solution.In the solution, relative to 100 mass parts of polymer
10 mass parts of isocyanic acid 2- methacryloyloxyethyls (Showa Denko K. K's manufacture, Karenz MOI) are mixed, to hydroxyl
Base imports ethylenically unsaturated groups, and thus synthesizing the acrylic copolymer polymer containing ethylenically unsaturated groups, (weight is equal
Molecular weight：750000, hydroxyl value 33.7mgKOH/g, acid value 5.6mgKOH/g).
CORONETL of the mixture as crosslinking agent in the acrylic copolymer polymer containing ethylenically unsaturated groups
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 2.0 mass parts, the EsacureKIP-150 as Photoepolymerizationinitiater initiater
(manufacture of Lamberte societies) 5.0 mass parts, obtain adhesive composition.
In such a way that the thickness of adhesive is 150 μm, obtained adhesive composition is applied to transparent stripping
It pads on (50 μm of thickness), is bonded with 80 μm polypropylene (PP) film of thickness, to obtain the adhesive tape of 230 μm of thickness.
<Embodiment 6>
Mixture methacrylic acid 1.0mol%, acrylic acid-2-ethyl caproite 78mol%, acrylic acid -2- hydroxyl ethyl esters
21mol% is polymerize in the solution, to obtain polymer solution.In the solution, relative to 100 mass parts of polymer
6 mass parts of isocyanic acid 2- methacryloyloxyethyls (Showa Denko K. K's manufacture, Karenz MOI) are mixed, to hydroxyl
Ethylenically unsaturated groups are imported, the acrylic copolymer polymer containing ethylenically unsaturated groups is thus synthesized and (divides equally again
Son amount：600000, hydroxyl value 55.6mgKOH/g, acid value 5.9mgKOH/g).
CORONETL of the mixture as crosslinking agent in the acrylic copolymer polymer containing ethylenically unsaturated groups
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 0.5 mass parts, the EsacureKIP-150 as Photoepolymerizationinitiater initiater
(manufacture of Lamberte societies) 5.0 mass parts, obtain adhesive composition.
In such a way that the thickness of adhesive is 150 μm, obtained adhesive composition is applied to transparent stripping
It pads on (50 μm of thickness), is bonded with 150 μm of EVA film of thickness, to obtain the adhesive tape of 300 μm of thickness.
<Comparative example 1>
Mixture acrylic acid-2-ethyl caproite 78mol%, acrylic acid -2- hydroxyl ethyl esters 21mol%, methacrylic acid 1mol%,
It is polymerize in the solution, to obtain the polymer solution that weight average molecular weight is 700,000.In the solution, relative to the polymer
100 mass parts mix 10 mass parts of isocyanic acid 2- methacryloyloxyethyls (Showa Denko K. K's manufacture, Karenz
MOI), ethylenically unsaturated groups are imported to hydroxyl, it is poly- thus synthesizes the acrylic copolymer containing ethylenically unsaturated groups
Close object (weight average molecular weight：600000, hydroxyl value 50.1mgKOH/g, acid value 6.1mgKOH/g).
CORONET L of the mixture as crosslinking agent in the acrylic copolymer polymer containing ethylenically unsaturated groups
(manufacture of Japanese polyurethane industry society) 1.5 mass parts, the Irgacure 184 (manufacture of BASF societies) 3.0 as Photoepolymerizationinitiater initiater
Mass parts, Ebecryl 350 (manufacture of DAICEL-ALLNEX societies) 0.3 mass parts as additive obtain adhesive combination
Object.
In such a way that the thickness of adhesive is 130 μm, obtained adhesive composition is applied to transparent stripping
On liner, the EVA film for being formed by 100 μm of adhesive phase and thickness is bonded, to obtain the adhesive tape of 230 μm of thickness.
<Comparative example 2>
Mixture methacrylic acid 20mol%, acrylic acid-2-ethyl caproite 30mol%, acrylic acid -2- hydroxyl ethyl esters
10mol%, methyl acrylate 40mol%, are polymerize in the solution, molten to obtain the polymer that weight average molecular weight is 600,000
Liquid.The hydroxyl value of the polymer is 28.1mgKOH/g, acid value 60.8mgKOH/g.
In the polymer solution, relative to 100 mass parts of polymer, mixture as ultraviolet light reaction resin 6
Urethane acrylate oligomer (manufacture of chemical industry Co., Ltd. of the villages Xin Zhong) 100 mass parts of function and 3 functions
Urethane acrylate oligomer (manufacture of chemical industry Co., Ltd. of the villages Xin Zhong) 50 mass parts, as crosslinking agent
CORONET L (Nippon Polyurethane Industry Co., Ltd.'s manufacture) 4.0 mass parts, the Irgacure 184 as Photoepolymerizationinitiater initiater
(manufacture of BASF societies) 10 mass parts, Ebecryl350 (manufacture of DAICEL-ALLNEX Co., Ltd.) 0.5 mass as additive
Part, obtain adhesive composition.
In such a way that the thickness of adhesive is 130 μm, obtained adhesive composition is applied to transparent stripping
On liner, LDPE (low density polyethylene (LDPE)) film for being formed by 100 μm of adhesive phase and thickness is bonded, to obtain thickness
230 μm of adhesive tape.
<Comparative example 3>
Mixture methacrylic acid 20mol%, acrylic acid-2-ethyl caproite 30mol%, acrylic acid -2- hydroxyl ethyl esters
10mol%, methyl acrylate 40mol%, are polymerize in the solution, molten to obtain the polymer that weight average molecular weight is 600,000
Liquid.The hydroxyl value of the polymer is 33.5mgKOH/g, acid value 48.6mgKOH/g.
In the polymer solution, relative to 100 mass parts of polymer, mixture as ultraviolet light reaction resin 5
Urethane acrylate oligomer (manufacture of chemical industry Co., Ltd. of the villages Xin Zhong) 100 mass parts of function and 3 functions
The carbamic acid of urethane acrylate oligomer (manufacture of chemical industry Co., Ltd. of the villages Xin Zhong) 10 mass parts and 2 functions
Ester acrylate oligomer (manufacture of chemical industry Co., Ltd. of the villages Xin Zhong) 30 mass parts, the CORONET L (days as crosslinking agent
This polyurethane industrial Co., Ltd. manufacture) 4.0 mass parts, the Irgacure 184 (manufacture of BASF societies) as Photoepolymerizationinitiater initiater
5 mass parts, Ebecryl 350 (manufacture of DAICEL-ALLNEX Co., Ltd.) 0.5 mass parts as additive, are bonded
Agent composition.
In such a way that the thickness of adhesive is 130 μm, obtained adhesive composition is applied to transparent stripping
On liner, the LDPE films for being formed by 100 μm of adhesive phase and thickness are bonded, to obtain the adhesive tape of 230 μm of thickness.
<Comparative example 4>
Mixture methacrylic acid 20mol%, acrylic acid-2-ethyl caproite 35mol%, acrylic acid -2- hydroxyl ethyl esters 5mol%,
Methyl acrylate 40mol%, is polymerize in the solution, to obtain the polymer solution that weight average molecular weight is 200,000.This is poly-
Close object hydroxyl value be 5.5mgKOH/g, acid value 60.8mgKOH/g.
In the polymer solution, relative to 100 mass parts of polymer, mixture as ultraviolet light reaction resin 6
The ammonia of urethane acrylate oligomer (manufacture of chemical industry Co., Ltd. of the villages Xin Zhong) 80 mass parts and 2 functions of function
Urethane acrylate oligomer (manufacture of chemical industry Co., Ltd. of the villages Xin Zhong) 20 mass parts, as crosslinking agent
CORONET L (Nippon Polyurethane Industry Co., Ltd.'s manufacture) 4.0 mass parts, the Irgacure 184 as Photoepolymerizationinitiater initiater
(manufacture of BASF societies) 2.5 mass parts, Ebecryl350 (manufacture of DAICEL-ALLNEX Co., Ltd.) 0.5 matter as additive
Part is measured, adhesive composition is obtained.
In such a way that the thickness of adhesive is 150 μm, obtained adhesive composition is applied to transparent stripping
On liner, the LDPE films for being formed by 100 μm of adhesive phase and thickness are bonded, to obtain the adhesive tape of 250 μm of thickness.
<Comparative example 5>
Mixture methacrylic acid 20mol%, acrylic acid-2-ethyl caproite 60mol%, methyl acrylate 20mol%, molten
It is polymerize in liquid, to obtain the polymer solution that weight average molecular weight is 400,000.The hydroxyl value of the polymer is 0mgKOH/g, acid
Value is 48.8mgKOH/g.
In the polymer solution, relative to 100 mass parts of polymer, CORONET L (day of the mixture as crosslinking agent
This polyurethane industrial Co., Ltd. manufacture) 1.0 mass parts, TETRAD-X (Mitsubishi Gas Chemical Co., Ltd's manufacture) 1.0 mass
Part, obtain adhesive composition.
In such a way that the thickness of adhesive is 130 μm, obtained adhesive composition is applied to transparent stripping
On liner, the LDPE films for being formed by 100 μm of adhesive phase and thickness are bonded, to obtain the adhesive tape of 230 μm of thickness.
<Comparative example 6>
Mixture acrylic acid-2-ethyl caproite 78mol%, acrylic acid -2- hydroxyl ethyl esters 21mol%, methacrylic acid 1mol%,
It is polymerize in the solution, to obtain the polymer solution that weight average molecular weight is 700,000.In the solution, relative to the polymer
100 mass parts mix 5.0 mass parts of isocyanic acid 2- methacryloyloxyethyls (Showa Denko K. K's manufacture, Karenz
MOI), ethylenically unsaturated groups are imported to hydroxyl, it is poly- thus synthesizes the acrylic copolymer containing ethylenically unsaturated groups
Close object (weight average molecular weight：700000, hydroxyl value 38.0mgKOH/g, acid value 6.5mgKOH/g).
CORONET L of the mixture as crosslinking agent in the acrylic copolymer polymer containing ethylenically unsaturated groups
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 1.0 mass parts, TETRAD-X (Mitsubishi Gas Chemical Co., Ltd's manufacture) 0.5 matter
Part, Irgacure 184 (manufacture of BASF societies) 5.0 mass parts as Photoepolymerizationinitiater initiater are measured, adhesive composition is obtained.
In such a way that the thickness of adhesive is 130 μm, obtained adhesive composition is applied to transparent stripping
On liner, the EVA film for being formed by 100 μm of adhesive phase and thickness is bonded, to obtain the adhesive tape of 230 μm of thickness.
<Comparative example 7>
By 95 mass parts of acrylic acid-2-ethyl caproite, 5 mass parts of acrylic acid -2- hydroxyl ethyl esters, as optical free radical initiator
Irgacure 651 (BASF societies manufacture, 50% ethyl acetate solution) 0.2 mass parts and 0.01 mass parts of lauryl mercaptan it is molten
Solution obtains solution in ethyl acetate.Ultraviolet light is irradiated to the solution and is polymerize, the ethyl acetate for obtaining polymer is molten
Liquid.In turn, make isocyanic acid 2- methacryloyloxyethyl (Showa electricians relative to 100 mass parts of the solid constituent of the solution
Co., Ltd.'s manufacture, Karenz MOI) 3.5 mass parts are reacted, synthesize that weight average molecular weight is 700,000, hydroxyl value is
11.1mgKOH/g, acid value are being handed over as (methyl) acrylic resin for containing ethylenically unsaturated groups for 0.9mgKOH/g
Conjuncted acrylic copolymer.
Mixture is as Photoepolymerizationinitiater initiater in the acrylic copolymer polymer containing ethylenically unsaturated groups
(manufacture of BASF societies) 1.0 mass parts of Irgacure 184 and U-324A as urethane acrylate oligomer are (in new
Chemical industry Co., Ltd. of village manufactures) 2.0 mass parts, obtain adhesive composition.
In such a way that the thickness of adhesive is 130 μm, obtained adhesive composition is applied to transparent stripping
On liner, the EVA film for being formed by 100 μm of adhesive phase and thickness is bonded, to obtain the adhesive tape of 230 μm of thickness.
<Comparative example 8>
By 95 mass parts of acrylic acid-2-ethyl caproite, 5 mass parts of acrylic acid -2- hydroxyl ethyl esters, as optical free radical initiator
Irgacure 651 (BASF societies manufacture, 50% ethyl acetate solution) 0.01 mass parts of 0.2 mass parts and lauryl mercaptan
It is dissolved in ethyl acetate, obtains solution.Ultraviolet light is irradiated to the solution and is polymerize, the ethyl acetate for obtaining polymer is molten
Liquid.In turn, make isocyanic acid 2- methacryloyloxyethyl (Showa electricians relative to 100 mass parts of the solid constituent of the solution
Co., Ltd.'s manufacture, Karenz MOI) 3.5 mass parts are reacted, synthesize that weight average molecular weight is 700,000, hydroxyl value is
12.2mgKOH/g, acid value are being handed over as (methyl) acrylic resin for containing ethylenically unsaturated groups for 0.9mgKOH/g
Conjuncted acrylic copolymer.
Mixture is as Photoepolymerizationinitiater initiater in the acrylic copolymer polymer containing ethylenically unsaturated groups
Irgacure 184 (manufacture of BASF societies) 1.0 mass parts, (villages Xin Zhong U-324A as urethane acrylate oligomer
Chemical industry Co., Ltd. manufactures) 2.0 mass parts and SE4050 (Co., Ltd. Admatechs manufactures) 150 matter as filler
Part is measured, adhesive composition is obtained.
In such a way that the thickness of adhesive is 130 μm, obtained adhesive composition is applied to transparent stripping
On liner, the EVA film for being formed by 100 μm of adhesive phase and thickness is bonded, to obtain the adhesive tape of 230 μm of thickness.
<Comparative example 9>
Mixture methacrylic acid 2.0mol%, acrylic acid-2-ethyl caproite 71mol%, acrylic acid -2- hydroxyl ethyl esters
27mol% is polymerize in the solution, to obtain the polymer solution that weight average molecular weight is 200,000.In the solution, relative to
100 mass parts of polymer mixing isocyanic acid 2- acryloyloxyethyl esters, 20 mass parts (Showa Denko K. K's manufacture,
Karenz AOI), ethylenically unsaturated groups are imported to hydroxyl, it is total thus to synthesize the acrylic acid containing ethylenically unsaturated groups
Polymerized polymers (weight average molecular weight：300000, hydroxyl value 12.3mgKOH/g, acid value 7.8mgKOH/g).
CORONET L of the mixture as crosslinking agent in the acrylic copolymer polymer containing ethylenically unsaturated groups
(Nippon Polyurethane Industry Co., Ltd.'s manufacture) 1.5 mass parts, (the BASF societies systems of Irgacure 184 as Photoepolymerizationinitiater initiater
Make) 5.0 mass parts, obtain adhesive composition.
In such a way that the thickness of adhesive is 150 μm, obtained adhesive composition is applied to transparent stripping
On liner, the LDPE films for being formed by 100 μm of adhesive phase and thickness are bonded, to obtain the adhesive tape of 250 μm of thickness.
<Comparative example 10>
Mixture butyl acrylate 96mol%, acrylic acid -2- hydroxyl ethyl ester 4mol%, are polymerize, in the solution to obtain
The polymer solution that weight average molecular weight is 700,000.The hydroxyl value of the polymer is 16.7mgKOH/g, acid value 0mgKOH/g.
In the polymer solution, relative to 100 mass parts of polymer, CORONET L (day of the mixture as crosslinking agent
This polyurethane industrial Co., Ltd. manufactures) 2.5 mass parts, obtain adhesive composition.
In such a way that the thickness of adhesive is 130 μm, obtained adhesive composition is applied to transparent stripping
On liner, the LDPE films for being formed by 100 μm of adhesive phase and thickness are bonded, to obtain the adhesive tape of 230 μm of thickness.
Experiment below is carried out for the adhesive tape made in above-described embodiment and comparative example, evaluates its performance.Evaluation result
It is recorded in following table 1 and 2.
<Measurement/analysis>
The measurement of contact angle and the calculating of surface free energy：
The face for being not provided with adhesive phase of base material film is fixed to the flat chip in surface using double faced adhesive tape.
Thereafter, release liner is removed, diiodomethane and pure water is added dropwise to mutually different position over the binder layer,
The FACE contact angle meter CA-S150 types manufactured using Kyowa Chemical Industry Co., Ltd are measured each contact angle θ.
Then, in order to measure through ultraviolet light irradiation and cured adhesive phase to the contact angle of diiodomethane and pure water, profit
Adhesive tape is fixed to the flat chip in surface with method same as described above.Then, using high-pressure sodium lamp from release liner side into
Row ultraviolet light irradiates, and accumulative exposure is made to reach 500mJ/cm2.After ultraviolet light irradiation, place 1 hour, thereafter by release liner
Stripping, and diiodomethane and pure water are added dropwise to mutually different position, it is manufactured using Kyowa Chemical Industry Co., Ltd
FACE contact angle meter CA-S150 types are measured each contact angle θ.
The value of contact angle θ obtained above is substituted into above-mentioned<Formula 1>Simultaneous equations, calculate adhesive layer surface
Surface free energy.
Hydroxyl value：
It is measured according to JIS K 0070.
Acid value：
According to JIS K5601-2-1:1999 are measured.
<Test example 1>The evaluation of marginal swell
Using Dong Jing machines society manufacture DR8500III (trade name), 725 μm of thickness, 8 inches of diameter silicon wafer on
The polyimide film [HD-8820 (trade name, the manufacture of HD MicroSystems Co., Ltd.)] for forming thick about 10 μm, using by
O2Wafer surface is cleaned in the etching that plasma carries out.Extremely by the adhesive tape gluing made in above-described embodiment and comparative example
The chip with polyimides.Thereafter, using the grinder [DFG8760 of Co., Ltd. DISCO manufactures with Xian Nei mechanisms
(trade name)] it carries out being ground to thickness being 250 μm.25 operations are implemented to each adhesive tape.By wafer storage after grinding defeated
In the box sent, box cover is closed, the protuberance at edge is visually observed.
(edge part protuberance evaluation criteria)
A：25 wholes can't see protuberance
B：Observe that protuberance is 12 or less
C：Observe that protuberance is 13 or more
<Test example 2>Fissility is tested
The fissility of the chip of bumpless is tested：
By the adhesive tape gluing made in Examples and Comparative Examples to the band prepared using method identical with above-mentioned test example 1
The surface of the chip of polyimides.Thereafter, using the grinder [DFG8760 of Co., Ltd. DISCO manufactures with Xian Nei mechanisms
(trade name)] it carries out being ground to thickness being 75 μm, use chip mounter RAD2700 (trade name, Lintec plant with Xian Nei mechanisms
Formula commercial firm manufactures) adhesive tape is removed from chip after grinding.Herein, apply the adhesive tape of the comparative example 5 of Pressuresensitive Adhesive into
Gone 50 DEG C heating stripping.In addition, applying the Examples 1 to 6 of ultraviolet-curing adhesive, comparative example 1~4,6~10
Adhesive tape using high-pressure sodium lamp to add up exposure as 500mJ/cm2Mode irradiate ultraviolet light after removed.
(fissility evaluation criteria)
A：Adhesive tape can all be removed
B：Peeling-off mistake (heat sealing adhesive bad or adhesive tape cutting) can not remove
The fissility of bumped wafer is tested：
By the adhesive tape gluing made in above-described embodiment and comparative example to the weldering with 100 μm of height, 200 μm of convex block spacing
Expect convex block 8 inches of diameter with convex block silicon wafer and height 50 μm, the copper pillar bumps of 100 μm of convex block spacing it is further
The surface of chip with 7 μm of polyimide films [HD-8820 (trade name, the manufacture of HD MicroSystems Co., Ltd.)].
Using method identical with the chip of above-mentioned bumpless by the grinding wafer with solder projection to 100 μ m-thicks, by band
The grinding wafer of copper pillar bumps to 50 μ m-thicks, and using method identical with above-mentioned bumpless chip from chip after grinding by glue
Band stripping.
(fissility evaluation criteria)
A：Adhesive tape can all be removed
B：Peeling-off mistake (mistake is removed because caused by heat sealing adhesive is bad or adhesive tape cutting) can not remove
<Test example 3>Residue glue is evaluated
Using light microscope to the chip with solder projection of adhesive tape has been removed in above-mentioned test example 2 and with copper post it is convex
The wafer surface of the chip of block is observed, and is evaluated the presence or absence of residue glue.
(residue glue evaluation criteria)
A：Without residue glue
B：Chip with copper pillar bumps or any one of the chip with solder projection have residue glue
C：Chip with solder projection and the chip with copper pillar bumps have residue glue
<Test example 4>Fitness test
The DR8500III (trade name) manufactured using Dong Jing machines society, in operating temperature and roll temperature：Room temperature (23
DEG C), laminate pressure：By the adhesive tape gluing made in above-described embodiment and comparative example to 100 μ of height under conditions of 0.4MPa
M, the surface with convex block silicon wafer of 8 inches of the diameter of the solder projection of 200 μm of convex block spacing.
Adaptation at this time is confirmed by visual observation, whether there is or not air to be mixed between investigation adhesive tape and chip.
(evaluation criteria of adaptation)
A：It was also mixed into without air more than 48 hours after fitting
B：After fitting more than 24 to 48 hours between have being mixed into for air
C：After rigid fitting~there is being mixed into for air between 24 hours
Show the result in following table 1.
The adhesive tape of comparative example 1~4 is the example that the surface free energy in the adhesive face after ultraviolet light (UV) irradiation reduces.If
Using the adhesive tape of comparative example 1~4, then the result that the marginal swell caused by box is stored occurs with high probability can be obtained.In turn, than
Compared with being poor result at least one assessment item of the adhesive tape of example 1~4 in fissility, residue glue and adaptation.
The adhesive tape of comparative example 5 and 10 has used Pressuresensitive Adhesive, is as a result easy to happen marginal swell (comparative example 5), separately
Outside, a large amount of residue glue (comparative example 5 and 10) is generated in stripping.
Although the surface free energy that the adhesive tape of comparative example 6~8 is the adhesive face after UV irradiations rises its degree and is less than
The example of range given to this invention.If using the adhesive tape of comparative example 6~8, the result that residue glue occurs after stripping is obtained.
In turn, become poor at least one assessment item of the adhesive tape of comparative example 6~8 in marginal swell, fissility and adaptation
As a result.
The surface free energy of the adhesive of the UV pre-irradiations of the adhesive tape of comparative example 9 is less than value given to this invention
Value.Its result：It is insufficient from the peeling force of convex block chip, although there is no residue glue in the chip with solder projection, with polyamides
The copper pillar bumps chip of imines film has residue glue.
In contrast, using the adhesive tape of Examples 1 to 6, all non-flanged is swelled.In addition, even for tool
There is the surface of the convex block of 100 μm of height to also show that excellent adaptation, even if also not confirming sky more than 48 hours after fitting
Gas is mixed into.In turn, in stripping, adhesive tape will not be cut off, and residue glue does not also occur.
In conjunction with embodiments thereof, the present invention is described, but applicants contemplate that, as long as no specifying, then originally
Invention is not limited in any details of explanation, should not violate spirit and range shown in the appended claims
In the case of carry out wide in range explanation.
This application claims the Japanese Patent Application 2014-205465's for carrying out patent submission in Japan based on October 6th, 2014
Priority is introduced by it with reference to this and using its content as a part for this specification contents.
Symbol description
10 adhesive tapes
11 base material films
12 adhesive phases
13 semiconductor wafers
Claims (7)
1. a kind of band convex block semiconductor wafer surface protection adhesive tape, to have ultra-violet solidified bonding on base material film
The band convex block semiconductor wafer surface protection adhesive tape of oxidant layer, which is characterized in that
It is 10,000 or more 200 ten thousand or less and with the carbon-to-carbon double bond of type containing radiation-curing that the adhesive phase, which contains weight average molecular weight,
(methyl) acrylate copolymer of group, hydroxyl and carboxyl,
The surface free energy of the adhesive layer surface of ultraviolet light pre-irradiation is 25.5mN/m less than 35mN/m,
The surface phase on the surface and the adhesive phase of ultraviolet light pre-irradiation of the adhesive phase after the solidification of ultraviolet light irradiation
The high 5mN/m or more of specific surface free energy,
The surface phase on the surface and the adhesive phase of ultraviolet light pre-irradiation of the adhesive phase after the solidification of ultraviolet light irradiation
Than, it is small to the contact angle of diiodomethane,
Before (methyl) acrylate copolymer is the importing radiation-curing type carbon-to-carbon double bond group for making to have hydroxyl and carboxyl
Polymer with radiation-curing type carbon-to-carbon double bond group compound react obtained from polymer, formation this lead
In the whole monomer components for entering the polymer before radiation-curing type carbon-to-carbon double bond group, including (methyl) acrylic acid 1mol%
~10mol%,
The hydroxyl value for constituting the polymer of described adhesive layer surface is 30mgKOH/g~100mgKOH/g,
The acid value for constituting the polymer of described adhesive layer surface is 10mgKOH/g~35mgKOH/g.
2. band convex block semiconductor wafer surface protection adhesive tape as described in claim 1, which is characterized in that described that there is radiation
The compound of line curing type carbon-to-carbon double bond group is isocyanic acid 2- (methyl) acryloyloxyethyl ester.
3. band convex block semiconductor wafer surface protection adhesive tape as claimed in claim 2, which is characterized in that relative to described
The blend amount of 100 mass parts of (methyl) acrylate copolymer, isocyanic acid 2- (methyl) acryloyloxyethyl ester is 1 mass parts
~20 mass parts.
4. band convex block semiconductor wafer surface protection adhesive tape according to any one of claims 1 to 3, which is characterized in that
Relative to 100 mass parts of (methyl) acrylate copolymer, the mass parts of 0.1 mass parts of mixture crosslinking agent~5.
5. a kind of processing method with convex block semiconductor wafer, to use the band convex block described in any one of Claims 1 to 44
The processing method with convex block semiconductor wafer of semiconductor wafer surface protection adhesive tape, which is characterized in that the processing method packet
Include following processes (A)~(D)：
Process (A) has the surface of convex block to be bonded the band convex block semiconductor wafer surface in the formation with convex block semiconductor wafer
The process of protection adhesive tape；
Process (B), to the convex block semiconductor wafer and patch with convex block semiconductor wafer surface protection adhesive tape
The process that the surface of conjunction face opposite side is ground；
Process (C) irradiates ultraviolet light with adhesive tape to the band convex block semiconductor wafer surface protection and the band convex block is made partly to lead
The cured process of body wafer surface protection adhesive tape；And
Process (D) removes the work with convex block semiconductor wafer surface protection adhesive tape from described with convex block semiconductor wafer
Sequence.
6. the processing method as claimed in claim 5 with convex block semiconductor wafer, which is characterized in that the band convex block semiconductor
Chip has insulating layer with the binding face with convex block semiconductor wafer surface protection adhesive tape.
7. such as the processing method described in claim 5 or 6 with convex block semiconductor wafer, which is characterized in that the height of the convex block
Degree is 15 μm or more.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014010821 | 2014-01-23 | ||
| JP2014205465A JP5718515B1 (en) | 2014-01-23 | 2014-10-06 | Adhesive tape for protecting semiconductor wafer surface and method for processing semiconductor wafer |
| JP2014-205465 | 2014-10-06 | ||
| PCT/JP2015/062946 WO2016056269A1 (en) | 2014-01-23 | 2015-04-30 | Adhesive tape for protecting semiconductor wafer surface and method for processing semiconductor wafer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107075322A CN107075322A (en) | 2017-08-18 |
| CN107075322B true CN107075322B (en) | 2018-09-18 |
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ID=53277434
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580056130.XA Active CN107075322B (en) | 2014-01-23 | 2015-04-30 | The processing method of semiconductor wafer surface protection adhesive tape and semiconductor wafer |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5718515B1 (en) |
| KR (1) | KR101840179B1 (en) |
| CN (1) | CN107075322B (en) |
| TW (1) | TWI573852B (en) |
| WO (1) | WO2016056269A1 (en) |
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|---|---|---|---|---|
| JP5718515B1 (en) * | 2014-01-23 | 2015-05-13 | 古河電気工業株式会社 | Adhesive tape for protecting semiconductor wafer surface and method for processing semiconductor wafer |
| JP6382240B2 (en) * | 2016-01-18 | 2018-08-29 | 古河電気工業株式会社 | Adhesive tape for electronic parts |
| JP6382239B2 (en) * | 2016-01-18 | 2018-08-29 | 古河電気工業株式会社 | Adhesive tape for electronic parts |
| JP6904368B2 (en) | 2017-01-23 | 2021-07-14 | 東京エレクトロン株式会社 | Semiconductor substrate processing method and semiconductor substrate processing equipment |
| JP6324573B1 (en) * | 2017-03-31 | 2018-05-16 | 古河電気工業株式会社 | Adhesive composition, method for producing semiconductor wafer surface protective tape using the same, and semiconductor wafer surface protective tape |
| JP7241022B2 (en) * | 2017-10-27 | 2023-03-16 | リンテック株式会社 | Film for forming protective film, composite sheet for forming protective film, and method for producing semiconductor chip |
| JP7079609B2 (en) * | 2018-01-19 | 2022-06-02 | 日東電工株式会社 | Masking tape for forming electromagnetic wave shield |
| JP7255241B2 (en) * | 2018-03-09 | 2023-04-11 | 三菱ケミカル株式会社 | Active energy ray-curable peelable pressure-sensitive adhesive composition and peelable pressure-sensitive adhesive sheet |
| KR102228537B1 (en) * | 2018-03-23 | 2021-03-15 | 주식회사 엘지화학 | Back-grinding tape |
| KR102220313B1 (en) | 2018-06-20 | 2021-02-25 | 주식회사 엘지화학 | Adhesieve composition |
| JPWO2020137980A1 (en) * | 2018-12-25 | 2021-11-18 | 積水化学工業株式会社 | Adhesive tape |
| JP2020150196A (en) * | 2019-03-15 | 2020-09-17 | 日東電工株式会社 | Dicing tape with adhesive film |
| KR20220002240A (en) * | 2019-04-26 | 2022-01-06 | 세키스이가가쿠 고교가부시키가이샤 | adhesive tape |
| WO2020225919A1 (en) * | 2019-05-09 | 2020-11-12 | 昭和電工マテリアルズ株式会社 | Adhesive set, and structure manufacturing method |
| KR102662154B1 (en) | 2019-07-02 | 2024-04-30 | 모건 애드히시브스 컴퍼니, 엘엘씨 | Silicone composition containing an acrylate cure accelerator |
| JP6756398B1 (en) * | 2019-10-11 | 2020-09-16 | 住友ベークライト株式会社 | Adhesive tape |
| JP7453831B2 (en) * | 2020-03-31 | 2024-03-21 | マクセル株式会社 | Laminated body with self-healing properties, method for manufacturing the same, and method for using the same |
| JPWO2022201789A1 (en) * | 2021-03-22 | 2022-09-29 | ||
| JP7479336B2 (en) | 2021-08-06 | 2024-05-08 | 古河電気工業株式会社 | Semiconductor manufacturing process transport tape |
| WO2023085409A1 (en) * | 2021-11-12 | 2023-05-19 | デンカ株式会社 | Adhesive tape and processing method |
| WO2023188714A1 (en) * | 2022-03-31 | 2023-10-05 | デンカ株式会社 | Adhesive tape and processing method |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2015157931A (en) | 2015-09-03 |
| TW201614022A (en) | 2016-04-16 |
| KR101840179B1 (en) | 2018-03-19 |
| TWI573852B (en) | 2017-03-11 |
| JP5718515B1 (en) | 2015-05-13 |
| WO2016056269A1 (en) | 2016-04-14 |
| CN107075322A (en) | 2017-08-18 |
| KR20170055552A (en) | 2017-05-19 |
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