KR20160039947A - Composition for removing silicone polymer - Google Patents
Composition for removing silicone polymer Download PDFInfo
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- KR20160039947A KR20160039947A KR1020140133289A KR20140133289A KR20160039947A KR 20160039947 A KR20160039947 A KR 20160039947A KR 1020140133289 A KR1020140133289 A KR 1020140133289A KR 20140133289 A KR20140133289 A KR 20140133289A KR 20160039947 A KR20160039947 A KR 20160039947A
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- composition
- silicone
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- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 229920005573 silicon-containing polymer Polymers 0.000 title 1
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229920002050 silicone resin Polymers 0.000 claims description 23
- -1 acetylenyl Chemical group 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 10
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 6
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 claims description 2
- ONQBOTKLCMXPOF-UHFFFAOYSA-N 1-ethylpyrrolidine Chemical compound CCN1CCCC1 ONQBOTKLCMXPOF-UHFFFAOYSA-N 0.000 claims description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012973 diazabicyclooctane Substances 0.000 claims description 2
- 239000012971 dimethylpiperazine Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- PASUDGKNNPSRBK-UHFFFAOYSA-N 2-ethoxy-2-methylbutanoic acid Chemical compound CCOC(C)(CC)C(O)=O PASUDGKNNPSRBK-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 description 1
- QGAKFUJUPKPDCN-UHFFFAOYSA-M tetraoctylazanium;fluoride Chemical compound [F-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QGAKFUJUPKPDCN-UHFFFAOYSA-M 0.000 description 1
- PTMFUWGXPRYYMC-UHFFFAOYSA-N triethylazanium;formate Chemical compound OC=O.CCN(CC)CC PTMFUWGXPRYYMC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/24—Organic compounds containing halogen
- C11D3/245—Organic compounds containing halogen containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
본 발명은 전자부품 등의 제조공정 예컨대, 반도체 웨이퍼의 이면 연삭, 이면 전극 형성 등의 공정에 사용되는 실리콘계 수지 제거용 조성물에 관한 것이다.TECHNICAL FIELD The present invention relates to a composition for removing a silicone resin used in a process for manufacturing electronic parts and the like, for example, a process for back grinding a semiconductor wafer, forming a back electrode, and the like.
반도체 소자의 제조 공정에 있어서, 반도체 웨이퍼(이하, 단순히 「웨이퍼」라고도 함)의 표면에 전자 회로 등을 형성한 후, 웨이퍼의 두께를 얇게 하기 위해 웨이퍼의 이면 연삭(소위, 백 그라인딩)을 행하는 경우가 있다. 이 경우, 웨이퍼 회로면의 보호, 웨이퍼의 고정 등을 위하여 통상적으로 웨이퍼의 회로면에 실리콘계 수지를 개재하여 지지체를 부착한다. 지지체를 웨이퍼의 회로면에 부착하면, 웨이퍼의 이면 연삭 후 두께가 얇아진 웨이퍼를 보강할 수 있고, 웨이퍼의 연삭면에 이면 전극 등을 형성할 수도 있다. BACKGROUND ART [0002] In an electronic device manufacturing process, an electronic circuit or the like is formed on the surface of a semiconductor wafer (hereinafter simply referred to as a " wafer ") and then subjected to back grinding (so-called back grinding) There is a case. In this case, for the purpose of protecting the wafer circuit surface and securing the wafer, a support body is usually attached to the circuit surface of the wafer via a silicone resin. When the support is attached to the circuit surface of the wafer, it is possible to reinforce the wafer having a reduced thickness after the back grinding of the wafer, and to form the back electrode or the like on the grinding surface of the wafer.
상기 웨이퍼의 이면 연삭, 이면 전극 형성 등의 공정이 완료되면, 웨이퍼의 회로면으로부터 지지체를 제거하고 전자부품에 부착된 실리콘계 수지를 박리하여 제거하고, 웨이퍼를 절단하여 칩을 제작한다.After the back grinding of the wafer and the formation of the back electrode are completed, the support is removed from the circuit surface of the wafer, the silicon resin attached to the electronic component is peeled and removed, and the wafer is cut to manufacture chips.
한편, 최근에는 웨이퍼를 관통하여 설치하는 관통 전극(예를 들어, 실리콘 관통 전극)을 이용한 칩 적층 기술이 개발되어 있다. 이 칩 적층 기술에 따르면, 종래의 와이어 대신 관통 전극을 이용하여 복수의 칩의 전자 회로를 전기적으로 접속하므로, 칩의 고집적화, 동작의 고속화를 도모할 수 있다. 이 칩 적층 기술을 이용하는 경우, 복수의 칩이 적층된 집합체의 두께를 얇게 하기 위해 웨이퍼의 이면 연삭을 행하는 경우가 많으며, 그로 인해, 지지체나 전자부품에 실리콘계 수지를 이용할 경우가 증가한다.On the other hand, in recent years, a chip stacking technique using a penetrating electrode (for example, a silicon penetrating electrode) that penetrates a wafer has been developed. According to this chip stacking technique, since electronic circuits of a plurality of chips are electrically connected to each other by using a through electrode instead of a conventional wire, high integration of chips and high operation speed can be achieved. In the case of using this chip stacking technique, back grinding of the wafer is often performed in order to reduce the thickness of the aggregate in which a plurality of chips are stacked, thereby increasing the number of cases in which a silicon resin is used for a support or an electronic component.
그런데, 통상적으로 웨이퍼의 회로면에 전자부품에 부착된 실리콘계 수지를 개재하여 지지체를 부착한 후, 상기 웨이퍼와 지지체의 견고한 부착을 위하여 열경화를 실시하기 때문에 전자부품에 부착된 실리콘계 수지를 박리하는 경우, 경화된 전자부품에 부착된 실리콘계 수지가 지지체 및 웨이퍼의 회로면에 잔존하는 경우가 발생한다. 그러므로, 상기 지지체 및 웨이퍼 회로면에 잔존하는 경화된 전자부품에 부착된 실리콘계 수지를 효율적으로 제거하는 수단이 필요하다.Conventionally, after attaching a support to a circuit surface of a wafer via a silicone-based resin attached to an electronic component and then thermally curing the wafer and the support for firm attachment, the silicone resin adhered to the electronic component is peeled off , A silicone resin adhered to the cured electronic component may remain on the circuit surface of the support and the wafer. Therefore, a means for efficiently removing the silicon-based resin adhered to the support and the cured electronic component remaining on the wafer circuit surface is needed.
대한민국 공개특허 제10-2014-0060389호는 불화알킬암모늄(TMAF, TEAF, TBAF, BTMAF) 0.1~30 중량%; 및 카보네이트계 용매, 아세테이트계 용매, 케톤계 용매, 에틸에톡시프로피오네이트(EEP), 에틸피롤리돈(NEP), 아마이드계 용매, 설폭사이드계 용매, 및 나이트릴계 용매로 이루어진 군으로부터 선택되는 1종 이상의 용매 70~99.9 중량%를 포함하는 전자부품에 부착된 실리콘계 수지 제거용 조성물을 개시하고 있다.Korean Patent Laid-Open No. 10-2014-0060389 discloses a composition comprising 0.1 to 30% by weight of alkyl ammonium fluoride (TMAF, TEAF, TBAF, BTMAF); And a solvent selected from the group consisting of a carbonate solvent, an acetate solvent, a ketone solvent, ethylethoxypropionate (EEP), ethylpyrrolidone (NEP), an amide solvent, a sulfoxide solvent and a nitrile solvent Discloses a composition for removing a silicone resin adhered to an electronic component containing 70 to 99.9% by weight of at least one solvent.
그러나, 상기 선행기술은 실리콘계 수지의 제거속도 면에서 개선의 여지가 있는 것으로 보인다.However, the above-mentioned prior art seems to have room for improvement in the removal rate of the silicone resin.
본 발명은 전자부품 등에 부착된 실리콘계 수지의 제거속도가 우수한 실리콘계 수지 제거용 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a silicone-based resin removing composition excellent in the removal rate of a silicone-based resin adhered to an electronic part or the like.
본 발명은, According to the present invention,
조성물 총 중량에 대하여, With respect to the total weight of the composition,
(a) 화합물 내에 1개의 질소원자와 20개~100개의 탄소원자와 1개의 불소원자를 포함하는 QAF(Quarternary ammonium Fluoride) 0.1~30 중량%; 및(a) 0.1 to 30% by weight of a quaternary ammonium fluoride (QAF) containing one nitrogen atom, 20 to 100 carbon atoms and one fluorine atom in the compound; And
(b) 하기 화학식 1로 표시되는 화합물로 이루어진 군으로부터 선택되는 1종 이상의 용매 70~99.9 중량%를 포함하는 실리콘계 수지 제거용 조성물을 제공한다:(b) 70 to 99.9% by weight of at least one solvent selected from the group consisting of compounds represented by the following formula (1):
[화학식 1][Chemical Formula 1]
상기 식에서In the above formula
R1, R2 및 R3는 각각 독립적으로, C1~C12의 직쇄 또는 분지쇄의 지방족 탄화수소; 할로겐, 비닐, 아세틸레닐 또는 C1~C5의 알콕시기로 치환된 C1~C4의 지방족 탄화수소; 또는 C1~C4의 알킬기에 의해서 치환 또는 비치환된 페닐기이다.R1, R2 and R3 are each independently a C1-C12 linear or branched aliphatic hydrocarbon; Halogen, vinyl, acetylenyl or C1-C4 aliphatic hydrocarbon substituted with C1-C5 alkoxy; Or a phenyl group substituted or unsubstituted by an alkyl group of C1-C4.
본 발명의 실리콘계 수지 제거용 조성물은 실리콘계 수지의 분해속도가 우수하며, 전자부품 등의 제조공정 예컨대, 반도체 웨이퍼의 이면 연삭, 이면 전극 형성 등의 공정에서 지지체 및 웨이퍼 회로면에 잔존하게 되는 실리콘계 수지를 효과적으로 제거할 수 있다. The composition for removing a silicone resin of the present invention is excellent in the decomposition rate of a silicone resin and is excellent in the production process of electronic parts and the like, for example, in the process of back grinding, back electrode formation of a semiconductor wafer, Can be effectively removed.
본 발명은, 조성물 총 중량에 대하여, The present invention relates to a composition,
(a) 화합물 내에 1개의 질소원자와 20개~100개의 탄소원자와 1개의 불소원자를 포함하는 QAF(Quarternary ammonium Fluoride) 0.1~30 중량%; 및(a) 0.1 to 30% by weight of a quaternary ammonium fluoride (QAF) containing one nitrogen atom, 20 to 100 carbon atoms and one fluorine atom in the compound; And
(b) 하기 화학식 1로 표시되는 화합물로 이루어진 군으로부터 선택되는 1종 이상의 용매 70~99.9 중량%를 포함하는 실리콘계 수지 제거용 조성물에 관한 것이다:(b) 70 to 99.9% by weight of at least one solvent selected from the group consisting of compounds represented by the following formula (1):
[화학식 1][Chemical Formula 1]
상기 식에서In the above formula
R1, R2 및 R3는 각각 독립적으로, C1~C12의 직쇄 또는 분지쇄의 지방족 탄화수소; 할로겐, 비닐, 아세틸레닐 또는 C1~C5의 알콕시기로 치환된 C1~C4의 지방족 탄화수소; 또는 C1~C4의 알킬기에 의해서 치환 또는 비치환된 페닐기이다.
R1, R2 and R3 are each independently a C1-C12 linear or branched aliphatic hydrocarbon; Halogen, vinyl, acetylenyl or C1-C4 aliphatic hydrocarbon substituted with C1-C5 alkoxy; Or a phenyl group substituted or unsubstituted by an alkyl group of C1-C4.
본 발명의 실리콘계 수지 제거용 조성물에서 (a) QAF(Quarternary ammonium Fluoride)는 전자부품 등에 부착된 실리콘계 수지의 분자량을 감소시키는 역할을 한다.(A) Quaternary ammonium fluoride (QAF) in the silicone-based resin removing composition of the present invention serves to reduce the molecular weight of a silicone resin adhered to electronic parts or the like.
상기 QAF로는 화합물 내에 1개의 질소원자와 20개~100개의 탄소원자와 1개의 불소원자를 포함하는 것이 사용되며, 상기 탄소원자는 20개~50개인 것이 더욱 바람직하다. 상기에서 QAF에 포함되는 탄소원자의 수가 20개 이상이 바람직한 이유는 질소원자에 결합된 탄소 쇄의 길이기 길수록 QAF의 소수성이 강해지고 물의 함유량이 줄어들게 되므로, 불소이온의 반응성이 커지기 때문이다. 즉, 불소이온을 둘러싸는 화합물이 많아지면 불소이온의 반응성이 약해지므로, 가능하면 불소이온의 외부에 대한 노출을 크게 하는 것이 불소이온의 반응성을 크게 하는 방법이 된다. 상기 불소이온을 둘러싸는 화합물은 불소이온과 수소결합을 형성할 수 있는 히드록시기 함유 화합물을 의미하며, 가장 수소결합을 잘할 수 있는 화합물은 물이다. 따라서, 암모늄염의 수분함유량이 불소의 활성을 결정하는 가장 중요한 인자가 된다. As the QAF, a compound containing one nitrogen atom, 20 to 100 carbon atoms and one fluorine atom is used in the compound, more preferably 20 to 50 carbon atoms. The reason why the number of carbon atoms contained in the QAF is preferably 20 or more is because the longer the carbon chain bonded to the nitrogen atom is, the stronger the hydrophobic property of the QAF and the smaller the content of water, and the greater the reactivity of the fluorine ion. That is, when the amount of the compound surrounding the fluorine ion increases, the reactivity of the fluorine ion becomes weak. Therefore, if possible, the exposure of the fluorine ion to the outside is increased, thereby increasing the reactivity of the fluorine ion. The compound that surrounds the fluorine ion means a compound containing a hydroxy group capable of forming a hydrogen bond with fluorine ions, and the compound that can best hydrogen bond is water. Therefore, the moisture content of the ammonium salt becomes the most important factor for determining the activity of fluorine.
상기에서 QAF에 포함되는 탄소원자의 수가 100개 이하로 한정된 것은 탄소원자의 수가 100개를 초과하면, 조성물의 점도가 너무 커지고, 가격도 고가가 되어 바람직하지 않기 때문이다.The reason why the number of carbon atoms contained in QAF is limited to 100 or less is because when the number of carbon atoms exceeds 100, the viscosity of the composition becomes too large and the price becomes high, which is not preferable.
상기 QAF의 대표적인 화합물의 예를 들면 다음과 같다:
Examples of representative compounds of the above QAF are as follows:
상기 화학식에서 m은 1~4의 정수이고, n은 0~4의 정수일 수 있다.
In the above formula, m is an integer of 1 to 4, and n may be an integer of 0 to 4.
본 발명에서 사용되는 QAF는 상기의 예로 한정되지 않으며, 상기 조건에 맞는 것으로서 이 분야에서 공지된 것은 모두 사용될 수 있다.
The QAF used in the present invention is not limited to the above examples, and any of the QAFs satisfying the above conditions and known in this field can be used.
상기 (a) QAF는 조성물 총 중량에 대하여 0.1~30 중량%로 포함되는 것이 바람직하며, 1~20 중량%로 포함되는 것이 더욱 바람직하다. 상기 불화알킬암모늄이 0.1 중량% 미만으로 포함되는 경우, 전자부품 등에 부착된 실리콘계 수지를 효과적으로 제거하지 못하는 문제가 발생될 수 있으며, 30 중량%를 초과하는 경우는, 가격이 비싸지며, 경시에 따른 수분함량이 증가되어, 오히려 실리콘 수지의 제거성능의 저하가 우려되며, 웨이퍼 회로면의 금속 부위가 부식되는 문제가 발생될 수 있다.
The amount of (a) QAF is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight based on the total weight of the composition. If the amount of the alkyl ammonium fluoride is less than 0.1% by weight, the problem may arise that the silicone resin adhered to an electronic part or the like can not be effectively removed. When the amount exceeds 30% by weight, The water content is increased, and the removal performance of the silicone resin is rather lowered, and the metal part of the wafer circuit surface may be corroded.
상기 (b) 화학식 1로 표시되는 화합물로 이루어진 군으로부터 선택되는 1종 이상의 용매는 경화 실리콘계 수지를 팽창시키고, QAF를 용해시키는 역할을 한다. 상기 화학식 1로 표시되는 화합물들은 극성이고 비양자성인 특징을 갖는다. 또한, 상기 용매는 극성이어서 QAF 및 실리콘계 수지를 잘 용해시키며, 비양자성이므로 불소이온과 실리콘계 수지의 반응 중간체를 잘 안정화시켜서 실리콘계 수지의 분해반응을 촉진시키기 때문에 바람직하다. 더욱 상세히 설명하면, 실리콘수지의 분해반응은 불소음이온의 친핵성 치환반응에 의해서 진행되는데, 친핵성 치환반응속도를 향상시키는 용매의 조건이 극성 비양자성 용매라는 관점에서 하기 화학식 1로 표시되는 용제의 큰 극성과 비양자성이 실리콘수지의 분해반응 속도를 향상시키는데 유리하다.
The at least one solvent selected from the group consisting of the compounds represented by the above-mentioned (b) formula (1) serves to expand the cured silicone resin and dissolve QAF. The compounds represented by the above formula (1) are polar and have a non-quantum characteristic. The solvent is preferably polar because it dissolves the QAF and the silicone resin well and stabilizes the reaction intermediate between the fluorine ion and the silicone resin to accelerate the decomposition reaction of the silicone resin because it is nonionic. More specifically, the decomposition reaction of the silicone resin proceeds by a nucleophilic substitution reaction of the fluorine anion. From the viewpoint that the condition of the solvent for improving the nucleophilic substitution reaction rate is polar aprotic solvent, the solvent of the solvent represented by the following formula The large polarity and the non-magnetic properties are advantageous for improving the decomposition reaction rate of the silicone resin.
하기 화학식 1로 표시되는 화합물은 구체적으로 피리딘 유도체들이다:The compounds represented by the formula (1) are specifically pyridine derivatives:
[화학식 1][Chemical Formula 1]
상기 식에서In the above formula
R1, R2 및 R3는 각각 독립적으로, C1~C12의 직쇄 또는 분지쇄의 지방족 탄화수소; 할로겐, 비닐, 아세틸레닐 또는 C1~C5의 알콕시기로 치환된 C1~C4의 지방족 탄화수소; 또는 C1~C4의 알킬기에 의해서 치환 또는 비치환된 페닐기이다.
R1, R2 and R3 are each independently a C1-C12 linear or branched aliphatic hydrocarbon; Halogen, vinyl, acetylenyl or C1-C4 aliphatic hydrocarbon substituted with C1-C5 alkoxy; Or a phenyl group substituted or unsubstituted by an alkyl group of C1-C4.
상기 C1~C12의 직쇄 또는 분지쇄의 지방족탄화수소로는 메틸, 에틸, n-프로필, iso-프로필, n-부틸, iso-부틸, sec-부틸, t-부틸, n-펜틸, iso-펜틸, sec-펜틸, t-펜틸, n-헥실, iso-헥실, sec-헥실, t-헥실, n-헵틸, iso-헵틸, sec-헵틸, t-헵틸, n-옥틸, iso-옥틸, sec-옥틸, t-옥틸 등을 들 수 있다.Examples of the straight-chain or branched aliphatic hydrocarbon having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- heptyl, isoheptyl, sec-heptyl, t-heptyl, n-octyl, iso-octyl, sec-butyl, isohexyl, sec-hexyl, Octyl, t-octyl and the like.
상기 C1~C4의 직쇄 또는 분지쇄의 지방족탄화수소로는 메틸, 에틸, n-프로필, iso-프로필, n-부틸, iso-부틸, sec-부틸, t-부틸 등을 들 수 있다.
Examples of the C1-C4 linear or branched aliphatic hydrocarbon include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl.
상기 화학식 1 화합물의 구체예는 다음과 같다:Specific examples of the compound of Formula 1 are as follows:
상기 화학식 1로 표시되는 화합물로 이루어진 군으로부터 선택되는 1종 이상의 용매는 조성물 총 중량에 대하여 70~99.9 중량%로 포함되는 것이 바람직하며, 80~99 중량%로 포함되는 것이 더욱 바람직하다. 상기 1종 이상의 용매가 70 중량% 미만으로 포함되는 경우, 조성물의 가격이 비싸지며, 웨이퍼 회로면의 금속 부위가 부식하는 문제가 발생될 수 있으며, 99.9 중량%를 초과하는 경우는 전자부품에 부착된 실리콘계 수지를 효과적으로 제거하지 못하는 문제가 발생될 수 있다.
The at least one solvent selected from the group consisting of the compounds represented by the formula (1) is preferably contained in an amount of 70 to 99.9% by weight, and more preferably 80 to 99% by weight based on the total weight of the composition. If the one or more solvents are contained in an amount of less than 70% by weight, the cost of the composition becomes high, the metal parts of the wafer circuit surface may be corroded, and when it exceeds 99.9% by weight, A problem that the silicon-based resin can not be effectively removed may occur.
본 발명의 실리콘계 수지 제거용 조성물에는 상기 성분들에 3차 아민 화합물이 더 포함될 수 있다. 상기 3차 아민 화합물로는 고리형 3차 아민이 가장 바람직하며, 고리형 3차아민으로서는, 1-메틸피롤리딘, 1-에틸피롤리딘, 1-메틸피페리딘, 디메틸피페라진, 1,4-디아자비싸이클로옥탄(DABCO), DBU, DBN 등이 사용될 수 있다. The silicone-based resin removing composition of the present invention may further contain a tertiary amine compound in the above components. The tertiary amine compound is most preferably a cyclic tertiary amine. Examples of the cyclic tertiary amine include 1-methylpyrrolidine, 1-ethylpyrrolidine, 1-methylpiperidine, dimethylpiperazine, 1 , 4-diazabicyclooctane (DABCO), DBU, DBN and the like can be used.
상기 3차 아민 화합물은 조성물 총 중량에 대하여, 0.1~10중량%로 포함되는 것이 바람직하며, 1~5중량% 중량%로 포함되는 것이 더욱 바람직하다. 3차 아민 화합물이 0.1 중량% 미만으로 포함되면 효과를 기대하기 어렵고, 10 중량%를 초과하면 세정액의 경시 성능저화 문제와 금속의 부식 문제가 발생할 수 있다.
The tertiary amine compound is preferably contained in an amount of 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the total weight of the composition. When the tertiary amine compound is contained in an amount of less than 0.1% by weight, the effect is not expected to be expected. If the tertiary amine compound is contained in an amount exceeding 10% by weight, deterioration of the detergent with time and deterioration of metal corrosion may occur.
본 발명의 전자부품에 부착된 실리콘계 수지 제거용 조성물은 상기 성분 외에 이 분야에서 통상적으로 사용되는 부식방지제, 계면활성제 등의 성분들을 더 포함할 수 있다.The silicone-based resin-removing composition attached to the electronic component of the present invention may further contain ingredients such as a corrosion inhibitor, a surfactant, etc. commonly used in this field in addition to the above components.
본 발명에서 상기 실리콘계 수지는, 수지내에 실록산결합을 포함하는 수지라면, 특별히 한정되지 않으며, 예컨대, 디메틸실록산의 공중합에 의해서 제조되는 접착용도로 사용되는 고분자를 의미하며, 구체적으로 상기 실록산 고분자는 일반적으로 분류되는 M, D, T, Q의 실리콘 단위를 포함하여 제조되는 수지이다. In the present invention, the silicone-based resin is not particularly limited as long as it is a resin containing a siloxane bond in the resin. For example, the silicone-based resin means a polymer used in an adhesive application produced by copolymerization of dimethylsiloxane. Specifically, , ≪ / RTI > M, D, T, Q,
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
실시예Example 1~6 및 1 to 6 and 비교예Comparative Example 1~2: 전자부품에 부착된 실리콘계 수지 제거용 조성물의 제조 및 성능 테스트 1 to 2: Preparation and performance test of composition for removing silicone resin adhered to electronic parts
(1) 전자부품에 부착된 실리콘계 수지 제거용 조성물의 제조 (1) Production of composition for removing silicone resin adhered to electronic parts
하기 표 1에 기재된 성분을 해당 조성비로 혼합하여 실시예 1~6 및 비교예 1~2의 실리콘계 수지 제거용 조성물을 제조하였다.
The components shown in the following Table 1 were mixed in the composition ratios to prepare the compositions for removing silicone resins in Examples 1 to 6 and Comparative Examples 1 and 2.
(2) 성능테스트(2) Performance test
경화된 실리콘계 수지가 80㎛의 두께로 코팅된 웨이퍼 시료를 2 X 2㎠의 크기로 잘라서 실시예 1~6 및 비교예 1~2의 실리콘계 수지 제거용 조성물에 1분간 침지시켰다. 상기 침지시 상기 조성물의 온도는 25℃로 조절하였으며, 교반기를 350rpm의 속도로 회전시켜 교반하였다. 상기 침지시킨 웨이퍼 시료를 꺼내어 IPA로 세정하고 건조시킨 후, SEM으로 경화 실리콘계 수지의 막두께를 측정하여 그 결과를 하기 표 1에 나타내었다.A wafer sample coated with a cured silicone resin to a thickness of 80 mu m was cut into a size of 2 X 2 cm 2 and immersed in the composition for removing silicone-based resin of Examples 1 to 6 and Comparative Examples 1 and 2 for 1 minute. During the immersion, the temperature of the composition was adjusted to 25 ° C, and the agitator was rotated at a speed of 350 rpm and stirred. The immersed wafer sample was taken out, washed with IPA and dried, and the thickness of the cured silicone resin was measured by SEM. The results are shown in Table 1 below.
용해속도
(㎛/min)Cured silicone
Dissolution rate
(탆 / min)
(함량: 중량%)(Content:% by weight)
주)week)
화학식 2: 테트라옥틸암모늄플로라이드(2): tetraoctylammonium fluoride
화학식 3: 
화학식 4: 테트라부틸암모늄플로라이드 Formula 4: tetrabutylammonium fluoride
화학식 5: 
화학식 6: 
화학식 7: 
화학식 8: 
화학식 9: 
(9)
상기 표 1의 시험결과로부터 본 발명의 실리콘계 수지 제거용 조성물은 비교예의 실리콘계 수지 제거용 조성물과 비교하여 매우 우수한 실리콘계 수지 제거력을 가짐을 알 수 있다. From the test results shown in Table 1, it can be seen that the silicone-based resin removing composition of the present invention has a very good silicon-based resin removing ability as compared with the silicone-based resin removing composition of the comparative example.
Claims (5)
(a) 화합물 내에 1개의 질소원자와 20개~100개의 탄소원자와 1개의 불소원자를 포함하는 QAF(Quarternary ammonium Fluoride) 0.1~30 중량%; 및
(b) 하기 화학식 1로 표시되는 화합물로 이루어진 군으로부터 선택되는 1종 이상의 용매 70~99.9 중량%를 포함하는 실리콘계 수지 제거용 조성물:
[화학식 1]
상기 식에서
R1, R2 및 R3는 각각 독립적으로, C1~C12의 직쇄 또는 분지쇄의 지방족 탄화수소; 할로겐, 비닐, 아세틸레닐 또는 C1~C5의 알콕시기로 치환된 C1~C4의 지방족 탄화수소; 또는 C1~C4의 알킬기에 의해서 치환 또는 비치환된 페닐기이다.With respect to the total weight of the composition,
(a) 0.1 to 30% by weight of a quaternary ammonium fluoride (QAF) containing one nitrogen atom, 20 to 100 carbon atoms and one fluorine atom in the compound; And
(b) 70 to 99.9% by weight of at least one solvent selected from the group consisting of compounds represented by the following formula (1):
[Chemical Formula 1]
In the above formula
R1, R2 and R3 are each independently a C1-C12 linear or branched aliphatic hydrocarbon; Halogen, vinyl, acetylenyl or C1-C4 aliphatic hydrocarbon substituted with C1-C5 alkoxy; Or a phenyl group substituted or unsubstituted by an alkyl group of C1-C4.
상기 QAF는 화합물 내에 1개의 질소원자와 20개~50개의 탄소원자와 1개의 불소원자를 포함하는 것임을 특징으로 하는 실리콘계 수지 제거용 조성물.The method according to claim 1,
Wherein the QAF comprises one nitrogen atom, 20 to 50 carbon atoms, and one fluorine atom in the compound.
3차 아민 화합물을 더 포함하는 것을 특징으로 하는 실리콘계 수지 제거용 조성물.The method according to claim 1,
A composition for removing a silicone resin, which further comprises a tertiary amine compound.
상기 3차 아민 화합물은 1-메틸피롤리딘, 1-에틸피롤리딘, 1-메틸피페리딘, 디메틸피페라진, 1,4-디아자비싸이클로옥탄(DABCO), DBU, 및 DBN으로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는 실리콘계 수지 제거용 조성물.The method of claim 3,
The tertiary amine compound may be selected from the group consisting of 1-methylpyrrolidine, 1-ethylpyrrolidine, 1-methylpiperidine, dimethylpiperazine, 1,4-diazabicyclooctane (DABCO), DBU, and DBN Wherein the silicone-based resin is at least one selected from the group consisting of a silicone-based resin and a silicone-based resin.
부식방지제 및 계면활성제로 이루어진 군으로부터 선택되는 1종 이상을 더 포함하는 것을 특징으로 하는 실리콘계 수지 제거용 조성물.The method according to claim 1,
Wherein the composition further comprises at least one member selected from the group consisting of an antioxidant, a corrosion inhibitor, and a surfactant.
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