CN113174214A - Thermal viscosity reduction protective film for wafer cutting and preparation method thereof - Google Patents
Thermal viscosity reduction protective film for wafer cutting and preparation method thereof Download PDFInfo
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- CN113174214A CN113174214A CN202110438112.5A CN202110438112A CN113174214A CN 113174214 A CN113174214 A CN 113174214A CN 202110438112 A CN202110438112 A CN 202110438112A CN 113174214 A CN113174214 A CN 113174214A
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- Prior art keywords
- thermal
- protective film
- sensitive adhesive
- viscosity reduction
- wafer
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- 230000001681 protective effect Effects 0.000 title claims abstract description 43
- 238000005520 cutting process Methods 0.000 title claims abstract description 35
- 230000009467 reduction Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 34
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 21
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 14
- -1 polyethylene terephthalate Polymers 0.000 claims description 12
- 229920000103 Expandable microsphere Polymers 0.000 claims description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 8
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 11
- 235000012431 wafers Nutrition 0.000 description 49
- 230000000052 comparative effect Effects 0.000 description 22
- 239000010410 layer Substances 0.000 description 15
- 229940051841 polyoxyethylene ether Drugs 0.000 description 15
- 229920000056 polyoxyethylene ether Polymers 0.000 description 15
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 10
- 239000012790 adhesive layer Substances 0.000 description 8
- 239000004005 microsphere Substances 0.000 description 8
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- HAUGVDQUSLPQBX-UHFFFAOYSA-N butanedioic acid;1-hydroxypyrrolidine-2,5-dione Chemical compound ON1C(=O)CCC1=O.OC(=O)CCC(O)=O HAUGVDQUSLPQBX-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 108700004121 sarkosyl Proteins 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- BACYUWVYYTXETD-UHFFFAOYSA-N N-Lauroylsarcosine Chemical compound CCCCCCCCCCCC(=O)N(C)CC(O)=O BACYUWVYYTXETD-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BZXMNFQDWOCVMU-UHFFFAOYSA-N 2-[dodecanoyl(methyl)amino]acetic acid;sodium Chemical compound [Na].CCCCCCCCCCCC(=O)N(C)CC(O)=O BZXMNFQDWOCVMU-UHFFFAOYSA-N 0.000 description 1
- QLHLYJHNOCILIT-UHFFFAOYSA-N 4-o-(2,5-dioxopyrrolidin-1-yl) 1-o-[2-[4-(2,5-dioxopyrrolidin-1-yl)oxy-4-oxobutanoyl]oxyethyl] butanedioate Chemical compound O=C1CCC(=O)N1OC(=O)CCC(=O)OCCOC(=O)CCC(=O)ON1C(=O)CCC1=O QLHLYJHNOCILIT-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003698 laser cutting Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229940079781 sodium cocoyl glutamate Drugs 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- 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
-
- 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
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
The invention provides a thermal viscosity reduction protective film for wafer cutting and a preparation method thereof. Wherein the raw materials for preparing the thermal viscosity-reducing acrylate pressure-sensitive adhesive comprise acrylate pressure-sensitive adhesive and an expansion material. The thermal anti-sticking protective film for wafer cutting, prepared by the invention, is used as a cutting bearing when in use, can lose sticking through heating after cutting is finished, is easy to peel, and can not cause the success rate of picking up chips to be reduced due to overlarge strength in the picking up process.
Description
Technical Field
The invention relates to the field of wafer cutting, in particular to a thermal viscosity reduction protective film for wafer cutting and a preparation method thereof.
Background
Wafer dicing is an essential process in manufacturing semiconductor chips, and mainly involves dicing a whole wafer into individual chips by an external force according to the size of the chips. The traditional wafer cutting is cutting by a blade scribing, but the blade scribing and cutting easily breaks the wafer, and the cutting success rate is reduced. In order to improve the success rate of cutting, a laser cutting technology is developed, wherein the wafer is cut by laser, a high-temperature laser beam is formed on the surface of the wafer through laser focusing, and the wafer is melted to achieve the purpose of cutting. However, the high temperature laser beam is likely to damage the wafer, and a protective film needs to be coated on the surface of the wafer, thereby reducing the wafer damage rate.
The protective film for wafer cutting is adhered to the surface of the wafer through the adhesive layer, and the protective film needs to be peeled off after the wafer is cut, but the colloid is easily remained on the surface of the wafer in the existing protective film peeling process, so that the complexity of subsequent treatment of the wafer is increased.
Disclosure of Invention
In order to solve the technical problems, the invention provides a thermal anti-sticking protective film for wafer cutting, which comprises a substrate layer, an adhesive layer and a release film from top to bottom, wherein the substrate layer is a PET substrate; the bonding layer is thermal viscosity reduction type acrylate pressure-sensitive adhesive.
Preferably, the raw materials for preparing the thermal viscosity reduction type acrylate pressure-sensitive adhesive comprise acrylate pressure-sensitive adhesive and an expansion material.
Preferably, the preparation raw materials of the acrylate comprise monomers, surfactants, initiators and deionized water.
Preferably, the monomer is selected from one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate and beta-carboxyethyl acrylate.
Preferably, the weight ratio of the monomer to the deionized water is 1: (5-8).
Preferably, the surfactant is selected from at least one of a cationic surfactant, an anionic surfactant and a nonionic surfactant.
Preferably, the expansion material is selected from thermally expandable microspheres.
Preferably, the heat-expandable microspheres have a particle size of 1 to 50 μm.
Preferably, the weight of the thermally expandable microspheres is 5 to 10 wt% of the weight of the monomer.
The invention provides a preparation method of a thermal viscosity-reducing protective film for wafer cutting, which comprises the following steps: coating the thermal viscosity reduction type acrylate pressure-sensitive adhesive on the substrate layer, heating and curing, and attaching a release film on one side of the thermal viscosity reduction type acrylate pressure-sensitive adhesive, which is far away from the substrate layer, to prepare the thermal viscosity reduction protective film.
Compared with the prior art, the invention has the following beneficial effects:
1. the protective film has excellent stability and retractility, is not easy to break when the film is stretched, does not cause damage to a wafer when the film is expanded, and is not easy to shrink, wrinkle or deform;
2. the special thermal viscosity-reducing acrylate pressure-sensitive adhesive is used, the adhesive can be lost when being heated, the wafer cutting protective film prepared by the method is used as a wafer cutting bearing, the adhesive can be lost when being heated after the cutting is finished, and the wafer can be easily peeled off from the wafer;
3. the thermal de-bonding protective film for wafer cutting prepared by the invention can not cause the success rate of picking up chips to be reduced due to overlarge bonding strength in the process of picking up the wafer;
4. the thermal de-bonding protective film for wafer cutting prepared by the invention also avoids the problem of chip crack generation in the picking process.
Detailed Description
In order to solve the technical problems, the invention provides a thermal anti-sticking protective film for wafer cutting, which comprises a substrate layer, an adhesive layer and a release film from top to bottom, wherein the substrate layer is a PET substrate; the bonding layer is thermal viscosity reduction type acrylate pressure-sensitive adhesive.
Preferably, the raw materials for preparing the thermal viscosity reduction type acrylate pressure-sensitive adhesive comprise acrylate pressure-sensitive adhesive and an expansion material.
Preferably, the raw materials for preparing the acrylate pressure-sensitive adhesive comprise monomers, a surfactant, an initiator and deionized water.
Preferably, the monomer is selected from one or more of methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate and beta-carboxyethyl acrylate.
Preferably, the weight ratio of the monomer to the deionized water is 1: (5-8).
Preferably, the monomer is selected from the group consisting of methyl methacrylate and beta-carboxyethyl acrylate.
Preferably, the weight ratio of the methyl methacrylate to the beta-carboxyethyl acrylate is (1.5-5): 2.
in the experimental process, the applicant finds that when methyl methacrylate and beta-carboxyethyl acrylate are selected as reaction monomers, the weight ratio of deionized water to the monomers seriously influences the quality of acrylate pressure-sensitive adhesive, and further influences the use effect of the protective film in wafer cutting.
The applicant is researched and found through a large number of creative experiments, and when the weight ratio of the monomers to the deionized water is 1: (5-8), the surface of the prepared acrylate pressure-sensitive adhesive is flat, and the tensile strength as a protective film is improved, and the applicant speculates that the phenomenon is caused by the following reasons: in the system, a transfer interface can be established between reaction monomers of methyl methacrylate and beta-carboxyethyl acrylate and a generated polymer through a water phase, a chain growth reaction occurs in the water phase, a nucleation phenomenon can occur in the system along with the progress of a polymerization reaction when a water phase chain is aggregated or densified to reach a critical molecular weight, and the weight ratio of a monomer to deionized water is 1: (5-8), can guarantee that it forms regular continuous structure, when receiving external force tensile, can disperse stress fast, avoided local stress concentration, promoted the stretch-proof ability of the polymer that forms, and then also guaranteed the tensile strength of protection film.
The applicant has also found that in the present system, methyl methacrylate and β -carboxyethyl acrylate are added, and when the weight ratio of methyl methacrylate to β -carboxyethyl acrylate is (1.5-5): 2, the crosslinking performance and the cohesive force of the system can be improved, and the tensile property of the formed polymer is improved. When the total amount of the added methyl methacrylate and the added beta-carboxyethyl acrylate is larger, the heat generated in the reaction process of the methyl methacrylate and the beta-carboxyethyl acrylate cannot be rapidly dispersed and transferred, the viscosity of the system is rapidly increased, the phenomenon of chain transfer or implosion occurs, and the toughness of the protective film is greatly reduced.
Preferably, the surfactant is selected from at least one of a cationic surfactant, an anionic surfactant and a nonionic surfactant.
Preferably, the surfactant is selected from anionic surfactants and nonionic surfactants.
Preferably, the anionic surfactant is at least one selected from the group consisting of sodium N-lauroyl sarcosinate, monolauryl phosphate, lauryl alcohol ether phosphate, sodium cocoyl glutamate and sodium alpha-alkenyl sulfonate.
Preferably, the nonionic surfactant is at least one selected from polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol lauryl ether, polyoxyethylene fatty acid methyl ester and polyoxyethylene isooctanol.
Preferably, the anionic surfactant is sodium N-lauroyl sarcosinate.
Preferably, the nonionic surfactant is selected from octylphenol polyoxyethylene ether.
Preferably, the weight ratio of the N-sodium lauroyl sarcosine to the octyl phenol polyoxyethylene ether is (1-3.5): 1.
preferably, the weight ratio of the N-lauroyl sarcosine sodium to the octyl phenol polyoxyethylene ether is 2.5: 1.
the applicant finds that the selection of the surfactant has certain influence on the preparation of the bonding layer material in the experimental process, and the applicant is obtained through a large number of creative experimental researches. The applicant speculates that the cause of this phenomenon occurs: in the experimental process, N-sodium lauroyl sarcosine can be ionized into ions in the system, can be adsorbed on the surfaces of methyl methacrylate and beta-carboxyethyl acrylate, a certain degree of hydration is generated, and octyl phenol polyoxyethylene ether in the system is cooperated, so that the electrostatic repulsion and the steric hindrance of a hydration layer are balanced, the flocculation of free particles in the system is avoided, the stability between a monomer and an emulsifier is improved, the smoothness of the surface of an adhesive layer when the adhesive layer is solidified and formed is further ensured, and the phenomena of wrinkling and deformation are further avoided when the wafer is cut and used.
Meanwhile, the applicant finds that although the added octyl phenol polyoxyethylene ether can generate solvation in the system when the amount of the added octyl phenol polyoxyethylene ether is increased, the stability of the system can be improved to a great extent, the emulsification effect on monomer beads is greatly reduced compared with the emulsification effect during compounding, and the pressure-sensitive adhesive has defects.
Preferably, the surfactant is used in an amount of 0.1 to 0.5% by weight of the monomer.
The applicant finds that the amount of the surfactant in the system seriously affects the quality of the acrylate pressure-sensitive adhesive, and when the amount of the surfactant is 0.1-0.5% of the weight of the monomer, the surfactant and OH contained in the system can be ensured-、COO-And the further combination of the acrylic ester pressure-sensitive adhesive and the acrylic ester pressure-sensitive adhesive forms hydrogen bond interaction force, prevents the self-polymerization of monomers in a system, promotes the convenient application in the process of gluing the adhesive layer, avoids the defects in the adhesive layer, and promotes the quality and the mechanical property of the acrylic ester pressure-sensitive adhesive.
Meanwhile, the applicant finds that when the amount of the used surfactant is less than 0.1% of the weight of the monomer, the polymerization reaction of the monomer is incomplete, and the prepared pressure-sensitive adhesive has a large smell; however, when the surfactant is used in an amount of more than 0.5% by weight based on the weight of the monomer, the interaction capacity between the systems is increased, the thickness of the intermolecular hydrated layer is increased remarkably, and the difficulty in sizing the adhesive layer is increased.
Preferably, the initiator is selected from potassium persulfate or ammonium persulfate.
Preferably, the preparation method of the thermal viscosity reduction type acrylate pressure-sensitive adhesive comprises the following steps: and uniformly mixing the prepared acrylic pressure-sensitive adhesive with the thermal expansibility microsphere to obtain the thermal viscosity reduction type acrylic ester pressure-sensitive adhesive.
Preferably, the expansion material is selected from thermally expandable microspheres.
Preferably, the heat-expandable microspheres have a particle size of 1 to 50 μm.
Preferably, the weight of the thermally expandable microspheres is 5 to 10 wt% of the weight of the monomer.
In the experimental process, the applicant finds that the prepared acrylate pressure-sensitive adhesive can be used as a cutting load during wafer cutting when being matched with an expansion material, and simultaneously enables a protective film to be easily peeled under the heating condition, and particularly shows better viscosity reduction and better peeling effect when the weight of the expansion material is 5-10 wt% of the weight of a monomer, and speculates that the phenomenon occurs: when the weight of the expansion material is 5-10 wt% of the weight of the monomer, the external temperature rises, the expansion material generates the change of the internal gas pressure, but the gas permeability is reduced due to the mixing with the acrylate, the expansion pressure is increased, the instantaneous viscosity is reduced when the protective film is used, and the release force of the protective film is ensured.
Applicants have found that the addition of an amount of intumescent material greater than 10 weight percent based on the weight of the monomer in the present application causes the intumescent material to swell, which causes the particle size of the intumescent material to become larger after swelling, which in turn affects the die during wafer picking.
Preferably, the raw materials for preparing the acrylate pressure-sensitive adhesive comprise, by weight, 15-30 parts of methyl methacrylate, 10-20 parts of beta-carboxyethyl acrylate, 0.025-0.15 part of N-sodium lauroyl sarcosine, 0.01-0.06 part of octyl phenol polyoxyethylene ether, 3 parts of potassium persulfate and 400 parts of deionized water 240-.
Preferably, the raw materials for preparing the acrylate pressure-sensitive adhesive also comprise 1-2 parts of a cross-linking agent.
Preferably, the structure of the cross-linking agent is as follows:
the invention provides a preparation method of a thermal viscosity-reducing protective film for wafer cutting, which comprises the following steps: coating the thermal viscosity reduction type acrylate pressure-sensitive adhesive on the substrate layer, heating and curing, and attaching a release film on one side of the thermal viscosity reduction type acrylate pressure-sensitive adhesive, which is far away from the substrate layer, to prepare the thermal viscosity reduction protective film.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
Example 1
The utility model provides a wafer cutting is with thermal visbreaking protection film, the structure from the top down is the substrate layer in proper order, and the bond line is from the type membrane, and the substrate layer is the PET substrate, and the bond line is thermal visbreaking type acrylic ester pressure-sensitive adhesive. The thermal viscosity reduction type acrylate pressure-sensitive adhesive is prepared from acrylate pressure-sensitive adhesive and thermal expansion microspheres, wherein the weight of the thermal expansion microspheres is 8 wt% of the weight of a monomer.
The preparation raw materials of the acrylate pressure-sensitive adhesive comprise the following components in parts by weight: 30 parts of methyl methacrylate, 20 parts of beta-carboxyethyl acrylate, 0.15 part of N-lauroyl sarcosine sodium, 0.06 part of octyl phenol polyoxyethylene ether, 3 parts of potassium persulfate, 1 part of ethylene glycol-bis (succinic acid N-hydroxysuccinimide ester) disulfonic acid sodium and 250 parts of deionized water.
Among them, N-lauroylsarcosine sodium is purchased from western chemical technology (shandong) ltd, CAS No.: 137-16-6.
Octyl phenol polyoxyethylene ether is purchased from Haian petrochemical plants of Jiangsu province, and has the model of OP-10.
Methyl methacrylate, CAS No.: 80-62-6.
Beta-carboxyethyl acrylate, CAS No.: 24615-84-7.
The heat-expandable microspheres were purchased from Nippon oil and fat pharmaceuticals, and were designated MSL-3030.
Ethylene glycol-bis (N-hydroxysuccinimide succinate) disulfonate was purchased from Hangzhou Xinqiao Biotech, Inc.
Also provides a preparation method of the thermal de-bonding protective film for wafer cutting, which comprises the following steps:
(1) uniformly mixing N-sodium lauroyl sarcosine, octyl phenol polyoxyethylene ether, deionized water, methyl methacrylate and beta-carboxyethyl acrylate; adding ethylene glycol-bis (N-hydroxysuccinimide succinate) disulfonate and potassium persulfate, and mixing to obtain acrylate pressure-sensitive adhesive;
(2) adding the thermal expansion microspheres, and uniformly stirring to obtain the thermal viscosity-reducing acrylate pressure-sensitive adhesive;
(3) coating the thermal viscosity reduction type acrylate pressure-sensitive adhesive on a PET (polyethylene terephthalate) substrate, heating and curing at 65 ℃, and attaching a release film on one side of the thermal viscosity reduction type acrylate pressure-sensitive adhesive, which is far away from the PET substrate, to obtain the thermal viscosity reduction protective film.
Example 2
The specific implementation mode is the same as that of example 1, and the differences are that 15 parts of methyl methacrylate, 20 parts of beta-carboxyethyl acrylate, 0.125 part of sodium N-lauroylsarcosine, 0.05 part of octylphenol polyoxyethylene ether, 3 parts of potassium persulfate, 1 part of ethylene glycol-bis (N-hydroxysuccinimide succinate) disulfonate, 250 parts of deionized water and 10 wt% of the thermal expansion microspheres based on the weight of the monomers.
Example 3
The specific implementation mode is the same as that of example 1, and the differences are that 25 parts of methyl methacrylate, 10 parts of beta-carboxyethyl acrylate, 0.025 part of sodium N-lauroylsarcosine, 0.01 part of polyoxyethylene octylphenol ether, 3 parts of potassium persulfate, 1 part of ethylene glycol-bis (N-hydroxysuccinimide succinate) disulfonate, 250 parts of deionized water and 5 wt% of the thermal expansion microspheres based on the weight of the monomers.
Comparative example 1
The specific implementation mode is the same as that of example 1, except that 150 parts of deionized water is used.
Comparative example 2
The specific implementation mode is the same as that of example 1, except that 500 parts of deionized water is used.
Comparative example 3
The specific implementation mode is the same as that of example 1, except that 15 parts of methyl methacrylate and 35 parts of beta-carboxyethyl acrylate are used.
Comparative example 4
The specific implementation mode is the same as that of example 1, except that 40 parts of methyl methacrylate and 10 parts of beta-carboxyethyl acrylate are used.
Comparative example 5
The specific implementation mode is the same as that of example 1, except that 0.105 parts of sodium N-lauroylsarcosine and 0.105 parts of octylphenol polyoxyethylene ether are used.
Comparative example 6
The specific implementation mode is the same as that of example 1, except that 0.18 part of sodium N-lauroylsarcosine and 0.03 part of octylphenol polyoxyethylene ether are used.
Comparative example 7
The specific implementation mode of the thermal de-bonding protective film for wafer cutting is the same as that of example 1, except that the weight of the thermal expansion microspheres is 20 wt% of the weight of the monomers.
Comparative example 8
The specific implementation mode of the thermal de-bonding protective film for wafer cutting is the same as that of example 1, except that the weight of the thermal expansion microspheres is 1 wt% of the weight of the monomers.
Comparative example 9
The specific implementation mode is the same as that of example 1, and the difference is that 0.4 part of N-sodium lauroyl sarcosine and 0.16 part of octyl phenol polyoxyethylene ether are adopted.
Comparative example 10
The specific implementation mode is the same as that of example 1, except that 0.025 parts of N-sodium lauroylsarcosine and 0.01 parts of octylphenol polyoxyethylene ether are used.
Performance testing
1. And (4) testing the tensile bonding strength.
The tensile bond strength of the thermal release protective films produced in examples and comparative examples was measured by a Kinmier tensile tester, model JM-101PT, according to the measurement method of GB/T29906-2013.
2. And testing the success rate of chip picking.
The cut wafers were tested for success in the pick up process. The thermal anti-sticking protective films prepared in examples and comparative examples were attached to wafers, and after the wafers were cut, the wafers were heated at 130 ℃ for 2min, and 100 heated wafers were picked up, and the number of intact wafers picked up was recorded as M. When the wafer is not picked up, cracks are generated on the picked-up wafer, and a thermal de-bonding protective film is adhered on the picked-up wafer, the wafer is classified as an imperfect wafer.
Pick-up success rate is (100-M)/100 x 10%.
The test data are recorded in table 1.
TABLE 1
| Tensile bond strength/MPa | Success rate of picking% | |
| Example 1 | 1.15 | 99 |
| Example 2 | 1.13 | 98 |
| Example 3 | 1.14 | 98 |
| Comparative example 1 | 2.15 | 92 |
| Comparative example 2 | 0.6 | 89 |
| Comparative example 3 | 1.84 | 91 |
| Comparative example 4 | 1.58 | 90 |
| Comparative example 5 | 0.8 | 85 |
| Comparative example 6 | 0.85 | 87 |
| Comparative example 7 | 0.98 | 89 |
| Comparative example 8 | 2.25 | 84 |
| Comparative example 9 | 0.5 | 85 |
| Comparative example 10 | 0.6 | 88 |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
1. The thermal anti-sticking protective film for wafer cutting is characterized by sequentially comprising a base material layer, a bonding layer and a release film from top to bottom, wherein the base material layer is a PET (polyethylene terephthalate) base material; the bonding layer is thermal viscosity reduction type acrylate pressure-sensitive adhesive.
2. The wafer cutting thermal viscosity reduction protective film as claimed in claim 1, wherein the thermal viscosity reduction type acrylate pressure sensitive adhesive is prepared from acrylate pressure sensitive adhesive and an expansion material.
3. The thermal viscosity reduction protective film for wafer cutting as claimed in claim 2, wherein the raw material for preparing the acrylate pressure sensitive adhesive comprises a monomer, a surfactant, an initiator and deionized water.
4. The thermal viscosity reduction protective film for wafer cutting as claimed in claim 3, wherein the monomer is one or more selected from methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate and beta-carboxyethyl acrylate.
5. The thermal de-bonding protective film for wafer dicing as claimed in claim 3, wherein the weight ratio of the monomer to the deionized water is 1: (5-8).
6. The thermal de-bonding protective film for wafer dicing as claimed in claim 3, wherein the surfactant is at least one selected from the group consisting of a cationic surfactant, an anionic surfactant and a nonionic surfactant.
7. The thermal de-bonding protective film for wafer dicing as claimed in claim 2, wherein the expansion material is selected from thermally expandable microspheres.
8. The thermal de-bonding protective film for wafer dicing as claimed in claim 7, wherein the thermally expandable microspheres have a particle size of 1 to 50 μm.
9. The thermal de-bonding protective film for wafer dicing as claimed in claim 8, wherein the weight of the thermally expandable microspheres is 5 to 10 wt% of the weight of the monomer.
10. The method for preparing a thermal de-bonding protective film for wafer dicing according to claim 8, comprising the steps of: coating the thermal viscosity reduction type acrylate pressure-sensitive adhesive on the substrate layer, heating and curing, and attaching a release film on one side of the thermal viscosity reduction type acrylate pressure-sensitive adhesive, which is far away from the substrate layer, to prepare the thermal viscosity reduction protective film.
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| CN113956800A (en) * | 2021-11-23 | 2022-01-21 | 苏州赛伍应用技术股份有限公司 | Viscosity-reducing adhesive composition and preparation method and application thereof |
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| CN101126001A (en) * | 2006-08-14 | 2008-02-20 | 日东电工株式会社 | Adhesive sheet, process for producing the same, and method of cutting multilayered ceramic sheet |
| CN102019737A (en) * | 2010-09-30 | 2011-04-20 | 南亚塑胶工业股份有限公司 | Aqueous thermally-foamed gluing adhesive plate |
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