CN103733316A - Surface protecting adhesive tape for use in semiconductor processing - Google Patents

Surface protecting adhesive tape for use in semiconductor processing Download PDF

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Publication number
CN103733316A
CN103733316A CN201380002367.0A CN201380002367A CN103733316A CN 103733316 A CN103733316 A CN 103733316A CN 201380002367 A CN201380002367 A CN 201380002367A CN 103733316 A CN103733316 A CN 103733316A
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CN
China
Prior art keywords
methyl
adhesion
acrylate
mass parts
wafer
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Granted
Application number
CN201380002367.0A
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Chinese (zh)
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CN103733316B (en
Inventor
内山具朗
横井启时
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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Publication of CN103733316A publication Critical patent/CN103733316A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic 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
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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 used during dicing or grinding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
    • H01L2221/6834—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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 used to protect an active side of a device or wafer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus 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
    • H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (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

Provided is a surface protecting adhesive tape for use in semiconductor processing, having an adhesive layer on a substrate, wherein the adhesive tape has a probe tack force B of 0.08 to 0.20 (MPa), and a ratio C (A/B) of an adhesive force A (N/25mm) of the adhesive tape to the probe tack force B (MPa) thereof is 10 (N/25mm/MPa) or more.

Description

Semiconductor machining surface protection adhesion zone
Technical field
The present invention relates to the surface protection adhesion zone that a kind of semiconductor device machining is used, more specifically, the present invention relates to grind preferred semiconductor machining surface protection adhesion zone while cutting for back surface of semiconductor wafer.
Background technology
In the procedure of processing of semiconductor wafer (being designated as below wafer), after wafer surface forms pattern, carry out the so-called back side and grind and cut, grind, chip back surface is ground and cut, be ground to specific thicknesses.Now, in order to protect wafer surface, at wafer surface coating surface protection adhesion zone, and under this state, chip back surface is ground and cut.As surface protection adhesion zone; proposed a kind of surface protection adhesion zone, it is provided with on the polyolefin substrate resin moldings such as EVAc (being designated as below EVA) usings the adhering agent layer (for example, with reference to patent documentation 1) of acrylic acid series polymeric compounds as principal component.
In the pattern of wafer surface, exist various electronic circuits or electrode, the diaphragms such as polyimides that these are protected and wafer monolithic is changed into chip cut brilliant step time the blade groove (line of rabbet joint) cut.Due to structure as above, cause wafer surface unsmooth, there is the jump, concavo-convex of number μ m～tens of μ m.
This rank extent or shape are various because of the kind of wafer or device, and industry expects to protect by coating surface the closely sealed gap of filling up of jump of adhesion zone and wafer surface.Yet; in the situation that jump is large or band is harder of wafer, surface protection adhesion zone is not enough to the attaching of wafer surface, thereby produces so-called percolation phenomenon; grind overleaf while cutting or during cmp, grind and cut water or lapping liquid (slurry) penetrates among the gap of wafer and band.
Owing to producing seepage flow, cause band to peel off and take this position from wafer and cause breakage as starting point produces slight crack in wafer, or become the reason that produces the pollution of the wafer surface being caused by water leaking-in or adhering to of thickener and make rate of finished products severe exacerbation.
For seepage flow, known have the methods such as modulus of elasticity of utilizing thickening sticker, reducing sticker to improve the method for the adaptation of wafer surface (for example, with reference to patent documentation 2).In addition, by improving adhesion strength, also can expect identical effect.
By adopting method as above, the adhesion of band rises simultaneously.So-called adhesion, stickiness sense when it refers to what is called by finger contact surface, it is in order to meet the necessary characteristic of fundamental prerequisite of the adhesion zone that is adhered to to-be-adhered object.
On the other hand, excessively strong adhesion will cause the adhesion zone drawback that is seen everywhere in use.For example, while, protection adhesion zone being conformed on wafer, use the device of so-called make-up machine.Band in roll coil of strip out position is supported and is peeled off mold release film by various rollers, fits on wafer and cuts into wafer shape, and finally batching need not part recovery.(for example, with reference to patent documentation 3)
When adhesion zone is fitted in and is batched after wafer, the part that exists sticker to contact with support roller.If the adhesion of band is larger, exist band to be difficult to peel off and the situation of direct winfing on roller from roller.
Therefore, industry expectation is a kind of has concurrently the comparatively sufficient adhesion strength of wafer surface protection and the band on the less adhesion of workability impact.
Prior art document
Patent documentation
[patent documentation 1] TOHKEMY 2000-8010 communique
[patent documentation 2] TOHKEMY 2002-53819 communique
[patent documentation 3] TOHKEMY 2010-98132 communique
Summary of the invention
Problem of the present invention is to address the above problem; a kind of semiconductor machining surface protection adhesion zone is provided; processing at semiconductor wafer; specifically; the back side of silicon wafer etc. is ground and is cut in step; even for jump or concavo-convex large wafer, can be because its adhesion strength causes producing seepage flow yet, and workability is good.
The inventor etc. concentrate on studies to above-mentioned problem, found that, the semiconductor machining of the ratio of adhesion strength and probe adhesion in particular range can be ground overleaf to cut in step with surface protection adhesion zone and be prevented from seepage flow from bringing good workability.The present invention completes based on this opinion.
That is, the present invention utilizes following method to solve above-mentioned problem.
(1) a semiconductor machining surface protection adhesion zone, it has adhering agent layer on base material,
The probe adhesion B of this adhesion zone is 0.08～0.20 (MPa), and the adhesion strength A of this adhesion zone (N/25mm) is more than 10 (N/25mm/MPa) with the ratio C (A/B) of probe adhesion B (MPa).
(2) the semiconductor machining surface protection adhesion zone as described in above-mentioned (1), wherein, above-mentioned adhesion strength A is 0.9～2.0 (N/25mm).
(3) the semiconductor machining surface protection adhesion zone as described in above-mentioned (1) or (2), wherein, the thickness of above-mentioned adhering agent layer is 15～55 μ m.
(4) the semiconductor machining surface protection adhesion zone as described in any one in above-mentioned (1) to (3), wherein, above-mentioned base material consists of vinyl-vinyl acetate copolymer.
According to the present invention, a kind of semiconductor machining surface protection adhesion zone can be provided, in the processing of semiconductor wafer, specifically, at the back side of silicon wafer etc., grind and cut in step, even if also can prevent seepage flow for jump or concavo-convex large wafer, and improve workability.
By following record, above-mentioned and further feature of the present invention and advantage are further illustrated.
Embodiment
Semiconductor machining of the present invention with surface protection with adhesion zone by base material and be formed at sticker (adhesion agent layer) on base material and form.
For the resin that forms base material used in the present invention, there is no particular restriction, can use existing known resin.The example of the resin using as base material of the present invention, can list high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE), polypropylene (PP), vinyl-vinyl acetate copolymer (EVA), ethene-(methyl) acrylic copolymer or their TPO such as metal corsslinking thing (ionomer); The polyesters such as polyethylene terephthalate (PET), Polyethylene Naphthalate (PEN), polybutylene terephthalate (PBT).Various resins can be used alone a kind of or two or more blending are used.Base material used in the present invention can be single layer structure, also resin of more than two kinds capable of being combined or make sandwich construction with blending resin.From grinding chip warpage cutting or the viewpoint of flexibility, more preferably use vinyl-vinyl acetate copolymer (EVA) base material.In the vinyl-vinyl acetate copolymer that base material is used, the content of vinyl acetate composition is preferably 5～30 quality %, more preferably 10～20 quality %.
In substrate resin, can add in order to identification, identification adhesion zone painted with pigment etc., can in the scope without impact, add additive to physical property.
Thickness to base material is not particularly limited, and can suitably set, and is preferably 50～200 μ m.
Manufacture method to above-mentioned base material is not particularly limited.Can use injection, extrude, the existing method such as blowing.
Sticker used in the present invention is that more than 10 (N/25mm/MPa) there is no particular restriction as long as meet the adhesion strength A (N/25mm) of the formed adhesion zone of this sticker of use with the ratio C (A/B) of probe adhesion B (MPa).For example, can list and using (methyl) acrylate as the homopolymers of constituent or there is two or more (methyl) acrylate as the copolymer of constituent.As this (methyl) acrylate, preferably carbon number be the straight chain below 30 or the alkyl with side chain (for example, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, isobutyl group, amyl group, isopentyl, hexyl, heptyl, cyclohexyl, 2-ethylhexyl, octyl group, iso-octyl, nonyl, different nonyl, decyl, isodecyl, undecyl, lauryl, tridecyl, myristyl, stearyl, octadecyl and dodecyl) (methyl) alkyl acrylate, more preferably the straight chain that carbon number is 4～18 or there is (methyl) alkyl acrylate of the alkyl of side chain.
In above-mentioned copolymer, as the constituent beyond above-mentioned (methyl) alkyl acrylate, such as listing the carboxylic monomer components such as acrylic acid, methacrylic acid, (methyl) acrylic acid carboxyl ethyl ester, (methyl) acrylic acid carboxyl pentyl ester, itaconic acid, maleic acid, fumaric acid and butenoic acid; The anhydride monomers such as maleic anhydride or itaconic anhydride composition; The monomer component of the hydroxyls such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, the own ester of (methyl) acrylic acid 6-hydroxyl, (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid 10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) acrylic acid 12-hydroxyl lauryl and (methyl) acrylic acid (4-hydroxymethyl cyclohexyl) methyl esters; Styrene sulfonic acid, allyl sulphonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide propane sulfonic acid, (methyl) acrylic acid sulphur propyl ester and (methyl) acryloxy naphthalene sulfonic acids etc. are containing sulfonic monomer component; The monomer component of the phosphorous acidic groups such as phosphoric acid 2-hydroxyethyl acryloyl group ester; (methyl) acrylamide, (methyl) acrylic acid N-hydroxymethyl acid amides, (methyl) acrylic acid alkyl amido Arrcostab (for example, dimethylaminoethyl acrylate methyl base amido ethyl ester, methacrylic acid tert-butyl group amido ethyl ester etc.), N-vinyl pyrrole pyridine ketone, acryloyl morpholine, vinyl acetate, styrene, acrylonitrile etc.In above-mentioned copolymer, can contain one or more these monomer components.
In addition, above-mentioned copolymer can contain following multi-functional monomer component as constituent.Example as this multi-functional monomer component, can list hexylene glycol two (methyl) acrylate, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol monohydroxy five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, epoxy (methyl) acrylate, (methyl) acrylic polyester and (methyl) acrylic amine carbamate etc.In above-mentioned copolymer, can contain one or more these multi-functional monomer component.
Above-mentioned copolymer is such as containing (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) glycidyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate etc. as (methyl) acrylate composition.
Sticker used in the present invention is preferably to comprise has two aspects of acrylate and methacrylate as the copolymer of constituent.In addition, sticker used in the present invention and then be preferably comprises alcohol portion and has two aspects of substituent (methyl) acrylate as the copolymer of constituent without (methyl) acrylate and the alcohol portion that replace.In addition, as alcohol portion, there is this substituting group in substituent situation, preferred alkyl, hydroxyl or epoxy radicals.As alcohol portion, there is substituent (methyl) acrylate, preferably (methyl) acrylic acid 2-hydroxy methacrylate or (methyl) glycidyl acrylate.
In the contained copolymer of sticker used in the present invention, preferred alcohols portion is 40～60 quality % without the content of (methyl) acrylate composition replacing.In addition, the alcohol portion in preferred copolymer is more without the methacrylate component content replacing than alcohol portion without the acrylate component content replacing.Without the acrylate composition replacing, the content in above-mentioned copolymer is preferably 25～50 quality % in alcohol portion.
On the other hand, the content of (methyl) 2-EHA composition that alcohol portion has a substituent form in above-mentioned copolymer is preferably 35～50 quality %, and preferred content is 40～50 quality %.Should be preferably 2-EHA by (methyl) 2-EHA.
And then above-mentioned copolymer preferably contains (methyl) glycidyl acrylate composition.Be somebody's turn to do more preferably 1～5 quality % of the content of (methyl) glycidyl acrylate in above-mentioned copolymer.Should be preferably glycidyl methacrylate by (methyl) glycidyl acrylate.
Above-mentioned copolymer preferably contains (methyl) acrylic component.The content of (methyl) acrylic component in above-mentioned copolymer is preferably 0.5～5 quality %.Should be preferably methacrylic acid by (methyl) acrylic acid.
For the above-mentioned copolymer that is preferably used as sticker used in the present invention, preferably use surfactant to carry out the copolymer of emulsion polymerization gained.As surfactant, preferred anionic is surfactant, the preferred sulfuric acid of polyoxyethylene alkyl phenyl ether, and wherein preferably addition has the sulfuric acid of allylic polyoxyethylene alkyl phenyl ether on phenyl ring.In addition, during preferred polymeric and with polypropylene glycol or polyethylene glycol.In addition, preferably use pure water through deionization as reaction dissolvent.Moreover, as polymerization initiator, can be any polymerization initiator, preferably persulfate.
In the present invention, in sticker, can use curing agent.
As curing agent, can use the curing agent of recording in TOHKEMY 2007-146104 communique.For example can list 1, two (the N of 3-, N-diglycidyl aminomethyl) cyclohexane, 1, two (N, the N-diglycidyl aminomethyl) toluene, 1 of 3-, the two (N of 3-, N-diglycidyl aminomethyl) benzene, N, N, N, has two epoxy compoundss of epoxy radicals above in N'-four glycidyl group m-xylene diamine equimolecular; 2,4-toluene di-isocyanate(TDI), 2,6-toluene di-isocyanate(TDI), 1,3-XDI, Isosorbide-5-Nitrae-XDI, diphenyl methane-4, have two isocyanate compounds of NCOs above in 4'-vulcabond equimolecular; In tetra methylol-tri--β-'-aziridino propionic ester, trihydroxy methyl-tri--β-'-aziridino propionic ester, trimethylolpropane-tri--β-'-aziridino propionic ester, trimethylolpropane-tri--β-(2-methylaziridine) propionic ester equimolecular, there is the aziridine cpd of two above '-aziridinos etc.The content of curing agent is adjusted according to required adhesion strength, and with respect to above-mentioned polymer 100 mass parts, the content of curing agent is preferably 0.01～10 mass parts, more preferably 0.1～5 mass parts.
In addition, in the present invention, also can make to contain in adhering agent layer optical polymerism compound and Photoepolymerizationinitiater initiater.By containing Photoepolymerizationinitiater initiater, can adhering agent layer be solidified by irradiation ultraviolet radiation, reduce the adhesion strength of adhering agent layer.As this optical polymerism compound, for example can use as in Japanese kokai publication sho 60-196956 communique and Japanese kokai publication sho 60-223139 communique disclosed can be by irradiation solid nettedization in molecule, at least there is the low molecular weight compound of more than two optical polymerism carbon-to-carbon double bond.
Particularly, for example can use trimethylolpropane triacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol monohydroxy five acrylate, dipentaerythritol acrylate or 1,4-butanediol diacrylate, 1,6-hexanediyl ester, polyethyleneglycol diacrylate, the commercially available few ester of acrylic acid.
As Photoepolymerizationinitiater initiater, can use the Photoepolymerizationinitiater initiater of recording in TOHKEMY 2007-146104 communique or TOHKEMY 2004-186429 communique.In addition, for example, can and use isopropyl benzoin ether, isobutyl group benzoin ether, benzophenone, meter Qi Le ketone, clopenthixal ketone, benzil methyl ketal, Alpha-hydroxy cyclohexyl-phenyl ketone, 2-hydroxymethyl phenyl-propane.
As adhering agent layer, can use the optical polymerism sticker that utilizes the resin combination contain polymer, Photoepolymerizationinitiater initiater and the curing agent in polymer with optical polymerism carbon-to-carbon double bond to form.As the polymer in polymer with carbon-to-carbon double bond, preferably utilize any means on one or more side chain, to there is (methyl) acrylic acid series polymeric compounds that carbon number is 4～12, more preferably the monomer of (methyl) acrylate etc. of the alkyl of carbon number 8 or the equal polymerization of combined polymerization upgrading monomer or combined polymerization form.
For the optical polymerism adhering agent layer forming in this way, by irradiating radioactive ray, being preferably ultraviolet ray, can make adhesion strength from initially significantly declining, can easily from to-be-adhered object, peel off adhesion zone.
In the present invention, the thickness of adhering agent layer can suitably be set according to the to-be-adhered object of wish application, and to it, there is no particular restriction, is preferably 15～55 μ m, more preferably 20～50 μ m.If surpass 55 μ m, produce the possibility of the residual grade of the paste of wafer is improved, otherwise, if lower than 15 μ m, cannot chase after the concavo-convex of attached wafer surface, thereby there is the possibility of the essential factor that becomes seepage flow etc.
Semiconductor machining of the present invention is more than 10 (N/25mm/MPa) with the adhesion strength A (N/25mm) of adhesive surface band and the ratio C (C=A/B) of probe adhesion B (MPa).By being set within the scope of this, even if can have for jump or concavo-convex large wafer, do not produce the adhesion strength of seepage flow yet, and make workability keep good.This is preferably 10～60 (N/25mm/MPa) than C, more preferably 10～40 (N/25mm/MPa).
Herein, adhesion strength A is preferably 0.8～4.0N/25mm, more preferably 0.9～2.0N/25mm.On the other hand, probe adhesion B is preferably below 0.20MPa, more preferably 0.08～0.20MPa, more preferably 0.10～0.20MPa.
For adhesion strength A and probe adhesion B, utilize following methods according to JIS Z0237, to measure respectively.
< adhesion strength A >
Use is carried out water mill by the SUS304 steel plate of washing, degreasing equably with the water-proof abrasive paper of #280; after grinding, place 1 hour; then the rubber rollers that makes 2kg loading is carried out 3 times to the wide semiconductor machining of 25mm with the surface of surface protection adhesion zone and is come and gone; this adhesion zone of fitting; place after 1 hour; with peel angle 180 degree, draw speed 300mm/min, the condition of measuring 23 ℃ of temperature, obtain the loading while peeling off, obtain thus adhesion strength A.
< probe adhesion B >
Use adherence test machine (TACII that for example Rhesca manufactures) by the substrate backside side (opposition side of sticker applicator surface) of surface protection adhesion zone, with the speed of 30mm/min, to be pressed into the cylindric probe of 3mm φ in semiconductor machining; under room temperature, with static load 100g, keep after 1sec; speed with 600mm/min lifts, and by the loading of measuring now, obtains probe adhesion B.
Kind and the amount of kind, the especially monomer component of the polymer that adhesion strength A and probe adhesion B can be used according to the kind of the type of polymer in adhering agent layer or additive or amount, especially sticker are adjusted.In addition,
Probe adhesion also can be adjusted according to the kind of base material.For by above-mentioned than C, be adjusted to 10 (N/25mm/MPa) more than, be preferably base material, adhering agent layer be made as to above-mentioned preferable range.
And then, the additives such as modulus of elasticity, molecular weight, glass transition temperature (Tg) or the curing agent of the polymer (above-mentioned polymer) that adhesion strength A and probe adhesion B are used because of adhering agent layer, plasticiser, release agent, filler change, and especially the impact of Tg, quality mean molecule quantity, curing agent is larger.Therefore, for by above-mentioned than C, be adjusted to 10 (N/25mm/MPa) more than, Tg after crosslinked is made as to-50～-10 ℃, is preferably-40～-20 ℃, or quality mean molecule quantity is made as more than 800,000, is preferably more than 1,000,000, or with respect to polymer 100 mass parts, the mixing umber of curing agent is adjusted to 0.3～1.8 mass parts, is preferably 0.5～1.5 mass parts, also can be set as target zone thus.
[embodiment]
Below, based on embodiment and comparative example, the present invention is described in detail, but the present invention is not limited to this.
(embodiment 1)
To make an addition to addition on phenyl ring in deionized pure water, have allylic polyoxyethylene alkyl phenyl ether compound and polypropylene glycol compound as surfactant, add ammonium persulfate as polymerization initiator, one side heating one side stirs.Then, methyl methacrylate 16 mass parts, butyl acrylate 40 mass parts, 2-EHA 40 mass parts, glycidyl methacrylate 2 mass parts and methacrylic acid 2 mass parts are dropped in agitating solution, and then lasting stirring carried out polymerization, acquisition acrylic emulsion adhesive composition A.
By extrusion molding, film forming goes out the base material consisting of vinyl-vinyl acetate copolymer (EVA) of thickness 165 μ m; use the adhesive composition A of above-mentioned composition; the mode that the thickness of take after coating is 40 μ m forms layer thereon, obtains semiconductor machining surface protection adhesion zone.Utilize method described later to measure adhesion strength and the probe adhesion of this adhesion zone, result adhesion strength is 1.18N/25mm, and probe adhesion is 0.10MPa.
(embodiment 2)
Respectively the methyl methacrylate of above-mentioned adhesive composition A is changed to 10 mass parts; 2-EHA is changed to 46 mass parts; change to thus adhesion strength is adjusted to 1.24N/25mm, probe adhesion is adjusted to the adhesive composition B of 0.11MPa; in addition, utilize the method identical with embodiment 1 to obtain semiconductor machining surface protection adhesion zone.
(embodiment 3)
To make an addition to addition on phenyl ring in deionized pure water, have the ammonium salt compound of allylic polyoxyethylene nonylplenyl ether sulfuric ester and polypropylene glycol compound as surfactant, add ammonium persulfate as polymerization initiator, one side heating one side stirs.Then, methyl methacrylate 15 mass parts, butyl acrylate 30 mass parts, 2-EHA 43 mass parts and glycidyl methacrylate 2 mass parts are dropped in agitating solution, and then lasting stirring carried out polymerization, acquisition acrylic emulsion adhesive composition C.
By extrusion molding, film forming goes out the base material consisting of vinyl-vinyl acetate copolymer (EVA) of thickness 70 μ m, polypropylene screen (PP) laminating by it with the 40 μ m that extend through twin shaft, and obtaining aggregate thickness is the sandwich construction base material of 110 μ m.Use the adhesive composition C of above-mentioned composition, the mode that becomes 20 μ m with the thickness after applying forms layer on this base material, obtains semiconductor machining surface protection adhesion zone.The adhesion strength of this adhesion zone is 3.20N/25mm, and adhesion is 0.16MPa.
(embodiment 4)
To add addition on phenyl ring in deionized pure water, have allylic polyoxyethylene alkyl phenyl ether compound and polypropylene glycol compound as surfactant, add ammonium persulfate as polymerization initiator, one side heating one side stirs.Then, methyl methacrylate 15 mass parts, butyl acrylate 35 mass parts, 2-EHA 45 mass parts, glycidyl methacrylate 2 mass parts and methacrylic acid 1 mass parts are dropped in agitating solution, and then lasting stirring carried out polymerization, acquisition acrylic emulsion adhesive composition D.
By extrusion molding, film forming goes out the base material consisting of vinyl-vinyl acetate copolymer (EVA) of thickness 120 μ m; the adhesive composition D of (methyl) acrylic copolymer as the above-mentioned composition of principal component usingd in use; the mode that becomes 50 μ m with the thickness after coating forms layer thereon, obtains semiconductor machining surface protection adhesion zone.The adhesion strength of this adhesion zone is 1.38N/25mm, and adhesion is 0.11MPa.
(embodiment 5)
By the methacrylic acid of above-mentioned adhesive composition D is changed to 5 mass parts; and be altered to, adhesion strength is adjusted to 3.75N/25mm, probe adhesion is adjusted to the adhesive composition E of 0.10MPa; in addition, utilize the method identical with embodiment 4 to obtain semiconductor machining surface protection adhesion zone.
(comparative example 1)
Make methyl acrylate 5 mass parts, 2-EHA 60 mass parts and the polymerization in ethyl acetate solution of methyl methacrylate 5 mass parts, and obtain acrylic acid series copolymer.To blending addition system isocyanate-based crosslinking agent Coronate L (trade name in the acrylic acid series copolymer being polymerized, the manufacture of Nippon Polyurethane company) 0.5 mass parts and epoxy are curing agent E-5XM (trade name, combine and grind chemistry manufacture) 2 mass parts, in order to be adjusted to the viscosity of easy coating, add ethyl acetate adjustment, obtain adhesive composition F.
By extrusion molding, film forming goes out the base material consisting of vinyl-vinyl acetate copolymer (EVA) of thickness 165 μ m; the adhesive composition F of (methyl) acrylic copolymer as the above-mentioned composition of principal component usingd in use; the mode that becomes 40 μ m with the thickness after coating forms layer thereon, obtains semiconductor machining surface protection adhesion zone.Adhesion strength is 0.31N/25mm, and probe adhesion is 0.11MPa.
(comparative example 2)
By being curing agent by the epoxy of above-mentioned adhesive composition F, combined amount changes to 0.5 mass parts; and be altered to, adhesion strength is adjusted to 1.88N/25mm, probe adhesion is adjusted to the adhesive composition G of 0.30MPa; in addition, utilize the method identical with comparative example 1 to obtain semiconductor machining surface protection adhesion zone.
(comparative example 3)
By extrusion molding, by vinyl-vinyl acetate copolymer (EVA) and high density polyethylene (HDPE) (HDPE) lamination, obtain EVA (70 μ m)/HDPE (30 μ m) the sandwich construction base material of thickness 100 μ m.In addition, obtained acrylic acid series copolymer, it makes butyl acrylate 85 mass parts and acrylic acid 2-hydroxy methacrylate 15 mass parts polymerization gained in ethyl acetate solution.To blending addition system isocyanate-based crosslinking agent Coronate L (trade name in the acrylic acid series copolymer being polymerized, Nippon Polyurethane company manufactures) 0.5 mass parts, in order to be adjusted to the viscosity of easy coating, add ethyl acetate adjustment, obtain adhesive composition H.Use this adhesive composition H, the mode that becomes 30 μ m with the thickness after applying forms layer, obtains semiconductor machining surface protection adhesion zone.The adhesion strength of this adhesion zone is 0.88N/25mm, and probe adhesion is 0.26MPa.
(comparative example 4)
With respect to as 2-EHA 60 mass parts, acrylic acid series copolymer 100 mass parts of the copolymer of acrylic acid 2-hydroxy methacrylate 38 mass parts and methacrylic acid 2 mass parts, add addition system isocyanate-based crosslinking agent Coronate L (trade name, Nippon Polyurethane company manufactures) 4 mass parts, as tetramethylol methane tetraacrylate 150 mass parts with optical polymerism carbon-to-carbon double bond of oligomer and as the Irgacure184 (trade name of Photoepolymerizationinitiater initiater, Ciba Japan company manufactures) 5 mass parts, in order to be adjusted to the viscosity of easy coating, add ethyl acetate adjustment, obtain adhesive composition I.
By extrusion molding, film forming goes out EVA (70 μ m)/HDPE (30 μ m) the sandwich construction base material of thickness 100 μ m; use above-mentioned adhesive composition I; the mode that becomes 30 μ m with the thickness after coating forms layer thereon, obtains semiconductor machining surface protection adhesion zone.The adhesion strength of this adhesion zone is 1.30N/25mm, and probe adhesion is 0.24MPa.
(performance evaluation of adhesion zone for surface protection)
Each semiconductor machining obtaining in above-described embodiment and comparative example is carried out following test and evaluated its performance with surface protection adhesion zone, obtained the result of following table 1 and 2.
(adhesion strength)
Use with the water-proof abrasive paper of #280 equably water mill by the SUS304 steel plate of washing, degreasing, after grinding, place after 1 hour, the rubber rollers that makes 2kg loading is carried out 3 times to the surface of the wide breadboard of 25mm and is come and gone and laminating test film, and then places after 1 hour and obtain the loading while peeling off.Peel angle is 180 degree, and draw speed is 300mm/min, and measuring temperature is 23 ℃.
(probe adhesion)
Use adherence test machine (trade name: TACII, Rhesca manufactures), in the substrate backside side (with the opposition side of sticker applicator surface) of test film, with the speed of 30mm/min, be pressed into the cylindric probe of 3mm φ, with the speed with 600mm/min after static load 100g maintenance 1sec, lift, measure loading now.
(seepage flow)
The diameter of silicon wafer is 8 inches; on whole surface, with 5mm interval, be formed with the groove of width 50 μ m, the degree of depth 30 μ m; use make-up machine (trade name: DR-8500II; eastern electrician of day (thigh) manufactures), laminated semiconductor processing surface protection adhesion zone on forming fluted.Utilize sand mill (trade name: DGP8760, Disc (thigh) manufactures) to being fitted with the wafer of this adhesion zone, carrying out the back side and grind and cut, grind and cut to 50 μ m, research, from grinding the infiltration to the cutting water of groove of wafer peripheral part after cutting, is evaluated by following grade by visual.
Opinion rating
A: have no infiltration.
B: infiltrate slightly as seen.
C: obviously visible infiltration.
(workability during laminating)
Utilize after the laminating of make-up machine, the band of reeling, the situation (fissility) of now by following grade, band being sticked in the support roller contacting with sticker is evaluated.
Opinion rating
A: band does not attach to and is present in by the arbitrary support roller in path, successfully coiling band.
B: band attaches in support roller, but is not wound in this support roller, can coiling band.
C: band attaches in support roller and be unstripped, and tape wrapping is to this support roller.
(warpage)
Above-mentioned grinding cut, and the naked wafer of the silicon of 8 inch diameters grinds and cut to the thickness of 50 μ m, makes with semiconductor machining with the wafer of surface protection adhesion zone, because of under the protruding side direction that warpage occurs produces, the wafer of having this adhesion zone to be statically placed on the platform of level.Warpage to the two ends of this wafer is measured, and the warpage using its mean value as wafer is evaluated by following grade.
Opinion rating
A: warpage is less than 25mm.
B: warpage is more than 25mm and is less than 30mm.
C: warpage is more than 30mm.
[table 1]
Figure BDA0000460783560000121
[table 2]
Known according to table 1,2 result, in comparative example 1～4, adhesion strength is less than 10 with the ratio C of probe adhesion; all there is problem the workability aspect when seepage flow or laminating; on the other hand, surface protection of the present invention has all prevented seepage flow with adhesion zone, and has good workability.
Though the present invention and its execution mode are illustrated, but as long as no specifying, even arbitrary detailed description of the present invention is described, be also all not used in restriction the present invention, as long as not violating under the invention spirit shown in the application's claim scope and scope, should do the explanation of maximum magnitude.
The application advocates the priority of the Patent 2012-118040 that files an application in Japan based on May 23rd, 2012, and the present invention adds with reference to this application and using its content the some of recording as this specification.

Claims (4)

1. a semiconductor machining surface protection adhesion zone, it has adhering agent layer on base material, wherein,
The probe adhesion B of this adhesion zone is 0.08～0.20 (MPa), and the adhesion strength A of this adhesion zone (N/25mm) is more than 10 (N/25mm/MPa) with the ratio C (A/B) of probe adhesion B (MPa).
2. semiconductor machining as claimed in claim 1 surface protection adhesion zone, wherein, this adhesion strength A is 0.9～2.0 (N/25mm).
3. semiconductor machining as claimed in claim 1 or 2 surface protection adhesion zone, wherein, the thickness of this adhering agent layer is 15～55 μ m.
4. the surface protection adhesion zone of the semiconductor machining as described in any one in claim 1～3, wherein, this base material consists of vinyl-vinyl acetate copolymer.
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