KR20240080365A - Protecting sheet for semiconductor wafer - Google Patents
Protecting sheet for semiconductor wafer Download PDFInfo
- Publication number
- KR20240080365A KR20240080365A KR1020220163640A KR20220163640A KR20240080365A KR 20240080365 A KR20240080365 A KR 20240080365A KR 1020220163640 A KR1020220163640 A KR 1020220163640A KR 20220163640 A KR20220163640 A KR 20220163640A KR 20240080365 A KR20240080365 A KR 20240080365A
- Authority
- KR
- South Korea
- Prior art keywords
- protective film
- semiconductor wafer
- forming layer
- film sheet
- film forming
- Prior art date
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 69
- 230000001681 protective effect Effects 0.000 claims abstract description 125
- 235000012431 wafers Nutrition 0.000 claims abstract description 80
- 239000010410 layer Substances 0.000 claims description 71
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- 229920000647 polyepoxide Polymers 0.000 claims description 41
- 239000003795 chemical substances by application Substances 0.000 claims description 23
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- 239000011347 resin Substances 0.000 claims description 19
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
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- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005678 polyethylene based resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-N trans-cinnamic acid Chemical compound OC(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Materials Engineering (AREA)
- Adhesive Tapes (AREA)
Abstract
본 발명의 실시예들에 따른 반도체 웨이퍼용 보호막 시트는 기재 필름 및 기재필름을 포함할 수 있다. 보호막 형성층의 점도는 120℃에서 100,000 내지 300,000Pa·s일 수 있고, 반도체 웨이퍼와의 박리력은 10 내지 200gf/inch일 수 있다. 반도체 웨이퍼용 보호막 시트의 인장 강도가 향상될 수 있으며, 리워크성이 향상될 수 있다.A protective film sheet for a semiconductor wafer according to embodiments of the present invention may include a base film and a base film. The viscosity of the protective film forming layer may be 100,000 to 300,000 Pa·s at 120°C, and the peeling force from the semiconductor wafer may be 10 to 200 gf/inch. The tensile strength of the protective film sheet for semiconductor wafers can be improved, and reworkability can be improved.
Description
본 발명은 반도체 웨이퍼용 보호막 시트에 관한 것이다. 보다 상세하게는, 기재 필름 및 보호막 형성층을 포함하는 반도체 웨이퍼용 보호막 시트에 관한 것이다.The present invention relates to a protective film sheet for semiconductor wafers. More specifically, it relates to a protective film sheet for semiconductor wafers including a base film and a protective film forming layer.
최근 반도체 장치의 제조에 있어, 페이스 다운(face down) 방식으로 불리는 실장법이 활용되고 있다. 페이스 다운 방식은 반도체 칩의 회로면 상에 범프 등의 전극을 갖는 반도체 칩이 탑재되고, 반도체 칩의 전극이 기판과 결합된다. 이에 따라, 기판과 결합된 측의 반대측 반도체 칩의 표면이 노출될 수 있다.Recently, in the manufacture of semiconductor devices, a mounting method called a face down method has been used. In the face-down method, a semiconductor chip with electrodes such as bumps is mounted on the circuit surface of the semiconductor chip, and the electrodes of the semiconductor chip are combined with the substrate. Accordingly, the surface of the semiconductor chip on the side opposite to the side coupled to the substrate may be exposed.
반도체 칩의 노출된 표면을 보호하기 위하여 반도체 웨이퍼의 일 면에 유기 재료 등으로 이루어진 수지막이 보호막으로 형성될 수 있다. 이에 따라, 다이싱 공정 등에서 크랙 등이 발생하는 것을 방지할 수 있다.In order to protect the exposed surface of the semiconductor chip, a resin film made of an organic material, etc. may be formed as a protective film on one side of the semiconductor wafer. Accordingly, it is possible to prevent cracks, etc. from occurring during the dicing process.
또한, 최근 반도체를 연마함에 있어, 연마 정밀도를 향상시키기 위하여 리워크(rework)라 불리는 재연마 방식이 활용되고 있다. 리워크는 연마된 웨이퍼의 막 두께를 측정하고, 측정된 막 두께와 목표 막 두께의 차이를 없애기 위해, 다시 웨이퍼를 연마하는 공정이다.In addition, recently, when polishing semiconductors, a re-polishing method called rework has been used to improve polishing precision. Rework is a process of measuring the film thickness of a polished wafer and polishing the wafer again to eliminate the difference between the measured film thickness and the target film thickness.
리워크를 용이하게 수행하기 위하여 리워크성이 우수할 필요가 있다. 리워크성이란 부착 목적 대상물부터 부착물을 용이하게 벗길 수 있는 성질과, 부착물이 재차 부착 목적 대상물에 강하게 흡착하려는 성질이다. 리워크성이 우수한 경우, 웨이퍼에 부착된 기재를 용이하게 박리할 수 있고, 기재가 웨이퍼의 잘못된 위치에 부착한 경우에도 용이하게 재부착할 수 있다.In order to easily perform rework, it is necessary to have excellent reworkability. Reworkability is the property of being able to easily peel off the attachment from the object to which it is attached, and the property of the attachment being strongly adsorbed to the object of attachment again. When reworkability is excellent, the substrate attached to the wafer can be easily peeled off, and even if the substrate is attached to the wrong location on the wafer, it can be easily reattached.
그러나, 반도체 칩의 노출된 표면을 보호하기 위하여 반도체 웨이퍼 일면에 형성된 보호막의 박리력 등이 너무 큰 경우 리워크 공정의 수행에 불리할 수 있다.However, if the peeling force of the protective film formed on one side of the semiconductor wafer to protect the exposed surface of the semiconductor chip is too great, it may be disadvantageous to perform the rework process.
예를 들면, 한국등록특허공보 제10-0681665호는 열경화성 성분을 포함하는 보호막 형성층을 개시하고 있다.For example, Korean Patent Publication No. 10-0681665 discloses a protective film forming layer containing a thermosetting component.
본 발명의 일 과제는 리워크성 및 인장특성이 향상된 반도체 웨이퍼용 보호막 시트를 제공하는 것이다.One object of the present invention is to provide a protective film sheet for semiconductor wafers with improved reworkability and tensile properties.
예시적인 실시예들에 따른 반도체 웨이퍼용 보호막 시트는, 기재 필름 및 상기 기재 필름 상에 형성되는 보호막 형성층을 포함할 수 있으며, 상기 보호막 형성층의 점도는 120℃에서 100,000 내지 300,000Pa·s일 수 있으며, 반도체 웨이퍼와의 박리력은 10 내지 200gf/inch일 수 있다.The protective film sheet for semiconductor wafers according to exemplary embodiments may include a base film and a protective film forming layer formed on the base film, and the viscosity of the protective film forming layer may be 100,000 to 300,000 Pa·s at 120°C. , the peeling force from the semiconductor wafer may be 10 to 200 gf/inch.
일부 실시예들에 있어서, 상기 박리력은 반도체 웨이퍼 일 면에 상기 보호막 형성층을 80℃에서 라미네이션 후, 25℃에서 인장 속도 5mm/s 및 인장 각도 180°의 박리 조건에서 측정한 것일 수 있다.In some embodiments, the peel force may be measured after lamination of the protective film forming layer on one side of the semiconductor wafer at 80°C and under peeling conditions of a tensile speed of 5 mm/s and a tensile angle of 180° at 25°C.
일부 실시예들에 있어서, 상기 보호막 형성층은 바인더, 에폭시 수지 및 경화제를 포함할 수 있다.In some embodiments, the protective film forming layer may include a binder, an epoxy resin, and a curing agent.
일부 실시예들에 있어서, 상기 바인더는 중량 평균 분자량이 400,000 내지 2,000,000g/mol의 아크릴산 에스테르 공중합체일 수 있다.In some embodiments, the binder may be an acrylic acid ester copolymer with a weight average molecular weight of 400,000 to 2,000,000 g/mol.
일부 실시예들에 있어서, 상기 바인더의 유리전이온도(glass transition temperature)는 1℃ 내지 21℃일 수 있다.In some embodiments, the glass transition temperature of the binder may be 1°C to 21°C.
일부 실시예들에 있어서, 상기 에폭시 수지는 노볼락형 에폭시 수지로 형성된 제1 수지 및 비스페놀계 에폭시 수지로 형성된 제2 수지를 포함할 수 있다.In some embodiments, the epoxy resin may include a first resin formed of a novolac-type epoxy resin and a second resin formed of a bisphenol-based epoxy resin.
일부 실시예들에 있어서, 상기 제1 수지에 대한 상기 제2 수지의 중량비는 2 내지 4일 수 있다.In some embodiments, the weight ratio of the second resin to the first resin may be 2 to 4.
일부 실시예들에 있어서, 상기 경화제는 아민계 경화제를 포함할 수 있다.In some embodiments, the curing agent may include an amine-based curing agent.
일부 실시예들에 있어서 상기 보호막 형성층은 경화 촉진제, 착색제, 커플링제 및 충전재를 더 포함할 수 있다.In some embodiments, the protective film forming layer may further include a curing accelerator, a colorant, a coupling agent, and a filler.
일부 실시예들에 있어서, 상기 경화 촉진제는 이미다졸계 경화 촉진제를 포함할 수 있다.In some embodiments, the curing accelerator may include an imidazole-based curing accelerator.
일부 실시예들에 있어서, 상기 커플링제는 실란 커플링제를 포함할 수 있다.In some embodiments, the coupling agent may include a silane coupling agent.
일부 실시예들에 있어서, 상기 기재 필름은 폴리올레핀계 수지를 포함할 수 있다.In some embodiments, the base film may include a polyolefin-based resin.
일부 실시예들에 있어서, 상기 보호막 형성층 상에 형성되는 이형 필름을 더 포함할 수 있다.In some embodiments, a release film formed on the protective film forming layer may be further included.
일부 실시예들에 있어서, 상기 보호막 형성층 상에 순차적으로 적층되는 점착층 및 다이싱 테이프를 더 포함할 수 있다.In some embodiments, it may further include an adhesive layer and a dicing tape sequentially stacked on the protective film forming layer.
본 발명의 실시예들에 따른 반도체 웨이퍼용 보호막 시트는 100,000 내지 300,000Pa·s의 점도를 가질 수 있다. 이에 따라, 상기 보호막 시트의 인장 강도가 향상될 수 있다. 따라서, 열 경화전 리워크 시 파단을 방지할 수 있다.The protective film sheet for semiconductor wafers according to embodiments of the present invention may have a viscosity of 100,000 to 300,000 Pa·s. Accordingly, the tensile strength of the protective film sheet may be improved. Therefore, breakage can be prevented during rework before heat curing.
일부 실시예들에 있어서, 상기 보호막 시트의 박리력은 10 내지 200gf/inch일 수 있다. 상기 보호막 시트가 상술한 점도 범위와 상기 박리력 범위를 갖는 경우, 재점착성이 향상되어 리워크성이 향상될 수 있다.In some embodiments, the peeling force of the protective film sheet may be 10 to 200 gf/inch. When the protective film sheet has the above-mentioned viscosity range and the above-described peeling force range, re-adhesion may be improved and reworkability may be improved.
일부 실시예들에 있어서, 상기 보호막 시트는 노볼락형 에폭시계 수지 및 상기 노볼락형 에폭시계 수지보다 중량 기준으로 과량 포함된 비스페놀계 에폭시 수지를 포함할 수 있다. 이에 따라, 상술한 박리력 및 점도를 갖는 보호막 시트가 제공될 수 있다.In some embodiments, the protective film sheet may include a novolak-type epoxy-based resin and a bisphenol-based epoxy resin in an excess amount by weight compared to the novolak-type epoxy resin. Accordingly, a protective film sheet having the above-described peeling force and viscosity can be provided.
일부 실시예들에 있어서, 상기 보호막 시트는 이미다졸계 경화 촉진제를 포함할 수 있다. 이에 따라, 상기 보호막 시트의 상온 안정성이 향상될 수 있다.In some embodiments, the protective film sheet may include an imidazole-based curing accelerator. Accordingly, room temperature stability of the protective film sheet may be improved.
도 1 내지 도 3은 예시적인 실시예들에 따른 반도체 웨이퍼용 보호막 시트의 단면도들이다.1 to 3 are cross-sectional views of protective film sheets for semiconductor wafers according to example embodiments.
본 발명의 실시예들은 인장 강도 및 리워크성이 향상된 반도체 웨이퍼용 보호막 시트를 제공한다.Embodiments of the present invention provide a protective film sheet for semiconductor wafers with improved tensile strength and reworkability.
이하 도면을 참고하여, 본 발명의 실시예를 보다 구체적으로 설명하도록 한다. 다만, 본 명세서에 첨부되는 다음의 도면 및 실시예들은 본 발명의 바람직한 실시예를 예시하는 것이며, 전술한 발명의 내용과 함께 본 발명의 기술사상을 더욱 이해시키는 역할을 하는 것이므로, 본 발명은 그러한 도면 및 실시예들에 기재된 사항에만 한정되어 해석되어서는 아니된다.With reference to the drawings below, embodiments of the present invention will be described in more detail. However, the following drawings and examples attached to the present specification illustrate preferred embodiments of the present invention, and serve to further understand the technical idea of the present invention together with the contents of the above-described invention, so the present invention does not provide such The interpretation should not be limited to the matters described in the drawings and examples.
도 1은 예시적인 실시예들에 따른 반도체 웨이퍼용 보호막 시트를 개략적으로 나타낸 단면도이다.1 is a cross-sectional view schematically showing a protective film sheet for a semiconductor wafer according to example embodiments.
도 1을 참조하면, 반도체 웨이퍼용 보호막 시트는 기재 필름(100) 및 기재 필름(100) 상에 형성되는 보호막 형성층(200)을 포함할 수 있다.Referring to FIG. 1, a protective film sheet for a semiconductor wafer may include a base film 100 and a protective film forming layer 200 formed on the base film 100.
보호막 형성층protective layer cambium
예시적인 실시예들에 따르면, 보호막 형성층(200)의 점도는 120℃에서 측정한 경우, 100,000 내지 300,000Pa·s, 바람직하게는 100,000 내지 270,000Pa·s일 수 있다.According to exemplary embodiments, the viscosity of the protective film forming layer 200 may be 100,000 to 300,000 Pa·s, preferably 100,000 to 270,000 Pa·s, when measured at 120°C.
보호막 형성층(200)의 점도가 100,000Pa·s 미만인 경우, 분자간 인력이 약하여, 인장 강도가 저하될 수 있다. 이에 따라, 열 경화 전 리워크 시 보호막 형성층(200)에서 파단이 발생할 수 있다.If the viscosity of the protective film forming layer 200 is less than 100,000 Pa·s, the intermolecular attraction force is weak, and the tensile strength may decrease. Accordingly, fracture may occur in the protective film forming layer 200 during rework before heat curing.
보호막 형성층(200)의 점도가 300,000Pa·s을 초과하는 경우, 박리력이 지나치게 향상될 수 있다. 이에 따라, 리워크 시 박리가 어려워져 리워크성이 저하될 수 있다.If the viscosity of the protective film forming layer 200 exceeds 300,000 Pa·s, the peeling force may be excessively improved. Accordingly, peeling becomes difficult during rework, which may deteriorate reworkability.
또한, 보호막 형성층(200)의 점도가 100,000 내지 270,000Pa·s인 경우, 인장 강도 및 리워크성이 향상될 수 있다.Additionally, when the viscosity of the protective film forming layer 200 is 100,000 to 270,000 Pa·s, tensile strength and reworkability can be improved.
예시적인 실시예들에 따르면, 보호막 형성층(200)의 박리력은 10 내지 200gf/inch, 바람직하게는 50 내지 120gf/inch일 수 있다.According to exemplary embodiments, the peeling force of the protective film forming layer 200 may be 10 to 200 gf/inch, preferably 50 to 120 gf/inch.
보호막 형성층(200)의 박리력이 10gf/inch 미만인 경우, 보호막 형성층(200) 및 반도체 웨이퍼가 결합한 경우, 결합력이 약하여 서로 분리될 수 있다.When the peeling force of the protective film forming layer 200 is less than 10 gf/inch, when the protective film forming layer 200 and the semiconductor wafer are bonded, the bonding force is weak and may be separated from each other.
보호막 형성층(200)의 박리력이 200gf/inch를 초과하는 경우, 리워크 시 보호막 형성층(200) 및 반도체 웨이퍼의 박리가 어려워져 리워크성이 저하될 수 있다.If the peeling force of the protective film forming layer 200 exceeds 200 gf/inch, it becomes difficult to peel the protective film forming layer 200 and the semiconductor wafer during rework, which may reduce reworkability.
또한, 보호막 형성층(200)의 박리력이 50 내지 120gf/inch인 경우, 보호막 형성층(200) 및 반도체 웨이퍼의 박리가 용이함과 동시에 재점착성이 향상될 수 있다. 이에 따라, 리워크성이 향상될 수 있다.In addition, when the peeling force of the protective film forming layer 200 is 50 to 120 gf/inch, the protective film forming layer 200 and the semiconductor wafer can be easily peeled off and re-adhesiveness can be improved. Accordingly, reworkability can be improved.
일부 실시예들에 있어서, 보호막 형성층(200)의 박리력은 반도체 웨이퍼 일면에 보호막 형성층(200)을 80℃에서 라미네이션 후, 25℃에서 인장속도 5mm/s 및 인장 각도 180°의 박리 조건에서 박리 강도를 측정한 것일 수 있다.In some embodiments, the peeling force of the protective film forming layer 200 is obtained by lamination of the protective film forming layer 200 on one side of the semiconductor wafer at 80°C, followed by peeling at 25°C under peeling conditions of a tensile speed of 5 mm/s and a tensile angle of 180°. It may be a measure of intensity.
일부 실시예들에 있어서, 보호막 형성층(200)의 두께는 10 내지 1,000㎛, 바람직하게는 10 내지 100㎛, 보다 바람직하게는 10 내지 40㎛일 수 있다.In some embodiments, the thickness of the protective film forming layer 200 may be 10 to 1,000 μm, preferably 10 to 100 μm, and more preferably 10 to 40 μm.
일부 실시예들에 있어서, 보호막 형성층(200)은 바인더, 에폭시 수지 및 경화제를 포함할 수 있다.In some embodiments, the protective film forming layer 200 may include a binder, an epoxy resin, and a curing agent.
일부 실시예들에 있어서, 보호막 형성층(200)은 경화 촉진제, 착색제, 커플링제 및 실리카 입자를 더 포함할 수 있다.In some embodiments, the protective film forming layer 200 may further include a curing accelerator, a colorant, a coupling agent, and silica particles.
바인더bookbinder
일부 실시예들에 있어서, 바인더는 중량 평균 분자량이 400,000g/mol 내지 2,000,000g/mol, 바람직하게는 600,000g/mol 내지 1,500,000g/mol, 보다 바람직하게는 800,000g/mol 내지 1,200,000g/mol의 아크릴산 공중합체일 수 있다.In some embodiments, the binder has a weight average molecular weight of 400,000 g/mol to 2,000,000 g/mol, preferably 600,000 g/mol to 1,500,000 g/mol, more preferably 800,000 g/mol to 1,200,000 g/mol. It may be an acrylic acid copolymer.
상기 범위에서, 아크릴산 공중합체 분자간 인력에 의해 바인더의 박리력이 지나치게 높거나 낮지 않을 수 있다. 이에 따라, 상기 아크릴산 공중합체를 포함하는 바인더를 포함한 보호막 형성층(200)의 점도 및 박리력이 상술한 범위 내로 유지될 수 있다.Within the above range, the peeling force of the binder may not be too high or too low due to the attraction between the acrylic acid copolymer molecules. Accordingly, the viscosity and peeling force of the protective film forming layer 200 including the binder containing the acrylic acid copolymer can be maintained within the above-mentioned range.
상기 아크릴산 에스테르 공중합체는 예를 들면, 아크릴산 에스테르 모노머 간의 중합 또는 아크릴산 에스테르 모노머 및 아크릴산 에스테르 이외의 모노머의 중합에 의하여 형성된 물질일 수 있다.The acrylic acid ester copolymer may be, for example, a material formed by polymerization between acrylic acid ester monomers or polymerization of an acrylic acid ester monomer and a monomer other than acrylic acid ester.
상기 아크릴산 에스테르 모노머는 예를 들면, 메틸 아크릴산 에스테르, 에틸 아크릴산 에스테르, 프로필 아크릴산 에스테르, 부틸 아크릴산 에스테르, 메틸 메타크릴산 에스테르 등의 아크릴산 알킬 에스테르 모노머; 이소 보르닐 아크릴산 에스테르, 디시클로펜타닐 아크릴산 에스테르 등의 아크릴산 시클로알킬 에스테르 모노머; 벤질 아크릴산 에스테르, 페닐 아크릴산 에스테르 등의 아크릴산 아릴 에스테르 모노머; 글리시딜 메타크릴산 에스테르 등의 글리시딜기 함유 아크릴산 에스테르 모노머; 히드록시 메틸 아크릴산 에스테르, 2-히드록시 에틸 아크릴산 에스테르, 2-히드록시 프로필 아크릴산 에스테르, 3-히드록시 프로필 아크릴산 에스테르, 2-히드록시 부틸 아크릴산 에스테르, 3-히드록시 부틸 아크릴산 에스테르, 4-히드록시 부틸 아크릴산 에스테르 등의 히드록시기 함유 아크릴산 에스테르 모노머; 중 적어도 하나의 모노머를 포함할 수 있다.The acrylic acid ester monomer includes, for example, alkyl acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester, propyl acrylic acid ester, butyl acrylic acid ester, and methyl methacrylic acid ester; Acrylic acid cycloalkyl ester monomers such as isobornyl acrylic acid ester and dicyclopentanyl acrylic acid ester; Aryl acrylic acid ester monomers such as benzyl acrylic acid ester and phenyl acrylic acid ester; Acrylic acid ester monomers containing a glycidyl group, such as glycidyl methacrylic acid ester; Hydroxy methyl acrylic acid ester, 2-hydroxy ethyl acrylic acid ester, 2-hydroxy propyl acrylic acid ester, 3-hydroxy propyl acrylic acid ester, 2-hydroxy butyl acrylic acid ester, 3-hydroxy butyl acrylic acid ester, 4-hydroxy Acrylic acid ester monomers containing hydroxy groups such as butyl acrylic acid ester; It may contain at least one monomer.
바람직하게는, 상기 아크릴산 에스테르 모노머는 에틸 아크릴산, 부틸 아크릴산, 메틸 메타크릴산, 글리시딜 메타크릴산 중 적어도 하나의 모노머를 포함할 수 있다.Preferably, the acrylic acid ester monomer may include at least one monomer selected from the group consisting of ethyl acrylic acid, butyl acrylic acid, methyl methacrylic acid, and glycidyl methacrylic acid.
상기 아크릴산 에스테르 이외의 모노머는 예를 들면, 2-(메타)아크릴아미드-2-메틸프로판술폰산, (메타)아크릴아미드프로판술폰산, 술포프로필(메타)아크릴레이트, (메타)아크릴로일옥시나프탈렌술폰산 등의 술폰산기 함유 모노머; 2-히드록시에틸아크릴로일포스페이트 등의 인산기 함유 모노머; 아크릴아미드, 아크릴로니트릴 등의 질소 함유 모노머; 중 적어도 하나의 모노머를 포함할 수 있다.Monomers other than the above acrylic acid ester include, for example, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, sulfopropyl (meth)acrylate, and (meth)acryloyloxynaphthalenesulfonic acid. monomers containing sulfonic acid groups, such as; Phosphate group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; Nitrogen-containing monomers such as acrylamide and acrylonitrile; It may contain at least one monomer.
바람직하게는, 상기 아크릴산 에스테르 이외의 모노머는, 아크릴로니트릴 모노머를 포함할 수 있다.Preferably, the monomer other than the acrylic acid ester may include an acrylonitrile monomer.
일 실시예에 있어서, 상기 바인더의 유리전도온도(glass transition temperature: Tg)는 0℃ 내지 25℃, 바람직하게는 1℃ 내지 25℃, 보다 바람직하게는 1℃ 내지 21℃일 수 있다.In one embodiment, the glass transition temperature (Tg) of the binder may be 0°C to 25°C, preferably 1°C to 25°C, and more preferably 1°C to 21°C.
상기 범위에서, 상기 바인더를 포함하는 보호막 형성층이 상온(예를 들면, 25℃)에 보관되는 경우, 상기 바인더가 유리화 되어 크랙이 생기는 것을 억제할 수 있다.Within the above range, when the protective film forming layer containing the binder is stored at room temperature (for example, 25°C), the binder is vitrified and cracks can be suppressed.
일부 실시예들에 있어서, 상기 바인더는 보호막 형성층(200)의 전체 중량 대비 10 내지 30 중량%, 바람직하게는 13 내지 25 중량%, 보다 바람직하게는 15 내지 20 중량%로 포함될 수 있다.In some embodiments, the binder may be included in an amount of 10 to 30% by weight, preferably 13 to 25% by weight, and more preferably 15 to 20% by weight, based on the total weight of the protective film forming layer 200.
상기 범위에서, 보호막 형성층(200)이 기재 필름(100)과 안정적으로 결합된 상태로 유지될 수 있고, 웨이퍼와 결합 시 박리 및 재결합이 가능하여 리워크성이 향상될 수 있다.Within the above range, the protective film forming layer 200 can be maintained in a stable bonded state to the base film 100, and peeling and recombination are possible when bonded to the wafer, thereby improving reworkability.
에폭시 수지epoxy resin
상기 에폭시 수지는 예를 들면, 비스페놀 A형(Bisphenol-A: BPA) 에폭시 수지, 비스페놀 F형(Bisphenol-F: BPF) 에폭시 수지, 비스페놀 S형(Bisphenol-S: BPS) 에폭시 수지, 브롬화비스페놀 A형 에폭시 수지, 수소 첨가 비스페놀 A형 에폭시 수지, 비스페놀 AF형 에폭시 수지 등의 비스페놀계 에폭시 수지; 페놀노볼락 에폭시 수지, 크레졸노볼락 에폭시 수지, 오르토크레졸노볼락 에폭시 수지 등의 노볼락형 에폭시 수지; 비페닐형 에폭시 수지, 나프탈렌형 에폭시 수지, 플루오렌형 에폭시 수지, 트리스히드록시페닐메탄형 에폭시 수지, 테트라페닐올에탄형 에폭시 수지, 히단토인형 에폭시 수지, 트리스글리시딜이소시아누레이트형 에폭시 수지, 글리시딜아민형 에폭시 수지 중 적어도 하나를 포함할 수 있다.The epoxy resin includes, for example, Bisphenol-A (BPA) epoxy resin, Bisphenol-F (BPF) epoxy resin, Bisphenol-S (BPS) epoxy resin, and brominated bisphenol A. bisphenol-based epoxy resins such as bisphenol-type epoxy resin, hydrogenated bisphenol A-type epoxy resin, and bisphenol AF-type epoxy resin; Novolak-type epoxy resins such as phenol novolak epoxy resin, cresol novolak epoxy resin, and orthocresol novolak epoxy resin; Biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylolethane type epoxy resin, hydantoin type epoxy resin, trisglycidyl isocyanurate type epoxy. It may include at least one of resin and glycidylamine-type epoxy resin.
일부 실시예들에 있어서, 상기 에폭시 수지는 노볼락형 에폭시 수지로 형성된 제1 수지 및 비스페놀계 에폭시 수지로 형성된 제2 수지를 모두 포함할 수 있다.In some embodiments, the epoxy resin may include both a first resin formed of a novolac-type epoxy resin and a second resin formed of a bisphenol-based epoxy resin.
일 실시예에 있어서, 상기 제1 수지는 상기 제2 수지에 비하여 중량 기준 소량 첨가될 수 있다. 예를 들면, 상기 제1 수지에 대한 상기 제2 수지의 중량비는 2 내지 4, 바람직하게는 2 내지 3, 보다 바람직하게는 2.4 내지 2.8일 수 있다.In one embodiment, the first resin may be added in a small amount by weight compared to the second resin. For example, the weight ratio of the second resin to the first resin may be 2 to 4, preferably 2 to 3, and more preferably 2.4 to 2.8.
상기 범위에서, 보호막 형성층(200)의 경화성이 노볼록형 에폭시 수지에 의해 향상되면서, 보호막 형성층(200)의 기계적, 열적 특성이 비스페놀계 에폭시 수지에 의해 향상될 수 있다.In the above range, the curability of the protective film forming layer 200 may be improved by the no-convex type epoxy resin, and the mechanical and thermal properties of the protective film forming layer 200 may be improved by the bisphenol-based epoxy resin.
일부 실시예들에 있어서, 보호막 형성층(200)의 전체 중량 대비 상기 에폭시 수지 총 중량은 15 내지 30 중량%, 바람직하게는 18 내지 25 중량%일 수 있다.In some embodiments, the total weight of the epoxy resin relative to the total weight of the protective film forming layer 200 may be 15 to 30% by weight, preferably 18 to 25% by weight.
상기 범위에서, 상기 에폭시 수지를 포함하는 보호막 형성층(200)의 흡습율이 감소하여 반도체 웨이퍼용 보호막 시트를 사용한 반도체 패키지의 신뢰성이 향상될 수 있다.In the above range, the moisture absorption rate of the protective film forming layer 200 containing the epoxy resin is reduced, so that the reliability of a semiconductor package using a protective film sheet for a semiconductor wafer can be improved.
경화제hardener
상기 경화제는 에폭시기와 반응할 수 있는 적어도 하나의 관능기를 갖는 화합물일 수 있다. 상기 관능기는 예를 들면, 아미노기, 카르복시기, 산 무수물 등일 수 있으며, 바람직하게는 아미노기를 포함할 수 있다.The curing agent may be a compound having at least one functional group capable of reacting with an epoxy group. The functional group may be, for example, an amino group, a carboxyl group, an acid anhydride, etc., and preferably includes an amino group.
관능기로 아미노기를 갖는 아민계 경화제는 예를 들면, 헥시메틸렌디아민, 옥타메틸렌디아민, 데카메틸렌디아민, 3,9-비스(3-아미노프로필)-2,4,8,10-테트라옥사스피로[5.5]운데칸, 비스(4-아미노시클로헥실)메탄, 메타페닐렌디아민, 4,4'-디아미노디페닐술폰, 디시안디아미드일 수 있다.Amine-based curing agents having an amino group as a functional group include, for example, hexymethylenediamine, octamethylenediamine, decamethylenediamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5 ] It may be undecane, bis(4-aminocyclohexyl)methane, metaphenylenediamine, 4,4'-diaminodiphenylsulfone, and dicyandiamide.
경화제로 아민계 경화제를 사용하는 경우, 보호막 형성층(200)으로부터 기재 필름(100)으로의 경화제 분자의 이동이 억제되어 보호막 형성층(200)의 안정성이 향상될 수 있다.When an amine-based curing agent is used as the curing agent, the movement of curing agent molecules from the protective film forming layer 200 to the base film 100 is suppressed, thereby improving the stability of the protective film forming layer 200.
일부 실시예들에 있어서, 상기 경화제는 보호막 형성층(200)의 전체 중량 대비 1 내지 10 중량%, 바람직하게는 3 내지 7 중량%로 포함될 수 있다.In some embodiments, the curing agent may be included in an amount of 1 to 10% by weight, preferably 3 to 7% by weight, based on the total weight of the protective film forming layer 200.
상기 범위에서, 보호막 형성층(200) 열 경화성이 향상되어 보호막 형성층(200)의 인장 강도가 향상될 수 있다.Within the above range, the thermal curability of the protective film forming layer 200 may be improved and the tensile strength of the protective film forming layer 200 may be improved.
경화 촉진제cure accelerator
상기 경화 촉진제는 이미다졸계 경화 촉진제일 수 있다. 상기 이미다졸계 경화 촉진제는 예를 들면, 2-메틸이미다졸, 2-운데실이미다졸, 2-헵타데실이미다졸, 1,2-디메틸이미다졸, 2-에틸-4-메틸이미다졸, 1-벤질-2-페닐이미다졸, 1-시아노에틸-2메틸이미다졸, 1-시아노에틸-2-운데실이미다졸, 1-시아노에틸-2-페닐이미다졸, 1-시아노에틸-2-페닐이미다졸륨트리멜리테이트, 2,4-디아미노-6-[2'-메틸이미다졸릴-(1')]-에틸-s-트리아진, 2,4-디마미노-6-[2'-운데실이미다졸릴-(1')]-에틸-s드리아진, 2,4-디아미노-6-[2'-메틸이미다졸릴-(1')]-에틸-s-트리아진이소시아눌산 부가물, 2-페닐이미다졸, 2-페닐-4-메틸이미다졸, 2-페닐-4,5-디히드록시메틸이미다졸, 2-페닐-4-메틸-5-히드록시메틸이미다졸 등일 수 있다.The curing accelerator may be an imidazole-based curing accelerator. The imidazole-based curing accelerator is, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenyl Imidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine , 2,4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-sdriazine, 2,4-diamino-6-[2'-methylimidazolyl- (1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole , 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc.
일부 실시예들에 있어서, 상기 경화 촉진제는 보호막 형성층(200)의 총 중량 대비 0.01 내지 0.5 중랑%, 바람직하게는 0.05 내지 0.4 중랑%, 보다 바람직하게는 0.1 내지 0.3 중량%로 포함될 수 있다.In some embodiments, the curing accelerator may be included in an amount of 0.01 to 0.5 wt%, preferably 0.05 to 0.4 wt%, and more preferably 0.1 to 0.3 wt%, based on the total weight of the protective film forming layer 200.
상기 범위에서, 고온 특성이 향상되며, 고온 조건에서 경화 촉진제의 편석 발생이 억제될 수 있다.Within the above range, high temperature properties are improved, and segregation of the curing accelerator can be suppressed under high temperature conditions.
착색제coloring agent
상기 착색제는 적외선 등을 차폐하기 위한 유기 또는 무기 안료 및 염료일 수 있다.The colorant may be an organic or inorganic pigment or dye for shielding infrared rays.
상기 유기 또는 무기 안료는 예를 들면, 카본 블랙, 산화철, 이산화망간, 아닐린 블랙, 활성탄 등일 수 있으며, 바람직하게는 카본 블랙일 수 있다.The organic or inorganic pigment may be, for example, carbon black, iron oxide, manganese dioxide, aniline black, activated carbon, etc., and is preferably carbon black.
상기 유기 또는 무기 염료는 예를 들면, 산성 염료, 반응 염료, 직접 염료, 분산 염료, 양이온 염료 등일 수 있다.The organic or inorganic dye may be, for example, an acid dye, a reactive dye, a direct dye, a disperse dye, or a cationic dye.
일부 실시예들에 있어서, 상기 착색제는 보호막 형성층(200)의 총 중량 대비 0.01 내지 0.5 중량%, 바람직하게는 0.05 내지 0.4 중량%, 보다 바람직하게는 0.1 내지 0.3 중량%로 포함될 수 있다.In some embodiments, the colorant may be included in an amount of 0.01 to 0.5% by weight, preferably 0.05 to 0.4% by weight, and more preferably 0.1 to 0.3% by weight, based on the total weight of the protective film forming layer 200.
상기 범위에서, 보호막 형성층(200)에 의한 광투과성이 지나치게 감소하는 것을 억제할 수 있다.Within the above range, excessive decrease in light transmittance due to the protective film forming layer 200 can be suppressed.
커플링제Coupling agent
상기 커플링제는 실란 커플링제일 수 있다. 실란 커플링제는 예를 들면, γ-글리시독시프로필트리메톡시실란, γ-글리시독시프로필메틸디에톡시실란, β-(3,4-에폭시시클로헥실)에틸트리메톡시실란, γ-(메타크릴옥시프로필)트리메톡시실란, γ-아미노프로필트리메톡시실란, N-6-(아미노에틸)- γ-아미노프로필트리메톡시실란, N-6-(아미노에틸)- γ-아미노프로필메틸디에톡시실란, N-페닐- γ-아미노프로필트리메톡시실란, γ-우레이드프로필트리에톡시실란, γ-머캅토프로필트리메톡시실란, γ-머캅토프로필메틸디메톡시실란, 메틸트리메톡시실란, 메틸트리에톡시실란, 비닐트리메톡시실란, 비닐트리아세톡시실란, 이미다졸실란 등일 수 있다.The coupling agent may be a silane coupling agent. Silane coupling agents include, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-( Methacryloxypropyl)trimethoxysilane, γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-6-(aminoethyl)-γ-aminopropyl Methyl diethoxysilane, N-phenyl- γ-aminopropyltrimethoxysilane, γ-ureide propyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltri It may be methoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, imidazolesilane, etc.
일부 실시예들에 있어서, 상기 커플링제는 보호막 형성층(200)의 총 중량대비 0.01 내지 5 중량%, 바람직하게는 0.05 내지 3 중량%, 보다 바람직하게는 0.1 내지 1.0 중량%로 포함될 수 있다.In some embodiments, the coupling agent may be included in an amount of 0.01 to 5% by weight, preferably 0.05 to 3% by weight, and more preferably 0.1 to 1.0% by weight, based on the total weight of the protective film forming layer 200.
상기 범위에서, 후술하는 충전제가 표면 처리되어 보호막 형성층(200)의 박리력 및 재점착성이 향상될 수 있다.Within the above range, the peeling force and re-adhesion of the protective film forming layer 200 may be improved by surface treatment with a filler described later.
충전재filling
상기 충전재는 예를 들면, 실리카 입자, 알루미나 입자, 탈크 입자, 탄산칼슘 입자, 산화티타늄 입자, 산화철 입자, 탄화규소 입자, 질화붕소 입자 등일 수 있으며, 바람직하게는 실리카 입자일 수 있다.The filler may be, for example, silica particles, alumina particles, talc particles, calcium carbonate particles, titanium oxide particles, iron oxide particles, silicon carbide particles, boron nitride particles, etc., and preferably may be silica particles.
상기 실리카 입자의 평균 입경은 예를 들면, 0.1 내지 2.0㎛ 또는 0.3 내지 2.0㎛, 바람직하게는 0.5 내지 2.0㎛ 또는 0.8 내지 2.0㎛, 보다 바람직하게는 1.0 내지 2.0㎛일 수 있다.The average particle diameter of the silica particles may be, for example, 0.1 to 2.0 μm or 0.3 to 2.0 μm, preferably 0.5 to 2.0 μm or 0.8 to 2.0 μm, and more preferably 1.0 to 2.0 μm.
상기 실리카 입자의 평균 비표면적은 예를 들면, 2.0 내지 12.0m2/g 또는 2.0 내지 10.0m2/g, 바람직하게는 2.0 내지 8.0m2/g 또는 2.0 내지 6.0m2/g, 보다 바람직하게는 3.0 내지 5.0m2/g일 수 있다.The average specific surface area of the silica particles is, for example, 2.0 to 12.0 m 2 /g or 2.0 to 10.0 m 2 /g, preferably 2.0 to 8.0 m 2 /g or 2.0 to 6.0 m 2 /g, more preferably may be 3.0 to 5.0 m 2 /g.
상기 실리카 입자의 평균 입경 및 평균 비표면적 범위에서, 실리카 입자끼리 과도하게 응집되거나 점착성이 과도하게 향상되어 박리성이 감소하는 것을 방지할 수 있다.Within the range of the average particle diameter and average specific surface area of the silica particles, it is possible to prevent excessive agglomeration of silica particles or excessive improvement in adhesion, thereby reducing peelability.
일부 실시예들에 있어서, 상기 실리카 입자는 보호막 형성층(200)의 총 중량 대비 30 내지 70 중량%, 바람직하게는 40 내지 60 중량%, 보다 바람직하게는 50 내지 60 중량%로 포함될 수 있다.In some embodiments, the silica particles may be included in an amount of 30 to 70% by weight, preferably 40 to 60% by weight, and more preferably 50 to 60% by weight, based on the total weight of the protective film forming layer 200.
상기 범위에서, 상기 충전제를 포함하는 보호막 형성층(200)의 열 팽창 계수가 조정되어 고온 조건에서도 과도하게 팽창하지 않을 수 있으며, 보호막 형성층(200)의 흡습율이 감소할 수 있다.Within the above range, the thermal expansion coefficient of the protective film forming layer 200 containing the filler is adjusted so that it does not expand excessively even under high temperature conditions, and the moisture absorption rate of the protective film forming layer 200 may be reduced.
기타 첨가제Other additives
보호막 형성층(200)은 기타 첨가제를 추가적으로 더 포함할 수 있다. 상기 첨가제는 예를 들면, 가교제, 레벨링제, 가소제, 대전 방지제, 산화 방지제, 이온 포착제, 연쇄 이동제 등일 수 있다.The protective film forming layer 200 may additionally include other additives. The additive may be, for example, a crosslinking agent, leveling agent, plasticizer, antistatic agent, antioxidant, ion trapping agent, chain transfer agent, etc.
상기 가교제는 예를 들면, 이소시아네이트계 가교제, 에폭시계 가교제, 멜라민계 가교제, 과산화물계 가교제, 요소계 가교제, 금속 알콕시계 가교제, 금속 킬레이트계 가교제, 금속 염계 가교제, 카르보디이미드계 가교제, 옥사졸린계 가교제, 아지리딘계 가교제, 아민계 가교제 등일 수 있다.The cross-linking agent is, for example, an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, a melamine-based cross-linking agent, a peroxide-based cross-linking agent, a urea-based cross-linking agent, a metal alkoxy-based cross-linking agent, a metal chelate-based cross-linking agent, a metal salt-based cross-linking agent, a carbodiimide-based cross-linking agent, and an oxazoline-based cross-linking agent. It may be a cross-linking agent, an aziridine-based cross-linking agent, or an amine-based cross-linking agent.
상기 레벨링제는 예를 들면, 플루오린계 레벨링제, 에테르계 레벨링제, 실리카 및 아크릴계 고분자 함유 레벨링제 등일 수 있다.The leveling agent may be, for example, a fluorine-based leveling agent, an ether-based leveling agent, or a leveling agent containing silica and acrylic polymers.
상기 가소제는 예를 들면, 에스테르계 가소제, 실리콘계 가소제, 뷰타다이엔 가소제, 아세틸계 가소제 등일 수 있다.The plasticizer may be, for example, an ester plasticizer, a silicone plasticizer, a butadiene plasticizer, an acetyl plasticizer, etc.
상기 대전 방지제는 예를 들면, 이온 액체, 도전성 중합체, 금속 이온 전도성 염, 도전성 금속 산화물 등일 수 있다.The antistatic agent may be, for example, an ionic liquid, a conductive polymer, a metal ion conductive salt, or a conductive metal oxide.
상기 산화 방지제는 예를 들면, 힌더드 페놀계 산화 방지제, 힌더드 아민계 산화 방지제, 알킬포스파이트계 산화 방지제, 티오 에테르계 산화 방지제 등일 수 있다.The antioxidant may be, for example, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, an alkyl phosphite-based antioxidant, a thioether-based antioxidant, etc.
상기 이온 포착제는 예를 들면, 하이드로탈사이트계 이온 포착제 및 다가 금속 산성염 등의 무기 이온 교환체일 수 있다.The ion trapping agent may be, for example, an inorganic ion exchanger such as a hydrotalcite-based ion trapping agent and a polyvalent metal acid salt.
상기 연쇄 이동제는 예를 들면, 티올 화합물일 수 있다.The chain transfer agent may be, for example, a thiol compound.
상기 기타 첨가제는 보호막 형성층(200)의 총 중량 대비 0.01 내지 10 중량%, 바람직하게는 0.1 내지 5 중량%로 포함될 수 있다.The other additives may be included in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the protective film forming layer 200.
기재 필름base film
기재 필름(100)은 예를 들면, 폴리올레핀계 수지, 폴리에틸렌테리프탈레이트계 수지, 폴리이미드계 수지, 불소 수지, 폴리에틸렌계 수지 등을 포함하는 필름일 수 있으며, 바람직하게는 폴리올레핀계 수지를 포함하는 필름일 수 있다.The base film 100 may be a film containing, for example, polyolefin-based resin, polyethylene teripthalate-based resin, polyimide-based resin, fluororesin, polyethylene-based resin, etc., and is preferably a film containing polyolefin-based resin. It can be.
상기 기재 필름의 두께는 예를 들면, 10 내지 300㎛, 바람직하게는 30 내지 200㎛, 보다 바람직하게는 36 내지 150㎛일 수 있다.The thickness of the base film may be, for example, 10 to 300 μm, preferably 30 to 200 μm, and more preferably 36 to 150 μm.
일부 실시예들에 있어서 기재 필름(100)은 반도체 웨이퍼용 보호막 시트가 웨이퍼에 부착된 후 박리될 수 있다. 기재 필름(100)이 박리된 반도체 웨이퍼용 보호막 시트는 웨이퍼와 함께 경화되어 사용될 수 있다.In some embodiments, the base film 100 may be peeled off after a protective film sheet for a semiconductor wafer is attached to the wafer. The protective film sheet for a semiconductor wafer from which the base film 100 has been peeled can be cured and used together with the wafer.
도 2 및 도 3은 각각 예시적인 실시예들에 따른 반도체 웨이퍼용 보호막 시트를 나타내는 개략적인 단면도들이다.2 and 3 are schematic cross-sectional views showing protective film sheets for semiconductor wafers according to example embodiments, respectively.
도 2를 참조하면, 반도체 웨이퍼용 보호막 시트는 기재 필름(100), 보호막 형성층(200) 및 이형층(300)이 순차적으로 적층된 구조일 수 있다.Referring to FIG. 2, the protective film sheet for a semiconductor wafer may have a structure in which a base film 100, a protective film forming layer 200, and a release layer 300 are sequentially stacked.
일부 실시예들에 있어서, 반도체 웨이퍼용 보호막 시트를 웨이퍼에 부착하는 경우, 이형층(300)을 분리한 후 외부로 노출된 보호막 형성층(200)을 웨이퍼에 부착할 수 있다. 반도체 웨이퍼용 보호막 시트가 웨이퍼에 부착된 후 기재 필름(100)은 박리될 수 있다.In some embodiments, when attaching a protective film sheet for a semiconductor wafer to a wafer, the release layer 300 may be separated and then the externally exposed protective film forming layer 200 may be attached to the wafer. After the protective film sheet for a semiconductor wafer is attached to the wafer, the base film 100 may be peeled off.
일부 실시예들에 있어서, 이형층(300)은 기재 필름(100)과 동일한 소재의 필름일 수 있다.In some embodiments, the release layer 300 may be a film made of the same material as the base film 100.
도 3을 참조하면, 반도체 웨이퍼용 보호막 시트는 보호막 형성층(200)과 다이싱 필름이 함께 배치된 일체형 패키지 시트일 수 있다. 예를 들면, 반도체 웨이퍼용 보호막 시트는 기재 필름(100), 보호막 형성층(200), 점착층(400) 및 다이싱 필름(500)이 순차적으로 적층된 구조일 수 있다.Referring to FIG. 3, the protective film sheet for a semiconductor wafer may be an integrated package sheet in which a protective film forming layer 200 and a dicing film are disposed together. For example, a protective film sheet for a semiconductor wafer may have a structure in which a base film 100, a protective film forming layer 200, an adhesive layer 400, and a dicing film 500 are sequentially stacked.
일부 실시예들에 있어서, 점착층(400)은 감압 접착제(Pressure Sensitive Adhesive; PSA)일 수 있다.In some embodiments, the adhesive layer 400 may be a pressure sensitive adhesive (PSA).
일 실시예에 있어서, 다이싱 필름(500)을 포함하는 반도체 웨이퍼용 보호막 시트를 웨이퍼에 부착하는 경우, 반도체 웨이퍼용 보호막 시트의 기재 필름(100)을 제거한 후 보호막 형성층(200)을 웨이퍼에 부착할 수 있다. 다이싱 필름(500)을 포함하는 반도체 웨이퍼용 보호막 시트가 부착된 웨이퍼를 다이싱 할 수 있다. 웨이퍼의 다이싱이 완료된 경우, 보호막 형성층(200)에 부착된 다이싱 필름(500)은 점착층(400)과 함께 제거될 수 있다.In one embodiment, when attaching a protective film sheet for a semiconductor wafer including a dicing film 500 to a wafer, the base film 100 of the protective film sheet for a semiconductor wafer is removed and then the protective film forming layer 200 is attached to the wafer. can do. A wafer to which a protective film sheet for semiconductor wafers including the dicing film 500 is attached can be diced. When dicing of the wafer is completed, the dicing film 500 attached to the protective film forming layer 200 may be removed along with the adhesive layer 400.
이하에서는, 본 발명의 이해를 돕기 위한 구체적인 실험예를 제시하나, 이는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.In the following, specific experimental examples are presented to aid understanding of the present invention, but these are merely illustrative of the present invention and do not limit the scope of the appended claims. Examples are provided within the scope and technical idea of the present invention. It is obvious to those skilled in the art that various changes and modifications are possible, and it is natural that such changes and modifications fall within the scope of the appended patent claims.
실시예들 및 비교예들Examples and Comparative Examples
실시예 1Example 1
반도체 웨이퍼용 보호막 시트 제조Manufacture of protective film sheets for semiconductor wafers
폴리올레핀계 수지를 중합하여 두께가 100㎛인 기재 필름을 제작하였다.Polyolefin-based resin was polymerized to produce a base film with a thickness of 100 μm.
이후, 바인더, 에폭시 수지, 경화제, 경화 촉진제, 착색제, 커플링제 및 충전재를 혼합한 조성물을 상기 기재 필름 상에 코팅하여 800㎛의 보호막 형성층을 제조하였다.Afterwards, a composition containing a binder, epoxy resin, curing agent, curing accelerator, colorant, coupling agent, and filler was coated on the base film to prepare an 800㎛ protective film forming layer.
구체적인 바인더, 에폭시 수지, 경화제, 경화 촉진제, 착색제, 커플링제 및 충전제의 조성 및 함량은 하기 표 1 및 2에 표시하였다.The composition and content of specific binders, epoxy resins, curing agents, curing accelerators, colorants, coupling agents, and fillers are shown in Tables 1 and 2 below.
보호막 형성층이 코팅된 기재 필름을 직경 8mm의 원형으로 절단하여 반도체 웨이퍼용 보호막 시트를 제조하였다.The base film coated with the protective film forming layer was cut into a circle with a diameter of 8 mm to prepare a protective film sheet for a semiconductor wafer.
실시예 2 내지 4 및 비교예 1 내지 4Examples 2 to 4 and Comparative Examples 1 to 4
보호막 형성층의 조성 및 함량을 하기 표 1 및 2와 같이 한 것을 제외하고는 실시예 1과 동일하게 반도체 웨이퍼용 보호막 시트를 제조하였다.A protective film sheet for a semiconductor wafer was manufactured in the same manner as in Example 1, except that the composition and content of the protective film forming layer were as shown in Tables 1 and 2 below.
(중량%)bookbinder
(weight%)
수지
(중량%)epoxy
profit
(weight%)
(중량%)hardener
(weight%)
(중량%)cure accelerator
(weight%)
(중량%)filling
(weight%)
(중량%)coloring agent
(weight%)
(중량%)Coupling agent
(weight%)
표 2의 바인더의 조성에 기재된 성분은 하기와 같다.The components listed in the binder composition in Table 2 are as follows.
BA: 부틸아크릴산(Butyl Acrylate)BA: Butyl Acrylate
EA: 에틸아크릴산(Ethyl Acrylate)EA: Ethyl Acrylate
AN: 아크릴로니트릴(Acrylonitrile)AN: Acrylonitrile
MMA: 메틸메타크릴산(Methyl Methacrylate)MMA: Methyl Methacrylate
GMA: 글리시딜메타크릴산(Glycidyl Methacrylate)GMA: Glycidyl Methacrylate
실험예Experiment example
(1) 점성(viscosity) 측정(1) Viscosity measurement
실시예들 및 비교예들에 따라 제작된 반도체 웨이퍼용 보호막 시트를 점도계(TA사 G2 ARES)에 삽입하여, 120℃에서의 복합 점도(Complex Viscosity)를 측정하였다.The protective film sheet for semiconductor wafers manufactured according to the Examples and Comparative Examples was inserted into a viscometer (TA G2 ARES), and the complex viscosity at 120°C was measured.
점도계의 조건은 -30℃에서 180℃까지 승온 조건(10℃/min), 5rad/s의 각속도 조건, 5N의 힘(force) 조건으로 설정하였다.The conditions of the viscometer were set to a temperature increase condition from -30°C to 180°C (10°C/min), an angular velocity condition of 5 rad/s, and a force condition of 5N.
(2) 박리력 측정(2) Peel force measurement
그라인딩된 실리콘 웨이퍼의 일 면에 실시예들 및 비교예들에 따라 제작된 반도체 웨이퍼용 보호막 시트를 80℃로 라미네이션 진행 후, 상온(25℃)에서 인장속도 5mm/s 및 인장 각도 180°의 박리 조건에서 박리력을 측정하였다. 사용된 시편의 폭은 25nm, 길이는 100mm로 하였다.The protective film sheet for semiconductor wafers manufactured according to the examples and comparative examples was laminated on one side of the ground silicon wafer at 80°C, and then peeled at room temperature (25°C) at a tensile speed of 5 mm/s and a tensile angle of 180°. Peel force was measured under these conditions. The width of the specimen used was 25 nm and the length was 100 mm.
(3) 리워크 공정성 평가(3) Rework fairness evaluation
8inch의 실리콘 웨이퍼 일 면에 실시예들 및 비교예들에 따라 제작된 반도체 웨이퍼용 보호막 시트를 80℃로 라미네이션 진행 후, 상온(25℃)에서 상기 반도체 웨이퍼용 보호막 시트가 박리되는지 여부를 평가하였다.After lamination of the semiconductor wafer protective film sheet manufactured according to the examples and comparative examples on one side of an 8-inch silicon wafer at 80°C, it was evaluated whether the semiconductor wafer protective film sheet would peel off at room temperature (25°C). .
박리가 되는 경우 Pass, 박리가 되지 않는 경우 Fail로 평가하였다.If peeling occurred, it was evaluated as Pass, and if peeling did not occur, it was evaluated as Fail.
(4) 잔여물 평가(4) Residue evaluation
리워크 공정성 평가에서 박리된 경우, 실리콘 웨이퍼 전면에 대하여 SEM(Scanning Electron Microscope)을 이용하여 잔여물을 확인하고, 잔여물이 존재하는 경우 EDS(Energy Dispersive Spectrometer)로 원소를 분석하였다.In the case of peeling in the rework fairness evaluation, residues were confirmed on the front surface of the silicon wafer using a SEM (Scanning Electron Microscope), and if residues were present, elements were analyzed using an EDS (Energy Dispersive Spectrometer).
EDS 원소 분석 시 규소(Si)만 검출되거나, 검출되지 않는 경우 Pass, 규소(Si) 이외의 원소 검출 시 Fail로 평가하였다.During EDS element analysis, if only silicon (Si) was detected or not detected, it was evaluated as Pass, and if elements other than silicon (Si) were detected, it was evaluated as Fail.
실험예들에 따른 평가 결과는 하기 표 3에 나타내었다.The evaluation results according to the experimental examples are shown in Table 3 below.
(Pa·s)viscosity
(Pa·s)
(gf/inch)Peel force
(gf/inch)
공정성rework
fairness
상기 표 3을 참조하면, 점성이 100,000 내지 300,000Pa·s인 동시에 박리력이 10 내지 200gf/inch인 실시예 1 내지 실시예 4는 실리콘 웨이퍼와 반도체 웨이퍼용 보호막 시트가 박리되어 리워크 공정성이 인정되었으며, 박리 후 규소(Si) 외의 원소가 잔여물로 검출되지 않았다.Referring to Table 3, in Examples 1 to 4, which have a viscosity of 100,000 to 300,000 Pa·s and a peeling force of 10 to 200 gf/inch, the silicon wafer and the protective film sheet for semiconductor wafer are peeled, and rework fairness is recognized. After peeling, elements other than silicon (Si) were not detected as residues.
박리력이 10 내지 200gf/inch 범위에 속하나, 점성이 100,000Pa·s 미만인 비교예 1의 경우, 실리콘 웨이퍼와 반도체 웨이퍼용 보호막 시트가 박리되지 않아 리워크 공정성이 인정되지 않았다.In the case of Comparative Example 1, in which the peeling force was in the range of 10 to 200 gf/inch, but the viscosity was less than 100,000 Pa·s, the silicon wafer and the protective film sheet for semiconductor wafer were not peeled, so rework fairness was not recognized.
점성이 100,000 내지 300,000Pa·s 범위에 속하나, 박리력이 200gf/inch 이상인 비교예 2 및 비교예 3의 경우, 실리콘 웨이퍼와 반도체 웨이퍼용 보호막 시트가 박리되지 않아 리워크 공정성이 인정되지 않았다.In the case of Comparative Examples 2 and 3, where the viscosity was in the range of 100,000 to 300,000 Pa·s, but the peeling force was 200 gf/inch or more, the silicon wafer and the protective film sheet for semiconductor wafer were not peeled, so rework fairness was not recognized.
점성이 100,000Pa·s 미만이고, 박리력이 200gf/inch 이상인 비교예 4의 경우, 실리콘 웨이퍼와 반도체 웨이퍼용 보호막 시트가 박리되지 않아 리워크 공정성이 인정되지 않았다.In the case of Comparative Example 4, where the viscosity was less than 100,000 Pa·s and the peeling force was more than 200 gf/inch, the silicon wafer and the protective film sheet for semiconductor wafer were not peeled, so rework fairness was not recognized.
100: 기재 필름
200: 보호막 형성층
300: 이형층
400: 점착층
500: 다이싱 테이프100: base film 200: protective film forming layer
300: release layer 400: adhesive layer
500: Dicing Tape
Claims (14)
상기 기재 필름 상에 형성되는 보호막 형성층;을 포함하고,
상기 보호막 형성층의 점도는 120℃에서 100,000 내지 300,000Pa·s이며, 반도체 웨이퍼와의 박리력은 10 내지 200gf/inch인, 반도체 웨이퍼용 보호막 시트.
base film; and
It includes a protective film forming layer formed on the base film,
A protective film sheet for a semiconductor wafer, wherein the viscosity of the protective film forming layer is 100,000 to 300,000 Pa·s at 120°C, and the peeling force from the semiconductor wafer is 10 to 200 gf/inch.
The protective film sheet for a semiconductor wafer according to claim 1, wherein the peeling force is measured under peeling conditions of a tensile speed of 5 mm/s and a tensile angle of 180° at 25°C after lamination of the protective film forming layer on one side of the semiconductor wafer at 80°C.
The protective film sheet for a semiconductor wafer according to claim 1, wherein the protective film forming layer includes a binder, an epoxy resin, and a curing agent.
The protective film sheet for semiconductor wafers according to claim 2, wherein the binder is an acrylic acid ester copolymer with a weight average molecular weight of 400,000 to 2,000,000 g/mol.
The protective film sheet for a semiconductor wafer according to claim 2, wherein the binder has a glass transition temperature of 1°C to 21°C.
The protective film sheet for a semiconductor wafer according to claim 2, wherein the epoxy resin includes a first resin formed of a novolak-type epoxy resin and a second resin formed of a bisphenol-based epoxy resin.
The protective film sheet for a semiconductor wafer according to claim 2, wherein a weight ratio of the second resin to the first resin is 2 to 4.
The protective film sheet for semiconductor wafers according to claim 2, wherein the curing agent includes an amine-based curing agent.
The protective film sheet for a semiconductor wafer according to claim 2, wherein the protective film forming layer further includes a curing accelerator, a colorant, a coupling agent, and a filler.
The protective film sheet for a semiconductor wafer according to claim 9, wherein the curing accelerator includes an imidazole-based curing accelerator.
The protective film sheet for a semiconductor wafer according to claim 9, wherein the coupling agent includes a silane coupling agent.
The protective film sheet for a semiconductor wafer according to claim 1, wherein the base film contains a polyolefin-based resin.
The protective film sheet for a semiconductor wafer according to claim 1, further comprising a release film formed on the protective film forming layer.
The protective film sheet for a semiconductor wafer according to claim 1, further comprising an adhesive layer and a dicing tape sequentially laminated on the protective film forming layer.
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