CN110494958A - Wafer adhesive sheet for processing - Google Patents

Wafer adhesive sheet for processing Download PDF

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Publication number
CN110494958A
CN110494958A CN201880024706.8A CN201880024706A CN110494958A CN 110494958 A CN110494958 A CN 110494958A CN 201880024706 A CN201880024706 A CN 201880024706A CN 110494958 A CN110494958 A CN 110494958A
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CN
China
Prior art keywords
adhesive
plasticizer
wafer
processing
adhesive sheet
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Pending
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CN201880024706.8A
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Chinese (zh)
Inventor
水野浩二
高桥智一
龟井胜利
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Nittosan Engineering Co Ltd
Nitto Denko Corp
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Nittosan Engineering Co Ltd
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Publication of CN110494958A publication Critical patent/CN110494958A/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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Abstract

Wafer adhesive sheet for processing (10) of the invention has stepped construction, and the stepped construction includes: the adhesive phase (12) as the substrate (11) of the polyolefin substrate containing plasticizer and containing plasticizer.Relative to 100 mass parts of adhesive in adhesive phase (12), the content of the plasticizer in adhesive phase (12) is, for example, 1~100 mass parts.This wafer adhesive sheet for processing is suitable for inhibiting the wafer attachment of generated dust to workpiece when cutting.

Description

Wafer adhesive sheet for processing
Technical field
The present invention relates to the wafer adhesive sheet for processing used in cutting of wafer etc..
Background technique
In the manufacturing process of semiconductor device, will do it the rotating blade being had using cutter device sometimes will partly be led Body wafer monolithic turns to the wafer cutting action of multiple semiconductor chips.In wafer cutting action, for example, by semiconductor die In the state that circle is held on the adhesive surface of the wafer adhesive sheet for processing with adhesive surface, the semiconductor crystal wafer is by rotating blade Cutting and monolithic turns to multiple semiconductor chips.Such as it is described in following Patent Documents 1 to 3 and is related to the skill of this wafer cutting Art.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2002-192465 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2014-158046 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2016-96239 bulletin
Summary of the invention
Problems to be solved by the invention
It can be inevitably generated the dust such as cutting clast in the cutting action for implementing machining, produced for removal Raw dust, the purpose of keeping cutting parts cooling and to rotating blade and semiconductor crystal wafer sustainable supply flowing water, cutting action Machining is carried out in this state.However, the cutting action even under flowing water supply, dust be would also adhere to sometimes By on the workpiece of the cutting action.In the manufacture of semiconductor device, having for this dust reduces adhesion amount It is required that especially when the machining object for cutting action is to want monolithic to turn to require the element of high surface cleanness Object is, for example, when monolithic being wanted to turn to the wafer laminated body of the solid-state imagers such as cmos image sensor, this requirement is high.
The present invention be based on it is above the fact that and find out, a kind of be suitable for inhibiting wafer cutting it is intended that providing When the attachment to workpiece of generated dust wafer adhesive sheet for processing.
The solution to the problem
Wafer adhesive sheet for processing provided by the invention has the stepped construction comprising polyolefin substrate and adhesive phase. Polyolefin substrate contains plasticizer, also, adhesive phase contains adhesive and plasticizer.In the present invention, polyolefin base Material refers to that in substrate constituent material polyolefin-based resins account for the substrate of biggest quality ratio.
The wafer adhesive sheet for processing of this composition can add in the manufacturing process of semiconductor device for implementing cutting The cutting action etc. of work.In cutting action, for example, for the adhesive phase of this wafer adhesive sheet for processing is closely sealed partly leads The workpieces such as body wafer, in the state of the rotating blade and workpiece sustainable supply flowing water that have to cutter device Lower carry out machining.This wafer adhesive sheet for processing contains plasticizer within the adhesive layer, also contains in substrate on this basis There is plasticizer, therefore, when rotating blade carries out workpiece and this wafer adhesive sheet for processing together in cutting action When cutting, rotating blade is easy to slide on contact interface of the rotating blade with this wafer adhesive sheet for processing relative to the piece It moves, as a result, the dust such as cutting clast can be efficiently removed from cutting position and its nearby using the flowing water of supply.Cutting action In the dust that from cutting position and its nearby removes it is more, then got over for dust accompanying on the workpiece of cutting action It is few.
On the other hand, the inventors of the present invention obtain following opinion: gluing with incisory rotating blade to not plasticizer-containing It is compared when mixture layer is cut, when rotating blade cuts the adhesive phase containing plasticizer, there are adhesives viscous The subtle tendency for being broken and dispersing occurs for the cutting position of mixture layer.Cutting of the adhesive phase containing plasticizer because of rotating blade And the adhesive clast generated is easy micronized., it can be said that the average grain diameter of the adhesive clast group generated in cutting action is got over Small, then the surface area of per unit volume is bigger, thus easier semiconductor clast, metal fragment of the capture from workpiece Etc. other dust.Adhesive clast has the specific gravity for being specially less than other dust such as semiconductor clast, metal fragment, thus passes through This adhesive clast, which captures other dust, to be meaned to will form the smaller compound dust of specific gravity dust more other than this itself.This is multiple It is smaller than the specific gravity of semiconductor clast, metal fragment etc. to close dust, therefore is not easy to settle in water, is not easy to remain in workpiece On.Therefore, there is this wafer adhesive sheet for processing the adhesive clast generated by the cutting of rotating blade to be easy micronized This composition of the adhesive phase of plasticizer-containing helps to inhibit attachment of the dust to workpiece.
As described above, generated dust is to workpiece when this wafer adhesive sheet for processing is suitable for inhibiting wafer cutting Attachment.In addition, as described above, the substrate of this wafer adhesive sheet for processing is polyolefin substrate, it can be as environmentally friendly nothing The sheet material supporting mass of vinyl chloride and play a role.This wafer adhesive sheet for processing for having this substrate will not in wafer cutting It generates and cuts clast as the vinyl-chloride-containing of the cutting clast from substrate, be suitable for inhibiting the dust such as cutting clast on this basis Attachment to workpiece.
About the content of the plasticizer in the adhesive phase of this wafer adhesive sheet for processing, relative to viscous in adhesive phase 100 mass parts of mixture, it is more than preferably 1 mass parts, it is more than more preferably 4 mass parts, it is more than more preferably 8 mass parts, it is more excellent It is selected as 12 mass parts or more.The content for depositing plasticizer within the adhesive layer is bigger, then can more benefit from plasticizer bring State the tendency of dust adhesion amount reducing effect.
From the viewpoint of the fundamental characteristics such as the cementability for suitably embodying adhesive contained in adhesive phase, this wafer adds The content of plasticizer in the adhesive phase of work bonding sheet is preferably relative to 100 mass parts of adhesive in adhesive phase 100 below the mass, more preferably 80 below the mass, more preferably 70 below the mass.
The adhesive phase of this wafer adhesive sheet for processing preferably comprises aromatic carboxylic acid esters system plasticizer and/or Polyester increases Agent is moulded as plasticizer.In addition, the Polyester substrate of this wafer adhesive sheet for processing preferably comprises the plasticising of aromatic carboxylic acid esters system Agent and/or polyester plasticizer are as plasticizer.As the aromatic carboxylic acid esters system plasticising in adhesive phase, in Polyester substrate Agent, preferably terephthalic acid (TPA) two (2- ethylhexyl) ester.These are in terms of being formed in the above-mentioned dust adhesion amount reducing effect of acquisition Suitable.
The polyolefin substrate of this wafer adhesive sheet for processing is preferably without vinyl chloride.It is this to be formed in obtain the wafer of environmental protection It is suitable in terms of adhesive sheet for processing.In addition, the polyolefin substrate of this wafer adhesive sheet for processing includes ethylene-acetate second Enoate copolymer or ethylene-propylene copolymer are as resin principal component.The resin principal component of substrate refers to: the tree contained by substrate The substance of biggest quality ratio is accounted in rouge ingredient.It can also be true when this substrate for being formed in wafer adhesive sheet for processing is without vinyl chloride It is suitable in terms of protecting the abundant characteristic for being related to intensity etc..
Detailed description of the invention
Fig. 1 is the schematic cross-section of the wafer adhesive sheet for processing of an embodiment of the invention.
Fig. 2 indicates an example using form for wafer adhesive sheet for processing shown in FIG. 1.
Specific embodiment
Fig. 1 is the schematic cross-section of the wafer adhesive sheet for processing 10 of an embodiment of the invention.Wafer processing is used Bonding sheet 10 has the stepped construction comprising substrate 11 and adhesive phase 12, in the manufacturing process of semiconductor device, Ke Yiyong In the cutting action etc. for implementing machining.In addition, wafer adhesive sheet for processing 10 has and semiconductor crystal wafer, wafer laminated body Such as disc-shape of the equal corresponding size of workpieces.
The substrate 11 of wafer adhesive sheet for processing 10 is the element to play a role in the piece as supporting mass, for example, The form of plastic film.In addition, substrate 11 is polyolefin substrate, polyene is contained with biggest quality ratio in its constituent material Hydrocarbon system resin.As this polyolefin-based resins, for example, can enumerate low density polyethylene (LDPE), straight-chain low density polyethylene (LDPE), in Density polyethylene, high density polyethylene (HDPE), ultra-low density polyethylene, ethylene-propylene copolymer (such as atactic copolymerized polypropene and embedding Section copolymer polypropylene), homopolypropylene, polybutene, polymethylpentene, vinyl-vinyl acetate copolymer (EVA), ionomer Resin, ethylene-(methyl) acrylic copolymer, ethylene-(methyl) acrylate copolymer, ethylene-butene copolymer, Yi Jiyi Alkene-hexene copolymer.As the constituent material of substrate 11, a kind of polyolefin-based resins can be used, also can be used two kinds with On polyolefin-based resins.In the present embodiment, substrate 11 preferably comprises vinyl-vinyl acetate copolymer or ethylene-the third Alkene copolymer is as resin principal component.
For substrate 11, other resins can be contained together with polyolefin-based resins in its constituent material.As this Other resins, such as polyvinyl chloride, Vingon, polyester, polyurethane, polycarbonate, polyether-ether-ketone, polyamides Asia can be enumerated Amine, polyetherimide, polyamide, fully aromatic polyamide, polyphenylene sulfide, aramid fiber, fluororesin, cellulose-based resin, Yi Jiyou Machine silicone resin.As polyester, for example, can enumerate polyethylene terephthalate (PET), polyethylene naphthalate, with And polybutylene terephthalate (PBT) (PBT).As the constituent material of substrate 11, other a kind of resins can be used, it can also be with Use other two or more resins.Substrate 11 is preferably without vinyl chloride.
The content ratio of resin material in substrate 11 is, for example, 100 mass % or less, preferably 90 mass % or less.
Substrate 11 also contains plasticizer while containing resin material as described above.As plasticizer, such as can enumerate Aromatic carboxylic acid esters system plasticizer, aliphatic carboxylic acid esters system plasticizer and polyester plasticizer out.As aromatic carboxylic acid esters system Plasticizer, for example, can enumerate phthalic acid ester, terephthalate, adipate ester, benzoic ether, trimellitic acid ester, And pyromellitic acid ester.As aliphatic carboxylic acid esters system plasticizer, such as sebacate, azelate, Malaysia can be enumerated Acid esters and citrate.As above-mentioned phthalic acid ester (phthalic acid ester system plasticizer), such as adjacent benzene can be enumerated Dioctyl phthalate di-n-octyl, phthalic acid two (2- ethylhexyl) ester, diisononyl phthalate, two isodecyl of phthalic acid Ester and dibutyl phthalate.As above-mentioned terephthalate (terephthalate system plasticizer), such as can enumerate Terephthalic acid (TPA) two (2- ethylhexyl) ester out.As adipate ester (adipate ester system plasticizer), such as oneself can be enumerated two Sour di-n-octyl, (2- ethylhexyl) ester of adipic acid two and diisononyl adipate.As above-mentioned benzoic ether (benzoic acid Ester system plasticizer), such as glycol benzoate can be enumerated.As (the trimellitic acid ester system plasticising of above-mentioned trimellitic acid ester Agent), such as can to enumerate three n-octyl of trimellitic acid, trimellitic acid three (2- ethylhexyl) ester, trimellitic acid three different Three isodecyl ester of nonyl ester, the positive last of the ten Heavenly stems ester of trimellitic acid three and trimellitic acid.As above-mentioned pyromellitic acid ester (equal benzene tetramethyl Acid esters system plasticizer), for example, can enumerate four n-octyl of Pyromellitic Acid, (2- ethylhexyl) ester of Pyromellitic Acid four and The positive last of the ten Heavenly stems ester of Pyromellitic Acid four.As above-mentioned citrate (citrate plasticizer), such as acetyl tributyl citrate can be enumerated Tributyl.In addition, as above-mentioned polyester plasticizer, such as aliphatic dicarboxylic acid (oneself by carbon atom number 2~10 can be enumerated Diacid, azelaic acid, decanedioic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA) etc.) and/or aromatic dicarboxylic acid and carbon it is former The polyester that glycol (ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexylene glycol etc.) polycondensation of subnumber 2~10 obtains.As base Material 11 contains ingredient, and a kind of plasticizer can be used, and two or more plasticizer also can be used.In the present embodiment, Substrate 11 preferably comprises aromatic carboxylic acid esters system plasticizer and/or polyester plasticizer as plasticizer.As in substrate 11 Aromatic carboxylic acid esters system plasticizer, preferably terephthalic acid (TPA) two (2- ethylhexyl) ester.
The content ratio of plasticizer in substrate 11 is preferably 1 mass % or more, is more preferably 3 mass % or more, is more excellent It is selected as 5 mass % or more, more preferably 7 mass % or more, more preferably 9 mass % or more, more preferably 11 mass % or more. The content ratio of plasticizer in substrate 11 is preferably 100 mass % or less, more preferably 70 mass % or less, more preferably 50 Quality % or less.
Substrate 11 can also contain other compositions other than containing resin material as described above and plasticizer.Substrate 11 can have single layer structure, it is possible to have multilayered structure.In the substrate 11 of single layer structure, above-mentioned resin material, plasticising The composition of agent can be uniformly, be also possible to non-uniform.In the substrate 11 of multilayered structure, there may be free of polyolefin It is the layer of resin, there may also be the layers of not plasticizer-containing.When substrate 11 is made of plastic film, non-stretched film can be, It is also possible to monodirectional tension film, can also be biaxially oriented film.In addition, the adhesive phase 12 on substrate 11 is being as be described hereinafter When ultraviolet hardening, substrate 11 preferably has ultraviolet light permeability.
The surface of 12 side of adhesive phase in substrate 11 can be implemented for improving and the object of the adaptation of adhesive phase 12 Reason processing, chemical treatment or primary coat processing.As physical treatment, such as sided corona treatment, corona treatment, sandblasting can be enumerated Working process, ozone exposure processing, fire exposure processing, high-voltage electric shock exposure treatment and ionising radiation processing.As chemistry Processing, such as chromic acid processing can be enumerated.
From the intensity ensured for making the performance of substrate 11 as the effect of the supporting mass in wafer adhesive sheet for processing 10 Viewpoint is set out, and the thickness of substrate 11 is preferably 40 μm or more, more preferably 50 μm or more, is more preferably 55 μm or more, is more preferable It is 60 μm or more.In addition, realizing the flexibility of appropriateness from the viewpoint of in wafer adhesive sheet for processing 10, the thickness of substrate 11 Preferably 200 μm or less, more preferably 180 μm or less, more preferably 150 μm or less.
The adhesive phase 12 of wafer adhesive sheet for processing 10 contains adhesive and plasticizer.
Adhesive in adhesive phase 12 can be can be special from external effect by irradiation with radiation, heating etc. Meaning ground reduces the adhesive (bonding force reduction type adhesive) of bonding force, and being also possible to bonding force nearly or completely will not be because coming from External effect and reduced adhesive (the non-reduced type adhesive of bonding force), can be according to being held in wafer processing bonding Processing method, processing conditions of the workpiece of processing etc. is subjected in the state of piece 10 suitably to select.
In the case where using bonding force reduction type adhesive as adhesive in adhesive phase 12, processes and use in wafer In the use process of bonding sheet 10, it can distinguish and show the state of opposite high adhesion using adhesive phase 12 and show relatively low The state of bonding force.For example, being added in the cutting action for semiconductor crystal wafer monolithic to be turned to semiconductor chip using wafer When work bonding sheet 10, the state of opposite high adhesion is shown using adhesive phase 12, is able to suppress/is prevented and is held in adhesive Semiconductor crystal wafer autoadhesion oxidant layer 12 on layer 12 floats, removes.Moreover, being used for after such cutting action from crystalline substance Circle adhesive sheet for processing 10 picks up in the pickup process of semiconductor chip, can reduce the bonding force of adhesive phase 12 and from bonding Oxidant layer 12 suitably picks up semiconductor chip.
As this bonding force reduction type adhesive, such as Radiation curing adhesive can be enumerated (with radiation The adhesive of curability), thermal expansion type adhesive etc..In the adhesive phase 12 of present embodiment, it can be used a kind of viscous Two or more bonding force reduction type adhesives also can be used in resultant force reduction type adhesive.Furthermore it is possible to be adhesive phase 12 Entirety formed by bonding force reduction type adhesive, be also possible to a part of adhesive phase 12 by bonding force reduction type adhesive It is formed.For example, the entirety that can be adhesive phase 12 is reduced by bonding force in the case where adhesive phase 12 has single layer structure Type adhesive is formed, and is also possible to the predetermined portion in adhesive phase 12 (such as workpieces such as semiconductor crystal wafers The middle section in adhering object region) it is formed by bonding force reduction type adhesive, other positions (for example, bonding pair of ring frame As region and the region of centrally located areas outside) it is formed by the non-reduced type adhesive of bonding force.In addition, having in adhesive phase 12 In the case where having stepped construction, it can be to form whole layers of stepped construction and formed by bonding force reduction type adhesive, it can also be with Be in stepped construction part layer formed by bonding force reduction type adhesive.
As the Radiation curing adhesive in adhesive phase 12, can be used for example through irradiating electron beam, ultraviolet Line, alpha ray, β ray, gamma-rays or X-ray and cured type adhesive, can be particularly suitablely using purple by irradiation Outside line and the adhesive (ultraviolet-curing adhesive) of cured type.
As the Radiation curing adhesive in adhesive phase 12, such as the radiation of following addition type can be enumerated Curing adhesive: it contains the base polymers such as the acrylic acid series polymeric compounds as acrylic adhesive and has spoke Radiation polymerizable monomer ingredient, the oligomer ingredient of the functional groups such as the carbon-to-carbon double bond of ray polymerization.
Above-mentioned acrylic acid series polymeric compounds preferably comprise the monomeric unit conduct from acrylate and/or methacrylate Most main monomer unit in terms of mass ratio.Hereinafter, indicating " acrylic acid " and/or " methyl-prop with " (methyl) acrylic acid " Olefin(e) acid ".
As (methyl) acrylate for the monomeric unit for being used to form acrylic acid series polymeric compounds, such as (first can be enumerated Base) (methyl) acrylic acid containing alkyl such as alkyl acrylate, (methyl) acrylate base ester, (methyl) benzyl acrylate Ester.As (methyl) alkyl acrylate, such as methyl esters, ethyl ester, propyl ester, the isopropyl ester, fourth of (methyl) acrylic acid can be enumerated Ester, isobutyl ester, secondary butyl ester, the tert-butyl ester, pentyl ester, isopentyl ester, own ester, heptyl ester, monooctyl ester, 2- ethylhexyl, different monooctyl ester, nonyl ester, Last of the ten Heavenly stems ester, isodecyl ester, hendecane base ester, dodecyl ester, that is, lauryl, tridecane base ester, tetradecane base ester, cetyl ester, ten Eight Arrcostabs and eicosane base ester.As (methyl) acrylate base ester, such as the ring of (methyl) acrylic acid can be enumerated Pentyl ester and cyclohexyl.As (methyl) benzyl acrylate, such as (methyl) phenyl acrylate and (methyl) propylene can be enumerated Acid benzyl ester.As (methyl) acrylate for the principal monomer for being used as acrylic acid series polymeric compounds, a kind of (methyl) third can be used Two or more (methyl) acrylate also can be used in olefin(e) acid ester.Adhesive phase 12 is set suitably to embody (methyl) acrylic acid When the fundamental characteristics such as adhesiveness brought by ester, it is used to form in whole monomer components of acrylic acid series polymeric compounds as main single The ratio of (methyl) acrylate of body is preferably 40 mass % or more, more preferably 60 mass % or more.
For acrylic acid series polymeric compounds, in order to be modified to its cohesive force, heat resistance etc., it may include that be originated from can be with The monomeric unit of other monomers of (methyl) acrylic ester copolymer.As such monomer component, such as can enumerate containing carboxyl Monomer, anhydride monomers, hydroxyl monomer, containing glycidyl monomer, monomer containing sulfonic group, phosphorous acid-based monomers, acrylamide, And acrylonitrile etc. is containing monomer etc..As carboxyl group-containing monomer, such as acrylic acid, methacrylic acid, (first can be enumerated Base) carboxyethyl acrylates, (methyl) acrylic acid carboxyl pentyl ester, itaconic acid, maleic acid, fumaric acid and crotonic acid.As acid Anhydride monomer, such as maleic anhydride and itaconic anhydride can be enumerated.As hydroxyl monomer, such as (methyl) acrylic acid can be enumerated 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 6- hydroxyl oneself Ester, (methyl) acrylic acid 8- hydroxyl monooctyl ester, (methyl) acrylic acid 10- hydroxyl last of the ten Heavenly stems ester, (methyl) acrylic acid 12- hydroxylauric ester, And (methyl) acrylic acid (4- hydroxymethylcyclohexyl) methyl esters.As glycidyl monomer is contained, such as (methyl) can be enumerated Glycidyl acrylate and (methyl) acrylic acid methylglycidyl esters.As monomer containing sulfonic group, such as benzene can be enumerated Vinyl sulfonic acid, allyl sulphonic acid, 2- (methyl) acrylamide-2-methyl propane sulfonic, (methyl) acrylamide propane sulfonic acid, (methyl) Acrylic acid sulfonic acid propyl ester and (methyl) propane sulfonic acid.As phosphorous acid-based monomers, such as 2- hydroxyl can be enumerated Ethyl propylene acyl phosphate.As acrylamide, such as N- acryloyl morpholine can be enumerated.As for acrylic polymeric Other monomers of object, can be used a kind of monomer, two or more monomers also can be used.Make 12 appropriate bulk of adhesive phase When the fundamental characteristics such as adhesiveness brought by existing (methyl) acrylate, be used to form whole monomers of acrylic acid series polymeric compounds at The ratio of other monomer components in point is preferably 60 mass % or less, more preferably 40 mass % or less.
For acrylic polymer, in order to form cross-linked structure in its polymer backbone, may include be originated from can With the monomeric unit of the multi-functional monomer of the monomer components copolymerization such as (methyl) acrylate as principal monomer.As in this way Multi-functional monomer, such as can enumerate hexylene glycol two (methyl) acrylate, (poly-) ethylene glycol two (methyl) acrylate, (poly-) propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite two (methyl) acrylate, Trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) propylene Acid esters, epoxy (methyl) acrylate (i.e. poly- (methyl) glycidyl acrylate), polyester (methyl) acrylate and ammonia Carbamate (methyl) acrylate.As the multi-functional monomer for acrylic acid series polymeric compounds, a kind of more officials can be used Energy property monomer, also can be used two or more multi-functional monomers.(methyl) propylene is suitably embodied in making adhesive phase 12 The aspect of the fundamental characteristics such as adhesiveness brought by acid esters is used to form more in whole monomer components of acrylic acid series polymeric compounds The ratio of functional monomer is preferably 40 mass % or less, more preferably 30 mass % or less.
The starting monomer for being used to form it can polymerize by acrylic acid series polymeric compounds to be obtained.As polymerization, such as Polymerisation in solution, emulsion polymerization, bulk polymerization and suspension polymerisation can be enumerated.From using partly leading for wafer adhesive sheet for processing 10 From the perspective of the high level of cleanliness of body device manufacturing method, in the adhesive phase 12 preferably in wafer adhesive sheet for processing 10 Low molecular weight substance is few, and the number-average molecular weight of acrylic acid series polymeric compounds is preferably 100,000 or more, more preferably 200,000~3,000,000.
For adhesive phase 12 or the adhesive for being used to form it, in order to improve the base polymers such as acrylic acid series polymeric compounds Number-average molecular weight, such as external crosslinker can be contained.As for being reacted with base polymers such as acrylic acid series polymeric compounds And the external crosslinker of cross-linked structure is formed, polyisocyanate compound, epoxide, polyol compound can be enumerated (polyphenol based compound etc.), aziridine cpd and melamine series crosslinking agent.Adhesive phase 12 is used to form the viscous of its The content of external crosslinker in mixture is preferably 10 below the mass, more preferably relative to 100 mass parts of base polymer 0.1~7 mass parts.
As being used to form the above-mentioned radiation polymerizable monomer ingredient of Radiation curing adhesive, such as can enumerate Oligourethane, carbamate (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, Ji Wusi Alcohol three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol monohydroxy five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate and 1,4- butanediol two (methyl) acrylate.As being used to form radiation The above-mentioned radiation polyreactive oligomers ingredient of curing adhesive, such as carbamate system, polyether system, polyester can be enumerated The various oligomer such as system, polycarbonate-based, polybutadiene system, the oligomer that molecular weight is 100~30000 or so is appropriate. The monomer component of radiation polymerism in Radiation curing adhesive, the total content of oligomer ingredient can suitably reduce institute It is determined in the range of the bonding force of the adhesive phase 12 of formation, relative to 100 mass of the base polymers such as acrylic acid series polymeric compounds Part, for example, 5~500 mass parts, preferably 40~150 mass parts.In addition, the radiation curable as addition type bonds Adhesive disclosed in Japanese Unexamined Patent Application 60-196956 bulletin can be used for example in agent.
As the Radiation curing adhesive in adhesive phase 12, such as it can also enumerate the radiation of following inherent type Line curing adhesive: it contains in polymer lateral chain, main polymer chain, main polymer chain end has radiation polymerism The functional groups such as carbon-to-carbon double bond base polymer.The Radiation curing adhesive of this inherence type is inhibiting by being formed Adhesive phase 12 in low molecular weight compositions movement caused by adhesion characteristic non-ongoing change specially in terms of be suitable Suitable.
Base polymer contained in Radiation curing adhesive as inherent type, preferably with acrylic acid series polymeric compounds For the polymer of basic framework.As the acrylic acid series polymeric compounds for forming this basic framework, above-mentioned acrylic acid series can be used Polymer.As into acrylic acid series polymeric compounds introduce radiation polymerism carbon-to-carbon double bond method, such as can enumerate as Lower method: the starting monomer copolymerization comprising the monomer with specified functional groups (the 1st functional group) is made to obtain acrylic polymeric Then object makes with the specified functional groups (the 2nd functional group) and radiation that can be reacted and be bonded between the 1st functional group The compound of polymerism carbon-to-carbon double bond, maintain carbon-to-carbon double bond radiation polymerism in the state of with acrylic acid series polymeric compounds Carry out condensation reaction or addition reaction.
As the combination of the 1st functional group and the 2nd functional group, for example, can enumerate carboxyl and epoxy group, epoxy group and carboxyl, Carboxyl and '-aziridino, '-aziridino and carboxyl, hydroxyl and isocyanate group, isocyanate group and hydroxyl.In these combinations, From the viewpoint of the easness of reactive tracing, the preferred group of the combination of hydroxyl and isocyanate group, isocyanate group and hydroxyl It closes.In addition, production has the polymer of isocyanate group with high reactivity, technically difficulty is big, thus from acrylic polymeric From the perspective of the complexity of production or the acquisition of object, above-mentioned 1st functional group of more preferable acrylic acid series polymeric compounds side is hydroxyl The case where base and above-mentioned 2nd functional group are isocyanate group.In this case, double as radiation polymerism carbon-to-carbon is had both The isocyanate compound of key and the isocyanate group as the 2nd functional group, such as methylacryloyl isocyanic acid can be enumerated Ester, 2- methacryloxyethyl isocyanates and isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate.In addition, making It is preferred comprising being originated from the substance of monomeric unit of above-mentioned hydroxyl monomer for the acrylic acid series polymeric compounds with the 1st functional group , comprising being originated from the ethers system chemical combination such as 2- hydroxyethyl vinyl ether, 4- hydroxybutyl vinyl ether, diethylene glycol monovinyl base ether The substance of the monomeric unit of object is also preferred.
Radiation curing adhesive in adhesive phase 12 preferably comprises Photoepolymerizationinitiater initiater.Cause as photopolymerization Agent, such as α -one alcohol based compound, acetophenone based compound, benzoin ether based compound, ketal based compound, virtue can be enumerated Fragrant race's sulfonic acid chloride based compound, photolytic activity oxime compound, benzophenone based compound, thioxanthones based compound, camphorquinone, halogen Change ketone, acylphosphine oxide and acyl phosphonate.As α -one alcohol based compound, such as 4- (2- '-hydroxyethoxy can be enumerated Base) phenyl (2- hydroxyl -2- propyl) ketone, Alpha-hydroxy-α, α '-dimethyl acetophenone, 2- methyl -2- hydroxypropiophenonepreparation and 1- Hydroxycyclohexylphenylketone.As acetophenone based compound, such as methoxyacetophenone, 2,2- dimethoxy -2- can be enumerated Acetophenone, 2,2- diethoxy acetophenone and 2- methyl-1-[4- (methyl mercapto)-phenyl]-2- morpholinopropane-1.As Benzoin ether based compound, such as benzoin ethyl ether, benzoin iso-propylether and anisoin methyl ether can be enumerated.As contracting Ketone based compound, such as benzyl dimethyl ketal can be enumerated.As aromatic sulfonyl based compound, such as 2- can be enumerated Naphthalene sulfonyl chloride.As photolytic activity oxime compound, such as 1- benzophenone -1,1- propanedione -2- (O- ethoxy carbonyl) can be enumerated Oxime.As benzophenone based compound, such as benzophenone, benzoyl benzoic acid and 3,3'- dimethyl-can be enumerated 4- methoxy benzophenone.As thioxanthones based compound, such as thioxanthones, 2-chlorothioxanthone, 2- methyl thioxanthene can be enumerated Ketone, 2,4- dimethyl thioxanthone, isopropyl thioxanthone, bis- clopenthixal ketone of 2,4-, 2,4- diethyl thioxanthone and 2,4- bis- are different Propyl thioxanthones.Radiation curing relative to 100 mass parts of the base polymers such as acrylic acid series polymeric compounds, in adhesive phase 12 The content of Photoepolymerizationinitiater initiater in type adhesive is, for example, 0.05~20 mass parts.
Above-mentioned thermal expansion type adhesive in adhesive phase 12 is containing the ingredient (hair by heating foaming, expansion Infusion, heat-expandable microsphere etc.) adhesive can enumerate various inorganic system's foaming agents and organic system foaming as foaming agent Agent as heat-expandable microsphere, such as can enumerate the structure for being sealed in shell and being easy the substance for gasifying and expanding by heating At microballoon.As inorganic system's foaming agent, such as ammonium carbonate, ammonium hydrogen carbonate, sodium bicarbonate, ammonium nilrite, boron hydrogen can be enumerated Change sodium and nitrine system.As organic system foaming agent, such as the chlorine fluorine such as trichlorofluoromethane, dichloro list fluoromethane can be enumerated Change alkane；The azo compounds such as azobis isobutyronitrile, azodicarbonamide, Barium azodicarboxylate；Unifor, hexichol The hydrazines based compounds such as base sulfone -3,3'- disulfonyl hydrazide, 4,4'- oxygen bis- (benzene sulfonyl hydrazides), allyl bis- (sulfohydrazides)；To toluene sulphur The semicarbazides based compounds such as acyl amino urea, 4,4'- oxygen bis- (benzenesulfonylamino ureas)；5- morpholinyl -1,2,3,4- thiatriazole Deng three azole compounds；And N, N'- dinitrosopentamethylene tetramine, N, N'- dimethyl-N, N'- dinitroso is to benzene two The N- nitroso based compound such as formamide.As be used to form heat-expandable microsphere as described above, be easy due to heating gas The substance changed and expanded, such as iso-butane, propane and pentane can be enumerated.By coacervation, interfacial polymerization etc. by it is easy because Heating and gasify and the substance expanded is sealing into shell forming material, so as to make heat-expandable microsphere.As hull shape at The substance for showing hot melt property, the substance that can be ruptured by enclosing the thermal expansion of substance can be used in substance.As Such substance, such as vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, poly- methyl-prop can be enumerated E pioic acid methyl ester, polyacrylonitrile, Vingon and polysulfones.
As the non-reduced type adhesive of above-mentioned bonding force, such as Pressuresensitive Adhesive can be enumerated.The Pressuresensitive Adhesive In include following form adhesive: make the Radiation curing adhesive as above described for bonding force reduction type adhesive Solidify and ensure simultaneously the form of defined bonding force by preparatory illumination radiation line.Spoke is made for preparatory illumination radiation line The adhesive (Radiation curing adhesive that irradiation with radiation is crossed) of the form of ray curing adhesive curing, even if bonding Power is reduced because of illumination radiation line, can also show the bonding from the component of polymer according to the content of component of polymer Property, so as to play the bonding force that can be used for carrying out bonding holding to adherend in cutting action etc..In present embodiment Adhesive phase 12 in, a kind of non-reduced type adhesive of bonding force can be used, it is non-that two or more bonding forces also can be used Reduction type adhesive.Furthermore it is possible to be that the entirety of adhesive phase 12 is formed by the non-reduced type adhesive of bonding force, it is also possible to glue A part of mixture layer 12 is formed by the non-reduced type adhesive of bonding force.For example, there are the feelings of single layer structure in adhesive phase 12 Under condition, the entirety that can be adhesive phase 12 is formed by the non-reduced type adhesive of bonding force, is also possible in adhesive phase 12 Predetermined portion (for example, the adhering object region of ring frame and is located at the pasted objects regions of the workpieces such as semiconductor crystal wafer The region in outside) it is formed by the non-reduced type adhesive of bonding force, other positions (such as pasted objects area as workpiece The middle section in domain) it is formed by bonding force reduction type adhesive.For example, in the present embodiment, being crossed using irradiation with radiation When Radiation curing adhesive, on the face propagation direction of adhesive phase 12, the whole by radiating of adhesive phase 12 can be The irradiated Radiation curing adhesive of line is formed, and the spoke that a part of adhesive phase 12 is crossed by irradiation with radiation is also possible to Ray curing adhesive is formed and other parts are formed by the Radiation curing adhesive of non-illumination radiation line.In addition, In In the case that adhesive phase 12 has stepped construction, it can be the whole layers to form stepped construction by the non-reduced type bonding of bonding force Dosage form is at the part layer being also possible in stepped construction is formed by the non-reduced type adhesive of bonding force.
On the other hand, pressure-sensitive other than the Radiation curing adhesive crossed as the irradiation with radiation in adhesive phase 12 Type adhesive, such as acrylic adhesive, rubber with acrylic acid series polymeric compounds for basic polymer can be properly used It is adhesive.When adhesive phase 12 contains acrylic adhesive as Pressuresensitive Adhesive, as the acrylic adhesive Base polymer acrylic acid series polymeric compounds preferably comprise from (methyl) acrylate monomeric unit be used as with mass ratio Example counts most main monomer units.As such acrylic acid series polymeric compounds, such as can enumerate as above solid for radiation The acrylic acid series polymeric compounds that change type adhesive is described.
As the plasticizer in adhesive phase 12, such as aromatic carboxylic acid esters system plasticizer, aliphatic carboxylic acid can be enumerated Ester system plasticizer and polyester plasticizer, specifically, the as above increasing described containing ingredient as substrate 11 can be enumerated Mould agent.In the present embodiment, adhesive phase 12 preferably comprises aromatic carboxylic acid esters system plasticizer and/or polyester plasticizer is made For plasticizer.As the aromatic carboxylic acid esters system plasticizer in adhesive phase 12, preferably terephthalic acid (TPA) two (2- ethylhexyl) Ester.The content of plasticizer in adhesive phase 12 is preferably 1 mass parts relative to 100 mass parts of adhesive in adhesive phase 12 Above, 4 mass parts or more are more preferably, are more preferably 8 mass parts or more, more preferably 12 mass parts or more.In addition, adhesive The content of plasticizer in layer 12 is preferably 100 below the mass, more relative to 100 mass parts of adhesive in adhesive phase 12 It is preferred that 80 below the mass, more preferably 70 below the mass.
Adhesive phase 12 within the scope of the effect of the invention, other than containing above-mentioned each ingredient, can also contain There are other ingredients.As other compositions, such as colorants such as crosslinking accelerator, age resister, pigments or dyes etc. can be contained. Colorant can be the compound coloured by irradiation with radiation.As such compound, such as procrypsis dye can be enumerated Material.
The thickness of adhesive phase 12 is preferably 1~50 μm, more preferably 2~30 μm, more preferably 5~25 μm.This structure At in the case where such as adhesive phase 12 includes Radiation curing adhesive, consolidate obtaining the adhesive phase 12 in radiation Changing front and back is suitable to the balance aspect of the bonding force of adherend.
Wafer adhesive sheet for processing 10 with the above this composition can be by the polyolefin base containing plasticizer Adhesive phase containing adhesive and plasticizer is set on material to make (the 1st method).Alternatively, wafer adhesive sheet for processing 10 It can then be carried out by the way that the adhesive phase containing adhesive and plasticizer is arranged on the polyolefin substrate as substrate 11 The maturation process of substrate (diffusing to substrate) is transferred to for realizing the plasticizer part in adhesive phase to make (the 2nd side Method).Substrate can be for example, by the tape casting in calendering film method, organic solvent, the inflation extrusion molding in enclosed system, T mould The film-forming methods such as extrusion molding, coetrusion, dry lamination method make.As needed, to after film film or substrate implement rule Fixed surface treatment.In the formation of adhesive phase, for example, after the binder solution for preparing adhesive phase formation, first By the binder solution be coated on substrate or defined isolation film (i.e. release liner) on and form adhesive film.As viscous The coating method of mixture solution, such as roller coating, silk screen coating and rotogravure application can be enumerated.Then, as needed, in the bonding Cross-linking reaction is caused by heating in agent film, in addition, carrying out desolventizing as needed.Heating temperature example for desolventizing For example 80~150 DEG C, the heating time for desolventizing is, for example, 0.5~5 minute.It is formed on isolation film in adhesive phase In the case of, the adhesive phase with the isolation film is fitted in into substrate.In above-mentioned 2nd method for example for the temperature of maturation process It is 80~150 DEG C, the time of the maturation process is, for example, 0.5~5 minute.
In wafer adhesive sheet for processing 10, isolation film (illustration omitted) can be carried out in the form of covering adhesive phase 12 Setting.Isolation film is for protecting so that the element that adhesive phase 12 does not expose, in wafer adhesive sheet for processing 10 to be used It is peelled off from the on piece.As isolation film, for example, can enumerate polyethylene terephthalate (PET) film, polyethylene film, Polypropylene film, the modeling that surface coating has been carried out using removers such as fluorine system remover, chain alkyl acrylate series stripping agents Expect film, stationery etc..
As described above, the wafer adhesive sheet for processing 10 of this composition can be used in the manufacturing process of semiconductor device Implement the cutting action etc. of machining.In cutting action, as shown in (a) of Fig. 2, it is laminated by semiconductor crystal wafer, wafer The workpieces such as body 20 are held in the state of the adhesive phase 12 of wafer adhesive sheet for processing 10, and driving cutter device is had Standby rotating blade (illustration omitted), to carry out machining to workpiece 20.The machining left-hand tools blade It is carried out in the state of 20 sustainable supply flowing water of workpiece.As shown in (b) of Fig. 2, incisory rotating blade shape is utilized At cutting slot G for example formed (in (b) of Fig. 2 schematically with thick line with reaching the depth of wafer adhesive sheet for processing 10 Indicate cutting slot G).By such cutting action, workpiece 20 is singulated as the element chips such as semiconductor chip 21.
In wafer adhesive sheet for processing 10, as described above, contain plasticizer in adhesive phase 12, substrate on this basis Also contain plasticizer in 11.Therefore, when rotating blade not only cuts, to wafer workpiece 20 in cutting action When adhesive sheet for processing 10 is also cut together, rotating blade is easy connecing in rotating blade and wafer adhesive sheet for processing 10 It touches and is slid on interface relative to the piece, as a result, can be cut using the flowing water of supply from cutting position and its neighbouring efficiently remove Cut the dust such as clast.The dust removed in cutting action from cutting position and its nearby is more, then for the processing of cutting action Accompanying dust is fewer on object 20.
On the other hand, the inventors of the present invention obtain following opinion: gluing with incisory rotating blade to not plasticizer-containing It is compared when mixture layer is cut, when rotating blade cuts the adhesive phase containing plasticizer, there are adhesives viscous The subtle tendency for being broken and dispersing occurs for the cutting position of mixture layer.Cutting of the adhesive phase containing plasticizer because of rotating blade And the adhesive clast generated is easy to happen micronized., it can be said that the average grain of the adhesive clast group generated in cutting action Diameter is smaller, then the surface area of per unit volume is bigger, thus is easy to capture semiconductor clast, the metal for being originated from workpiece 20 Other dust such as clast.Adhesive clast has the specific gravity for being specially less than other dust such as semiconductor clast, metal fragment, thus Capturing other dust by this adhesive clast means to will form the smaller compound dust of specific gravity dust more other than this itself. The compound dust is smaller than the specific gravity of semiconductor clast, metal fragment etc., therefore is not easy to settle in water, is not easy to remain in processing pair As on object 20.Therefore, wafer adhesive sheet for processing 10 has holds containing the adhesive clast generated by the cutting of rotating blade This composition of the easy adhesive phase 12 of plasticizer of micronized facilitates the attachment for inhibiting dust to workpiece 20.
As described above, generated dust is to workpiece when wafer adhesive sheet for processing 10 is suitable for inhibiting wafer cutting 20 attachment.
For the content of the plasticizer in the adhesive phase 12 of wafer adhesive sheet for processing 10, as discussed previously with respect to viscous 100 mass parts of adhesive in mixture layer 12 are preferably 1 mass parts or more, are more preferably 4 mass parts or more, more preferably 8 matter Measure part or more, more preferably 12 mass parts or more.There are the content of the plasticizer in adhesive phase 12 is bigger, then can more benefit from The tendency of the above-mentioned dust adhesion amount reducing effect of plasticizer bring.In addition, being glued contained in adhesive phase 12 from appropriate embody From the perspective of the fundamental characteristics such as the cementability of mixture, as described above, the content of the plasticizer in adhesive phase 12 is relative to viscous 100 mass parts of adhesive in mixture layer 12 are preferably 100 below the mass, more preferably 80 below the mass, more preferably 70 below the mass.
The substrate 11 of wafer adhesive sheet for processing 10 is preferably without vinyl chloride.This wafer processing for being formed in obtain environmental protection is used It is suitable in terms of bonding sheet 10.In addition, substrate 11 is made containing vinyl-vinyl acetate copolymer or ethylene-propylene copolymer For resin principal component.It is this abundant characteristic for being related to intensity etc. is also ensured that when being formed in substrate 11 without vinyl chloride in terms of be suitable 's.
As described above, the substrate 11 of wafer adhesive sheet for processing 10 preferably comprise aromatic carboxylic acid esters system plasticizer and/or Polyester plasticizer is as plasticizer.In addition, as described above, the adhesive phase 12 of wafer adhesive sheet for processing 10 preferably comprises virtue Fragrant race's carboxylate system's plasticizer and/or polyester plasticizer are as plasticizer.As the virtue in substrate 11 and in adhesive phase 12 Fragrant race's carboxylate system plasticizer, preferably terephthalic acid (TPA) two (2- ethylhexyl) ester.These, which are formed in, obtains above-mentioned dust attachment It is suitable in terms of measuring reducing effect.
Embodiment
1 ﹞ of ﹝ embodiment
<preparation of binder solution>
As have Liebig condenser (Liebig condenser), nitrogen ingress pipe, separatory funnel, thermometer and It will include lauryl methacrylate (trade name in the removable flask of round bottom of the capacity 1L of the reaction vessel of agitating device " EXCEPARL L-MA ", Kao Corp's manufacture) 83 mass parts, 2-hydroxyethyl methacrylate (trade name " ACRYESTER HO ", Mitsubishi Rayon Co., Ltd's manufacture) 9 mass parts, 2- methacryloxyethyl isocyanates (commodity Name " Karenz MOI ", Showa Denko K. K's manufacture) 8 mass parts, 2, the 2'- azobisisobutylonitrile as thermal polymerization The mixture of nitrile (manufacture of bank field Chemical Co., Ltd.) 0.2 mass parts and 50 mass parts of ethyl acetate as solvent is 60 Under the conditions of DEG C ± 2 DEG C of temperature, 6 hours (polymerization reaction) is stirred in a nitrogen atmosphere.It is obtained as a result, containing base polymer P1 Base polymer solution.Then, the 1- hydroxy-cyclohexyl as Photoepolymerizationinitiater initiater is added in the base polymer solution Phenyl ketone (trade name " Irgacure 184 ", BASF AG manufacture), as the polyisocyanate compound (trade name of crosslinking agent " Coronate L ", Japanese polyurethane Co., Ltd. manufacture), as terephthalic acid (TPA) two (2- ethylhexyl) ester of plasticizer (trade name " ADEKIZER D-810 ", Asahi Denka Co., Ltd. manufacture) and ethyl acetate and mixing as solvent, preparation Binder solution.In the binder solution, relative to 100 mass parts of base polymer, the content of Photoepolymerizationinitiater initiater is 5 matter Part is measured, the content of crosslinking agent is 2.5 mass parts, and the content of terephthalic acid (TPA) two (2- ethylhexyl) ester as plasticizer is 5 Mass parts, solid component concentration (concentration of the ingredient other than ethyl acetate) are 20 mass %.
The production > of < substrate
Substrate (the EVA being made of the vinyl-vinyl acetate copolymer (EVA) as polyolefin-based resins is made as follows Substrate).Firstly, passing through T mould extrusion molding for ethylene-vinyl acetate copolymer resins (trade name " Evflex P1007 ", Du Pont Mitsui Polychemicals co., LTD. manufacture) film is made, obtain 100 μm of thickness of eva film.Then, right The single side of the eva film implements sided corona treatment.Thus EVA substrate (100 μm of thickness) has been made.
<production of wafer adhesive sheet for processing>
In the organosilicon process face of the PET release liner with the face for implementing the organosilicon for being intended to light separation processing It is coated with the above-mentioned binder solution of the present embodiment and forms film.Then, which is heated to 2 minutes at 80 DEG C to take off Solvent forms 15 μm of thickness of adhesive phase.Then, above-mentioned EVA is bonded in the exposed surface of the adhesive phase using hand pressure roller Then substrate carries out 72 hours maturation process at 50 DEG C.By the maturation process, adhesive phase is realized to substrate Closely sealedization, and realize the plasticizer in adhesive phase and shift, to the part of substrate i.e. to the diffusion of substrate.Thus tool has been made There is the wafer adhesive sheet for processing of the embodiment 1 of the stepped construction comprising substrate and adhesive phase.The wafer of embodiment 1 is processed The composition involved in bonding sheet is listed in table 1, and (aftermentioned embodiment and comparative example are also the same.In addition, indicating composition in table 1 The unit of each numerical value is opposite " mass parts ").
(embodiment 2,3)
Except terephthalic acid (TPA) two (2- ethylhexyl) ester (commodity replaced in the preparation of binder solution as plasticizer Name " ADEKIZER D-810 ", Asahi Denka Co., Ltd. manufacture) 5 mass parts of blend amount and be set as 20 mass parts (embodiment 2) and Other than 40 mass parts (embodiment 3), embodiment 2,3 is made in a manner of same as the wafer adhesive sheet for processing of embodiment 1 Wafer adhesive sheet for processing.
(embodiment 4)
Except in the preparation of binder solution use polyester plasticizer (trade name " Polycizer W-360-ELS ", Dainippon Ink Chemicals's manufacture) 20 mass parts replace terephthalic acid (TPA) two (2- ethylhexyl) ester (trade name as plasticizer " ADEKIZER D-810 ", Asahi Denka Co., Ltd.'s manufacture) other than 5 mass parts, with the wafer adhesive sheet for processing with embodiment 1 Same mode makes the wafer adhesive sheet for processing of embodiment 4.
(embodiment 5)
In the reaction vessel for having Liebig condenser, nitrogen ingress pipe, separatory funnel, thermometer and agitating device In toluene solvant, make 2-EHA 0.75mol, N- acryloyl morpholine 0.25mol and acrylic acid 2- hydroxy methacrylate 0.22mol copolymerization, to obtain acrylic acid series copolymer.In the polymerization reaction, reaction temperature is set as 60 DEG C, and the reaction time sets It is 8 hours.Then, for the acrylic acid series copolymer, make its 2- methacryloxyethyl isocyanates with 0.11mol Addition reaction is carried out, side chain imports carbon-to-carbon double bond in polymer molecule.In the addition reaction, reaction temperature is set as 50 DEG C, it will be set as in the reaction time 6 hours.The base polymer solution containing base polymer P2 is obtained as a result,.Then, in the base In plinth polymer solution be added as Photoepolymerizationinitiater initiater 1- hydroxycyclohexylphenylketone (trade name " Irgacure 184 ", BASF AG manufacture), as polyisocyanate compound (trade name " Coronate L ", the Japanese polyurethane strain formula of crosslinking agent Commercial firm manufacture), as terephthalic acid (TPA) two (2- ethylhexyl) ester (trade name " ADEKIZER D-810 ", the strain formula of plasticizer Commercial firm ADEKA manufacture) and ethyl acetate and mixing as solvent, prepare binder solution.In the binder solution, Relative to 100 mass parts of base polymer, the content of Photoepolymerizationinitiater initiater is 5 mass parts, and the content of crosslinking agent is 2.5 mass Part, the content of terephthalic acid (TPA) two (2- ethylhexyl) ester as plasticizer is 20 mass parts, solid component concentration (acetic acid second The concentration of ingredient other than ester) it is 20 mass %.Then, except use the binder solution replace above-described embodiment 1 described in Other than binder solution, the wafer processing that embodiment 5 is made in a manner of same as the wafer adhesive sheet for processing of embodiment 1 is used Bonding sheet.
(embodiment 6)
The substrate (EPR substrate) being made of the ethylene-propylene copolymer (EPR) as polyolefin-based resins is made as follows. Firstly, by T mould extrusion molding by the resin being made of ethylene-propylene copolymer (trade name " Vistamaxx 3000 ", The manufacture of ExxonMobil company) film is made, obtain 100 μm of thickness of EPR film.Then, electricity is implemented to the single side of the EPR film Dizzy processing.Thus it is prepared for EPR substrate (thickness: 100 μm).Then, it removes and replaces institute in above-described embodiment 1 using the EPR substrate Except the EVA substrate stated, the wafer processing of embodiment 6 is made in a manner of same as the wafer adhesive sheet for processing of embodiment 1 Use bonding sheet.
(comparative example 1)
Except in the preparation in binder solution do not use terephthalic acid (TPA) two (2- ethylhexyl) ester in addition to, with embodiment The wafer adhesive sheet for processing of the same mode comparison example 1 of 1 wafer adhesive sheet for processing.
(comparative example 2)
Except without using in addition to terephthalic acid (TPA) two (2- ethylhexyl) ester, by with the binder solution system in embodiment 5 The same method of Preparation Method prepares binder solution.Then, except use the binder solution replace above-described embodiment 1 described in Except binder solution, the wafer of comparison example 2, which is processed, in a manner of identical with the wafer adhesive sheet for processing of embodiment 1 is used Bonding sheet.
(comparative example 3)
Single side, which has been made, by method identical with substrate production method described in above-described embodiment 6 carries out sided corona treatment EPR substrate (100 μm of thickness).Then, except use the EPR substrate replace above-described embodiment 1 described in EVA substrate, Yi Ji It is not used other than terephthalic acid (TPA) two (2- ethylhexyl) ester in the preparation of binder solution, to be processed with the wafer of embodiment 1 With the wafer adhesive sheet for processing of the same mode comparison example 3 of bonding sheet.
< bonding force >
For each wafer adhesive sheet for processing of Examples 1 to 6 and comparative example 1~3,90 ° of removings are measured as follows Bonding force.Firstly, being cut out from the wafer adhesive sheet for processing of adhesive phase non-irradiated with ultraviolet radiation for bonding force measurement Sample strip (wide 20mm × long 150mm).Then, for the mirror surface Silicon Wafer (trade name " CZN<100>for implementing mirror-polishing processing 2.5-3.5 ", 4 inches of diameter, Shinetsu Handotai KK's manufacture), by by round-trip 1 crimping operation of the hand pressure roller of 2kg To be bonded the sample strip.Then, after placing 1 hour under normal temperature environment, electronic stripping tester (trade name " Tensilon type is used Electronic stripping tester TMC-1kNB ", Co., Ltd. NTS manufacture), 90 ° peel adhesions of the measurement sample strip to the mirror surface Silicon Wafer (N/20mm).In this measurement, measuring temperature or exfoliation temperature are 23 DEG C, and draw angle is 90 °, and tensile speed is 300mm/ points Clock.Its measurement result is listed in table 1.
< dust adhesion amount >
For each wafer adhesive sheet for processing of Examples 1 to 6 and comparative example 1~3, investigates cutting as follows Cut dust adhesion amount when using in process.Firstly, to mirror surface Silicon Wafer, (8 inches of diameter, 600 μm of thickness, chemical industry is answered in Tokyo Co., Ltd.'s manufacture) back side grinding is carried out so that thickness reaches 250 μm, for the non-grinding surface of the wafer, in its adhesive phase Side is bonded wafer adhesive sheet for processing.Fitting be at 23 DEG C and under conditions of 50%RH using the crimping operation using hand roller into Capable.Then, using cutter device (trade name " DFD6361 ", Co., Ltd. Disco manufacture), by using Z1 blade (commodity Name " ZH05-SD3500-N1-70 ", Co., Ltd. Disco manufacture) the 1st grinding with later use Z2 blade (trade name " ZH05-SD4000-N1-70 ", Co., Ltd. Disco manufacture) the 2nd grinding the grinding of 2 stages, be held in crystalline substance to being in The wafer in the state of circle adhesive sheet for processing is cut entirely.In the cutting action, cut mode is incision, blade Revolving speed is 35000rpm, and cutting speed is 50mm/ seconds, and the cutting depth of Z1 blade is 190 μm, and the cutting depth of Z2 blade is 90 μm, cut lengths are 4.0mm × 5.0mm, form more than the wafer on wafer adhesive sheet for processing and also extend to wafer and add The cutting slot (280 μm) of depth in work bonding sheet.In this cutting action, to rotating blade and wafer sustainable supply stream Water.In addition, carrying out cleaning process under conditions of wafer revolving speed 1000rpm and 90 seconds after cutting action.Then, it uses Shape measure laser microscope VK-X150 (manufacture of KEYENCE Co., Ltd.) is with multiplying power 200 times of (10 times of multiplying powers of eyepiece, object lens 20 times of multiplying power) surface of the chip obtained by the wafer singualtion in cutting action is observed, to chip The quantity of dust is measured present on surface (surface with the opposite side of the closely sealed side of wafer adhesive sheet for processing).By powder Situation of the dirt number less than 50 is evaluated as "○", and the situation by 50 or more and less than 100 is evaluated as " △ ", by 100 with On situation be evaluated as "×".Its evaluation result is listed in table 1.
[table 1]
Description of symbols
10 wafer adhesive sheet for processing
11 substrates
12 adhesive phases
20 workpieces
21 element chips
G cutting slot

Claims (8)

1. a kind of wafer adhesive sheet for processing, with stepped construction, the stepped construction includes:
Polyolefin substrate containing plasticizer；And
Adhesive phase containing plasticizer.
2. wafer adhesive sheet for processing according to claim 1, wherein the plasticizer in described adhesive layer contains Amount is 1 mass parts or more relative to 100 mass parts of adhesive in described adhesive layer.
3. wafer adhesive sheet for processing according to claim 1 or 2, wherein the plasticizer in described adhesive layer Content relative to 100 mass parts of adhesive in described adhesive layer be 100 below the mass.
4. wafer adhesive sheet for processing described in any one of claim 1 to 3, wherein described adhesive layer includes virtue Fragrant race's carboxylate system's plasticizer and/or polyester plasticizer are as plasticizer.
5. wafer adhesive sheet for processing according to any one of claims 1 to 4, wherein the polyolefin substrate packet The plasticizer of system containing aromatic carboxylic acid esters and/or polyester plasticizer are as plasticizer.
6. wafer adhesive sheet for processing according to claim 4 or 5, wherein aromatic carboxylic acid esters system plasticizer is Terephthalic acid (TPA) two (2- ethylhexyl) ester.
7. wafer adhesive sheet for processing described according to claim 1~any one of 6, wherein the polyolefin substrate packet Containing vinyl-vinyl acetate copolymer or ethylene-propylene copolymer as resin principal component.
8. wafer adhesive sheet for processing according to any one of claims 1 to 7, wherein the polyolefin substrate without Vinyl chloride.
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