KR20120008270A - Adhesive sheet, preparation method thereof and semiconductor wafer processing method - Google Patents
Adhesive sheet, preparation method thereof and semiconductor wafer processing method Download PDFInfo
- Publication number
- KR20120008270A KR20120008270A KR1020100069030A KR20100069030A KR20120008270A KR 20120008270 A KR20120008270 A KR 20120008270A KR 1020100069030 A KR1020100069030 A KR 1020100069030A KR 20100069030 A KR20100069030 A KR 20100069030A KR 20120008270 A KR20120008270 A KR 20120008270A
- Authority
- KR
- South Korea
- Prior art keywords
- adhesive sheet
- weight
- acrylate
- parts
- photocurable
- Prior art date
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 44
- 239000000853 adhesive Substances 0.000 title claims abstract description 41
- 239000004065 semiconductor Substances 0.000 title claims abstract description 22
- 238000003672 processing method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 7
- 239000000203 mixture Substances 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000012545 processing Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000000016 photochemical curing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 51
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 47
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 43
- 230000009477 glass transition Effects 0.000 claims description 16
- 239000012790 adhesive layer Substances 0.000 claims description 15
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical group OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 5
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 2
- VIESAWGOYVNHLV-UHFFFAOYSA-N 1,3-dihydropyrrol-2-one Chemical compound O=C1CC=CN1 VIESAWGOYVNHLV-UHFFFAOYSA-N 0.000 claims description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 2
- 102000010029 Homer Scaffolding Proteins Human genes 0.000 claims 3
- 108010077223 Homer Scaffolding Proteins Proteins 0.000 claims 3
- 229920000642 polymer Polymers 0.000 claims 3
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims 2
- OIQGXRHGRAISNA-UHFFFAOYSA-N 2-benzylidene-5-hydroxypentanoic acid Chemical compound OCCCC(C(O)=O)=CC1=CC=CC=C1 OIQGXRHGRAISNA-UHFFFAOYSA-N 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000002356 single layer Substances 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 35
- -1 1,3-diisocyanato-2-methylcyclohexane (1,3-diisocyanato-2-methylcyclohexane) Chemical compound 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 22
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- 230000000052 comparative effect Effects 0.000 description 6
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
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- 229910052782 aluminium Inorganic materials 0.000 description 3
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- 125000003118 aryl group Chemical group 0.000 description 3
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- 125000000524 functional group Chemical group 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- FFBZKUHRIXKOSY-UHFFFAOYSA-N aziridine-1-carboxamide Chemical compound NC(=O)N1CC1 FFBZKUHRIXKOSY-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WYOXPIKARMAQFM-UHFFFAOYSA-N n,n,n',n'-tetrakis(oxiran-2-ylmethyl)ethane-1,2-diamine Chemical compound C1OC1CN(CC1OC1)CCN(CC1OC1)CC1CO1 WYOXPIKARMAQFM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- UOMUPDCRXJLVGR-UHFFFAOYSA-N propane-1,2,2-triol Chemical compound CC(O)(O)CO UOMUPDCRXJLVGR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- IUCJMVBFZDHPDX-UHFFFAOYSA-N tretamine Chemical compound C1CN1C1=NC(N2CC2)=NC(N2CC2)=N1 IUCJMVBFZDHPDX-UHFFFAOYSA-N 0.000 description 1
- 229950001353 tretamine Drugs 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
- H01L21/46—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428
- H01L21/461—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/428 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
-
- 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
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67132—Apparatus for placing on an insulating substrate, e.g. tape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
본 발명은 점착 시트, 그 제조 방법 및 반도체 웨이퍼 가공 방법에 관한 것이다.
The present invention relates to an adhesive sheet, a method for producing the same, and a method for processing a semiconductor wafer.
최근 전자 제품의 소형화 및 경량화가 급격히 진행되고 있으며, 이에 따라 반도체 패키지의 리드레스(leadless)화, 박형화 및 고집적화에 대한 요구와 반도체 패키지에 포함되는 웨이퍼의 대구경화 및 박형화에 대한 요구 등이 증가하고 있다.In recent years, miniaturization and lightening of electronic products have been rapidly progressed. As a result, the demand for leadless, thinner and higher integration of semiconductor packages, and the demand for larger and thinner wafers included in semiconductor packages have increased. have.
반도체 웨이퍼의 대구경화 및 초박형화 추세에 효과적으로 대응하기 위해서는, 웨이퍼 연마공정인 백그라인딩(backgrinding)이나 개편화 공정인 다이싱(dicing) 공정의 정밀한 제어가 중요하며, 이를 위해서는 상기 공정들을 제어할 수 있는 고성능 기술이 필요하다. In order to effectively cope with the trend of large-sized and ultra-thin semiconductor wafers, it is important to precisely control the backgrinding, which is a wafer polishing process, or the dicing, which is a fragmentation process. High performance technology is required.
백그라인딩 공정은 고집적 배선회로를 갖는 웨이퍼의 표면을 기계적 또는 화학적으로 연마하여 얇게 하는 공정이다. 기존 백그라인딩 공정 시에는, 예를 들어 8 인치 웨이퍼를 공정 전의 절반 가량인 약 200 ㎛ 내지 400 ㎛ 정도까지 연마하는 것이 일반적이었다. 그러나, 박형화 요구에 따라 현재는 웨이퍼를 200 ㎛ 이하로 연마하는 것이 요구되고, 이에 따라 연마 시에 웨이퍼의 보호에 추가로 박형 웨이퍼를 핸들링하기 위한 보강 용도로도 보호 필름을 사용하는 경우가 발생하고 있다. The backgrinding process is a process of mechanically or chemically polishing and thinning the surface of a wafer having a highly integrated wiring circuit. In the conventional backgrinding process, for example, it was common to grind an 8 inch wafer to about 200 to 400 μm, which is about half before the process. However, in accordance with the demand for thinning, the wafer is currently required to be polished to 200 μm or less, and thus, a protective film is also used as a reinforcement for handling the thin wafer in addition to the protection of the wafer during polishing. have.
백그라인딩 또는 다이싱과 같은 웨이퍼 가공 공정에서 반도체 웨이퍼는 급격한 온도 변화에 노출된다. 예를 들어, 백그라인딩 또는 다이싱 과정은, 높은 온도에서 수행되지만, 상기 가공이 종료되면 온도가 다시 낮아지게 된다. 이와 같이, 보호 필름, 즉 점착 시트가 부착되어 있는 웨이퍼가 고온에서 저온으로의 온도 변화에 노출되면, 잔류 응력에 의해 필름이 수축 또는 팽창하게 되고, 이에 따라 박형의 웨이퍼가 쉽게 손상되는 문제점이 있다. 즉, 통상적으로 압출이나 카렌더링 공법으로 제조되는 기재가 보호 필름에 사용되는데, 상기와 같이 제조된 필름은 특히 잔류 응력에 의해 크게 휘어지는 문제가 있다.In wafer processing processes such as backgrinding or dicing, semiconductor wafers are exposed to rapid temperature changes. For example, the backgrinding or dicing process is performed at a high temperature, but the temperature is lowered again when the processing is finished. As such, when the protective film, that is, the wafer to which the adhesive sheet is attached, is exposed to a temperature change from high temperature to low temperature, the film shrinks or expands due to residual stress, and thus, the thin wafer is easily damaged. . That is, a substrate prepared by an extrusion or calendering method is usually used in the protective film, but the film prepared as described above has a problem of large bending due to residual stress.
이에 따라 보호 필름에 캐스팅 공법으로 제조된 필름을 사용하거나, 보호 필름을 다층 구조로 설계하여, 잔류 응력에 의한 팽창, 수축 또는 변형을 최소화하고자 하는 시도가 있다. Accordingly, there is an attempt to minimize expansion, contraction or deformation due to residual stress by using a film manufactured by a casting method for the protective film or by designing the protective film into a multilayer structure.
그렇지만, 캐스팅 공법으로 제조된 필름의 경우도, 제조에 사용된 조성물 자체가 경화 후 수축하는 성질을 가지기 때문에, 웨이퍼 가공 후에 잔류 응력에 의해 쉽게 수축하게 되는 문제가 있다. 또한, 필름을 다층 구조로 형성하는 경우에는, 제조 공정이 복잡해지게 되며, 또한 다층으로 구성된 각 층간의 접착도 어려운 문제가 있다.However, even in the case of the film produced by the casting method, since the composition itself used in the production has a property of shrinkage after curing, there is a problem that shrinkage easily due to residual stress after wafer processing. In addition, when the film is formed in a multilayer structure, the manufacturing process becomes complicated, and there is also a problem that adhesion between the layers composed of the multilayer is also difficult.
본 발명은, 점착 시트, 그 제조 방법 및 반도체 웨이퍼 가공 방법을 제공하는 것을 목적으로 한다.
An object of this invention is to provide the adhesive sheet, its manufacturing method, and a semiconductor wafer processing method.
본 발명은 상기 과제를 해결하기 위한 수단으로서, 광경화형 올리고머 및 특정 화학식으로 표시되는 단량체를 포함하는 광경화형 조성물의 경화물인 기재를 가지는 점착 시트를 제공한다.This invention provides the adhesive sheet which has a base material which is a hardened | cured material of the photocurable composition containing a photocurable oligomer and the monomer represented by a specific formula as a means for solving the said subject.
본 발명은 상기 과제를 해결하기 위한 다른 수단으로서, 광경화형 올리고머 및 특정 화학식으로 표시되는 단량체를 포함하는 광경화형 조성물을 제막하는 제 1 단계; 및 제 1 단계에서 제막된 광경화형 조성물을 경화시켜, 기재를 제조하는 제 2 단계를 포함하는 점착 시트의 제조 방법을 제공한다.As another means for solving the above problems, the present invention comprises a first step of forming a photocurable composition comprising a photocurable oligomer and a monomer represented by a specific formula; And a second step of curing the photocurable composition formed in the first step to prepare a substrate.
본 발명은 상기 과제를 해결하기 위한 또 다른 수단으로서, (1) 반도체 웨이퍼의 일면에 본 발명에 따른 점착 시트를 부착하는 단계; 및 (2) 점착 시트가 부착된 반도체 웨이퍼를 가공하는 단계를 포함하는 반도체 웨이퍼 가공 방법을 제공한다.
The present invention as another means for solving the above problems, (1) attaching the adhesive sheet according to the present invention on one surface of the semiconductor wafer; And (2) processing the semiconductor wafer with the adhesive sheet.
본 발명의 점착 시트는, 특정 화학식으로 표시되는 단량체를 포함하는 광경화형 조성물의 경화물인 기재를 가진다. 본 발명에서는, 기재 시트를 단층 구조로 형성하면서도 반도체 웨이퍼의 가공 과정 또는 가공 전후의 잔류 응력에 의한 휨 또는 균열 등의 변형 발생을 방지할 수 있는 점착 시트를 제공할 수 있다.
The adhesive sheet of this invention has a base material which is a hardened | cured material of the photocurable composition containing the monomer represented by a specific chemical formula. In the present invention, an adhesive sheet capable of preventing deformation such as warpage or cracking due to residual stress before or after processing or processing a semiconductor wafer can be provided while the base sheet is formed in a single layer structure.
도 1 및 2는 본 발명의 예시에 따른 점착 시트의 단면도이다.1 and 2 are cross-sectional views of an adhesive sheet according to an example of the present invention.
본 발명은, 광경화형 올리고머 및 하기 화학식 1로 표시되는 단량체를 포함하는 광경화형 조성물의 경화물인 기재를 가지는 점착 시트에 관한 것이다.This invention relates to the adhesive sheet which has a base material which is a hardened | cured material of the photocurable composition containing the photocurable oligomer and the monomer represented by following formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서, n은 1 내지 8의 정수를 나타낸다.
In Chemical Formula 1, n represents an integer of 1 to 8.
이하, 본 발명의 점착 시트를 보다 상세히 설명한다.Hereinafter, the adhesive sheet of this invention is demonstrated in detail.
본 발명의 점착 시트는, 기재로서 광경화형 조성물의 경화물을 포함한다. 본 명세서에서 용어 「광경화형 조성물」은 전자기파의 조사에 의해 경화되는 조성물을 의미하고, 이 경우 전자기파로는 마이크로파(microwaves), 적외선(IR), 자외선(UV), X선 및 γ선은 물론, α-입자선(α-particle beam), 프로톤빔(proton beam), 뉴트론빔(neutron beam) 및 전자선(electron beam)과 같은 입자빔을 총칭하는 의미로 사용된다.The adhesive sheet of this invention contains the hardened | cured material of a photocurable composition as a base material. As used herein, the term “photocurable composition” refers to a composition that is cured by irradiation of electromagnetic waves. In this case, as electromagnetic waves, microwaves, infrared rays (IR), ultraviolet rays (UV), X-rays, and γ-rays, It is used generically to mean particle beams such as α-particle beams, proton beams, neutron beams, and electron beams.
본 발명의 광경화형 조성물에 포함되는 광경화형 올리고머의 종류는 특별히 제한되지 않으나, 유리전이온도(Tg; Glass Transition Temperature)가 50℃ 이하, 바람직하게는 30℃ 이하인 올리고머를 사용할 수 있다. 본 발명에서는, 상기와 같은 범위의 유리전이온도를 가지는 올리고머를 사용하여, 기재가 우수한 신축성 및 재단성을 가지도록 할 수 있다. 본 발명에서 올리고머의 유리전이온도의 하한은 특별히 제한되지 않으나, 0 ~ 50 ℃의 범위에서 제어되는 것이 바람직하다.The type of the photocurable oligomer included in the photocurable composition of the present invention is not particularly limited, but an oligomer having a glass transition temperature (Tg) of 50 ° C. or less, preferably 30 ° C. or less may be used. In the present invention, an oligomer having a glass transition temperature in the above range can be used so that the substrate can have excellent elasticity and cutting properties. In the present invention, the lower limit of the glass transition temperature of the oligomer is not particularly limited, but is preferably controlled in the range of 0 to 50 ° C.
본 발명의 하나의 예시에서 상기 광경화형 올리고머는, 우레탄 아크릴레이트, 폴리에스테르형 우레탄 아크릴레이트 또는 폴리에테르형 우레탄 아크릴레이트일 수 있다.In one example of the present invention, the photocurable oligomer may be urethane acrylate, polyester urethane acrylate or polyether urethane acrylate.
본 발명에서 사용할 수 있는 상기 우레탄 아크릴레이트의 종류는 특별히 제한되지 않으며, 예를 들면, 폴리이소시아네이트 화합물을 히드록시알킬 (메타)아크릴레이트 등의 히드록시기를 가지는 화합물과 반응시켜 얻어지는 아크릴레이트를 사용할 수 있다. 상기에서 폴리이소시아네이트는, 분자 내에 2개 이상의 이소시아네이트기(NCO)를 가지는 화합물로서, 그 예에는, 지방족(aliphatic), 지환족(cycloaliphatic) 또는 방향족(aromatic) 폴리이소시아네이트가 포함될 수 있다. 상기에서 지방족 폴리이소시아네이트의 예로는, 1,4-디이소시아네이토부탄(1,4-diisocyanatobutane), 1,6-디이소시아네이토헥산(1,6-diisocyanatohexane), 1,6-디이소시아네이토-2,2,4-트리메틸헥산(1,6-diisocyanato-2,2,4-trimethylhexane) 또는 1,12-디이소시아네이토데칸(1,12-diisocyanatodecane) 등을 들 수 있고, 지환족 폴리이소시아네이트의 예로는, 1,3-디이소시아네이토시클로헥산(1,3 diisocyanatocyclohexane) 1,4-디이소시아네이토시클로헥산(1,4-diisocyanatocyclohexane), 2,4-디이소시아네이토-1-메틸시클로헥산(2,4-diisocyanato-1-methylcyclohexane), 1,3-디이소시아네이토-2-메틸시클로헥산(1,3-diisocyanato-2-methylcyclohexane), 1-이소시아네이토-2-(이소시아네이토메틸)시클로펜탄(1-isocyanato-2-(isocyanatomethyl)cyclopentane), 1,1'-메틸렌비스[4-이소시아네이토시클로헥산](1,1'-methylenebis[4-isocyanatocyclohexane]), 1,1'-(1-메틸에틸리덴)비스[4-이소시아네이토시클로헥산](1,1'-(1-methylethylidene)bis[4-isocyanatocyclohexane]), 5-이소시아네이토-1-이소시아네이토메틸-1,3,3-트리메틸시클로헥산(5-isocyanato-1-isocyanatomethyl-1,3,3-trimethylcyclohexane, isophorone diisocyanate), 1,3-비스(이소시아네이토메틸)시클로헥산(1,3-bis(isocyanatomethyl)cyclohexane), 1,4-비스(이소시아네이토메틸)시클로헥산(1,4-bis(isocyanatomethyl)cyclohexane), 1,1'-메틸렌비스[4-이소시아네이토-3-메틸시클로헥산](1,1'-methylenebis[4-isocyanato-3-methylcyclohexane]), 1-이소시아네이토-4-이소시아네이토메틸-1-메틸시클로헥산(1-isocyanato-4-isocyanatomethyl-1-methylcyclohexane), 1-이소시아네이토-3-이소시아네이토메틸-1-메틸시클로헥산(1-isocyanato-3-isocyanatomethyl-1-methylcyclohexane) 및 디시클로헥실메탄 디이소시아네이트(and dicyclohexylmethane diisocyanate) 등을 들 수 있으며, 방향족 폴리이소시아네이트의 예로는, 톨루엔 2,4-디이소시아네이트(toluene 2,4-diisocyanate), 1,4-디이소시아네이토벤젠(1,4-diisocyanatobenzene), 1,1'-메틸렌비스[4-이소시아네이토벤젠](1,1'-methylenebis[4-isocyanatobenzene]), 2,4-디이소시아네이토-1-메틸벤젠(2,4-diisocyanato-1-methylbenzene), 1,3-디이소시아네이토-2-메틸벤젠(1,3-diisocyanato-2-methylbenzene), 1,5-디이소시아네이토나프탈렌(1,5-diisocyanatonaphthalene), 1,1'-(1-메틸에틸리덴)비스[4-이소시아네이토벤젠](1,1'-(1-methylethylidene)bis[4-isocyanatobenzene]), 1,3-비스(1-이소시아네이토-1-메틸에틸)벤젠(1,3-bis(1-isocyanato-1-methylethyl)benzene), 1,4-비스(1-이소시아네이토-1-메틸에틸)벤젠(1,4-bis(1-isocyanato-1-methylethyl)benzene) 및 디페닐메탄 디이소시아네이트(diphenylmethane diisocyanate) 등을 들 수 있으나, 이에 제한되는 것은 아니다. 본 발명에서는 또한 3개 이상의 이소시아네이트기를 가지는 방향족 또는 지방족 폴리이소시아네이트도 사용될 수 있으며, 그 예로는, 1,1',1"-메틸리딘트리스[4-이소시아네이토벤젠](1,1',1"-methylidynetris[4-isocyanatobenzene]), 헥사메틸렌 디이소시아네이트의 삼량체(the trimer of hexamethylene diisocyanate) 및 아닐린/포름알데히드 축합물(aniline/formaldehyde condensates)을 포스겐화(phosgenation)하여 얻어지는 폴리페닐폴리메틸렌 폴리이소시아네이트(polyphenylpolymethylene polyisocyanates) 등을 들 수 있으나, 이에 제한되는 것은 아니다. The kind of the urethane acrylate that can be used in the present invention is not particularly limited, and for example, an acrylate obtained by reacting a polyisocyanate compound with a compound having a hydroxy group such as hydroxyalkyl (meth) acrylate can be used. . The polyisocyanate is a compound having two or more isocyanate groups (NCO) in a molecule, and examples thereof may include aliphatic, cycloaliphatic or aromatic polyisocyanates. Examples of the aliphatic polyisocyanate include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, and 1,6-diisocyanate. Ito-2,2,4-trimethylhexane (1,6-diisocyanato-2,2,4-trimethylhexane) or 1,12-diisocyanatodecane (1,12-diisocyanatodecane) etc. are mentioned, Alicyclic Examples of the polyisocyanate include 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, and 2,4-diisocyanato-1. -Methylcyclohexane (2,4-diisocyanato-1-methylcyclohexane), 1,3-diisocyanato-2-methylcyclohexane (1,3-diisocyanato-2-methylcyclohexane), 1-isocyanato-2 -(Isocyanatomethyl) cyclopentane (1-isocyanato-2- (isocyanatomethyl) cyclopentane), 1,1'-methylenebis [4-isocyanatocyclohexane] (1,1'-methylenebis [4- isocyanatocyclohexane]), 1,1 '-(1-methylethyl Den) bis [4-isocyanatocyclohexane] (1,1 '-(1-methylethylidene) bis [4-isocyanatocyclohexane]), 5-isocyanato-1-isocyanatomethyl-1,3 , 3-trimethylcyclohexane (5-isocyanato-1-isocyanatomethyl-1,3,3-trimethylcyclohexane, isophorone diisocyanate), 1,3-bis (isocyanatomethyl) cyclohexane (1,3-bis (isocyanatomethyl) cyclohexane), 1,4-bis (isocyanatomethyl) cyclohexane (1,4-bis (isocyanatomethyl) cyclohexane), 1,1'-methylenebis [4-isocyanato-3-methylcyclohexane] (1,1'-methylenebis [4-isocyanato-3-methylcyclohexane]), 1-isocyanato-4-isocyanatomethyl-1-methylcyclohexane (1-isocyanato-4-isocyanatomethyl-1-methylcyclohexane ), 1-isocyanato-3-isocyanatomethyl-1-methylcyclohexane, 1-isocyanato-3-isocyanatomethyl-1-methylcyclohexane, and dicyclohexylmethane diisocyanate Can and aromatic polyisocy Examples of anate include toluene 2,4-diisocyanate, 1,4-diisocyanatobenzene, 1,1'-methylenebis [4-iso Cyanatobenzene] (1,1'-methylenebis [4-isocyanatobenzene]), 2,4-diisocyanato-1-methylbenzene (2,4-diisocyanato-1-methylbenzene), 1,3-diisoxy 1,3-diisocyanato-2-methylbenzene, 1,5-diisocyanatonaphthalene, 1,1 '-(1-methylethylidene) bis [4-isocyanatobenzene] (1,1 '-(1-methylethylidene) bis [4-isocyanatobenzene]), 1,3-bis (1-isocyanato-1-methylethyl) benzene (1, 3-bis (1-isocyanato-1-methylethyl) benzene, 1,4-bis (1-isocyanato-1-methylethyl) benzene (1,4-bis (1-isocyanato-1-methylethyl) benzene ) And diphenylmethane diisocyanate, but are not limited thereto. In the present invention, aromatic or aliphatic polyisocyanates having three or more isocyanate groups may also be used, for example, 1,1 ', 1 "-methylidritris [4-isocyanatobenzene] (1,1', 1 "-methylidynetris [4-isocyanatobenzene]), the trimer of hexamethylene diisocyanate and polyphenylpolymethylene obtained by phosgenation of aniline / formaldehyde condensates Polyisocyanate (polyphenylpolymethylene polyisocyanates) and the like, but is not limited thereto.
본 발명에서는 상기와 같은 폴리이소시아네이트 중에서 2개의 이소시아네이트기를 가지는 화합물, 구체적으로는 방향족 디이소시아네이트 화합물을 사용하는 것이 바람직하지만, 이에 제한되는 것은 아니다.In the present invention, it is preferable to use a compound having two isocyanate groups, specifically an aromatic diisocyanate compound, in the above polyisocyanate, but is not limited thereto.
또한, 본 발명에서, 상기 폴리이소시아네이트와 반응하여 우레탄 아크릴레이트를 형성하는 히드록시알킬 (메타)아크릴레이트의 종류는 특별히 제한되지 않고, 예를 들면, 2-히드록시에틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, 4-히드록시부틸 (메타)아크릴레이트, 6-히드록시헥실 (메타)아크릴레이트 또는 8-히드록시옥틸 (메타)아크릴레이트 등을 사용할 수 있다.In addition, in this invention, the kind of hydroxyalkyl (meth) acrylate which reacts with the said polyisocyanate to form a urethane acrylate is not specifically limited, For example, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, and the like can be used.
본 발명에서, 상기 화합물을 반응시켜 우레탄 아크릴레이트를 제조하는 과정에서, 각 화합물의 사용량 및 반응 조건 등은 특별히 제한되지 않고, 공지의 범주 내에서 적절히 선택될 수 있다.In the present invention, in the process of preparing the urethane acrylate by reacting the compound, the amount of use of each compound, reaction conditions, and the like are not particularly limited and may be appropriately selected within a known range.
본 발명에서는, 상기 폴리에스테르형 아크릴레이트로서, 예를 들면, 폴리에스테르 폴리올을 폴리이소시아네이트 화합물과 반응시켜 얻어지는 화합물을 사용할 수 있다.In the present invention, as the polyester acrylate, for example, a compound obtained by reacting a polyester polyol with a polyisocyanate compound can be used.
본 발명에서 사용할 수 있는 상기 폴리에스테르 폴리올의 종류는 특별히 제한되지 않고, 이 분야에서 공지되어 있는 일반적인 종류의 폴리에스테르 폴리올을 사용할 수 있다. 또한, 상기에서 사용할 수 있는 폴리이소시아네이트의 예로는, 전술한 우레탄 아크릴레이트 항목에서 기술한 화합물을 사용할 수 있다. The kind of the polyester polyol which can be used in the present invention is not particularly limited, and a general kind of polyester polyol known in the art may be used. Moreover, as an example of the polyisocyanate which can be used above, the compound described in the urethane acrylate item mentioned above can be used.
본 발명에서, 상기 화합물을 반응시켜 폴리에스테르형 아크릴레이트를 제조하는 과정에서, 각 화합물의 사용량 및 반응 조건 등은 특별히 제한되지 않고, 공지의 범주 내에서 적절히 선택될 수 있다.In the present invention, in the process of preparing the polyester acrylate by reacting the compound, the amount of use of each compound and the reaction conditions are not particularly limited and may be appropriately selected within a known range.
본 발명에서는, 상기 폴리에테르형 아크릴레이트로서, 예를 들면, 폴리에테르 폴리올을 폴리이소시아네이트 화합물과 반응시켜 얻어지는 화합물을 사용할 수 있다. In the present invention, as the polyether acrylate, for example, a compound obtained by reacting a polyether polyol with a polyisocyanate compound can be used.
본 발명에서 사용할 수 있는 상기 폴리에테르 폴리올의 종류는 특별히 제한되지 않으며, 이 분야에서 공지되어 일반적인 종류의 폴리에테르 폴리올을 사용할 수 있다. 또한, 상기에서 사용할 수 있는 폴리이소시아네이트의 예로는, 전술한 우레탄 아크릴레이트 항목에서 기술한 화합물을 사용할 수 있다. The kind of the polyether polyol which can be used in the present invention is not particularly limited, and a general kind of polyether polyol known in the art may be used. Moreover, as an example of the polyisocyanate which can be used above, the compound described in the urethane acrylate item mentioned above can be used.
본 발명에서, 상기 화합물을 반응시켜 폴리에테르형 아크릴레이트를 제조하는 과정에서, 각 화합물의 사용량 및 반응 조건 등은 특별히 제한되지 않고, 공지의 범주 내에서 적절히 선택될 수 있다.In the present invention, in the process of producing a polyether acrylate by reacting the compound, the amount of use of each compound and the reaction conditions are not particularly limited and may be appropriately selected within a known range.
본 발명의 광경화형 조성물은, 전술한 범주 중에서 발명의 목적에 따라 1종 또는 2종 이상의 올리고머를 적절히 포함할 수 있다.The photocurable composition of this invention can contain suitably 1 type, or 2 or more types of oligomers according to the objective of invention in the said range.
본 발명의 하나의 예시에서 상기 광경화형 올리고머는, 중량평균분자량(Mw: Weight Average Molecular Weight)이 1,000 내지 50,000, 바람직하게는 2,000 내지 30,000일 수 있다. 본 발명에서는 상기 범위의 중량평균분자량을 가지는 올리고머를 사용하여, 경화물인 기재의 신축성 및 재단성을 탁월하게 유지할 수 있다.In one example of the present invention, the photocurable oligomer may have a weight average molecular weight (M w ) of 1,000 to 50,000, preferably 2,000 to 30,000. In this invention, the oligomer which has the weight average molecular weight of the said range can be used and the elasticity and cutting property of the base material which are hardened | cured material can be outstandingly maintained.
본 발명의 광경화형 조성물은, 상기 광경화형 올리고머와 함께 하기 화학식 1로 표시되는 단량체를 포함한다. 본 발명에서 하기 단량체는 전체적인 장력을 낮추어, 잔류 응력이 최소화된 기재를 제공할 수 있게 한다;The photocurable composition of this invention contains the monomer represented by following formula (1) with the said photocurable oligomer. In the present invention, the following monomers lower the overall tension, thereby making it possible to provide a substrate with a minimum of residual stress;
[화학식 1][Formula 1]
상기 화학식 1에서, n은 1 내지 8의 정수를 나타낸다.In Chemical Formula 1, n represents an integer of 1 to 8.
본 발명의 하나의 예시에서, 상기 화학식 1의 n은, 바람직하게는 1 내지 8, 보다 바람직하게는 1, 4 또는 8, 더욱 바람직하게는 4일 수 있다.In one example of the present invention, n in Chemical Formula 1 may be preferably 1 to 8, more preferably 1, 4 or 8, even more preferably 4.
본 발명에서 사용할 수 있는 상기 화학식 1의 단량체는, 노닐 페놀 에톡시화(4) 아크릴레이트가 가장 바람직하다.The monomer of the general formula (1) which can be used in the present invention is most preferably nonyl phenol ethoxylated (4) acrylate.
본 발명에서, 광경화형 조성물은, 상기 화학식 1의 단량체를 상기 광경화형 올리고머 100 중량부에 대하여, 10 중량부 내지 100 중량부, 바람직하게는 30 중량부 내지 60 중량부로 포함할 수 있다. 본 발명에서는 화학식 1의 단량체의 함량을 상기 범위로 조절하여, 기재에서 발생할 수 있는 잔류 응력을 최소화하면서, 기재의 인성(toughness) 등의 다른 물성도 적정 수준으로 유지할 수 있다.In the present invention, the photocurable composition, the monomer of Formula 1 may comprise 10 parts by weight to 100 parts by weight, preferably 30 parts by weight to 60 parts by weight with respect to 100 parts by weight of the photocurable oligomer. In the present invention, by adjusting the content of the monomer of the general formula (1) in the above range, it is possible to keep other physical properties such as toughness (toughness) of the substrate to an appropriate level while minimizing the residual stress that may occur in the substrate.
본 발명에서 기재의 인성(toughness) 개선을 목적으로 호머폴리머(homopolymer)로 중합되었을 때 유리전이온도가 50 ℃ 이상인 단량체를 추가로 포함할 수 있다.In the present invention, when the polymerization of the homopolymer (homopolymer) for the purpose of improving the toughness (toughness) of the substrate may further include a monomer having a glass transition temperature of 50 ℃ or more.
본 발명에서 상기 화학식 1의 단량체는, 조성물의 전체적인 장력을 낮추고, 잔류 응력이 낮은 기재를 제공할 수 있게 하나, 최종적인 기재의 인성을 다소 떨어뜨릴 수 있다. 이에 따라, 본 발명에서는 광경화형 조성물에 상기와 같이 높은 유리전이온도를 가지는 단량체를 적절히 배합하여 화학식 1의 사용으로 인한 인성의 저하를 보상할 수 있다. 본 발명에서 상기 단량체는, 호모폴리머로 중합시의 유리전이온도가 바람직하게는 50 ℃ 이상, 보다 바람직하게는 90 ℃ 이상일 수 있다. 또한, 본 발명에서 상기 유리전이온도의 상한은 특별히 제한되지 않으며, 예를 들면, 200 ℃ 이하의 범위에서 조절될 수 있다. In the present invention, the monomer of Formula 1 may lower the overall tension of the composition and provide a substrate having a low residual stress, but may slightly reduce the toughness of the final substrate. Accordingly, in the present invention, a monomer having a high glass transition temperature may be appropriately blended in the photocurable composition to compensate for the decrease in toughness due to the use of Formula 1. In the present invention, the monomer, the glass transition temperature at the time of polymerization with a homopolymer is preferably 50 ° C or more, more preferably 90 ° C or more. In addition, the upper limit of the glass transition temperature in the present invention is not particularly limited, for example, it may be adjusted in the range of 200 ℃ or less.
본 발명에서 사용할 수 있는 상기와 같은 단량체의 구체적인 종류는, 전술한 범위의 유리전이온도를 가지는 한 특별히 제한되지 않으며, 예를 들면, 이소보닐 (메타)아크릴레이트(isobornyl (meth)acrylate), 페닐히드록시프로필 아크릴레이트 및 벤질 아크릴레이트와 같은 방향족 화합물 또는 N-피롤리돈, N-비닐카프로락탐과 같은 헤테로시클릭 화합물 등을 들 수 있다.Specific types of the monomers as described above that can be used in the present invention are not particularly limited as long as they have a glass transition temperature in the above-described range, for example, isobornyl (meth) acrylate, phenyl Aromatic compounds such as hydroxypropyl acrylate and benzyl acrylate or heterocyclic compounds such as N-pyrrolidone, N-vinylcaprolactam and the like.
본 발명의 광경화형 조성물은, 상기와 같은 단량체를 광경화형 올리고머 100 중량부에 대하여, 10 중량부 내지 80 중량부로 포함할 수 있다. 본 발명에서 상기 단량체의 중량 비율이 10 중량부 미만이면 필름의 인성(Toughness)이 너무 낮아 잘 끊어질 우려가 있고, 80 중량부를 초과하면 필름이 너무 딱딱해져 재단성이 나빠질 우려가 있다.The photocurable composition of the present invention may contain the above monomers in an amount of 10 parts by weight to 80 parts by weight based on 100 parts by weight of the photocurable oligomer. In the present invention, when the weight ratio of the monomer is less than 10 parts by weight, the toughness of the film may be too low, so that the film may be easily broken. If the content exceeds 80 parts by weight, the film may be too hard, resulting in poor cutting properties.
본 발명에서 상기 광경화형 조성물은, 광개시제를 추가로 포함할 수 있다.In the present invention, the photocurable composition may further include a photoinitiator.
본 발명에서 사용할 수 있는 광개시제의 종류는 특별히 제한되지 않으며, 예를 들면, 벤조인계, 히드록시케톤계, 아세토페논계, 아미노케톤계 또는 포스핀 옥시드계 등과 같은 개시제를 사용할 수 있다.The kind of photoinitiator that can be used in the present invention is not particularly limited. For example, an initiator such as benzoin, hydroxyketone, acetophenone, amino ketone or phosphine oxide can be used.
본 발명에서 광경화형 조성물은 광개시제를, 광경화성 올리고머 100 중량부에 대하여, 0.1 중량부 내지 2 중량부로 포함할 수 있다. 본 발명에서는 광개시제의 함량을 상기 범위로 제어함으로써, 효과적인 경화 반응을 유도하고, 경화 후 잔존 성분으로 인한 물성 저하를 방지할 수 있다.In the present invention, the photocurable composition may include a photoinitiator in an amount of 0.1 parts by weight to 2 parts by weight based on 100 parts by weight of the photocurable oligomer. In the present invention, by controlling the content of the photoinitiator in the above range, it is possible to induce an effective curing reaction, and to prevent a decrease in physical properties due to the remaining components after curing.
본 발명에서 상기와 같은 성분을 포함하는 광경화형 조성물을 사용하여 기재를 제조하는 방법은 특별히 제한되지 않으며, 압출, 캐스팅, 카렌더링 또는 기타 공지의 필름 형성 기술을 제한 없이 이용할 수 있다. In the present invention, the method for preparing the substrate using the photocurable composition including the above components is not particularly limited, and extrusion, casting, calendaring, or other known film forming techniques may be used without limitation.
본 발명에서는 특히 후술하는 바와 같이 캐스팅 공법을 이용하여 기재를 제조하는 것이 바람직할 수 있다.In the present invention, it may be preferable to prepare the substrate using a casting method as described below.
본 발명에서 상기 광경화형 조성물의 경화물인 기재의 두께는 특별히 한정되지 않으며, 목적하는 용도 및 이 분야의 평균적 수준을 고려하여 적절히 선택될 수 있다. 본 발명에서는, 예를 들면, 상기 기재가 약 50 ㎛ 내지 300 ㎛ 또는 약 100 ㎛ 내지 200 ㎛의 두께를 가질 수 있다. 또한, 본 발명에서 상기 기재에는 후술하는 점착제층 또는 다른 층과의 밀착성 향상의 관점에서, 프라이머 처리 또는 코로나 처리 등과 같은 표면 처리가 수행되어 있을 수 있으며, 공정 효율성을 고려한 적절한 색상이 부여되어 있을 수도 있다.In the present invention, the thickness of the substrate, which is a cured product of the photocurable composition, is not particularly limited and may be appropriately selected in consideration of the intended use and the average level in the art. In the present invention, for example, the substrate may have a thickness of about 50 μm to 300 μm or about 100 μm to 200 μm. In addition, in the present invention, the substrate may be subjected to a surface treatment such as a primer treatment or a corona treatment, from the viewpoint of improving the adhesion to the adhesive layer or another layer described later, and may be given an appropriate color considering the process efficiency. have.
본 발명의 점착 시트는, 또한 상기 기재의 일면 또는 양면에 형성된 점착제층을 추가로 포함할 수 있다. 도 1은, 본 발명의 하나의 예시에 따른 점착 시트(1)의 단면도로서, 기재(11)의 일면에 점착제층(12)이 형성된 구조를 나타낸다. The pressure sensitive adhesive sheet of the present invention may further include a pressure sensitive adhesive layer formed on one or both surfaces of the substrate. FIG. 1: is sectional drawing of the adhesive sheet 1 which concerns on one example of this invention, and shows the structure in which the
본 발명의 점착 필름에 포함되는 점착제층의 구체적인 종류는, 웨이퍼 표면에 대한 저오염성을 가지면서, 웨이퍼 연마 또는 다이싱 과정에서 들뜸 현상을 방지할 수 있도록 조성된다면, 특별히 한정되지 않는다. 본 발명에서는, 예를 들면, 점착제층으로서, 실리콘계 점착제, 합성 고무계 점착제, 천연 고무계 점착제 또는 아크릴계 점착제를 사용할 수 있다.The specific kind of the pressure-sensitive adhesive layer included in the pressure-sensitive adhesive film of the present invention is not particularly limited as long as it has a low staining property on the surface of the wafer and is formed so as to prevent the lifting phenomenon during the wafer polishing or dicing process. In the present invention, for example, a silicone pressure sensitive adhesive, a synthetic rubber pressure sensitive adhesive, a natural rubber pressure sensitive adhesive or an acrylic pressure sensitive adhesive can be used as the pressure sensitive adhesive layer.
본 발명에서 기재상에 형성되는 점착제층으로서 아크릴계 점착제를 사용할 경우, 상기 점착제층은, 예를 들면, 가교성 아크릴계 수지 및 다관능성 가교제를 포함하는 점착제 조성물의 경화물일 수 있다.When the acrylic pressure sensitive adhesive is used as the pressure sensitive adhesive layer formed on the substrate in the present invention, the pressure sensitive adhesive layer may be, for example, a cured product of the pressure sensitive adhesive composition containing a crosslinkable acrylic resin and a polyfunctional crosslinking agent.
상기에서 가교성 아크릴계 수지는, 예를 들면, (메타)아크릴산 에스테르계 단량체 90 중량부 내지 99.9 중량부; 및 가교성 단량체 0.1 중량부 내지 10 중량부를 포함하는 단량체의 중합체일 수 있다.The crosslinkable acrylic resin may be, for example, 90 parts by weight to 99.9 parts by weight of a (meth) acrylic acid ester monomer; And 0.1 to 10 parts by weight of the crosslinkable monomer.
상기에서 (메타)아크릴산 에스테르계 단량체의 종류는 특별히 한정되지 않으며, 예를 들면 알킬 (메타)아크릴레이트를 사용할 수 있다. 이 때, 단량체에 포함되는 알킬기가 지나치게 장쇄가 되면, 점착제의 응집력이 저하되고, 유리전이온도나 점착성 조절이 어려워질 우려가 있으므로, 탄소수가 1 내지 14인 알킬기를 갖는 알킬 (메타)아크릴레이트를 사용하는 것이 바람직하다. 이와 같은 단량체의 예로는 메틸 (메타)아크릴레이트, 에틸 (메타)아크릴레이트, n-프로필 (메타)아크릴레이트, 이소프로필 (메타)아크릴레이트, n-부틸 (메타)아크릴레이트, t-부틸 (메타)아크릴레이트, sec-부틸 (메타)아크릴레이트, 펜틸 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트, 2-에틸부틸 (메타)아크릴레이트, n-옥틸 (메타)아크릴레이트, 이소옥틸 (메타)아크릴레이트, 이소보닐 (메타)아크릴레이트, 이소노닐 (메타)아크릴레이트, 라우릴 (메타)아크릴레이트 및 테트라데실 (메타)아크릴레이트를 들 수 있으며, 본 발명에서는 상기 중 일종 또는 이종 이상의 혼합을 사용할 수 있다. The kind of the (meth) acrylic acid ester monomer is not particularly limited, and alkyl (meth) acrylate can be used, for example. At this time, when the alkyl group contained in the monomer is too long, the cohesive force of the pressure-sensitive adhesive may be lowered, and the glass transition temperature and the adhesion control may become difficult. Therefore, an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms is used. It is preferable to use. Examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl ( Meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) acrylate, Isooctyl (meth) acrylate, isobonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate and tetradecyl (meth) acrylate, and in the present invention, one of the above Or a mixture of two or more kinds may be used.
본 발명의 단량체 혼합물에 포함되는 가교성 단량체는, 분자 구조 중에 α,β-불포화 탄소탄소 이중 결합과 같은 중합성 관능기 및 가교성 관능기를 동시에 가지는 것이라면 특별히 제한되지 않는다. 상기 가교성 단량체는, 수지에 다관능성 가교제와 반응할 수 있는 가교성 관능기를 부여할 수 있다. The crosslinkable monomer contained in the monomer mixture of the present invention is not particularly limited as long as it has a polymerizable functional group such as α, β-unsaturated carbon carbon double bond and a crosslinkable functional group at the same time in its molecular structure. The said crosslinkable monomer can provide the resin with the crosslinkable functional group which can react with a polyfunctional crosslinking agent.
본 발명에서 사용할 수 있는 가교성 단량체의 예로는 히드록시기 함유 단량체, 카복실기 함유 단량체 및 질소 함유 단량체를 들 수 있으나, 이에 제한되는 것은 아니다. 상기에서 히드록시기 함유 단량체의 예로는, 2-히드록시에틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, 4-히드록시부틸 (메타)아크릴레이트, 6-히드록시헥실 (메타)아크릴레이트, 8-히드록시옥틸 (메타)아크릴레이트, 2-히드록시에틸렌글리콜 (메타)아크릴레이트 또는 2-히드록시프로필렌글리콜 (메타)아크릴레이트를 들 수 있고, 카복실기 함유 단량체의 예로는 (메타)아크릴산, 2-(메타)아크릴로일옥시 아세트산, 3-(메타)아크릴로일옥시 프로필산, 4-(메타)아크릴로일옥시 부틸산, 아크릴산 이중체, 이타콘산, 말레산 및 말레산 무수물을 들 수 있으며, 질소 함유 단량체의 예로는 (메타)아크릴아미드, N-비닐 피롤리돈 또는 N-비닐 카프로락탐을 들 수 있으나, 이에 제한되는 것은 아니다. 본 발명에서는 상기 중 일종 또는 이종 이상의 혼합을 사용할 수 있다.Examples of the crosslinkable monomer that can be used in the present invention include, but are not limited to, hydroxy group-containing monomers, carboxyl group-containing monomers and nitrogen-containing monomers. Examples of the hydroxy group-containing monomers above include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) Acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate, and examples of the carboxyl group-containing monomer include ( Meta) acrylic acid, 2- (meth) acryloyloxy acetic acid, 3- (meth) acryloyloxy propyl acid, 4- (meth) acryloyloxy butyl acid, acrylic acid duplex, itaconic acid, maleic acid and male Acid anhydrides, and examples of nitrogen-containing monomers include, but are not limited to, (meth) acrylamide, N-vinyl pyrrolidone or N-vinyl caprolactam. In the present invention, a mixture of one or more of the above can be used.
본 발명에서 상기 단량체 혼합물은, (메타)아크릴산 에스테르계 단량체 10 중량부 내지 99.9 중량부 및 가교성 단량체 0.1 중량부 내지 10 중량부를 포함할 수 있으나, 상기 중량 비율은 목적하는 점착제의 물성을 고려하여 적절히 조절될 수 있다.In the present invention, the monomer mixture may include 10 parts by weight to 99.9 parts by weight of the (meth) acrylic acid ester monomer and 0.1 parts by weight to 10 parts by weight of the crosslinkable monomer, but the weight ratio is considered in consideration of physical properties of the desired adhesive. Can be adjusted appropriately.
본 발명에서 상기 가교성 아크릴계 수지는, 유리전이온도가 -50℃ 내지 15℃의 범위에 있을 수 있다. 수지의 유리전이온도를 상기와 같이 제어하여, 박리 속도에 따른 박리력을 효과적으로 조절함으로써, 웨이퍼 가공 공정에서의 박리에 따른 웨이퍼 손상을 방지하고, 웨이퍼 등의 피착체에 대하여 탁월한 젖음성을 나타내도록 할 수 있다.In the present invention, the crosslinkable acrylic resin may have a glass transition temperature in the range of -50 ° C to 15 ° C. By controlling the glass transition temperature of the resin as described above, by effectively controlling the peeling force according to the peeling rate, it is possible to prevent wafer damage due to peeling in the wafer processing process, and to exhibit excellent wettability to adherends such as wafers. Can be.
또한, 본 발명에서 상기 가교성 아크릴계 수지는 중량평균분자량(Mw: Weight Average Molecular Weight)이 5만 내지 70만일 수 있다. 상기에서 「중량평균분자량」은, GPC(Gel Permeation Chromatography)로 측정한 표준 폴리스티렌에 대한 환산 수치이다. 본 발명에서는 수지의 중량평균분자량을 위와 같이 조절하여, 응집력 및 점착 특성을 탁월하게 유지할 수 있다.In addition, in the present invention, the crosslinkable acrylic resin may have a weight average molecular weight (M w ) of 50,000 to 700,000. The "weight average molecular weight" is a conversion value with respect to standard polystyrene measured by GPC (Gel Permeation Chromatography). In the present invention, by adjusting the weight average molecular weight of the resin as described above, it is possible to maintain excellent cohesive force and adhesive properties.
본 발명에서 상기와 같은 가교성 아크릴계 수지를 제조하는 방법은 특별히 한정되지 않으며, 예를 들면 용액 중합, 광중합, 벌크 중합, 서스펜션 중합 또는 에멀션 중합과 같은 일반적인 중합법을 통하여 제조할 수 있다. In the present invention, a method for producing such a crosslinkable acrylic resin is not particularly limited, and for example, may be prepared by a general polymerization method such as solution polymerization, photopolymerization, bulk polymerization, suspension polymerization or emulsion polymerization.
본 발명의 점착제층을 형성하는 점착제 조성물은, 또한 다관능성 가교제를 포함할 수 있다. 상기 가교제는 사용량에 따라 점착제의 점착 특성을 조절하고, 응집력을 향상시키는 작용을 할 수 있다. The adhesive composition which forms the adhesive layer of this invention can also contain a polyfunctional crosslinking agent. The crosslinking agent may act to adjust the adhesive properties of the pressure-sensitive adhesive according to the amount of use, and improve the cohesion.
본 발명에서 사용될 수 있는 구체적인 가교제의 종류는 특별히 한정되지 않으며, 예를 들면 이소시아네이트계 화합물, 에폭시계 화합물, 아지리딘계 화합물 및 금속 킬레이트계 화합물과 같은 일반적인 가교제를 사용할 수 있다. 이때, 이소시아네이트계 화합물의 예로는 톨리렌 디이소시아네이트, 크실렌 디이소시아네이트, 디페닐메탄 디이소시아네이트, 헥사메틸렌 디이소시아네이트, 이소포름 디이소시아네이트, 테트라메틸크실렌 디이소시아네이트 또는 나프탈렌 디이소시아네이트 등이나, 상기 이소시아네이트 화합물 중 하나 이상의 화합물과 폴리올(ex. 트리메틸롤 프로판)과 반응물 등을 사용할 수 있고; 에폭시계 화합물로는 에틸렌글리콜 디글리시딜에테르, 트리글리시딜에테르, 트리메틸올프로판 트리글리시딜에테르, N,N,N',N'-테트라글리시딜 에틸렌디아민 또는 글리세린 디글리시딜에테르 등을 사용할 수 있으며; 아지리딘계 화합물로는 N,N'-톨루엔-2,4-비스(1-아지리딘카르복사미드), N,N'-디페닐메탄-4,4'-비스(1-아지리딘카르복사미드), 트리에틸렌 멜라민, 비스이소프로탈로일-1-(2-메틸아지리딘) 또는 트리-1-아지리디닐포스핀옥시드 등을 사용할 수 있다. 또한, 상기 금속 킬레이트계 화합물로는, 알루미늄, 철, 아연, 주석, 티탄, 안티몬, 마그네슘 및/또는 바나듐과 같은 다가 금속이 아세틸 아세톤 또는 아세토초산 에틸 등에 배위하고 있는 화합물을 사용할 수 있으나, 이에 제한되는 것은 아니다. 본 발명에서는 전술한 가교제 중 일종 또는 이종 이상을 적절히 혼합하여 사용할 수 있다.The kind of specific crosslinking agent that can be used in the present invention is not particularly limited, and for example, a general crosslinking agent such as an isocyanate compound, an epoxy compound, an aziridine compound and a metal chelate compound may be used. At this time, examples of the isocyanate compound include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoform diisocyanate, tetramethylxylene diisocyanate or naphthalene diisocyanate, or one of the above isocyanate compounds. The above compounds, polyols (ex. Trimethylol propane), reactants and the like can be used; Epoxy compounds include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N ', N'-tetraglycidyl ethylenediamine or glycerin diglycidyl ether Can be used; Examples of aziridine compounds include N, N'-toluene-2,4-bis (1-aziridinecarboxamide) and N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxamide ), Triethylene melamine, bisisoprotaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide and the like can be used. In addition, as the metal chelate compound, a compound in which a polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and / or vanadium is coordinated with acetyl acetone, ethyl acetoacetate, or the like may be used. It doesn't happen. In the present invention, one kind or two or more kinds of the above-mentioned crosslinking agents may be appropriately mixed.
본 발명에서, 상기 가교제는 전술한 수지 100 중량부에 대하여 0.1 중량부 내지 10 중량부로 포함될 수 있다. 가교제의 함량비를 위와 같이 조절하여, 점착 물성 및 내구성이 우수한 점착제층을 제조할 수 있다.In the present invention, the crosslinking agent may be included in an amount of 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the aforementioned resin. By adjusting the content ratio of the crosslinking agent as described above, it is possible to produce a pressure-sensitive adhesive layer excellent in adhesive properties and durability.
본 발명의 점착제층을 형성하는 상기 점착제 조성물은, 필요에 따라서, 실란 커플링제, 점착성 부여 수지, 저분자량체, 에폭시 수지, 경화제, 자외선 안정제, 산화 방지제, 조색제, 보강제, 소포제, 계면 활성제, 발포제, 유기염, 증점제 및 난연제로 이루어진 군으로부터 선택된 하나 이상의 첨가제를 추가로 포함할 수 있다.The said adhesive composition which forms the adhesive layer of this invention is a silane coupling agent, tackifying resin, low molecular weight, an epoxy resin, a hardening | curing agent, an ultraviolet stabilizer, antioxidant, a coloring agent, a reinforcing agent, an antifoamer, surfactant, a foaming agent, as needed. It may further comprise one or more additives selected from the group consisting of organic salts, thickeners and flame retardants.
본 발명의 점착 시트에서 상기 점착제층의 두께는 특별히 제한되지 않으며, 예를 들면, 0.5 ㎛ 내지 50 ㎛ 또는 1 ㎛ 내지 30 ㎛일 수 있다. 점착제층의 두께를 상기와 같이 조절하여, 두께 및 물성이 균일한 점착제층을 얻을 수 있다. The thickness of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of the present invention is not particularly limited, and may be, for example, 0.5 μm to 50 μm or 1 μm to 30 μm. By adjusting the thickness of the pressure-sensitive adhesive layer as described above, a pressure-sensitive adhesive layer having a uniform thickness and physical properties can be obtained.
본 발명의 점착 시트는 또한 상기 점착제층 상에 적층된 박리 필름을 추가로 포함할 수 있다. 도 2는 본 발명의 다른 예시에 따른 점착 시트(2)의 단면도로서, 기재(11)의 일면에 점착제층(12)이 형성되고, 상기 점착층(12) 상에 박리 필름(21)이 형성된 구조를 나타낸다. 본 발명에서 상기 박리 필름의 구체적인 종류는 특별히 한정되지 않으며, 예를 들면 폴리에스테르계 필름(ex. PET) 필름 또는 올레핀계 필름 등의 일면 또는 양면을 실리콘 또는 알키드 계열의 이형제로 이형 처리한 필름을 사용할 수 있다. 상기와 같은 박리 필름의 두께는 그 용도에 따라 적절히 설정되는 것으로 특별히 한정되지 않고, 예를 들면 10 ㎛ 내지 70 ㎛의 범위에서 적절히 선택될 수 있다.The pressure sensitive adhesive sheet of the present invention may further include a release film laminated on the pressure sensitive adhesive layer. 2 is a cross-sectional view of the adhesive sheet 2 according to another embodiment of the present invention, wherein the
본 발명은 또한, 광경화형 올리고머 및 상기 화학식 1로 표시되는 단량체를 포함하는 광경화형 조성물을 제막하는 제 1 단계; 및 제 1 단계에서 제막된 광경화형 조성물을 광경화시켜, 기재를 제조하는 제 2단계를 포함하여 점착 시트의 제조 방법에 관한 것이다.The present invention also comprises a first step of forming a photocurable composition comprising a photocurable oligomer and a monomer represented by the formula (1); And a second step of photocuring the photocurable composition formed in the first step to prepare a substrate.
본 발명의 제 1 단계에서는 광경화형 조성물을 제막하며, 이 때 상기 조성물에 포함되는 각 성분의 구체적인 설명은 전술한 바와 같다. 본 발명에서 상기 조성물을 제막하는 방법은 특별히 제한되지 않으며, 예를 들면, 캐스팅(casting)법을 적용할 수 있다. 구체적으로, 본 발명의 제 1 단계에서는, 바코트, 나이프 코트, 롤 코트, 스프레이 코트, 그라비어 코트, 커튼 코트, 콤마 코트 및/또는 립 코트 등의 통상의 수단으로, 적절한 공정 기재상에 상기 광경화형 조성물을 코팅함으로써, 제막 공정을 수행할 수 있다. 이와 같은 방식으로 제막을 수행하고, 후술하는 광조사에 의한 경화 공정을 수행함으로써, 두께 균일성, 고온 치수 안정성, 절단성 및 투명성 등의 물성이 향상된 기재를 얻을 수 있다. 구체적으로, 본 발명에서는 전술한 조성물을 적절한 공정 기재상에 캐스팅(casting)한 후, 이를 필름화하고, 공정 기재를 제거하는 방식으로 기재를 제조할 수 있다. 이와 같은 방식을 사용한 경우, 성막 시에 수지에 걸리는 응력이 최소화되고, 시간의 흐름 또는 가열에 의한 치수 변화가 발생하지 않게 된다. 또한, 고형의 불순물의 제거가 용이하여, 제막된 필름에서 돌출부(fish eye) 등의 발생이 억제되고, 이것에 의해 막 두께의 균일성과 두께 정밀도가 향상될 수 있다. 또한, 상기 방식을 적용할 경우, 필름의 응력 완화성이 향상될 수 있고, 이에 따라 피착체에 부착하였을 때, 발생하는 잔류 응력을 신속하게 해소할 수 있다.In the first step of the present invention, a photocurable composition is formed. At this time, detailed description of each component included in the composition is as described above. In the present invention, the method of forming the composition is not particularly limited, and for example, a casting method may be applied. Specifically, in the first step of the present invention, the sight on the appropriate process substrate by conventional means such as a bar coat, knife coat, roll coat, spray coat, gravure coat, curtain coat, comma coat and / or lip coat, etc. By coating the chemical composition, a film forming process can be performed. By forming a film in such a manner and performing a curing process by light irradiation described later, a substrate having improved physical properties such as thickness uniformity, high temperature dimensional stability, cutability and transparency can be obtained. Specifically, in the present invention, the above-described composition may be cast on an appropriate process substrate, and then the substrate may be prepared by forming a film and removing the process substrate. When such a method is used, the stress applied to the resin during film formation is minimized, and the dimensional change due to the passage of time or heating does not occur. In addition, the removal of solid impurities is easy, and the occurrence of a fish eye or the like in the film formed is suppressed, whereby the uniformity and thickness precision of the film thickness can be improved. In addition, when the above method is applied, the stress relieving property of the film can be improved, and thus, the residual stress generated when adhered to the adherend can be quickly resolved.
한편, 상기 제막 공정에서 사용될 수 있는 공정 기재의 종류는 특별히 제한되지 않으며, 예를 들면, 통상의 플라스틱 기재(ex. PET 기재), 종이, 부직포, 유리 또는 금속성 기재를 사용할 수 있다. 본 발명에서는 또한 상기와 같은 공정 기재에 적절한 이형 처리를 수행하여 사용할 수도 있다.On the other hand, the type of process substrate that can be used in the film forming process is not particularly limited, and for example, a conventional plastic substrate (ex. PET substrate), paper, nonwoven fabric, glass or metallic substrate can be used. In the present invention, it can also be used by performing a suitable release treatment to the above-described process substrate.
본 발명의 제 2 단계는, 제 1 단계에서 제막된 조성물을 경화시킴으로써 기재를 형성하는 단계이며, 이 때 경화는 통상적인 광경화 공정, 예를 들면, 자외선 경화 공정 등을 통해 수행할 수 있다. 본 발명의 제 2 단계에서, 자외선을 조사하는 방법은 특별히 제한되지 않으며, 예를 들면, 고압수은 램프, 무전극 램프 또는 크세논 램프(xenon lamp) 등의 수단을 사용하여 수행할 수 있다. 또한, 본 발명의 제 2 단계는, 예를 들면, 조도가 5 mW/cm2 내지 200 mW/cm2인 자외선(파장: 230 nm 내지 400 nm)을 약 2초 내지 20분 동안 조사하여 수행할 수 있다. 또한, 상기 단계에서, 자외선의 광량은 4 mJ/cm2 내지 2,000 mJ/cm2의 범위 내에서 제어될 수 있다.The second step of the present invention is a step of forming a substrate by curing the composition formed in the first step, wherein the curing may be carried out through a conventional photocuring process, for example, an ultraviolet curing process. In the second step of the present invention, the method of irradiating ultraviolet rays is not particularly limited, and for example, may be performed using a means such as a high pressure mercury lamp, an electrodeless lamp or a xenon lamp. In addition, the second step of the present invention, for example, may be carried out by irradiating ultraviolet light (wavelength: 230 nm to 400 nm) having an illuminance of 5 mW / cm 2 to 200 mW / cm 2 for about 2 seconds to 20 minutes. Can be. In addition, in the above step, the amount of ultraviolet light can be controlled within the range of 4 mJ / cm 2 to 2,000 mJ / cm 2 .
그러나, 상기 자외선 조사 조건은, 본 발명의 하나의 예시에 불과하다. 즉, 본 발명에서는, 제반 물성을 훼손하지 않으면서, 수지 시럽의 충분한 경화가 이루어질 정도의 범위 내에서, 제 2 단계의 자외선 조사 조건을 자유롭게 변경할 수 있다.However, the ultraviolet irradiation condition is merely one example of the present invention. That is, in this invention, the ultraviolet irradiation conditions of a 2nd step can be changed freely within the range of sufficient hardening of a resin syrup, without compromising all physical properties.
본 발명의 점착 시트의 제조 방법은 상기 제 2 단계에 이어서, 기재의 일면 또는 양면에 점착제층을 형성하는 공정을 추가로 수행할 수 있다. 본 발명에서, 점착제층을 기재 상에 형성하는 방법은 특별히 한정되지 않는다. 예를 들면, 본 발명에서는 기재 표면에 직접 바코트, 나이프 코트, 롤 코트, 스프레이 코트, 그라비어 코트, 커튼 코트, 콤마 코트 및/또는 립 코트 등의 수단을 사용하여 전술한 점착제 조성물 또는 그를 포함하는 코팅액을 도포 및 건조시키는 방법, 점착제 조성물 또는 코팅액을 박리성 기재 표면에 도포 및 건조시킨 후, 상기 박리성 기재 표면에 형성된 점착제층을 기재 표면에 전사하고 숙성시키는 방법 등을 사용할 수 있다. In the method of manufacturing an adhesive sheet of the present invention, after the second step, a process of forming an adhesive layer on one or both surfaces of the substrate may be further performed. In this invention, the method of forming an adhesive layer on a base material is not specifically limited. For example, in the present invention, the above-described pressure-sensitive adhesive composition or the same comprising the above-mentioned means using a means such as a bar coat, knife coat, roll coat, spray coat, gravure coat, curtain coat, comma coat and / or lip coat directly on the substrate surface. After coating and drying the coating liquid, the pressure-sensitive adhesive composition or the coating liquid is applied and dried on the surface of the peelable substrate, a method of transferring and aging the pressure-sensitive adhesive layer formed on the surface of the peelable substrate to the substrate surface and the like can be used.
본 발명에서는 상기와 같은 점착제층의 형성 단계에서 적절한 건조 및 숙성 과정을 거쳐, 점착층의 가교 구조를 조절하는 것이 바람직하다. 이와 같은 가교 구조의 조절을 통하여, 탄성을 가지고, 응집력이 강한 점착층을 얻을 수 있으며, 이에 따라 점착 필름의 내구신뢰성 등의 점착물성 및 절단성을 향상시킬 수 있다. 구체적으로, 본 발명의 점착 필름의 점착층은 80 내지 99%의 가교 밀도를 가지는 것이 바람직하다. 상기 가교밀도가 80% 미만이면, 점착층의 응집력이 저하되고, 점착층 성분이 웨이퍼 등 피착체로 전사되어 잔사가 남게 될 우려가 있다. 또한, 상기 점착층의 가교 밀도가 99%를 초과하면, 박리력이 저하되어 웨이퍼 가공 시 수분사에 의한 수침이 발생할 우려가 있다.In the present invention, it is preferable to control the crosslinked structure of the pressure-sensitive adhesive layer through an appropriate drying and aging process in the step of forming the pressure-sensitive adhesive layer as described above. Through the control of such a crosslinked structure, an adhesive layer having elasticity and strong cohesive force can be obtained, thereby improving adhesiveness and cutability such as durability and durability of the adhesive film. Specifically, the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention preferably has a crosslinking density of 80 to 99%. If the crosslinking density is less than 80%, the cohesion force of the adhesive layer is lowered, and the adhesive layer component may be transferred to an adherend such as a wafer, and the residue may remain. In addition, when the crosslinking density of the pressure-sensitive adhesive layer exceeds 99%, the peeling force is lowered, there is a fear that water immersion by water spray during wafer processing occurs.
본 발명의 점착 시트의 제조 방법에서는 상기 공정에 이어서 점착제층 상에 박리 필름을 형성하는 공정을 추가로 수행할 수도 있다.In the manufacturing method of the adhesive sheet of this invention, the process of forming a peeling film on an adhesive layer may be further performed following the said process.
본 발명은 또한, (1) 반도체 웨이퍼의 일면에 전술한 점착 시트를 부착하는 단계; 및 (2) 점착 시트가 부착된 반도체 웨이퍼를 가공하는 단계를 포함하는 반도체 웨이퍼의 가공 방법에 관한 것이다.The present invention also comprises the steps of: (1) attaching the above-mentioned pressure-sensitive adhesive sheet on one surface of the semiconductor wafer; And (2) processing the semiconductor wafer to which the adhesive sheet is attached.
본 발명의 반도체 웨이퍼 가공 방법은 전술한 본 발명의 점착 시트를 웨이퍼 가공용 보호 필름으로 사용한 것을 특징으로 하며, 그 외의 구체적인 공정 조건은 특별히 한정되지 않는다. 예를 들면, 본 발명에서는 전술한 점착 필름을 프레스법 또는 핫 롤 라미네이트법 등의 수단으로 웨이퍼에 합판한 후, 웨이퍼의 가공을 수행할 수 있다. The semiconductor wafer processing method of the present invention is characterized by using the above-described pressure-sensitive adhesive sheet of the present invention as a protective film for wafer processing, and other specific process conditions are not particularly limited. For example, in the present invention, the above-mentioned pressure-sensitive adhesive film is laminated on the wafer by means such as a press method or a hot roll lamination method, and then the wafer can be processed.
이 경우, 반도체 웨이퍼의 가공은, 백그라인딩 또는 다이싱 공정 등을 포함하고, 상기 공정의 수행되는 구체적인 조건은 이 분야에서 공지되어 있다.
In this case, processing of the semiconductor wafer includes a backgrinding or dicing process and the like, and specific conditions under which the process is performed are known in the art.
[실시예][Example]
이하, 본 발명에 따르는 실시예 및 본 발명에 따르지 않는 비교예를 통하여 본 발명을 보다 상세히 설명하나, 본 발명의 범위가 하기 제시된 실시예에 의해 제한되는 것은 아니다.
Hereinafter, the present invention will be described in more detail through examples according to the present invention and comparative examples not according to the present invention, but the scope of the present invention is not limited to the examples given below.
[기재 제조][Substrate manufacturing]
제조예Manufacturing example 1 One
중량평균분자량이 약 50,000 정도이며, 유리전이온도가 20 ℃인 우레탄 아크릴레이트 수지 100 중량부에 노닐 페닐 (EO)4 아크릴레이트 40 중량부, IBA 20 중량부를 첨가하고, 아세토페논계 광개시제인 Irgacure 651 0.5 중량부를 첨가하여 30분간 교반하였다. 점도는 1100 cps 이고, 진공상태에서 탈포하여 코팅 시 기포가 없게 하였다. 하부 PET 는 하드코팅을 한 것이며, 상부는 이형 PET를 덮고, 자외선의 강도가 5 내지 8 mW/cm2의 단일 파장을 갖는 블랙 라이트를 이용하여 5분간 단면 조사를 실시하여 기재를 제조하였다.
40 parts by weight of nonyl phenyl (EO) 4 acrylate and 20 parts by weight of IBA are added to 100 parts by weight of a urethane acrylate resin having a weight average molecular weight of about 50,000 and a glass transition temperature of 20 ° C., Irgacure 651, an acetophenone-based photoinitiator. 0.5 parts by weight was added and stirred for 30 minutes. The viscosity is 1100 cps, and degassed in vacuum to eliminate bubbles during coating. The lower PET was hard-coated, and the upper part covered the release PET, and the substrate was prepared by performing cross-sectional irradiation for 5 minutes using black light having a single wavelength of 5 to 8 mW / cm 2 .
제조예Manufacturing example 2 2
IBA 20 중량부를 첨가하지 않고, 노닐 페닐 (EO)4 아크릴레이트 60 중량부 첨가하는 것 외에는 상기 제조예 1과 동일하게 실시하였다.
The same process as in Preparation Example 1 was carried out except that 20 parts by weight of IBA was not added and 60 parts by weight of nonyl phenyl (EO) 4 acrylate was added.
제조예Manufacturing example 3 3
IBA 20 중량부를 첨가하지 않은 것 외에는 상기 제조예 1과 동일하게 실시하였다.
The same procedure as in Preparation Example 1 was repeated except that 20 parts by weight of IBA was not added.
비교제조예Comparative Production Example 1 One
노닐 페닐 (EO)4 아크릴레이트 40 중량부를 첨가하지 않고, IBA 20 중량부를 첨가하는 것 외에는 상기 제조예 1과 동일하게 실시하였다.
40 parts by weight of nonyl phenyl (EO) 4 acrylate was not added, and 20 parts by weight of IBA was added to carry out in the same manner as in Preparation Example 1 above.
[점착제 제조][Adhesive preparation]
실시예Example 1 ~ 3 및 1 to 3 and 비교예Comparative example 1 One
먼저, 2-에틸 헥실 아크릴레이트와 아크릴산이 90:10으로 용액중합법에 의해 공중합을 시켰다. 제조된 점착제는 고형분이 약 20% 정도며, 점도가 3500 cps였다. 이형필름 위에 상기 제조예 1 ~ 3 및 비교제조예 1에서 각각 제조된 점착제를 코팅 후 약 100 ℃에서 3분간 건조 후 최종 25 um 두께가 되도록 제조하였다. 이 점착제와 상기 제조된 기재와 합판을 하여 원하는 점착 시트를 완성하였다.
First, 2-ethylhexyl acrylate and acrylic acid were copolymerized by solution polymerization at 90:10. The prepared pressure-sensitive adhesive had a solid content of about 20% and a viscosity of 3500 cps. The pressure-sensitive adhesives prepared in Preparation Examples 1 to 3 and Comparative Preparation Example 1 were coated on the release film, and then dried at about 100 ° C. for 3 minutes to prepare a final thickness of 25 μm. The pressure-sensitive adhesive and the base material prepared above were laminated with plywood to complete the desired pressure-sensitive adhesive sheet.
실험예Experimental Example 1: 물성 측정 1: Physical property measurement
상기 실시예 1 ~ 3 및 비교예 1에서 제조된 점착 시트는 아래에 열거한 측정방법들에 의해 평가되었다.The adhesive sheets prepared in Examples 1 to 3 and Comparative Example 1 were evaluated by the measurement methods listed below.
1) 내구성 1) durable
아령형의 샘플을 제작하여 텍스쳐 분석기(Texture Analyzer)를 이용해서 측정하였다. 시험 속도는 5.0 mm/sec 이며, 각 샘플에 대하여 장력탄성율(tensile modulus), 신장(elongation), 인성(toughness)를 평가하였다.Dumbbell-shaped samples were prepared and measured using a texture analyzer. The test speed was 5.0 mm / sec and the tensile modulus, elongation and toughness were evaluated for each sample.
2) 뒤틀림( Warpage ) 2) twisting (Warpage)
실리콘 웨이퍼를 그린딩(Grinding) 시 두께가 얇아지면서 점착시트가 열을 받아 수축을 하게 되면 웨이퍼에 크랙이 가거나 깨지는 경우가 있다. 이를 간이적으로 평가하기 위해 실리콘 웨이퍼 대신 150 um 두께의 알루미늄 시트를 사용하였다. 5cm×5cm 크기의 알루미늄시트에 점착시트를 합지하여, 100 ℃ 오븐에 30분간 방치 후 상온에서 식히면서 뒤틀림 정도를 확인하였다. 뒤틀림은 필름 끝단이 바닥에서 떨어진 정도를 자로 측정하여 mm로 표기하였다.When the silicon wafer is thinned and the adhesive sheet shrinks due to heat, the wafer may be cracked or broken. To simplify this evaluation, a 150 um thick aluminum sheet was used instead of the silicon wafer. The adhesive sheet was laminated on a 5 cm × 5 cm aluminum sheet, and left for 30 minutes in an oven at 100 ° C., followed by cooling at room temperature. Warpage is expressed in mm by measuring the extent to which the film ends fall off the floor.
노닐 페놀 에폭시화(4) 아크릴레이트가 들어간 경우 뒤틀림 특성이 매우 우수함을 알 수 있었다. 하지만 단독으로 사용되었을 경우 인성 값이 너무 낮아 잘 끊어질 수 있어, Tg가 90℃ 이상인 IBA와 같은 단량체를 추가함으로써 인성 값도 올릴 수 있다.
When the nonyl phenol epoxidized (4) acrylate is contained, it was found that the warping characteristics are very excellent. However, when used alone, the toughness value is too low and can be easily broken, thereby increasing the toughness value by adding a monomer such as IBA having a Tg of 90 ° C or more.
1, 2: 점착 시트 11: 기재
12: 점착제층 21: 박리 필름1, 2: adhesive sheet 11: base material
12: pressure-sensitive adhesive layer 21: release film
Claims (16)
[화학식 1]
상기 화학식 1에서, n은 1 내지 8의 정수를 나타낸다.
A pressure sensitive adhesive sheet having a substrate that is a cured product of a photocurable composition comprising a photocurable oligomer and a monomer represented by Formula 1 below:
[Formula 1]
In Chemical Formula 1, n represents an integer of 1 to 8.
The adhesive sheet according to claim 1, wherein the photocurable oligomer has a glass transition temperature of 0 ° C to 50 ° C.
The adhesive sheet according to claim 1, wherein the photocurable oligomer is urethane acrylate, polyester acrylate or polyether acrylate.
The adhesive sheet according to claim 1, wherein n is 1, 4 or 8 in the monomer represented by the formula (1).
The pressure-sensitive adhesive sheet of claim 1, wherein the photocurable composition comprises 10 parts by weight to 100 parts by weight of the monomer of Formula 1 based on 100 parts by weight of the photocurable oligomer.
The adhesive sheet according to claim 1, wherein the photocurable composition further comprises a monomer having a glass transition temperature of 50 ° C or higher when polymerized with a homer polymer.
7. The monomer according to claim 6, wherein the monomer having a glass transition temperature of 50 ° C or higher when polymerized with a homer polymer is isobornyl (meth) acrylate, phenylhydroxypropylacrylate, benzyl acrylate, N-pyrrolidone or N-vinyl Adhesive sheet which is caprolactam.
The pressure-sensitive adhesive sheet of claim 6, wherein the photocurable composition comprises 10 parts by weight to 80 parts by weight of a monomer having a glass transition temperature of 50 ° C or higher when polymerized with a homer polymer, based on 100 parts by weight of the photocurable oligomer.
The adhesive sheet according to claim 1, wherein the photocurable composition further comprises a photoinitiator.
The pressure-sensitive adhesive sheet of claim 9, wherein the photocurable composition comprises 0.1 part by weight to 2 parts by weight with respect to 100 parts by weight of the photocurable oligomer.
The adhesive sheet according to claim 1, further comprising an adhesive layer formed on the substrate.
The adhesive sheet of Claim 11 in which the adhesive layer contains the hardened | cured material of the adhesive composition containing a crosslinkable acrylic resin and a polyfunctional crosslinking agent.
제 1 단계에서 제막된 광경화형 조성물을 광경화시켜, 기재를 제조하는 제 2 단계를 포함하는 점착 시트의 제조 방법:
[화학식 1]
상기 화학식 1에서, n은 1 내지 8의 정수를 나타낸다.
A first step of forming a photocurable composition comprising a photocurable oligomer and a monomer represented by Formula 1 below; And
A method for producing a pressure-sensitive adhesive sheet comprising a second step of photocuring a photocurable composition formed in a first step to prepare a substrate.
[Formula 1]
In Chemical Formula 1, n represents an integer of 1 to 8.
The manufacturing method of the adhesive sheet of Claim 13 which further performs the process of forming an adhesive layer on a base material after a 2nd step.
(2) 점착 시트가 부착된 반도체 웨이퍼를 가공하는 단계를 포함하는 반도체 웨이퍼 가공 방법.
(1) attaching the adhesive sheet according to any one of claims 1 to 12 on one surface of the semiconductor wafer; And
(2) A semiconductor wafer processing method comprising the step of processing a semiconductor wafer with an adhesive sheet.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020100069030A KR101682720B1 (en) | 2010-07-16 | 2010-07-16 | Semiconductor wafer processing method |
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| KR1020100069030A KR101682720B1 (en) | 2010-07-16 | 2010-07-16 | Semiconductor wafer processing method |
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| KR101682720B1 KR101682720B1 (en) | 2016-12-06 |
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| KR101351624B1 (en) * | 2010-12-31 | 2014-01-15 | 제일모직주식회사 | Adhesive composition and a method for assembling module of mobile phone using the same |
| WO2014010933A1 (en) * | 2012-07-10 | 2014-01-16 | (주)엘지하우시스 | Semiconductor wafer surface protecting semi-adhesive film and production method for same |
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| JP2001262077A (en) * | 2000-03-23 | 2001-09-26 | Toppan Forms Co Ltd | Uv-setting pressure-sensitive adhesive and pressure- sensitive adhesive printing sheet using the same |
| JP2004256595A (en) * | 2003-02-24 | 2004-09-16 | Lintec Corp | Adhesive sheet and method for using the same |
| KR100910685B1 (en) * | 2007-06-21 | 2009-08-04 | 에스에스씨피 주식회사 | Optical filter for display panel comprising impact resistant photopolymerized resin layer |
| KR20100024531A (en) * | 2008-08-26 | 2010-03-08 | 에스에스씨피 주식회사 | Radiation curable resin composition and optical fiber made by using thereof |
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|---|---|---|---|---|
| JP2001262077A (en) * | 2000-03-23 | 2001-09-26 | Toppan Forms Co Ltd | Uv-setting pressure-sensitive adhesive and pressure- sensitive adhesive printing sheet using the same |
| JP2004256595A (en) * | 2003-02-24 | 2004-09-16 | Lintec Corp | Adhesive sheet and method for using the same |
| KR100910685B1 (en) * | 2007-06-21 | 2009-08-04 | 에스에스씨피 주식회사 | Optical filter for display panel comprising impact resistant photopolymerized resin layer |
| KR20100024531A (en) * | 2008-08-26 | 2010-03-08 | 에스에스씨피 주식회사 | Radiation curable resin composition and optical fiber made by using thereof |
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| KR101351624B1 (en) * | 2010-12-31 | 2014-01-15 | 제일모직주식회사 | Adhesive composition and a method for assembling module of mobile phone using the same |
| WO2014010933A1 (en) * | 2012-07-10 | 2014-01-16 | (주)엘지하우시스 | Semiconductor wafer surface protecting semi-adhesive film and production method for same |
| KR101539133B1 (en) * | 2012-07-10 | 2015-07-23 | (주)엘지하우시스 | Surface protecting adhesive film for semiconductor wafer and method manufacturing the same |
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| KR101682720B1 (en) | 2016-12-06 |
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