JP7420664B2 - Cleaning composition for removing resin masks - Google Patents
Cleaning composition for removing resin masks Download PDFInfo
- Publication number
- JP7420664B2 JP7420664B2 JP2020110883A JP2020110883A JP7420664B2 JP 7420664 B2 JP7420664 B2 JP 7420664B2 JP 2020110883 A JP2020110883 A JP 2020110883A JP 2020110883 A JP2020110883 A JP 2020110883A JP 7420664 B2 JP7420664 B2 JP 7420664B2
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- Prior art keywords
- component
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- cleaning composition
- resin mask
- Prior art date
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- 238000004140 cleaning Methods 0.000 title claims description 186
- 239000000203 mixture Substances 0.000 title claims description 152
- 229920005989 resin Polymers 0.000 title claims description 132
- 239000011347 resin Substances 0.000 title claims description 132
- 238000000034 method Methods 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 229910001868 water Inorganic materials 0.000 claims description 30
- -1 glycol ethers Chemical class 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000002738 chelating agent Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 150000008365 aromatic ketones Chemical class 0.000 claims description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000003599 detergent Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 description 38
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 238000012360 testing method Methods 0.000 description 24
- 239000007788 liquid Substances 0.000 description 23
- 238000007747 plating Methods 0.000 description 22
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000012459 cleaning agent Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 125000001453 quaternary ammonium group Chemical group 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000000908 ammonium hydroxide Substances 0.000 description 10
- 238000011161 development Methods 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 238000005476 soldering Methods 0.000 description 9
- 150000003863 ammonium salts Chemical class 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 235000010724 Wisteria floribunda Nutrition 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 4
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 4
- CUZKCNWZBXLAJX-UHFFFAOYSA-N 2-phenylmethoxyethanol Chemical compound OCCOCC1=CC=CC=C1 CUZKCNWZBXLAJX-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 4
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229960005323 phenoxyethanol Drugs 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 150000005846 sugar alcohols Chemical class 0.000 description 4
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004111 Potassium silicate Substances 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000004193 piperazinyl group Chemical group 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 2
- 229910052913 potassium silicate Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- XKQMKMVTDKYWOX-UHFFFAOYSA-N 1-[2-hydroxypropyl(methyl)amino]propan-2-ol Chemical compound CC(O)CN(C)CC(C)O XKQMKMVTDKYWOX-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 description 1
- CYOIAXUAIXVWMU-UHFFFAOYSA-N 2-[2-aminoethyl(2-hydroxyethyl)amino]ethanol Chemical compound NCCN(CCO)CCO CYOIAXUAIXVWMU-UHFFFAOYSA-N 0.000 description 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 1
- ZFDNAYFXBJPPEB-UHFFFAOYSA-M 2-hydroxyethyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCO ZFDNAYFXBJPPEB-UHFFFAOYSA-M 0.000 description 1
- SHAMRMCOVNDTCS-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC(O)C[N+](C)(C)C SHAMRMCOVNDTCS-UHFFFAOYSA-M 0.000 description 1
- YSDSJBOULHYPCB-UHFFFAOYSA-M 2-hydroxypropyl(tripropyl)azanium hydroxide Chemical compound [OH-].OC(C[N+](CCC)(CCC)CCC)C YSDSJBOULHYPCB-UHFFFAOYSA-M 0.000 description 1
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical group OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 description 1
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- RKTGAWJWCNLSFX-UHFFFAOYSA-M bis(2-hydroxyethyl)-dimethylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(C)CCO RKTGAWJWCNLSFX-UHFFFAOYSA-M 0.000 description 1
- IUEJJWYUYRJJBJ-UHFFFAOYSA-M bis(2-hydroxyethyl)-dipropylazanium hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCO)CCO IUEJJWYUYRJJBJ-UHFFFAOYSA-M 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- MYRLVAHFNOAIAI-UHFFFAOYSA-M diethyl-bis(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].OCC[N+](CC)(CC)CCO MYRLVAHFNOAIAI-UHFFFAOYSA-M 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- XBRDBODLCHKXHI-UHFFFAOYSA-N epolamine Chemical compound OCCN1CCCC1 XBRDBODLCHKXHI-UHFFFAOYSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- KGVNNTSVYGJCRV-UHFFFAOYSA-M ethyl-tris(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].OCC[N+](CC)(CCO)CCO KGVNNTSVYGJCRV-UHFFFAOYSA-M 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YNOGYQAEJGADFJ-UHFFFAOYSA-N oxolan-2-ylmethanamine Chemical compound NCC1CCCO1 YNOGYQAEJGADFJ-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- VHLDQAOFSQCOFS-UHFFFAOYSA-M tetrakis(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].OCC[N+](CCO)(CCO)CCO VHLDQAOFSQCOFS-UHFFFAOYSA-M 0.000 description 1
- MSSZNJYLEVGNAK-UHFFFAOYSA-M tetrakis(2-hydroxypropyl)azanium;hydroxide Chemical compound [OH-].CC(O)C[N+](CC(C)O)(CC(C)O)CC(C)O MSSZNJYLEVGNAK-UHFFFAOYSA-M 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- GRNRCQKEBXQLAA-UHFFFAOYSA-M triethyl(2-hydroxyethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CCO GRNRCQKEBXQLAA-UHFFFAOYSA-M 0.000 description 1
- RBUVMOSJYGXQEK-UHFFFAOYSA-M triethyl(2-hydroxypropyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC(C)O RBUVMOSJYGXQEK-UHFFFAOYSA-M 0.000 description 1
- IJGSGCGKAAXRSC-UHFFFAOYSA-M tris(2-hydroxyethyl)-methylazanium;hydroxide Chemical compound [OH-].OCC[N+](C)(CCO)CCO IJGSGCGKAAXRSC-UHFFFAOYSA-M 0.000 description 1
- FQSMVJXSANYLPV-UHFFFAOYSA-M tris(2-hydroxyethyl)-propylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCO)(CCO)CCO FQSMVJXSANYLPV-UHFFFAOYSA-M 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
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- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/263—Ethers
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- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/264—Aldehydes; Ketones; Acetals or ketals
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- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
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- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5022—Organic solvents containing oxygen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- 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
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—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
- H01L21/18—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 comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Emergency Medicine (AREA)
- Health & Medical Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Detergent Compositions (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Description
本開示は、樹脂マスク剥離用洗浄剤組成物、これを用いる電子部品の製造方法及び洗浄方法に関する。 The present disclosure relates to a cleaning agent composition for removing a resin mask, and a method for manufacturing and cleaning electronic components using the same.
近年、パーソナルコンピュータや各種電子デバイスにおいては、低消費電力化、処理速度の高速化、小型化が進み、これらに搭載されるパッケージ基板などの配線は年々微細化が進んでいる。このような微細配線並びにピラーやバンプといった接続端子形成にはこれまでメタルマスク法が主に用いられてきたが、汎用性が低いことや配線等の微細化への対応が困難になってきたことから、他の新たな方法へと変わりつつある。 In recent years, personal computers and various electronic devices have become lower in power consumption, faster in processing speed, and smaller in size, and the wiring on package substrates and the like mounted on these devices is becoming smaller and smaller year by year. The metal mask method has been mainly used to form such fine wiring and connection terminals such as pillars and bumps, but it has become less versatile and difficult to respond to miniaturization of wiring etc. This is changing to other new methods.
新たな方法の一つとして、ドライフィルムレジストをメタルマスクに代えて厚膜樹脂マスクとして使用する方法が知られている。この樹脂マスクは最終的に剥離・除去されるが、剥離・除去等の洗浄に使用する洗浄剤として、アルカリ剤と水とを含む樹脂マスク剥離用洗浄剤が知られている。 As one of the new methods, a method is known in which a dry film resist is used as a thick film resin mask instead of a metal mask. This resin mask is eventually peeled off and removed, and as a cleaning agent used for cleaning such as peeling and removal, a resin mask peeling cleaning agent containing an alkaline agent and water is known.
例えば、特許文献１には、液晶ディスプレイ用のカラーフィルター基板上のカラーレジスト、ブラックマトリクス樹脂、ポリイミド系配向膜およびホトスペーサーなどの硬化後フォトレジストを短時間に剥離・洗浄できるアルカリ洗浄剤として、特定の４級アンモニウム塩と特定の多価カルボン酸塩からなる群から得ばれる１種以上、親水性有機溶剤及びアルカリ成分を含有する洗浄剤組成物が記載されている。そして、実施例には、エチレンジアミン四酢酸四ナトリウム２．５部、ジエチレングリコールジエチルエーテル５部、ジエチレングリコールモノメチルエーテル２０部、テトラメチルアンモニウムハイドロオキサイド１０部及び水が残部で合計１００部である洗浄剤が記載されている。
特許文献２には、はんだバンプの加熱処理後の樹脂マスク層の除去の促進とはんだ腐食の抑制とを両立でき、はんだ接続信頼性を向上させうる洗浄剤として、特定の第四級アンモニウム水酸化物、水溶性アミン、酸又はそのアンモニウム塩、水を含有する樹脂マスク層用洗浄剤組成物が記載されている。そして、実施例には、テトラメチルアンモニウムヒドロキシド１質量部、モノエタノールアミン５質量部、ギ酸アンモニウム１質量部、水８５質量部、ジエチレングリコールブチルエーテル４質量部及びジメチルスルホキシド４質量部である洗浄剤組成物が記載されている。
特許文献３には、環境に対する負荷が低く、低温で短時間の洗浄条件下においても、アッシング後に発生するレジスト残渣および金属配線由来の金属酸化生成物の剥離性に優れ、かつ、金属配線に対する防食性に優れる剥離剤組成物として、有機アミンの含有量が０．２～３０重量％、有機ホスホン酸の含有量が０．０５～１０重量％、水の含有量が６０～９９．７重量％であり、２０℃ における該組成物のｐＨが９～１３である剥離剤組成物が記載されている。そして、実施例には、１，２－プロパンジアミン７．３重量％、１－ヒドロキシエチリデン－１，１－ジホスホン酸２．０重量％及び水９０．７重量％である剥離剤組成物が記載されている。
特許文献４には、半導体デバイス用の処理液であって、ヒドロキシルアミン化合物と、塩基化合物と、還元剤及びキレート剤からなる群より選ばれる少なくとも１種とを含有し、ｐＨが１０以上である、処理液が記載されている。そして、実施例には、ヒドロキシルアミン１０．０％、テトラヒドロフルフリルアミン１０％、３－メトキシ－３－メチル－１－ブタノール４０％、ジエチレントリアミン五酢酸５．０％、５－ＭＢＴＡ５－メチル－１Ｈ－ベンゾトリアゾール１％及び水が残部（３４％）である処理液が記載されている。
For example, Patent Document 1 describes an alkaline cleaning agent that can quickly remove and clean hardened photoresists such as color resists, black matrix resins, polyimide alignment films, and photospacers on color filter substrates for liquid crystal displays. A cleaning composition containing one or more selected from the group consisting of a specific quaternary ammonium salt and a specific polycarboxylic acid salt, a hydrophilic organic solvent, and an alkaline component is described. Examples describe a cleaning agent containing 2.5 parts of tetrasodium ethylenediaminetetraacetate, 5 parts of diethylene glycol diethyl ether, 20 parts of diethylene glycol monomethyl ether, 10 parts of tetramethylammonium hydroxide, and the balance of water for a total of 100 parts. has been done.
Patent Document 2 describes a specific quaternary ammonium hydroxide as a cleaning agent that can promote the removal of the resin mask layer after heat treatment of solder bumps, suppress solder corrosion, and improve solder connection reliability. A cleaning composition for a resin mask layer containing a compound, a water-soluble amine, an acid or an ammonium salt thereof, and water is described. Examples include 1 part by mass of tetramethylammonium hydroxide, 5 parts by mass of monoethanolamine, 1 part by mass of ammonium formate, 85 parts by mass of water, 4 parts by mass of diethylene glycol butyl ether, and 4 parts by mass of dimethyl sulfoxide. things are listed.
Patent Document 3 describes a method that has a low environmental impact, has excellent peelability of resist residue generated after ashing and metal oxidation products derived from metal wiring even under low temperature and short-time cleaning conditions, and has corrosion protection for metal wiring. As a release agent composition with excellent properties, the content of organic amine is 0.2 to 30% by weight, the content of organic phosphonic acid is 0.05 to 10% by weight, and the content of water is 60 to 99.7% by weight. A stripping agent composition is described in which the pH of the composition at 20° C. is 9 to 13. Examples describe a release agent composition containing 7.3% by weight of 1,2-propanediamine, 2.0% by weight of 1-hydroxyethylidene-1,1-diphosphonic acid, and 90.7% by weight of water. has been done.
Patent Document 4 describes a processing liquid for semiconductor devices, which contains a hydroxylamine compound, a basic compound, and at least one selected from the group consisting of a reducing agent and a chelating agent, and has a pH of 10 or more. , processing liquids are described. Examples include hydroxylamine 10.0%, tetrahydrofurfurylamine 10%, 3-methoxy-3-methyl-1-butanol 40%, diethylenetriaminepentaacetic acid 5.0%, 5-MBTA5-methyl-1H- A treatment solution is described that has 1% benzotriazole and the remainder (34%) water.
プリント基板等に微細配線を形成する上で、樹脂マスクの残存はもちろんのこと、微細配線やバンプ形成に用いられるはんだやめっき液等に含まれる助剤等の残存を低減するため、洗浄剤組成物には高い洗浄性が要求される。
ここで、樹脂マスクとは、光や電子線等によって現像液に対する溶解性等の物性が変化するレジストを用いて形成されるものである。レジストは、光や電子線との反応方法から、ネガ型とポジ型に大きく分けられている。ネガ型レジストは、露光されると現像液に対する溶解性が低下する特性を有し、ネガ型レジストを含む層（以下、「ネガ型レジスト層」ともいう）は、露光及び現像処理後に露光部が樹脂マスクとして使用される。ポジ型レジストは、露光されると現像液に対する溶解性が増大する特性を有し、ポジ型レジストを含む層（以下、「ポジ型レジスト層」ともいう）は、露光及び現像処理後に露光部が除去され、未露光部が樹脂マスクとして使用される。このような特性を有する樹脂マスクを使用することで、金属配線、金属ピラーやハンダバンプといった回路基板の微細な接続部を形成することができる。
When forming fine wiring on printed circuit boards, etc., cleaning agent compositions are used to reduce not only residual resin masks but also residual auxiliaries contained in solder and plating solutions used for fine wiring and bump formation. Objects need to be highly washable.
Here, the resin mask is formed using a resist whose physical properties such as solubility in a developer change depending on light, electron beam, or the like. Resists are broadly divided into negative-type and positive-type resists based on the way they react with light and electron beams. A negative resist has the property that its solubility in a developer decreases when it is exposed to light, and a layer containing a negative resist (hereinafter also referred to as a "negative resist layer") has a property that the exposed area decreases after exposure and development processing. Used as a resin mask. A positive resist has the property that its solubility in a developing solution increases when exposed to light, and a layer containing a positive resist (hereinafter also referred to as a "positive resist layer") has a structure in which the exposed area remains after exposure and development processing. The unexposed area is used as a resin mask. By using a resin mask having such characteristics, fine connections on circuit boards such as metal wiring, metal pillars, and solder bumps can be formed.
しかしながら、配線が微細化するにつれて、微細な隙間にある樹脂マスクを除去することが困難になってきた。また、単に洗浄力を強化すると、基板表面を溶解したり、変質させる等、基板にダメージを与えることが懸念された。すなわち、洗浄剤組成物には、高い樹脂マスク除去性が要求される一方で、基板に対する影響が少ないことが要求される。 However, as wiring becomes finer, it has become difficult to remove the resin mask located in the fine gaps. Furthermore, there was a concern that simply increasing the cleaning power would cause damage to the substrate, such as dissolving or altering the surface of the substrate. That is, while the cleaning composition is required to have high resin mask removability, it is also required to have little influence on the substrate.
そこで、本開示は、基板に対する影響を低減でき、樹脂マスク除去性に優れる樹脂マスク剥離用洗浄剤組成物を提供する。 Therefore, the present disclosure provides a cleaning composition for removing a resin mask that can reduce the influence on the substrate and has excellent resin mask removability.
本開示は、一態様において、アルカリ剤（成分Ａ）、有機溶剤（成分Ｂ）、キレート剤（成分Ｃ）及び水（成分Ｄ）を含有し、成分Ｂが、グリコールエーテル及び芳香族ケトンから選ばれる少なくとも１種の溶剤であり、成分Ｃが、カルボキシ基及びホスホン酸基から選ばれる少なくとも１種の酸基を２以上有する化合物であり、使用時における成分Ｂの含有量が、１質量％以上１２質量％以下、使用時における成分Ｄの含有量が、６５質量％以上９５質量％以下である、樹脂マスク剥離用洗浄剤組成物に関する。 The present disclosure, in one aspect, comprises an alkaline agent (component A), an organic solvent (component B), a chelating agent (component C), and water (component D), wherein component B is selected from glycol ethers and aromatic ketones. Component C is a compound having two or more of at least one acid group selected from a carboxy group and a phosphonic acid group, and the content of Component B at the time of use is 1% by mass or more. The present invention relates to a detergent composition for removing a resin mask, in which the content of component D at the time of use is 12% by mass or less and 65% by mass or more and 95% by mass or less.
本開示は、一態様において、本開示の洗浄剤組成物を用いて、樹脂マスクが付着した被洗浄物から樹脂マスクを剥離する工程を含む、電子部品の製造方法に関する。 In one aspect, the present disclosure relates to a method for manufacturing an electronic component, which includes a step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning composition of the present disclosure.
本開示は、一態様において、本開示の洗浄剤組成物を用いて、樹脂マスクが付着した被洗浄物から樹脂マスクを剥離する工程を含む、洗浄方法に関する。 In one embodiment, the present disclosure relates to a cleaning method that includes a step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning composition of the present disclosure.
本開示によれば、一態様において、基板に対する影響を低減でき、樹脂マスク除去性に優れる洗浄方法を提供できる。 According to the present disclosure, in one aspect, it is possible to provide a cleaning method that can reduce the influence on the substrate and has excellent resin mask removability.
本開示は、一態様において、アルカリ剤（成分Ａ）、有機溶剤（成分Ｂ）、キレート剤（成分Ｃ）及び水（成分Ｄ）を含有し、成分Ｂが、グリコールエーテル及び芳香族ケトンから選ばれる少なくとも１種の溶剤であり、成分Ｃが、カルボキシ基及びホスホン酸基から選ばれる少なくとも１種の酸基を２以上有する化合物であり、使用時における成分Ｂの含有量が、１質量％以上１２質量％以下、使用時における成分Ｄの含有量が、６５質量％以上９５質量％以下である、樹脂マスク剥離用洗浄剤組成物（以下、「本開示の洗浄剤組成物」ともいう）に関する。 The present disclosure, in one aspect, comprises an alkaline agent (component A), an organic solvent (component B), a chelating agent (component C), and water (component D), wherein component B is selected from glycol ethers and aromatic ketones. Component C is a compound having two or more of at least one acid group selected from a carboxy group and a phosphonic acid group, and the content of Component B at the time of use is 1% by mass or more. Regarding a cleaning composition for removing a resin mask (hereinafter also referred to as "cleaning composition of the present disclosure"), the content of component D at the time of use is 12% by mass or less and 65% by mass or more and 95% by mass or less. .
本開示によれば、樹脂マスク除去性に優れる洗浄方法を提供できる。よって、本開示の洗浄剤組成物は、被洗浄物である基板に対する影響を低減しつつ、被洗浄物から樹脂マスクを効率よく除去できる。そして、本開示の洗浄方法を用いることによって、高い収率で高品質の電子部品が得られうる。更に、本開示の洗浄剤組成物を用いることによって、微細な配線パターンを有する電子部品を効率よく製造できる。 According to the present disclosure, a cleaning method with excellent resin mask removability can be provided. Therefore, the cleaning composition of the present disclosure can efficiently remove the resin mask from the object to be cleaned while reducing the influence on the substrate, which is the object to be cleaned. By using the cleaning method of the present disclosure, high-quality electronic components can be obtained with high yield. Furthermore, by using the cleaning composition of the present disclosure, electronic components having fine wiring patterns can be efficiently manufactured.
本開示の洗浄剤組成物における効果の作用メカニズムの詳細は不明な部分があるが、以下のように推定される。
銅めっきなどで形成された回路パターンの微細な隙間に樹脂マスクの微小残渣が発生することがある。
本開示では、アルカリ剤（成分Ａ）、グリコールエーテル及び芳香族ケトンから選ばれる少なくとも１種の有機溶剤（成分Ｂ）及び水（成分Ｄ）が樹脂マスクに浸透することにより、樹脂マスクに配合されているアルカリ可溶性樹脂の解離を促進し、更に電荷反発を起こすことによって樹脂マスクの剥離を促進すると考えられる。一方、アルカリ剤（成分Ａ）の存在下で特定のキレート剤（成分Ｃ）が、銅めっきなどで形成された回路パターン表面へと吸着することで、回路パターンの微細な隙間に残留する樹脂マスクが脱離しやすくなることが考えられる。これらの樹脂の剥離促進と隙間からの離脱のしやすさの向上により洗浄性が向上すると推定される。
さらに、本開示の洗浄剤組成物に含まれる成分Ｂ及び水（成分Ｄ）の含有量を所定範囲内とすることで、成分Ｂ及び／又は成分Ｃによる基板への影響を抑制しつつ、優れた洗浄性を発現すると考えられる。
但し、本開示はこのメカニズムに限定して解釈されなくてもよい。
Although the details of the mechanism of action of the cleaning composition of the present disclosure are unclear, it is presumed as follows.
Minute residue from the resin mask may occur in minute gaps in circuit patterns formed by copper plating or the like.
In the present disclosure, at least one organic solvent (component B) selected from an alkaline agent (component A), a glycol ether, and an aromatic ketone and water (component D) are blended into the resin mask by permeating the resin mask. It is thought that this promotes the dissociation of the alkali-soluble resin contained in the resin, and further promotes the peeling of the resin mask by causing charge repulsion. On the other hand, in the presence of an alkaline agent (component A), a specific chelating agent (component C) is adsorbed onto the surface of a circuit pattern formed by copper plating, etc., resulting in a resin mask remaining in minute gaps in the circuit pattern. It is thought that it becomes easier to desorb. It is presumed that the cleaning performance is improved by promoting the peeling of these resins and improving the ease with which they can be removed from the gaps.
Furthermore, by controlling the contents of component B and water (component D) contained in the cleaning composition of the present disclosure within a predetermined range, the influence of component B and/or component C on the substrate can be suppressed, while providing excellent It is thought that this material exhibits excellent detergency.
However, the present disclosure does not need to be interpreted as being limited to this mechanism.
本開示において剥離・除去される樹脂マスクとは、エッチング、めっき、加熱等の処理から物質表面を保護するためのマスク、すなわち、保護膜として機能するマスクである。樹脂マスクとしては、一又は複数の実施形態において、露光及び現像工程後のレジスト層、露光及び現像の少なくとも一方の処理が施された（以下、「露光及び／又は現像処理された」ともいう）レジスト層、あるいは、硬化したレジスト層が挙げられる。樹脂マスクを形成する樹脂材料としては、一又は複数の実施形態において、フィルム状の感光性樹脂、レジストフィルム、又はフォトレジストが挙げられる。レジストフィルムは汎用のものを使用できる。 In the present disclosure, the resin mask to be peeled off and removed is a mask for protecting a material surface from treatments such as etching, plating, and heating, that is, a mask that functions as a protective film. In one or more embodiments, the resin mask includes a resist layer after exposure and development, and is subjected to at least one of exposure and development (hereinafter also referred to as "exposed and/or developed"). Examples include a resist layer or a hardened resist layer. In one or more embodiments, examples of the resin material forming the resin mask include a film-like photosensitive resin, a resist film, and a photoresist. A general-purpose resist film can be used.
［成分Ａ：アルカリ剤］
本開示の洗浄剤組成物に含まれるアルカリ剤（以下、単に「成分Ａ」ともいう）としては、一又は複数の実施形態において、無機アルカリ及び有機アルカリから選ばれる少なくとも１種が挙げられ、排水処理負荷低減の観点から、無機アルカリが好ましい。成分Ａは、１種でもよいし、２種以上の組合せでもよい。
[Component A: Alkaline agent]
In one or more embodiments, the alkaline agent (hereinafter also simply referred to as "component A") contained in the cleaning composition of the present disclosure includes at least one selected from inorganic alkalis and organic alkalis, and From the viewpoint of reducing processing load, inorganic alkalis are preferred. Component A may be used alone or in combination of two or more.
無機アルカリとしては、一又は複数の実施形態において、アルカリ金属又はアルカリ土類金属の、水酸化物、炭酸塩又は珪酸塩等が挙げられ、具体的には、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化カルシウム、炭酸ナトリウム、炭酸カリウム、珪酸ナトリウム及び珪酸カリウムから選ばれる少なくとも１種が挙げられる。これらの中でも、樹脂マスク除去性向上の観点から、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム及び炭酸カリウムから選ばれる１種又は２種以上の組合せが好ましく、水酸化ナトリウム及び水酸化カリウムの少なくとも一方がより好ましく、水酸化カリウムが更に好ましい。本開示において、無機アルカリには、アンモニアは含まれない。 In one or more embodiments, the inorganic alkali includes hydroxides, carbonates, silicates, etc. of alkali metals or alkaline earth metals, and specifically, sodium hydroxide, potassium hydroxide, water, etc. At least one selected from lithium oxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, and potassium silicate can be used. Among these, from the viewpoint of improving the removability of the resin mask, one or a combination of two or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate is preferred, and at least one of sodium hydroxide and potassium hydroxide is preferred. is more preferred, and potassium hydroxide is even more preferred. In the present disclosure, the inorganic alkali does not include ammonia.
有機アルカリとしては、一又は複数の実施形態において、下記式（Ｉ）で表される第４級アンモニウム水酸化物、下記式（ＩＩ）で表されるアミン等が挙げられる。成分Ａとしては、一又は複数の実施形態において、樹脂マスク除去性向上の観点から、式（Ｉ）で表される第４級アンモニウム水酸化物と式（ＩＩ）で表されるアミンとの組合せを用いることが好ましい。 Examples of the organic alkali include, in one or more embodiments, a quaternary ammonium hydroxide represented by the following formula (I), an amine represented by the following formula (II), and the like. In one or more embodiments, component A is a combination of a quaternary ammonium hydroxide represented by formula (I) and an amine represented by formula (II) from the viewpoint of improving resin mask removability. It is preferable to use
上記式（Ｉ）において、Ｒ１、Ｒ２、Ｒ３及びＲ４は、それぞれ独立に、メチル基、エチル基、プロピル基、ヒドロキシメチル基、ヒドロキシエチル基及びヒドロキシプロピル基から選ばれる少なくとも１種である。 In the above formula (I), R 1 , R 2 , R 3 and R 4 are each independently at least one member selected from a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group. It is.
上記式（ＩＩ）において、Ｒ５は、水素原子、メチル基、エチル基又はアミノエチル基を示し、Ｒ６は、水素原子、ヒドロキシエチル基、ヒドロキシプロピル基、メチル基又はエチル基から選ばれる少なくとも１種であって、Ｒ７は、アミノエチル基、ヒドロキシエチル基又はヒドロキシプロピル基から選ばれる少なくとも１種か、あるいは、式（ＩＩ）において、Ｒ５は、メチル基、エチル基、アミノエチル基、ヒドロキシエチル基又はヒドロキシプロピル基から選ばれる少なくとも１種であって、Ｒ６とＲ７は互いに結合して式（ＩＩ）中のＮ原子と共にピロリジン環又はピペラジン環を形成する。 In the above formula (II), R 5 represents a hydrogen atom, a methyl group, an ethyl group, or an aminoethyl group, and R 6 represents at least one selected from a hydrogen atom, a hydroxyethyl group, a hydroxypropyl group, a methyl group, or an ethyl group. R 7 is at least one selected from aminoethyl group, hydroxyethyl group, and hydroxypropyl group, or in formula (II), R 5 is methyl group, ethyl group, and aminoethyl group. , a hydroxyethyl group, or a hydroxypropyl group, and R 6 and R 7 combine with each other to form a pyrrolidine ring or a piperazine ring with the N atom in formula (II).
式（Ｉ）で表される第４級アンモニウム水酸化物としては、例えば、第４級アンモニウムカチオンとヒドロキシドとからなる塩等が挙げられる。第４級アンモニウム水酸化物の具体例としては、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、２－ヒドロキシエチルトリメチルアンモニウムヒドロキシド（コリン）、２－ヒドロキシエチルトリエチルアンモニウムヒドロキシド、２－ヒドロキシエチルトリプロピルアンモニウムヒドロキシド、２－ヒドロキシプロピルトリメチルアンモニウムヒドロキシド、２－ヒドロキシプロピルトリエチルアンモニウムヒドロキシド、２－ヒドロキシプロピルトリプロピルアンモニウムヒドロキシド、ジメチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、ジエチルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、ジプロピルビス（２－ヒドロキシエチル）アンモニウムヒドロキシド、トリス（２－ヒドロキシエチル）メチルアンモニウムヒドロキシド、トリス（２－ヒドロキシエチル）エチルアンモニウムヒドロキシド、トリス（２－ヒドロキシエチル）プロピルアンモニウムヒドロキシド、テトラキス（２－ヒドロキシエチル）アンモニウムヒドロキシド、及びテトラキス（２－ヒドロキシプロピル）アンモニウムヒドロキシドから選ばれる少なくとも１種が挙げられる。これらの中でも、樹脂マスク除去性向上の観点から、テトラメチルアンモニウムヒドロキシド及びテトラエチルアンモニウムヒドロキシドが好ましく、テトラメチルアンモニウムヒドロキシドがより好ましい。 Examples of the quaternary ammonium hydroxide represented by formula (I) include salts consisting of a quaternary ammonium cation and a hydroxide. Specific examples of quaternary ammonium hydroxide include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide (choline), 2-hydroxyethyltriethyl Ammonium hydroxide, 2-hydroxyethyltripropylammonium hydroxide, 2-hydroxypropyltrimethylammonium hydroxide, 2-hydroxypropyltriethylammonium hydroxide, 2-hydroxypropyltripropylammonium hydroxide, dimethylbis(2-hydroxyethyl) Ammonium hydroxide, diethylbis(2-hydroxyethyl)ammonium hydroxide, dipropylbis(2-hydroxyethyl)ammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, tris(2-hydroxyethyl)ethylammonium hydroxide, At least one selected from tris(2-hydroxyethyl)propylammonium hydroxide, tetrakis(2-hydroxyethyl)ammonium hydroxide, and tetrakis(2-hydroxypropyl)ammonium hydroxide is mentioned. Among these, from the viewpoint of improving resin mask removability, tetramethylammonium hydroxide and tetraethylammonium hydroxide are preferred, and tetramethylammonium hydroxide is more preferred.
式（ＩＩ）で表されるアミンとしては、例えば、アルカノールアミン、１～３級アミン及び複素環化合物等が挙げられる。アミンの具体例としては、モノエタノールアミン、モノイソプロパノールアミン、Ｎ－メチルモノエタノールアミン、Ｎ－メチルイソプロパノールアミン、Ｎ－エチルモノエタノールアミン、Ｎ－エチルイソプロパノールアミン、ジエタノールアミン、ジイソプロパノールアミン、Ｎ－ジメチルモノエタノールアミン、Ｎ－ジメチルモノイソプロパノールアミン、Ｎ－メチルジエタノールアミン、Ｎ－メチルジイソプロパノールアミン、Ｎ－ジエチルモノエタノールアミン、Ｎ－ジエチルモノイソプロパノールアミン、Ｎ－エチルジエタノールアミン、Ｎ－エチルジイソプロパノールアミン、Ｎ－（β－アミノエチル）エタノールアミン、Ｎ－（β－アミノエチル）イソプロパノールアミン、Ｎ－（β－アミノエチル）ジエタノールアミン、Ｎ－（β－アミノエチル）ジイソプロパノールアミン、１－メチルピペラジン、１－（２－ヒドロキシエチル）ピロリジン、１－（２－ヒドロキシエチル）ピペラジン、エチレンジアミン及びジエチレントリアミンから選ばれる少なくとも１種が挙げられる。これらの中でも、樹脂マスク除去性向上の観点から、モノエタノールアミン及びジエタノールアミンが好ましく、モノエタノールアミンがより好ましい。 Examples of the amine represented by formula (II) include alkanolamines, primary to tertiary amines, and heterocyclic compounds. Specific examples of amines include monoethanolamine, monoisopropanolamine, N-methylmonoethanolamine, N-methylisopropanolamine, N-ethylmonoethanolamine, N-ethylisopropanolamine, diethanolamine, diisopropanolamine, N-dimethyl Monoethanolamine, N-dimethylmonoisopropanolamine, N-methyldiethanolamine, N-methyldiisopropanolamine, N-diethylmonoethanolamine, N-diethylmonoisopropanolamine, N-ethyldiethanolamine, N-ethyldiisopropanolamine, N -(β-aminoethyl)ethanolamine, N-(β-aminoethyl)isopropanolamine, N-(β-aminoethyl)diethanolamine, N-(β-aminoethyl)diisopropanolamine, 1-methylpiperazine, 1- At least one selected from (2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)piperazine, ethylenediamine, and diethylenetriamine is mentioned. Among these, from the viewpoint of improving resin mask removability, monoethanolamine and diethanolamine are preferred, and monoethanolamine is more preferred.
本開示の洗浄剤組成物の使用時における成分Ａの含有量は、樹脂マスク除去性向上の観点から、１質量％以上が好ましく、４質量％以上がより好ましく、６質量％以上が更に好ましく、そして、同様の観点から、２０質量％以下が好ましく、１６質量％以下がより好ましく、１２質量％以下が更に好ましい。より具体的には、本開示の洗浄剤組成物の使用時における成分Ａの含有量は、１質量％以上２０質量％以下が好ましく、４質量％以上１６質量％以下がより好ましく、６質量％以上１６質量％以下が更に好ましい。成分Ａが２種以上の組合せである場合、成分Ａの含有量はそれらの合計含有量をいう。 The content of component A when using the cleaning composition of the present disclosure is preferably 1% by mass or more, more preferably 4% by mass or more, even more preferably 6% by mass or more, from the viewpoint of improving the removability of the resin mask. From the same viewpoint, the content is preferably 20% by mass or less, more preferably 16% by mass or less, and even more preferably 12% by mass or less. More specifically, the content of component A when using the cleaning composition of the present disclosure is preferably 1% by mass or more and 20% by mass or less, more preferably 4% by mass or more and 16% by mass or less, and 6% by mass. The content is more preferably 16% by mass or less. When component A is a combination of two or more types, the content of component A refers to their total content.
本開示において「洗浄剤組成物の使用時における各成分の含有量」とは、洗浄時、すなわち、洗浄剤組成物の洗浄への使用を開始する時点での各成分の含有量をいう。 In the present disclosure, "the content of each component at the time of use of the cleaning composition" refers to the content of each component at the time of cleaning, that is, at the time when the cleaning composition starts to be used for cleaning.
［成分Ｂ：有機溶剤］
本開示の洗浄剤組成物に含まれる有機溶剤（以下、「成分Ｂ」ともいう）は、一又は複数の実施形態において、グリコールエーテル及び芳香族ケトンから選ばれる少なくとも１種の溶剤である。成分Ｂは、１種でもよいし、２種以上の組合せでもよい。
グリコールエーテルとしては、樹脂マスク除去性向上、及び基板に対する影響低減の観点から、炭素数１以上８以下のアルコールにエチレングリコールが１以上３モル以下付加した構造を有する化合物が挙げられる。グリコールエーテルの具体例としては、ジエチレングリコールモノブチルエーテル、エチレングリコールモノベンジルエーテル、ジエチレングリコールモノヘキシルエーテル、エチレングリコールモノフェニルエーテル、及びジエチレングリコールジエチルエーテルから選ばれる少なくとも１種が挙げられる。
芳香族ケトンとしては、樹脂マスク除去性向上、及び基板に対する影響低減の観点から、アセトフェノン等が挙げられる。
[Component B: Organic solvent]
In one or more embodiments, the organic solvent (hereinafter also referred to as "component B") contained in the cleaning composition of the present disclosure is at least one solvent selected from glycol ethers and aromatic ketones. Component B may be used alone or in combination of two or more.
Examples of the glycol ether include compounds having a structure in which 1 to 3 moles of ethylene glycol are added to an alcohol having 1 to 8 carbon atoms, from the viewpoint of improving the removability of the resin mask and reducing the influence on the substrate. Specific examples of glycol ether include at least one selected from diethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether, ethylene glycol monophenyl ether, and diethylene glycol diethyl ether.
Examples of the aromatic ketone include acetophenone and the like from the viewpoint of improving the removability of the resin mask and reducing the influence on the substrate.
本開示の洗浄剤組成物の使用時における成分Ｂの含有量は、樹脂マスク除去性向上の観点からは、１質量％以上であって、１．５質量％以上が好ましく、２質量％以上がより好ましく、そして、排水処理負荷低減、及び基板に対する影響低減の観点から、１２質量％以下であって、８質量％以下が好ましく、４質量％以下がより好ましい。より具体的には、使用時における成分Ｂの含有量は、１質量％以上１２質量％以下であって、１．５質量％以上８質量％以下が好ましく、２質量％以上４質量％以下がより好ましい。成分Ｂが２種以上の組合せである場合、成分Ｂの含有量はそれらの合計含有量をいう。 The content of component B when using the cleaning composition of the present disclosure is 1% by mass or more, preferably 1.5% by mass or more, and 2% by mass or more from the viewpoint of improving the removability of the resin mask. More preferably, the content is 12% by mass or less, preferably 8% by mass or less, and more preferably 4% by mass or less, from the viewpoint of reducing wastewater treatment load and reducing influence on the substrate. More specifically, the content of component B during use is 1% by mass or more and 12% by mass or less, preferably 1.5% by mass or more and 8% by mass or less, and 2% by mass or more and 4% by mass or less. More preferred. When component B is a combination of two or more types, the content of component B refers to their total content.
［成分Ｃ：キレート剤］
本開示の洗浄剤組成物に含まれるキレート剤（以下、「成分Ｃ」ともいう）は、カルボキシ基及びホスホン酸基から選ばれる少なくとも１種の酸基を２以上有する化合物である。また、成分Ｃは、樹脂マスク除去性向上の観点から、前記酸基を好ましくは４以下有する化合物であることが好ましい。成分Ｃとしては、一又は複数の実施形態において、アミノトリメチレンホスホン酸、２－ホスホノブタン－１，２，４－トリカルボン酸、エチドロン酸などが挙げられる。これらの中でも、環境負荷低減の観点から、窒素原子を含まない化合物である２－ホスホノブタン－１，２，４－トリカルボン酸、エチドロン酸等が好ましい。成分Ｃは、１種でもよいし、２種以上の組合せでもよい。
[Component C: Chelating agent]
The chelating agent (hereinafter also referred to as "component C") included in the cleaning composition of the present disclosure is a compound having two or more acid groups of at least one type selected from carboxy groups and phosphonic acid groups. In addition, from the viewpoint of improving the removability of the resin mask, component C is preferably a compound having preferably 4 or less of the acid groups. In one or more embodiments, component C includes aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, etidronic acid, and the like. Among these, 2-phosphonobutane-1,2,4-tricarboxylic acid, etidronic acid, and the like, which are nitrogen atom-free compounds, are preferred from the viewpoint of reducing environmental impact. Component C may be used alone or in combination of two or more.
成分Ｃの分子量は、樹脂マスク除去性向上の観点から、１０００以下が好ましく、５００以下がより好ましい。 The molecular weight of component C is preferably 1000 or less, more preferably 500 or less, from the viewpoint of improving the removability of the resin mask.
本開示の洗浄剤組成物の使用時における成分Ｃの含有量は、樹脂マスク除去性向上の観点から、０．５質量％以上が好ましく、１質量％以上がより好ましく、そして、同様の観点から、５質量％以下が好ましく、３質量％以下がより好ましい。より具体的には、使用時における成分Ｃの含有量は、０．５質量％以上５質量％以下が好ましく、１質量％以上３質量％以下がより好ましい。成分Ｃが２種以上の組合せである場合、成分Ｃの含有量はそれらの合計含有量をいう。 The content of component C when using the cleaning composition of the present disclosure is preferably 0.5% by mass or more, more preferably 1% by mass or more, from the viewpoint of improving resin mask removability, and from the same viewpoint , is preferably 5% by mass or less, more preferably 3% by mass or less. More specifically, the content of component C during use is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 3% by mass or less. When component C is a combination of two or more types, the content of component C refers to their total content.
本開示の洗浄剤組成物において、成分Ｂに対する成分Ｃの質量比（Ｃ／Ｂ）は、樹脂マスク除去性向上、基板に対する影響低減の観点から、０．１以上が好ましく、０．３以上がより好ましく、０．４以上が更に好ましく、そして、同様の観点から、１以下が好ましく、０．８以下がより好ましく、０．７以下が更に好ましい。より具体的には、質量比（Ｃ／Ｂ）は、０．１以上１以下が好ましく、０．３以上０．８以下がより好ましく、０．４以上０．７以下が更に好ましい。 In the cleaning composition of the present disclosure, the mass ratio (C/B) of component C to component B is preferably 0.1 or more, and 0.3 or more, from the viewpoint of improving the resin mask removability and reducing the influence on the substrate. More preferably, it is 0.4 or more, and from the same point of view, it is preferably 1 or less, more preferably 0.8 or less, and even more preferably 0.7 or less. More specifically, the mass ratio (C/B) is preferably 0.1 or more and 1 or less, more preferably 0.3 or more and 0.8 or less, and even more preferably 0.4 or more and 0.7 or less.
本開示の洗浄剤組成物において、成分Ｃに対する成分Ａの質量比（Ａ／Ｃ）は、樹脂マスク除去性向上、基板に対する影響低減の観点から、１以上が好ましく、１．５以上がより好ましく、２以上が更に好ましく、そして、同様の観点から、１０以下が好ましく、８以下がより好ましく、６以下が更に好ましい。より具体的には、質量比（Ａ／Ｃ）は、１以上１０以下が好ましく、１．５以上８以下がより好ましく、２以上６以下が更に好ましい。 In the cleaning composition of the present disclosure, the mass ratio (A/C) of component A to component C is preferably 1 or more, more preferably 1.5 or more, from the viewpoint of improving resin mask removability and reducing influence on the substrate. , 2 or more is more preferable, and from the same viewpoint, 10 or less is preferable, 8 or less is more preferable, and 6 or less is still more preferable. More specifically, the mass ratio (A/C) is preferably 1 or more and 10 or less, more preferably 1.5 or more and 8 or less, and even more preferably 2 or more and 6 or less.
［成分Ｄ：水］
本開示の洗浄剤組成物に含まれる水（以下、「成分Ｄ」ともいう）としては、一又は複数の実施形態において、イオン交換水、ＲＯ水、蒸留水、純水、超純水等が挙げられる。
[Component D: Water]
In one or more embodiments, the water contained in the cleaning composition of the present disclosure (hereinafter also referred to as "component D") includes ion exchange water, RO water, distilled water, pure water, ultrapure water, etc. Can be mentioned.
本開示の洗浄剤組成物中の成分Ｄの含有量は、成分Ａ、成分Ｂ、成分Ｃ及び後述する任意成分を除いた残余とすることができる。具体的には、本開示の洗浄剤組成物の使用時における成分Ｄの含有量は、樹脂マスク除去性向上、排水処理負荷低減、及び基板に対する影響低減の観点から、６５質量％以上であって、７５質量％以上が好ましく、８２質量％以上がより好ましく、そして、樹脂マスク除去性向上の観点から、９５質量％以下であって、９０質量％以下が好ましく、８７質量％以下がより好ましい。より具体的には、本開示の洗浄剤組成物の使用時における成分Ｄの含有量は、６５質量％以上９５質量％以下であって、７５質量％以上９０質量％以下が好ましく、８２質量％以上８７質量％以下がより好ましい。 The content of component D in the cleaning composition of the present disclosure can be the remainder after removing component A, component B, component C, and optional components described below. Specifically, the content of component D when using the cleaning composition of the present disclosure is 65% by mass or more from the viewpoint of improving resin mask removability, reducing wastewater treatment load, and reducing influence on the substrate. , is preferably 75% by mass or more, more preferably 82% by mass or more, and from the viewpoint of improving the removability of the resin mask, the content is 95% by mass or less, preferably 90% by mass or less, and more preferably 87% by mass or less. More specifically, the content of component D when using the cleaning composition of the present disclosure is 65% by mass or more and 95% by mass or less, preferably 75% by mass or more and 90% by mass or less, and 82% by mass. The content is more preferably 87% by mass or less.
本開示の洗浄剤組成物において、成分Ｂに対する成分Ｄの質量比（Ｄ／Ｂ）は、樹脂マスク除去性向上、排水処理負荷低減、及び基板に対する影響低減の観点から、５以上が好ましく、１３以上がより好ましく、２５以上が更に好ましく、そして、樹脂マスク除去性向上の観点から、４５以下が好ましく、４０以下がより好ましく、３５以下が更に好ましい。より具体的には、質量比（Ｄ／Ｂ）は、５以上４５以下が好ましく、１３以上４０以下がより好ましく、２５以上３５以下が更に好ましい。 In the cleaning composition of the present disclosure, the mass ratio (D/B) of component D to component B is preferably 5 or more, from the viewpoint of improving resin mask removability, reducing wastewater treatment load, and reducing influence on the substrate. The above is more preferable, 25 or more is still more preferable, and from the viewpoint of improving resin mask removability, 45 or less is preferable, 40 or less is more preferable, and 35 or less is still more preferable. More specifically, the mass ratio (D/B) is preferably 5 or more and 45 or less, more preferably 13 or more and 40 or less, and even more preferably 25 or more and 35 or less.
本開示の洗浄剤組成物において、成分Ｃに対する成分Ｄの質量比（Ｄ／Ｃ）は、樹脂マスク除去性向上、排水処理負荷低減、及び基板に対する影響低減の観点から、３０以上が好ましく、３５以上がより好ましく、４０以上が更に好ましく、そして、樹脂マスク除去性向上の観点から、９０以下が好ましく、６５以下がより好ましく、５５以下が更に好ましい。より具体的には、質量比（Ｄ／Ｃ）は、３０以上９０以下が好ましく、３５以上６５以下がより好ましく、４０以上５５以下が更に好ましい。 In the cleaning composition of the present disclosure, the mass ratio (D/C) of component D to component C is preferably 30 or more, from the viewpoint of improving resin mask removability, reducing wastewater treatment load, and reducing influence on the substrate. The above is more preferable, 40 or more is even more preferable, and from the viewpoint of improving resin mask removability, 90 or less is preferable, 65 or less is more preferable, and 55 or less is still more preferable. More specifically, the mass ratio (D/C) is preferably 30 or more and 90 or less, more preferably 35 or more and 65 or less, and even more preferably 40 or more and 55 or less.
［成分Ｅ：アンモニア又は有機酸のアンモニウム塩］
本開示の洗浄剤組成物は、一又は複数の実施形態において、樹脂マスク除去性の観点から、アンモニア及び有機酸のアンモニウム塩の少なくとも１種（以下、「成分Ｅ」ともいう）をさらに含むことが好ましい。有機酸のアンモニウム塩としては、樹脂マスク除去性の観点から、炭素数１～５のカルボン酸のアンモニウム塩が好ましく、ギ酸アンモニウムがより好ましい。成分Ｅは、１種でもよいし、２種以上の組合せでもよい。
本開示の洗浄剤組成物の使用時における成分Ｅの含有量は、樹脂マスク除去性向上の観点から、０．１質量％以上２質量％以下が好ましく、０．２質量％以上１．５質量％以下がより好ましく、０．３質量％以上１質量％以下がより好ましい。成分Ｅが２種以上の組合せである場合、成分Ｅの含有量はそれらの合計含有量をいう。
[Component E: Ammonia or ammonium salt of organic acid]
In one or more embodiments, the cleaning composition of the present disclosure further includes at least one of ammonia and an ammonium salt of an organic acid (hereinafter also referred to as "component E") from the viewpoint of resin mask removability. is preferred. As the ammonium salt of an organic acid, from the viewpoint of resin mask removability, an ammonium salt of a carboxylic acid having 1 to 5 carbon atoms is preferable, and ammonium formate is more preferable. Component E may be used alone or in combination of two or more.
The content of component E when using the cleaning composition of the present disclosure is preferably 0.1% by mass or more and 2% by mass or less, and 0.2% by mass or more and 1.5% by mass from the viewpoint of improving resin mask removability. % or less, more preferably 0.3% by mass or more and 1% by mass or less. When component E is a combination of two or more types, the content of component E refers to their total content.
［その他の成分］
本開示の洗浄剤組成物は、前記成分Ａ～Ｅ以外に、必要に応じてその他の成分を更に含有することができる。その他の成分としては、通常の洗浄剤に用いられうる成分を挙げることができ、例えば、成分Ｂ以外の有機溶剤、界面活性剤、成分Ｃ以外のキレート剤、増粘剤、分散剤、防錆剤、高分子化合物、可溶化剤、酸化防止剤、防腐剤、消泡剤、抗菌剤等が挙げられる。
本開示の洗浄剤組成物の使用時におけるその他の成分の含有量は、０質量％以上２質量％以下が好ましく、０質量％以上１．５質量％以下がより好ましく、０質量％以上１．３質量％以下が更に好ましく、０質量％以上１質量％以下がより更に好ましい。
[Other ingredients]
In addition to the components A to E, the cleaning composition of the present disclosure may further contain other components as necessary. Other components include components that can be used in ordinary cleaning agents, such as organic solvents other than component B, surfactants, chelating agents other than component C, thickeners, dispersants, and rust preventives. agents, polymer compounds, solubilizers, antioxidants, preservatives, antifoaming agents, antibacterial agents, and the like.
The content of other components when using the cleaning composition of the present disclosure is preferably 0% by mass or more and 2% by mass or less, more preferably 0% by mass or more and 1.5% by mass or less, and 0% by mass or more and 1.5% by mass or less. It is more preferably 3% by mass or less, and even more preferably from 0% by mass to 1% by mass.
本開示の洗浄剤組成物は、一又は複数の実施形態において、ヒドロキシルアミン及び／又はその塩を含有しないものとすることができる。 In one or more embodiments, the cleaning composition of the present disclosure may not contain hydroxylamine and/or a salt thereof.
本開示の洗浄剤組成物は、一又は複数の実施形態において、直鎖糖アルコールを実質的に含まないものとすることができる。例えば、本開示の洗浄剤組成物の使用時における直鎖糖アルコールの含有量は、一複数の実施形態において、０．１重量％未満である。 In one or more embodiments, the cleaning composition of the present disclosure can be substantially free of linear sugar alcohols. For example, the content of linear sugar alcohol in use in the cleaning composition of the present disclosure is less than 0.1% by weight in one or more embodiments.
本開示の洗浄剤組成物の使用時における成分Ａ、成分Ｂ、成分Ｃ及び任意成分由来の有機物の総含有量は、排水処理負荷低減、及び基板に対する影響低減の観点から、３０質量％以下が好ましく、２５質量％以下がより好ましく、２０質量％以下が更に好ましく、１６質量％以下がより更に好ましく、そして、樹脂マスク除去性向上の観点から、２質量％以上が好ましく、４質量％以上がより好ましく、８質量％以上が更に好ましく、１２質量％以上がより更に好ましい。より具体的には、本開示の洗浄剤組成物の使用時における成分Ａ、成分Ｂ、成分Ｃ及び任意成分由来の有機物の総含有量は、２質量％以上３０質量％以下が好ましく、４質量％以上２５質量％以下がより好ましく、８質量％以上２０質量％以下が更に好ましく、１２質量％以上１６質量％以下がより更に好ましい。 When using the cleaning composition of the present disclosure, the total content of organic matter derived from component A, component B, component C, and optional components should be 30% by mass or less from the viewpoint of reducing wastewater treatment load and reducing the impact on the substrate. It is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 16% by mass or less, and from the viewpoint of improving the removability of the resin mask, 2% by mass or more is preferred, and 4% by mass or more. It is more preferably 8% by mass or more, still more preferably 12% by mass or more. More specifically, the total content of organic matter derived from component A, component B, component C, and optional components when using the cleaning composition of the present disclosure is preferably 2% by mass or more and 30% by mass or less, and 4% by mass % or more and 25% by mass or less, still more preferably 8% by mass or more and 20% by mass or less, and even more preferably 12% by mass or more and 16% by mass or less.
本開示の洗浄剤組成物の使用時のｐＨは、樹脂マスク除去性向上、及び基板に対する影響低減の観点から、１０以上が好ましく、１１以上がより好ましく、１２以上が更に好ましく、１３以上がより更に好ましい。本開示において、「使用時のｐＨ」とは、２５℃におけるｐＨであり、ｐＨメータを用いて測定できる。具体的には、実施例に記載の方法で測定できる。 The pH during use of the cleaning composition of the present disclosure is preferably 10 or more, more preferably 11 or more, even more preferably 12 or more, and even more preferably 13 or more, from the viewpoint of improving resin mask removability and reducing the influence on the substrate. More preferred. In the present disclosure, "pH during use" is pH at 25° C., and can be measured using a pH meter. Specifically, it can be measured by the method described in Examples.
［洗浄剤組成物の製造方法］
本開示の洗浄剤組成物は、前記成分Ａ～Ｄ及び必要に応じて上述の任意成分を公知の方法で配合することにより製造できる。例えば、本開示の洗浄剤組成物は、少なくとも前記成分Ａ～Ｄを配合してなるものとすることができる。したがって、本開示は、少なくとも前記成分Ａ～Ｄを配合する工程を含む、洗浄剤組成物の製造方法に関する。本開示において「配合する」とは、成分Ａ～Ｄ及び必要に応じて上述した任意成分を同時に又は任意の順に混合することを含む。本開示の洗浄剤組成物の製造方法において、各成分の好ましい配合量は、上述した本開示の洗浄剤組成物の各成分の好ましい含有量と同じとすることができる。
[Method for manufacturing cleaning composition]
The cleaning composition of the present disclosure can be produced by blending the above-mentioned components A to D and, if necessary, the above-mentioned optional components by a known method. For example, the cleaning composition of the present disclosure can contain at least the components A to D described above. Therefore, the present disclosure relates to a method for producing a cleaning composition, which includes at least the step of blending the components A to D. In the present disclosure, "blending" includes mixing components A to D and, if necessary, the above-mentioned optional components simultaneously or in any order. In the method for manufacturing the cleaning composition of the present disclosure, the preferred blending amount of each component can be the same as the preferred content of each component of the cleaning composition of the present disclosure described above.
本開示の洗浄剤組成物は、分離や析出等を起こして保管安定性を損なわない範囲で水（成分Ｄ）の量を減らした濃縮物として調製してもよい。洗浄剤組成物の濃縮物は、輸送及び貯蔵の観点から、希釈倍率３倍以上の濃縮物とすることが好ましく、保管安定性の観点から、希釈倍率３０倍以下の濃縮物とすることが好ましい。洗浄剤組成物の濃縮物は、使用時に成分Ａ～Ｄ及び任意成分が上述した含有量（すなわち、洗浄時の含有量）になるよう水（成分Ｄ）で希釈して使用することができる。更に洗浄剤組成物の濃縮物は、使用時に各成分を別々に添加して使用することもできる。本開示において濃縮液の洗浄剤組成物の「使用時」又は「洗浄時」とは、洗浄剤組成物の濃縮物が希釈された状態をいう。 The cleaning composition of the present disclosure may be prepared as a concentrate in which the amount of water (component D) is reduced within a range that does not cause separation, precipitation, etc. and impair storage stability. From the viewpoint of transportation and storage, the concentrate of the cleaning composition is preferably a concentrate with a dilution rate of 3 times or more, and from the viewpoint of storage stability, it is preferably a concentrate with a dilution rate of 30 times or less. . The concentrate of the cleaning composition can be used by diluting it with water (component D) so that the components A to D and optional components have the above-mentioned contents (that is, the contents at the time of cleaning). Furthermore, the concentrate of the cleaning composition can also be used by adding each component separately at the time of use. In the present disclosure, "at the time of use" or "at the time of cleaning" of a concentrated cleaning composition refers to a state in which the concentrated cleaning composition is diluted.
［被洗浄物］
本開示の洗浄剤組成物は、一又は複数の実施形態において、樹脂マスクが付着した被洗浄物の洗浄に使用されうる。被洗浄物としては、一又は複数の実施形態において、表面に金属部位を有する被洗浄物が挙げられ、例えば、電子部品及びその製造中間物が挙げられる。電子部品としては、例えば、プリント基板、ウエハ、銅板及びアルミニウム板等の金属板から選ばれる少なくとも１つの部品が挙げられる。前記製造中間物は、電子部品の製造工程における中間製造物であって、樹脂マスク処理後の中間製造物を含む。
樹脂マスクが付着した被洗浄物の具体例としては、例えば、樹脂マスクを使用した半田付け及びめっき処理（銅めっき、アルミニウムめっき、ニッケルめっき等）の少なくとも一方の処理を行う工程を経ることにより、配線や接続端子等が基板表面に形成された電子部品等が挙げられる。本開示において、半田付けとは、基板上の樹脂マスク非存在部に半田を存在させ、加熱により半田バンプ形成することをいう。本開示において、めっき処理とは、基板上の樹脂マスク非存在部に銅めっき、アルミニウムめっき及びニッケルめっきから選ばれる少なくとも１種のめっき処理を行うことをいう。樹脂マスク非存在部とは、基板にラミネートされた樹脂マスクを現像処理することにより形成されたレジストパターンにおいて、現像処理により樹脂マスクが除去された部分のことである。したがって、本開示は、一態様において、本開示の洗浄剤組成物の、電子部品の製造における洗浄剤としての使用に関する。被洗浄物は、一又は複数の実施形態において、基板にラミネートされた樹脂マスクを現像処理することにより形成されたレジストパターンを有する基板に、半田付け及びめっき処理の少なくとも一方の処理を行う工程を経たものである。例えば、被洗浄物として、硬化したレジスト層が基板上に形成された樹脂マスク存在部である部位と、樹脂マスク非存在部に半田バンプ又はめっき層が形成された部位、とを有する基板が挙げられる。
[Object to be cleaned]
In one or more embodiments, the cleaning composition of the present disclosure can be used to clean an object to be cleaned to which a resin mask is attached. In one or more embodiments, the object to be cleaned includes an object having a metal portion on its surface, and includes, for example, an electronic component and a manufacturing intermediate thereof. Examples of the electronic component include at least one component selected from printed circuit boards, wafers, and metal plates such as copper plates and aluminum plates. The manufacturing intermediate is an intermediate product in the manufacturing process of electronic components, and includes an intermediate product after resin mask processing.
As a specific example of an object to be cleaned to which a resin mask is attached, for example, by undergoing a step of performing at least one of soldering and plating treatment (copper plating, aluminum plating, nickel plating, etc.) using a resin mask, Examples include electronic components in which wiring, connection terminals, etc. are formed on the surface of a substrate. In the present disclosure, soldering refers to making solder exist in a portion of a substrate where a resin mask does not exist, and forming solder bumps by heating. In the present disclosure, plating treatment refers to performing at least one type of plating treatment selected from copper plating, aluminum plating, and nickel plating on a portion of the substrate where the resin mask does not exist. The resin mask non-existing portion refers to a portion of a resist pattern formed by developing a resin mask laminated on a substrate, where the resin mask is removed by the development process. Accordingly, the present disclosure relates in one aspect to the use of the cleaning compositions of the present disclosure as cleaning agents in the manufacture of electronic components. In one or more embodiments, the object to be cleaned includes a step of performing at least one of soldering and plating on a substrate having a resist pattern formed by developing a resin mask laminated on the substrate. It's something that has gone through a lot of time. For example, the object to be cleaned may be a substrate that has a part where a hardened resist layer is formed on the substrate where a resin mask is present, and a part where a solder bump or a plating layer is formed in the part where the resin mask is not present. It will be done.
本開示の洗浄剤組成物は、一又は複数の実施形態において、洗浄効果の点から、樹脂マスク、あるいは、更にめっき処理及び／又は加熱処理された樹脂マスクが付着した被洗浄物の洗浄に好適に用いられうる。樹脂マスクとしては、例えば、ネガ型樹脂マスクでもよいし、ポジ型樹脂マスクでもよい。本開示においてネガ型樹脂マスクとは、ネガ型レジストを用いて形成されるものであり、例えば、露光及び／又は現像処理されたネガ型レジスト層が挙げられる。本開示においてポジ型樹脂マスクとは、ポジ型レジストを用いて形成されるものであり、例えば、露光及び／又は現像処理されたポジ型レジスト層が挙げられる。 In one or more embodiments, the cleaning composition of the present disclosure is suitable for cleaning a resin mask or an object to be cleaned to which a resin mask that has been further plated and/or heat-treated is attached in terms of cleaning effect. It can be used for The resin mask may be, for example, a negative resin mask or a positive resin mask. In the present disclosure, a negative resin mask is formed using a negative resist, and includes, for example, a negative resist layer that has been exposed and/or developed. In the present disclosure, a positive resin mask is formed using a positive resist, and includes, for example, a positive resist layer that has been exposed and/or developed.
本開示の洗浄剤組成物は、一又は複数の実施形態において、樹脂マスクを使用した半田付け及びめっき処理の少なくとも一方の処理を行う工程を経た被洗浄物から樹脂マスクを剥離するための剥離剤として使用できる。
すなわち、本開示は、一態様において、樹脂マスクを使用した半田付け及びめっき処理の少なくとも一方の処理を行う工程を経た被洗浄物からの樹脂マスクの剥離における、洗浄剤組成物の剥離剤としての使用であって、
前記洗浄剤組成物は、アルカリ剤（成分Ａ）、有機溶剤（成分Ｂ）、キレート剤（成分Ｃ）及び水（成分Ｄ）を含有し、
成分Ｂが、グリコールエーテル及び芳香族ケトンから選ばれる少なくとも１種の溶剤であり、
成分Ｃが、カルボキシ基及びホスホン酸基から選ばれる少なくとも１種の酸基を２以上有する化合物であり、
使用時における成分Ｂの含有量が、１質量％以上１２質量％以下、
使用時における成分Ｄの含有量が、６５質量％以上９５質量％以下である、使用に関する。
In one or more embodiments, the cleaning composition of the present disclosure provides a peeling agent for peeling a resin mask from an object to be cleaned that has undergone at least one of soldering and plating using a resin mask. Can be used as
That is, in one embodiment, the present disclosure provides a method for using a cleaning composition as a stripping agent in stripping a resin mask from an object to be cleaned that has undergone at least one of soldering and plating using a resin mask. use,
The cleaning composition contains an alkaline agent (component A), an organic solvent (component B), a chelating agent (component C), and water (component D),
Component B is at least one solvent selected from glycol ethers and aromatic ketones,
Component C is a compound having two or more at least one acid group selected from a carboxy group and a phosphonic acid group,
The content of component B during use is 1% by mass or more and 12% by mass or less,
The content of component D at the time of use is 65% by mass or more and 95% by mass or less.
［洗浄方法］
本開示は、一態様において、本開示の洗浄剤組成物を用いて、樹脂マスクが付着した被洗浄物から樹脂マスクを剥離する工程を含む、洗浄方法（以下、「本開示の洗浄方法」ともいう）に関する。本開示の洗浄方法において、被洗浄物から樹脂マスクを剥離する工程は、一又は複数の実施形態において、樹脂マスクが付着した被洗浄物を本開示の洗浄剤組成物に接触させることを含む。本開示の洗浄方法であれば、基板への影響を抑制しつつ、樹脂マスクを効率よく除去できる。
[Cleaning method]
In one aspect, the present disclosure provides a cleaning method (hereinafter also referred to as the "cleaning method of the present disclosure") that includes a step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning composition of the present disclosure. concerning). In the cleaning method of the present disclosure, the step of peeling off the resin mask from the object to be cleaned includes, in one or more embodiments, bringing the object to be cleaned to which the resin mask is attached into contact with the cleaning agent composition of the present disclosure. With the cleaning method of the present disclosure, the resin mask can be efficiently removed while suppressing the influence on the substrate.
本開示の洗浄剤組成物を用いて被洗浄物から樹脂マスクを剥離する方法、又は、被洗浄物に本開示の洗浄剤組成物を接触させる方法としては、例えば、洗浄剤組成物を入れた洗浄浴槽内へ浸漬することで接触させる方法、洗浄剤組成物をスプレー状に射出して接触させる方法（シャワー方式）、浸漬中に超音波照射する超音波洗浄方法等が挙げられる。本開示の洗浄剤組成物は、希釈することなくそのまま洗浄に使用できる。被洗浄物としては、上述した被洗浄物を挙げることができる。 A method of peeling off a resin mask from an object to be cleaned using the cleaning composition of the present disclosure or a method of contacting the cleaning composition of the present disclosure with an object to be cleaned includes, for example, Examples include a method of contacting the product by immersing it in a cleaning bath, a method of contacting the product by spraying a cleaning composition (shower method), and an ultrasonic cleaning method of irradiating it with ultrasonic waves during immersion. The cleaning composition of the present disclosure can be used for cleaning as is without being diluted. Examples of the object to be cleaned include the objects to be cleaned described above.
本開示の洗浄方法は、一又は複数の実施形態において、洗浄剤組成物に被洗浄物を接触させた後、水でリンスし、乾燥する工程を含むことができる。本開示の洗浄方法は、一又は複数の実施形態において、洗浄剤組成物に被洗浄物を接触させた後、水ですすぐ工程を含むことができる。 In one or more embodiments, the cleaning method of the present disclosure can include the steps of bringing the object to be cleaned into contact with the cleaning agent composition, rinsing with water, and drying. In one or more embodiments, the cleaning method of the present disclosure can include a step of bringing the object to be cleaned into contact with the cleaning agent composition and then rinsing with water.
本開示の洗浄方法は、本開示の洗浄剤組成物の洗浄力が発揮されやすい点から、本開示の洗浄剤組成物と被洗浄物との接触時に超音波を照射することが好ましく、その超音波は比較的高周波数であることがより好ましい。前記超音波の照射条件は、同様の観点から、例えば、２６～７２ｋＨｚ、８０～１５００Ｗが好ましく、３６～７２ｋＨｚ、８０～１５００Ｗがより好ましい。 In the cleaning method of the present disclosure, it is preferable to irradiate ultrasonic waves when the cleaning composition of the present disclosure contacts the object to be cleaned, since the cleaning power of the cleaning composition of the present disclosure is likely to be exhibited. More preferably, the sound waves have a relatively high frequency. From the same viewpoint, the ultrasonic irradiation conditions are preferably, for example, 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.
本開示の洗浄方法において、本開示の洗浄剤組成物の洗浄力が発揮されやすい点から、洗浄剤組成物の温度は４０℃以上が好ましく、５０℃以上がより好ましく、そして、基板に対する影響低減の観点から、７０℃以下が好ましく、６０℃以下がより好ましい。 In the cleaning method of the present disclosure, the temperature of the cleaning composition is preferably 40°C or higher, more preferably 50°C or higher, from the viewpoint that the cleaning power of the cleaning composition of the present disclosure is easily exhibited, and the influence on the substrate is reduced. From this viewpoint, the temperature is preferably 70°C or lower, more preferably 60°C or lower.
［電子部品の製造方法］
本開示は、一態様において、本開示の洗浄方法を用いて、樹脂マスクが付着した被洗浄物から樹脂マスクを剥離する工程を含む、電子部品の製造方法（以下、「本開示の電子部品の製造方法」ともいう）に関する。被洗浄物としては、上述した被洗浄物を挙げることができる。本開示の電子部品の製造方法は、本開示の洗浄方法を用いて洗浄を行うことにより、電子部品に付着した樹脂マスクを効果的に除去できるため、信頼性の高い電子部品の製造が可能になる。更に、本開示の洗浄方法を行うことにより、電子部品に付着した樹脂マスクの除去が容易になることから、洗浄時間が短縮化でき、電子部品の製造効率を向上できる。
[Manufacturing method of electronic components]
In one aspect, the present disclosure provides a method for manufacturing an electronic component (hereinafter referred to as "the electronic component manufacturing method of the present disclosure"), which includes a step of peeling a resin mask from an object to be cleaned to which the resin mask is attached, using the cleaning method of the present disclosure. (also referred to as "manufacturing method"). Examples of the object to be cleaned include the objects to be cleaned described above. The electronic component manufacturing method of the present disclosure can effectively remove the resin mask attached to the electronic components by cleaning using the cleaning method of the present disclosure, making it possible to manufacture highly reliable electronic components. Become. Furthermore, by performing the cleaning method of the present disclosure, the resin mask attached to the electronic component can be easily removed, so the cleaning time can be shortened and the manufacturing efficiency of the electronic component can be improved.
［キット］
本開示は、一態様において、本開示の洗浄方法及び本開示の電子部品の製造方法のいずれかに使用するためのキット（以下、「本開示のキット」ともいう）に関する。本開示のキットは、一又は複数の実施形態において、本開示の洗浄剤組成物を製造するためのキットである。本開示のキットによれば、基板への影響を低減でき、樹脂マスク除去性に優れる洗浄剤組成物が得られうる。
[kit]
In one aspect, the present disclosure relates to a kit for use in either the cleaning method of the present disclosure or the electronic component manufacturing method of the present disclosure (hereinafter also referred to as "the kit of the present disclosure"). In one or more embodiments, the kit of the present disclosure is a kit for producing the cleaning composition of the present disclosure. According to the kit of the present disclosure, a cleaning composition that can reduce the influence on the substrate and has excellent resin mask removability can be obtained.
本開示のキットの一実施形態としては、成分Ａを含有する溶液（第１液）と、成分Ｂを含有する溶液（第２液）と、成分Ｃを含有する溶液（第３液）とを、相互に混合されない状態で含み、第１液、第２液及び第３液から選ばれる少なくとも１つは、成分Ｄの一部又は全部を更に含有し、第１液と第２液と第３液は使用時に混合されるキット（３液型洗浄剤組成物）が挙げられる。第１液と第２液と第３液が混合された後、必要に応じて成分Ｃ（水）で希釈されてもよい。第１液、第２液及び第３液の各々には、必要に応じて上述した任意成分が含まれていてもよい。
本開示のキットのその他の実施形態としては、成分Ａ及び成分Ｃを含有する溶液（第１液）と、成分Ｂを含有する溶液（第２液）とを、相互に混合されない状態で含み、第１液及び第２液の少なくとも一方は、成分Ｄ（水）の一部又は全部を更に含有し、第１液と第２液とは使用時に混合される、キット（２液型洗浄剤組成物）が挙げられる。第１液と第２液とが混合された後、必要に応じて成分Ｄ（水）で希釈されてもよい。第１液及び第２液の各々には、必要に応じて上述した任意成分が含まれていてもよい。
An embodiment of the kit of the present disclosure includes a solution containing component A (first solution), a solution containing component B (second solution), and a solution containing component C (third solution). , in a mutually unmixed state, at least one selected from the first liquid, the second liquid and the third liquid further contains part or all of component D, and the first liquid, the second liquid and the third liquid The liquid may be a kit (three-component cleaning composition) that is mixed at the time of use. After the first liquid, second liquid, and third liquid are mixed, they may be diluted with component C (water) as necessary. Each of the first liquid, second liquid, and third liquid may contain the above-mentioned optional components as necessary.
Other embodiments of the kit of the present disclosure include a solution containing component A and component C (first solution) and a solution containing component B (second solution) in a state that they are not mixed with each other, At least one of the first liquid and the second liquid further contains part or all of component D (water), and the first liquid and the second liquid are mixed at the time of use. things). After the first liquid and the second liquid are mixed, they may be diluted with component D (water) as necessary. Each of the first liquid and the second liquid may contain the above-mentioned optional components as necessary.
本開示は、さらに以下の一又は複数の実施形態に関する。
＜１＞ アルカリ剤（成分Ａ）、有機溶剤（成分Ｂ）、キレート剤（成分Ｃ）及び水（成分Ｄ）を含有し、成分Ｂが、グリコールエーテル及び芳香族ケトンから選ばれる少なくとも１種の溶剤であり、成分Ｃが、カルボキシ基及びホスホン酸基から選ばれる少なくとも１種の酸基を２以上有する化合物であり、使用時における成分Ｂの含有量が、１質量％以上１２質量％以下、使用時における成分Ｄの含有量が、６５質量％以上９５質量％以下である、樹脂マスク剥離用洗浄剤組成物。
The present disclosure further relates to one or more embodiments below.
<1> Contains an alkaline agent (component A), an organic solvent (component B), a chelating agent (component C) and water (component D), where component B is at least one selected from glycol ether and aromatic ketone. is a solvent, component C is a compound having two or more at least one acid group selected from a carboxy group and a phosphonic acid group, and the content of component B at the time of use is 1% by mass or more and 12% by mass or less, A detergent composition for removing a resin mask, in which the content of component D during use is 65% by mass or more and 95% by mass or less.
＜２＞ 使用時における成分Ｃの含有量が、０．５質量％以上が好ましく、１質量％以上がより好ましく、そして、５質量％以下が好ましく、３質量％以下がより好ましく、より具体的には、使用時における成分Ｃの含有量が、０．５質量％以上５質量％以下が好ましく、１質量％以上３質量％以下がより好ましい、＜１＞に記載の洗浄剤組成物。
＜３＞ 成分Ｂに対する成分Ｃの質量比（Ｃ／Ｂ）が、０．１以上が好ましく、０．３以上がより好ましく、０．４以上が更に好ましく、そして、１以下が好ましく、０．８以下がより好ましく、０．７以下が更に好ましく、より具体的には、質量比（Ｃ／Ｂ）は、０．１以上１以下が好ましく、０．３以上０．８以下がより好ましく、０．４以上０．７以下が更に好ましい、＜１＞又は＜２＞に記載の洗浄剤組成物。
＜４＞ 成分Ｂに対する成分Ｄの質量比（Ｄ／Ｂ）が、５以上が好ましく、１３以上がより好ましく、２５以上が更に好ましく、そして、４５以下が好ましく、４０以下がより好ましく、３５以下が更に好ましく、より具体的には、質量比（Ｄ／Ｂ）は、５以上４５以下が好ましく、１３以上４０以下がより好ましく、２５以上３５以下が更に好ましい、＜１＞から＜３＞のいずれかに記載の洗浄剤組成物。
＜５＞ ２５℃におけるｐＨが、１０以上が好ましく、１１以上がより好ましく、１２以上が更に好ましく、１３以上がより更に好ましい、＜１＞から＜４＞のいずれかに記載の洗浄剤組成物。
＜６＞ 成分Ｂが、炭素数１以上８以下のアルコールにエチレングリコールが１以上３モル以下付加した構造を有する化合物であることが好ましく、ジエチレングリコールモノブチルエーテル、エチレングリコールモノベンジルエーテル、ジエチレングリコールモノヘキシルエーテル、エチレングリコールモノフェニルエーテル、及びジエチレングリコールジエチルエーテルから選ばれる少なくとも１種であることがより好ましい、＜１＞から＜５＞のいずれかに記載の洗浄剤組成物。
＜７＞ アンモニア及び有機酸のアンモニウム塩の少なくとも１種（成分Ｅ）をさらに含むことが好ましく、炭素数１～５のカルボン酸のアンモニウム塩がより好ましく、ギ酸アンモニウムが更に好ましい、＜１＞から＜６＞のいずれかに記載の洗浄剤組成物。
＜８＞ 成分Ａが、無機アルカリ及び有機アルカリから選ばれる少なくとも１種であり、無機アルカリが、アルカリ金属又はアルカリ土類金属の、水酸化物、炭酸塩又は珪酸塩が好ましく、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化カルシウム、炭酸ナトリウム、炭酸カリウム、珪酸ナトリウム及び珪酸カリウムから選ばれる少なくとも１種がより好ましく、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム及び炭酸カリウムから選ばれる１種又は２種以上の組合せが更に好ましく、水酸化ナトリウム及び水酸化カリウムの少なくとも一方が更に好ましく、水酸化カリウムが更に好ましい、＜１＞から＜７＞のいずれかに記載の洗浄剤組成物。
＜９＞ 成分Ａが、下記式（Ｉ）で表される第４級アンモニウム水酸化物である、＜１＞から＜７＞のいずれかに記載の洗浄剤組成物。
＜１０＞成分Ａが、無機アルカリ及び有機アルカリから選ばれる少なくとも１種であり、有機アルカリが下記式（Ｉ）で表される第４級アンモニウム水酸化物及び下記式（ＩＩ）で表されるアミンの少なくとも一方が好ましく、式（Ｉ）で表される第４級アンモニウム水酸化物と式（ＩＩ）で表されるアミンとの組合せを用いることがより好ましい、＜１＞から＜７＞のいずれかに記載の洗浄剤組成物。
＜１１＞ 式（Ｉ）で表される第４級アンモニウム水酸化物が、テトラメチルアンモニウムヒドロキシド及びテトラエチルアンモニウムヒドロキシドから選ばれる少なくとも１種が好ましく、テトラメチルアンモニウムヒドロキシドがより好ましい、＜９＞又は＜１０＞に記載の洗浄剤組成物。
＜１２＞ 式（ＩＩ）で表されるアミンが、モノエタノールアミン及びジエタノールアミンから選ばれる少なくとも１種が好ましく、モノエタノールアミンがより好ましい、＜１０＞に記載の洗浄剤組成物。
＜１３＞ 洗浄剤組成物の使用時における成分Ａの含有量が、１質量％以上が好ましく、４質量％以上がより好ましく、６質量％以上が更に好ましく、そして、同様の観点から、２０質量％以下が好ましく、１６質量％以下がより好ましく、１２質量％以下が更に好ましく、より具体的には、本開示の洗浄剤組成物の使用時における成分Ａの含有量は、１質量％以上２０質量％以下が好ましく、４質量％以上１６質量％以下がより好ましく、６質量％以上１６質量％以下が更に好ましい、＜１＞から＜１２＞のいずれかに記載の洗浄剤組成物。
＜１４＞ 成分Ｂが、アセトフェノンである、＜１＞から＜１３＞のいずれかに記載の洗浄剤組成物。
＜１５＞ 使用時における成分Ｂの含有量が、１．５質量％以上が好ましく、２質量％以上がより好ましく、そして、８質量％以下が好ましく、４質量％以下がより好ましく、より具体的には、使用時における成分Ｂの含有量は、１．５質量％以上８質量％以下が好ましく、２質量％以上４質量％以下がより好ましい、＜１＞から＜１４＞のいずれかに記載の洗浄剤組成物。
＜１６＞ 成分Ｃが、カルボキシ基及びホスホン酸基から選ばれる少なくとも１種の酸基を４以下有する化合物であることが好ましく、アミノトリメチレンホスホン酸、２－ホスホノブタン－１，２，４－トリカルボン酸、エチドロン酸がより好ましく、２－ホスホノブタン－１，２，４－トリカルボン酸、エチドロン酸が更に好ましい、＜１＞から＜１５＞のいずれかに記載の洗浄剤組成物。
＜１７＞ 成分Ｃの分子量が、１０００以下が好ましく、５００以下がより好ましい、＜１＞から＜１６＞のいずれかに記載の洗浄剤組成物。
＜１８＞ 成分Ｃに対する成分Ａの質量比（Ａ／Ｃ）が、１以上が好ましく、１．５以上がより好ましく、２以上が更に好ましく、そして、１０以下が好ましく、８以下がより好ましく、６以下が更に好ましく、質量比（Ａ／Ｃ）は、１以上１０以下が好ましく、１．５以上８以下がより好ましく、２以上６以下が更に好ましい、＜１＞から＜１７＞のいずれかに記載の洗浄剤組成物。
＜１９＞ 使用時における成分Ｄの含有量が、７５質量％以上が好ましく、８２質量％以上がより好ましく、そして、９５質量％以下であって、９０質量％以下が好ましく、８７質量％以下がより好ましく、より具体的には、使用時における成分Ｄの含有量が、７５質量％以上９０質量％以下が好ましく、８２質量％以上８７質量％以下がより好ましい、＜１＞から＜１８＞のいずれかに記載の洗浄剤組成物。
＜２０＞ 成分Ｃに対する成分Ｄの質量比（Ｄ／Ｃ）が、３０以上が好ましく、３５以上がより好ましく、４０以上が更に好ましく、そして、９０以下が好ましく、６５以下がより好ましく、５５以下が更に好ましく、より具体的には、質量比（Ｄ／Ｃ）は、３０以上９０以下が好ましく、３５以上６５以下がより好ましく、４０以上５５以下が更に好ましい、＜１＞から＜１９＞のいずれかに記載の洗浄剤組成物。
＜２１＞ 使用時における成分Ｅの含有量が、０．１質量％以上２質量％以下が好ましく、０．２質量％以上１．５質量％以下がより好ましく、０．３質量％以上１質量％以下がより好ましい、＜１＞から＜２０＞のいずれかに記載の洗浄剤組成物。
＜２２＞ 使用時における直鎖糖アルコールの含有量は、一複数の実施形態において、０．１重量％未満であることが好ましく、直鎖糖アルコールを実質的に含まないことがより好ましい、＜１＞から＜２１＞のいずれかに記載の洗浄剤組成物。
＜２３＞ 使用時における成分Ａ、成分Ｂ、成分Ｃ及び任意成分由来の有機物の総含有量が、３０質量％以下が好ましく、２５質量％以下がより好ましく、２０質量％以下が更に好ましく、１６質量％以下がより更に好ましく、そして、２質量％以上が好ましく、４質量％以上がより好ましく、８質量％以上が更に好ましく、１２質量％以上がより更に好ましく、より具体的には、使用時における成分Ａ、成分Ｂ、成分Ｃ及び任意成分由来の有機物の総含有量が、２質量％以上３０質量％以下が好ましく、４質量％以上２５質量％以下がより好ましく、８質量％以上２０質量％以下が更に好ましく、１２質量％以上１６質量％以下がより更に好ましい、＜１＞から＜２２＞のいずれかに記載の洗浄剤組成物。
＜２４＞ 前記洗浄剤組成物が、アンモニア及び有機酸のアンモニウム塩の少なくとも１種（成分Ｅ）をさらに含み、前記洗浄剤組成物の成分Ａ～Ｅ以外のその他の成分の含有量が、０質量％以上２質量％以下が好ましく、０質量％以上１．５質量％以下がより好ましく、０質量％以上１．３質量％以下が更に好ましく、０質量％以上１質量％以下がより更に好ましい、＜１＞から＜２３＞のいずれかに記載の洗浄剤組成物。
＜２５＞ ＜１＞から＜２４＞のいずれかに記載の洗浄剤組成物を用いて、樹脂マスクが付着した被洗浄物から樹脂マスクを剥離する工程を含む、電子部品の製造方法。
＜２６＞ 電子部品は、プリント基板、ウエハ、金属板から選ばれる少なくとも１つの部品である＜２５＞に記載の電子部品の製造方法。
＜２７＞ ＜１＞から＜２４＞のいずれかに記載の洗浄剤組成物を用いて、樹脂マスクが付着した被洗浄物から樹脂マスクを剥離する工程を含む、洗浄方法であって、
被洗浄物が、樹脂マスクを使用した半田付け及びめっき処理の少なくとも一方の処理を行う工程を経たものである、洗浄方法。
＜２８＞ 樹脂マスクが付着した被洗浄物が、好ましくは樹脂マスクを使用した半田付け及びめっき処理の少なくとも一方の処理を行う工程を経ることにより、配線及び接続端子の少なくとも一方が基板表面に形成された電子部品である、＜２６＞に記載の洗浄方法。
＜２９＞ 被洗浄物が、基板にラミネートされた樹脂マスクを現像処理することにより形成されたレジストパターンを有する基板に、半田付け及びめっき処理の少なくとも一方の処理を行う工程を経たものである、＜２７＞又は＜２８＞に記載の洗浄方法。
＜３０＞ 被洗浄物から樹脂マスクを剥離する工程が、好ましくは樹脂マスクが付着した被洗浄物を洗浄剤組成物に接触させることを含む、＜２７＞から＜２９＞のいずれかに記載の洗浄方法。
＜３１＞ 被洗浄物に本開示の洗浄剤組成物を接触させる方法が、洗浄剤組成物を入れた洗浄浴槽内へ浸漬することで接触させる方法、洗浄剤組成物をスプレー状に射出して接触させる方法及び浸漬中に超音波照射する超音波洗浄方法から選ばれる１以上であることが好ましい、＜３０＞に記載の洗浄方法。
＜３２＞ 洗浄剤組成物の温度が、４０℃以上が好ましく、５０℃以上がより好ましく、そして、７０℃以下が好ましく、６０℃以下がより好ましい、＜２７＞から＜３１＞のいずれかに記載の洗浄方法。
＜３３＞ ＜１＞から＜２４＞のいずれかに記載の洗浄剤組成物の、樹脂マスクが付着した被洗浄物の洗浄剤としての使用。
＜３４＞ 樹脂マスクを使用した半田付け及びめっき処理の少なくとも一方の処理を行う工程を経た被洗浄物からの樹脂マスクの剥離における、洗浄剤組成物の剥離剤としての使用であって、前記洗浄剤組成物が、＜１＞から＜２４＞のいずれかに記載の洗浄剤組成物である、使用。
<2> The content of component C during use is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, and more specifically The cleaning composition according to <1>, wherein the content of component C during use is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 3% by mass or less.
<3> The mass ratio (C/B) of component C to component B is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.4 or more, and preferably 1 or less, and 0. 8 or less is more preferable, 0.7 or less is still more preferable, and more specifically, the mass ratio (C/B) is preferably 0.1 or more and 1 or less, more preferably 0.3 or more and 0.8 or less, The cleaning composition according to <1> or <2>, which is more preferably 0.4 or more and 0.7 or less.
<4> The mass ratio (D/B) of component D to component B is preferably 5 or more, more preferably 13 or more, even more preferably 25 or more, and is preferably 45 or less, more preferably 40 or less, and 35 or less. is more preferable, and more specifically, the mass ratio (D/B) is preferably 5 or more and 45 or less, more preferably 13 or more and 40 or less, and even more preferably 25 or more and 35 or less, from <1> to <3>. The cleaning composition according to any one of the above.
<5> The cleaning composition according to any one of <1> to <4>, wherein the pH at 25° C. is preferably 10 or more, more preferably 11 or more, even more preferably 12 or more, even more preferably 13 or more. .
<6> Component B is preferably a compound having a structure in which 1 to 3 moles of ethylene glycol is added to an alcohol having 1 to 8 carbon atoms, such as diethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, diethylene glycol monohexyl ether The cleaning composition according to any one of <1> to <5>, which is more preferably at least one selected from , ethylene glycol monophenyl ether, and diethylene glycol diethyl ether.
<7> From <1>, which preferably further contains at least one of ammonia and an ammonium salt of an organic acid (component E), more preferably an ammonium salt of a carboxylic acid having 1 to 5 carbon atoms, and even more preferably ammonium formate. The cleaning composition according to any one of <6>.
<8> Component A is at least one selected from inorganic alkalis and organic alkalis, and the inorganic alkali is preferably an alkali metal or alkaline earth metal hydroxide, carbonate, or silicate, sodium hydroxide, More preferably, at least one selected from potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, and potassium silicate, and one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. The cleaning composition according to any one of <1> to <7>, wherein a species or a combination of two or more species is more preferred, at least one of sodium hydroxide and potassium hydroxide is more preferred, and potassium hydroxide is even more preferred.
<9> The cleaning composition according to any one of <1> to <7>, wherein component A is a quaternary ammonium hydroxide represented by the following formula (I).
<10> Component A is at least one selected from an inorganic alkali and an organic alkali, and the organic alkali is a quaternary ammonium hydroxide represented by the following formula (I) and a quaternary ammonium hydroxide represented by the following formula (II). At least one of the amines is preferred, and it is more preferred to use a combination of the quaternary ammonium hydroxide represented by formula (I) and the amine represented by formula (II), <1> to <7>. The cleaning composition according to any one of the above.
<11> The quaternary ammonium hydroxide represented by formula (I) is preferably at least one selected from tetramethylammonium hydroxide and tetraethylammonium hydroxide, and more preferably tetramethylammonium hydroxide, <9 > or the cleaning composition according to <10>.
<12> The cleaning composition according to <10>, wherein the amine represented by formula (II) is preferably at least one selected from monoethanolamine and diethanolamine, and more preferably monoethanolamine.
<13> The content of component A during use of the cleaning composition is preferably 1% by mass or more, more preferably 4% by mass or more, even more preferably 6% by mass or more, and from the same viewpoint, 20% by mass or more. % or less, more preferably 16% by mass or less, even more preferably 12% by mass or less, and more specifically, the content of component A when using the cleaning composition of the present disclosure is 1% by mass or more and 20% by mass or less. The cleaning composition according to any one of <1> to <12>, wherein the cleaning composition is preferably at most 4% by mass and at most 16% by mass, and even more preferably at least 6% by mass and at most 16% by mass.
<14> The cleaning composition according to any one of <1> to <13>, wherein component B is acetophenone.
<15> The content of component B during use is preferably 1.5% by mass or more, more preferably 2% by mass or more, and preferably 8% by mass or less, more preferably 4% by mass or less, and more specifically According to any one of <1> to <14>, the content of component B during use is preferably 1.5% by mass or more and 8% by mass or less, more preferably 2% by mass or more and 4% by mass or less. cleaning composition.
<16> Component C is preferably a compound having 4 or less at least one acid group selected from a carboxy group and a phosphonic acid group, such as aminotrimethylenephosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid group, etc. The cleaning composition according to any one of <1> to <15>, wherein etidronic acid is more preferred, and 2-phosphonobutane-1,2,4-tricarboxylic acid and etidronic acid are even more preferred.
<17> The cleaning composition according to any one of <1> to <16>, wherein the molecular weight of component C is preferably 1000 or less, more preferably 500 or less.
<18> The mass ratio (A/C) of component A to component C is preferably 1 or more, more preferably 1.5 or more, even more preferably 2 or more, and preferably 10 or less, more preferably 8 or less, Any one of <1> to <17>, more preferably 6 or less, the mass ratio (A/C) is preferably 1 or more and 10 or less, more preferably 1.5 or more and 8 or less, and even more preferably 2 or more and 6 or less. The cleaning composition described in .
<19> The content of component D during use is preferably 75% by mass or more, more preferably 82% by mass or more, and 95% by mass or less, preferably 90% by mass or less, and 87% by mass or less. More preferably, more specifically, the content of component D at the time of use is preferably 75% by mass or more and 90% by mass or less, more preferably 82% by mass or more and 87% by mass or less, <1> to <18>. The cleaning composition according to any one of the above.
<20> The mass ratio (D/C) of component D to component C is preferably 30 or more, more preferably 35 or more, even more preferably 40 or more, and preferably 90 or less, more preferably 65 or less, and 55 or less. is more preferable, and more specifically, the mass ratio (D/C) is preferably 30 or more and 90 or less, more preferably 35 or more and 65 or less, and even more preferably 40 or more and 55 or less, <1> to <19>. The cleaning composition according to any one of the above.
<21> The content of component E during use is preferably 0.1% by mass or more and 2% by mass or less, more preferably 0.2% by mass or more and 1.5% by mass or less, and 0.3% by mass or more and 1% by mass. % or less, the cleaning composition according to any one of <1> to <20>.
<22> In one or more embodiments, the content of the linear sugar alcohol during use is preferably less than 0.1% by weight, and more preferably substantially free of linear sugar alcohol. The cleaning composition according to any one of 1> to <21>.
<23> The total content of organic substances derived from component A, component B, component C, and optional components during use is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, 16 It is even more preferably at most 2% by mass, more preferably at least 4% by mass, even more preferably at least 8% by mass, even more preferably at least 12% by mass, and more specifically, at the time of use. The total content of organic matter derived from component A, component B, component C, and optional components is preferably 2% by mass or more and 30% by mass or less, more preferably 4% by mass or more and 25% by mass or less, and 8% by mass or more and 20% by mass. % or less, and even more preferably 12% by mass or more and 16% by mass or less, the cleaning composition according to any one of <1> to <22>.
<24> The cleaning composition further contains at least one of ammonia and an ammonium salt of an organic acid (component E), and the content of other components other than components A to E of the cleaning composition is 0. It is preferably 0 to 2 mass%, more preferably 0 to 1.5 mass%, even more preferably 0 to 1.3 mass%, even more preferably 0 to 1 mass%. , the cleaning composition according to any one of <1> to <23>.
<25> A method for manufacturing an electronic component, the method comprising using the cleaning composition according to any one of <1> to <24> to peel off a resin mask from an object to be cleaned to which the resin mask is attached.
<26> The method for manufacturing an electronic component according to <25>, wherein the electronic component is at least one component selected from a printed circuit board, a wafer, and a metal plate.
<27> A cleaning method comprising the step of using the cleaning composition according to any one of <1> to <24> to peel off a resin mask from an object to be cleaned to which the resin mask is attached,
A cleaning method in which an object to be cleaned has undergone at least one of soldering and plating using a resin mask.
<28> The object to be cleaned to which the resin mask is attached is preferably subjected to at least one of soldering and plating using a resin mask, so that at least one of wiring and connection terminals is formed on the surface of the substrate. The method for cleaning an electronic component according to <26>.
<29> The object to be cleaned has undergone a process of performing at least one of soldering and plating on a substrate having a resist pattern formed by developing a resin mask laminated on the substrate, The cleaning method according to <27> or <28>.
<30> The process according to any one of <27> to <29>, wherein the step of peeling the resin mask from the object to be cleaned preferably includes contacting the object to be cleaned to which the resin mask is attached with the cleaning composition. Cleaning method.
<31> The method of bringing the cleaning composition of the present disclosure into contact with the object to be cleaned includes a method of contacting the object by immersing the object in a cleaning bath containing the cleaning agent composition, and a method of bringing the cleaning agent composition into contact with the object by injecting the cleaning agent composition in the form of a spray. The cleaning method according to <30>, which is preferably one or more methods selected from a contacting method and an ultrasonic cleaning method of applying ultrasound during immersion.
<32> Any one of <27> to <31>, wherein the temperature of the cleaning composition is preferably 40°C or higher, more preferably 50°C or higher, and preferably 70°C or lower, more preferably 60°C or lower. Cleaning method as described.
<33> Use of the cleaning composition according to any one of <1> to <24> as a cleaning agent for an object to be cleaned to which a resin mask is attached.
<34> Use of a cleaning composition as a stripping agent in peeling off a resin mask from an object to be cleaned that has undergone at least one of soldering and plating using a resin mask, the cleaning composition comprising: Use in which the detergent composition is the detergent composition according to any one of <1> to <24>.
以下に、実施例により本開示を具体的に説明するが、本開示はこれらの実施例によって何ら限定されるものではない。 EXAMPLES The present disclosure will be specifically explained below with reference to Examples, but the present disclosure is not limited to these Examples in any way.
１．実施例１～１１、比較例１～５、参考例１～２の洗浄剤組成物の調製
有効分換算で成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ、その他成分を表１に記載の組成比で配合し、それを攪拌して混合することにより、実施例１～１１、比較例１～５及び参考例１～２の洗浄剤組成物を調製した。表１の組成は固形分量である。表１に示す各洗浄剤組成物の２５℃におけるｐＨは、ｐＨメータ（東亜電波工業株式会社、ＨＭ－３０Ｇ）を用いて測定した値であり、ｐＨメータの電極を洗浄剤組成物に浸漬して３分後の数値である。
1. Preparation of cleaning compositions of Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 to 2 Component A, component B, component C, component D, and other components in the composition ratios listed in Table 1 in terms of active ingredients The cleaning compositions of Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 to 2 were prepared by stirring and mixing. The composition in Table 1 is the solid content. The pH at 25°C of each cleaning composition shown in Table 1 is a value measured using a pH meter (Toa Denpa Kogyo Co., Ltd., HM-30G), and the pH of the pH meter was immersed in the cleaning composition. This is the value after 3 minutes.
実施例１～１１、比較例１～５及び参考例１～２の洗浄剤組成物の成分には、下記のものを使用した。
（成分Ａ）
テトラメチルアンモニウムヒドロキシド［昭和電工株式会社製、TMAH（２５％）］
水酸化カリウム［関東化学株式会社製、特級、固形分４８質量％］
モノエタノールアミン［株式会社日本触媒製］
１，２－プロパンジアミン［富士フィルム和光純薬株式会社］
（非成分Ａ）
ヒドロキシルアミン［富士フィルム和光純薬株式会社、一級、５０％水溶液］
（成分Ｂ）
ブチルジグリコール［日本乳化剤株式会社製、ジエチレングリコールモノブチルエーテル］
ベンジルグリコール［日本乳化剤株式会社製、エチレングリコールモノベンジルエーテル］
ヘキシルジグリコール［日本乳化剤株式会社製、ジエチレングリコールモノヘキシルエーテル］
フェノキシエタノール［富士フィルム和光純薬株式会社製、特級、エチレングリコールモノフェニルエーテル］
ジエチルジグリコール［富士フィルム和光純薬株式会社製、一級、ジエチレングリコールジエチルエーテル］
アセトフェノン［富士フィルム和光純薬株式会社製、特級］
（成分Ｃ）
エチドロン酸［イタルマッチジャパン株式会社製、Dequest2010、含有量60%］
2-ホスホノブタン-1,2,4-トリカルボン酸［イタルマッチジャパン株式会社製、Dequest7000(CN)、含有量50%］
アミノトリメチレンホスホン酸［イタルマッチジャパン株式会社製、Dequest2000、含有量50%］
（成分Ｄ）
水［オルガノ株式会社製純水装置G-10DSTSETで製造した1μS/ｃｍ以下の純粋］
（成分Ｅ）
ギ酸アンモニウム［富山薬品工業株式会社］
アンモニア［富士フィルム和光純薬株式会社、一級、２５％水溶液］
（その他の成分）
５－メチル－１Ｈ-ベンゾトリアゾール［東京化成工業株式会社］
The following components were used in the cleaning compositions of Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 to 2.
(Component A)
Tetramethylammonium hydroxide [manufactured by Showa Denko K.K., TMAH (25%)]
Potassium hydroxide [manufactured by Kanto Kagaku Co., Ltd., special grade, solid content 48% by mass]
Monoethanolamine [manufactured by Nippon Shokubai Co., Ltd.]
1,2-Propanediamine [Fuji Film Wako Pure Chemical Industries, Ltd.]
(Non-ingredient A)
Hydroxylamine [Fuji Film Wako Pure Chemical Industries, Ltd., first class, 50% aqueous solution]
(Component B)
Butyl diglycol [manufactured by Nippon Nyukazai Co., Ltd., diethylene glycol monobutyl ether]
Benzyl glycol [manufactured by Nippon Nyukazai Co., Ltd., ethylene glycol monobenzyl ether]
Hexyl diglycol [manufactured by Nippon Nyukazai Co., Ltd., diethylene glycol monohexyl ether]
Phenoxyethanol [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., special grade, ethylene glycol monophenyl ether]
Diethyl diglycol [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., first class, diethylene glycol diethyl ether]
Acetophenone [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., special grade]
(Component C)
Etidronic acid [manufactured by Italmatch Japan Co., Ltd., Dequest2010, content 60%]
2-phosphonobutane-1,2,4-tricarboxylic acid [manufactured by Italmatch Japan Co., Ltd., Dequest7000 (CN), content 50%]
Aminotrimethylenephosphonic acid [manufactured by Italmatch Japan Co., Ltd., Dequest2000, content 50%]
(Component D)
Water [Pure below 1 μS/cm produced using the water purifier G-10DSTSET manufactured by Organo Co., Ltd.]
(Component E)
Ammonium formate [Toyama Pharmaceutical Co., Ltd.]
Ammonia [Fuji Film Wako Pure Chemical Industries, Ltd., first grade, 25% aqueous solution]
(Other ingredients)
5-Methyl-1H-benzotriazole [Tokyo Kasei Kogyo Co., Ltd.]
２．洗浄剤組成物の評価
調製した実施例１～１１、比較例１～５及び参考例１～２の洗浄剤組成物について下記評価を行った。
2. Evaluation of Cleaning Compositions The cleaning compositions prepared in Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 to 2 were evaluated as follows.
［テストピースの作製］
ＰＫＧ基板回路形成用感光性フィルム（フォテックＲＹ－５５６０、厚み６０μｍ、ネガ型ドライフィルムレジスト）を無電解めっき後のポリイミドの表面に下記条件でラミネートし、選択的に露光処理して露光部を硬化した後（露光工程）、現像処理することで未露光部を除去し（現像工程）、レジストパターン（パターン形状のネガ型樹脂マスク）を有する基板を得た。そして、前記現像処理で未露光部が除去された領域を銅めっき処理（厚さ５０μｍ）することで、テストピース（３０ｍｍ×５０ｍｍ及び１２０ｍｍ×１２０ｍｍ）を得た。
（１）ラミネート：クリーンローラー（株式会社レヨーン工業製、ＲＹ－５０５Ｚ）及び真空アプリケータ（ローム＆ハース社製、ＶＡ７０２４／ＨＰ５）を用いてローラー温度５０℃、ローラー圧１．４Ｂａｒで行う。
（２）露光：プリント基板用直接描画装置（株式会社ＳＣＲＥＥＮグラフィックアンドプレシジョンソリューションズ製、Ｍｅｒｃｕｒｅｘ ＬＩ－９５００）を用い、露光量１５ｍＪ／ｃｍ２で露光を行う。
（３）パターン形状：Ｌ／Ｓ＝２０μｍ／２０μｍの縞状パターン
（４）現像：基板用現像装置（揚博科技株式会社製、ＬＴ－９８０３６６）、３０℃の１％炭酸ナトリウム水溶液を用いて、スプレー圧０．２ＭＰａ、未露光部の樹脂マスクを除去する。
[Preparation of test piece]
A photosensitive film for PKG board circuit formation (Photoc RY-5560, thickness 60 μm, negative dry film resist) is laminated on the surface of the polyimide after electroless plating under the following conditions, and the exposed areas are cured by selective exposure. After that (exposure step), the unexposed portion was removed by development treatment (development step) to obtain a substrate having a resist pattern (a pattern-shaped negative resin mask). Then, test pieces (30 mm x 50 mm and 120 mm x 120 mm) were obtained by copper plating the areas from which the unexposed areas were removed in the development process (thickness: 50 μm).
(1) Lamination: Lamination is carried out using a clean roller (RY-505Z, manufactured by Rayon Kogyo Co., Ltd.) and a vacuum applicator (VA7024/HP5, manufactured by Rohm & Haas) at a roller temperature of 50° C. and a roller pressure of 1.4 Bar.
(2) Exposure: Exposure is performed using a direct writing device for printed circuit boards (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions Co., Ltd.) at an exposure dose of 15 mJ/cm 2 .
(3) Pattern shape: Striped pattern with L/S = 20 μm/20 μm (4) Development: Using a substrate development device (manufactured by Yangbo Technology Co., Ltd., LT-980366) and a 1% aqueous sodium carbonate solution at 30°C. , the spray pressure was 0.2 MPa, and the resin mask in the unexposed area was removed.
［洗浄試験・樹脂マスク残渣数の評価（ディップ条件）］
トール型の２００ｍＬガラスビーカーに、実施例１～１１、比較例１～５及び参考例１～２の各洗浄剤組成物を１００ｇ添加して５０℃に加温し、回転子（フッ素樹脂（ＰＴＦＥ）、φ８ｍｍ×２５ｍｍ）を用いて回転数６００ｒｐｍで撹拌した状態で、テストピースを１０分間浸漬する。そして、１００ｍＬガラスビーカーに水を１００ｇ添加したすすぎ槽へ浸漬してすすいだ後、窒素ブローにて乾燥する。
光学顕微鏡「デジタルマイクロスコープＶＨＸ－２０００」（株式会社キーエンス製）を用いて、洗浄試験を行った後のテストピースの特定パターン領域の細線部とベタ部の境界となる部位に残存する樹脂マスクの有無を３００倍に拡大して目視確認し、残渣数を数える。結果を表１に示した。残存する樹脂マスクが連続して残存しているなど、明らかに残存数が多い場合は、「＞５０」として表１に記載した。
なお、テストピースは、３０ｍｍ×５０ｍｍのサイズで、細線部とベタ部とを有する銅の回路パターンを有しており、パターンの厚さ５０μｍ、細線部の幅２０μｍ、ベタ部の幅３００～１５００μｍである。
[Cleaning test/evaluation of the number of resin mask residues (dipping conditions)]
100 g of each of the cleaning compositions of Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 to 2 was added to a tall-shaped 200 mL glass beaker, heated to 50°C, and the rotor (fluororesin (PTFE) ), φ8 mm x 25 mm) at a rotational speed of 600 rpm, and the test piece was immersed for 10 minutes. Then, after immersing a 100 mL glass beaker in a rinsing tank containing 100 g of water for rinsing, drying with nitrogen blowing.
Using an optical microscope "Digital Microscope VHX-2000" (manufactured by Keyence Corporation), we examined the residual resin mask at the boundary between the thin line part and the solid part in the specific pattern area of the test piece after the cleaning test. Visually check the presence or absence at 300x magnification and count the number of residues. The results are shown in Table 1. When the number of remaining resin masks is clearly large, such as when the remaining resin masks remain continuously, it is listed in Table 1 as ">50".
The test piece has a copper circuit pattern with a size of 30 mm x 50 mm and has a thin line part and a solid part, the thickness of the pattern is 50 μm, the width of the fine line part is 20 μm, and the width of the solid part is 300 to 1500 μm. It is.
［洗浄試験・樹脂マスクの剥離開始速度の評価］
トール型の２００ｍＬガラスビーカーに、実施例１～１１、比較例１～５及び参考例１～２の各洗浄剤組成物を１００ｇ添加して５０℃に加温し、回転子（フッ素樹脂（ＰＴＦＥ）、φ８ｍｍ×２５ｍｍ）を用いて回転数６００ｒｐｍで撹拌した状態で、テストピースを浸漬する。目視観察にて、樹脂マスクが剥離されて洗浄剤組成物内に舞っているのが確認できた時間を測定し、以下のように判定する。結果を表１に示した。
なお、テストピースは、洗浄試験のディップ条件と同様の形態ものを用いた。
＜評価基準＞
Ａ：５分以内
Ｂ：５分より長く、１０分以内
Ｃ：１０分より長く、１５分以内
Ｄ：１５分より長い
[Cleaning test/Evaluation of peeling start speed of resin mask]
100 g of each of the cleaning compositions of Examples 1 to 11, Comparative Examples 1 to 5, and Reference Examples 1 to 2 was added to a tall-shaped 200 mL glass beaker, heated to 50°C, and the rotor (fluororesin (PTFE) ), φ8 mm x 25 mm) at a rotational speed of 600 rpm, the test piece is immersed. The time required for the resin mask to be peeled off and floating in the cleaning composition was determined by visual observation, and the determination was made as follows. The results are shown in Table 1.
Note that the test piece used had the same shape as the dipping conditions of the cleaning test.
<Evaluation criteria>
A: Within 5 minutes B: More than 5 minutes but less than 10 minutes C: More than 10 minutes but less than 15 minutes D: More than 15 minutes
［基板ダメージの評価］
上記のディップ条件での洗浄試験の前後で、基板外観にパターン部の色等の変化が生じるかを目視で確認し、下記評価基準で評価した結果を表１に示す。
＜評価基準＞
Ａ：洗浄試験の前後で変化が見られない。
Ｂ：洗浄試験の前後で変化が見られる。
[Evaluation of board damage]
Before and after the cleaning test under the above dipping conditions, it was visually confirmed whether the appearance of the substrate changed in the color of the patterned portion, etc., and the results were evaluated using the following evaluation criteria, and the results are shown in Table 1.
<Evaluation criteria>
A: No change was observed before and after the cleaning test.
B: Changes are seen before and after the cleaning test.
表１に示すとおり、ディップ条件での洗浄試験の結果、実施例１～１１の洗浄剤組成物は、成分Ｃを含まない参考例１～２、成分Ｂを含まない比較例１、４、成分Ａを含まない比較例２、成分Ｂ及びＤの含有量が所定範囲内ではない比較例３、５に比べて、基板への影響が低減され、かつ、樹脂マスク除去性に優れていることがわかった。
なお、比較例３は、特許文献４の実施例に準じた例、比較例４は特許文献３の実施例に準じた例である。
As shown in Table 1, as a result of the cleaning test under dip conditions, the cleaning compositions of Examples 1 to 11 were: Reference Examples 1 to 2, which did not contain component C, Comparative Examples 1 and 4, which did not contain component B, and Comparative Examples 1 and 4, which did not contain component B. Compared to Comparative Example 2, which does not contain A, and Comparative Examples 3 and 5, in which the contents of components B and D are not within the predetermined range, the influence on the substrate is reduced and the resin mask removability is excellent. Understood.
Note that Comparative Example 3 is an example based on the example of Patent Document 4, and Comparative Example 4 is an example based on the example of Patent Document 3.
さらに、実施例１～２及び参考例２の洗浄剤組成物について、下記に示すディップとシャワーを連続で行う条件での洗浄試験を行い、樹脂マスク除去性を評価した。 Further, the cleaning compositions of Examples 1 to 2 and Reference Example 2 were subjected to a cleaning test under the following conditions of continuous dipping and showering to evaluate resin mask removability.
［洗浄試験・樹脂マスク残渣数の評価（ディップ＋シャワー条件）］
以下の要領でディップとシャワーを連続で行う。１Ｌガラスビーカーに、実施例１～２及び参考例２の各洗浄剤組成物を１ｋｇ添加して５０℃に加温し、回転子（フッ素樹脂（ＰＴＦＥ）、φ８ｍｍ×２５ｍｍ）を用いて回転数３００ｒｐｍで撹拌した状態で、テストピースを３分間浸漬する。別途準備した１０Ｌステンレスビーカーを貯槽とし、１Ｌガラスビーカーと同じ洗浄剤組成物を１０ｋｇ添加して５０℃に加温する。そして、１流体ノズル（扇形）ＶＶＰ９０６０（株式会社いけうち製）をスプレーノズルとして取り付けたボックス型スプレー洗浄機にて貯槽中の洗浄剤組成物をテストピースに２分間スプレー（圧力：０．１ＭＰａ、スプレー距離：１０ｃｍ）する。なお、スプレーされた洗浄剤組成物は、貯槽に回収し循環して再使用する。次いで、１Ｌガラスビーカーに水を１ｋｇ添加したすすぎ槽へ浸漬してすすいだ後、窒素ブローにて乾燥する。
光学顕微鏡「デジタルマイクロスコープＶＨＸ－２０００」（株式会社キーエンス製）を用いて、洗浄試験を行った後のテストピースの特定パターン領域の細線部とベタ部の境界となる部位に残存する樹脂マスクの有無を３００倍に拡大して目視確認し、残渣数を数える。結果を表２に示した。
なお、テストピースは、１２０ｍｍ×１２０ｍｍのサイズである以外は、ディップ条件のテストピースと同様の回路パターンを有している。
[Cleaning test/evaluation of the number of resin mask residues (dip + shower conditions)]
Perform the dip and shower in succession as follows. 1 kg of each of the cleaning compositions of Examples 1 to 2 and Reference Example 2 was added to a 1 L glass beaker, heated to 50°C, and the number of rotations was adjusted using a rotor (fluororesin (PTFE), φ8 mm x 25 mm). The test piece is immersed for 3 minutes while stirring at 300 rpm. A separately prepared 10 L stainless steel beaker is used as a storage tank, and 10 kg of the same detergent composition as in the 1 L glass beaker is added and heated to 50°C. Then, using a box-type spray washer equipped with a one-fluid nozzle (fan-shaped) VVP9060 (manufactured by Ikeuchi Co., Ltd.) as a spray nozzle, the cleaning agent composition in the storage tank was sprayed onto the test piece for 2 minutes (pressure: 0.1 MPa, spray distance: 10cm). The sprayed cleaning composition is collected in a storage tank, circulated, and reused. Next, a 1 L glass beaker was immersed in a rinsing tank containing 1 kg of water for rinsing, and then dried with nitrogen blow.
Using an optical microscope "Digital Microscope VHX-2000" (manufactured by Keyence Corporation), we examined the residual resin mask at the boundary between the thin line part and the solid part in the specific pattern area of the test piece after the cleaning test. Visually check the presence or absence at 300x magnification and count the number of residues. The results are shown in Table 2.
Note that the test piece had the same circuit pattern as the test piece under the dip condition, except for the size of 120 mm x 120 mm.
表２に示すとおり、ディップ及びシャワー条件での洗浄試験の結果、実施例１～２の洗浄剤組成物は、成分Ｃを参考例２に比べて、樹脂マスク除去性に優れていることがわかった。 As shown in Table 2, the cleaning test results under dip and shower conditions showed that the cleaning compositions of Examples 1 and 2 had better resin mask removability than Reference Example 2 with component C. Ta.
本開示によれば、基板に対する影響を低減でき、樹脂マスク除去性に優れる樹脂マスク剥離用洗浄剤組成物を提供できる。よって、本開示の洗浄剤組成物は、電子部品の製造工程で用いられる洗浄剤組成物として有用であり、樹脂マスクが付着した電子部品の洗浄工程の短縮化及び製造される電子部品の性能・信頼性の向上が可能となり、半導体装置の生産性を向上できる。
According to the present disclosure, it is possible to provide a cleaning agent composition for removing a resin mask that can reduce the influence on the substrate and has excellent resin mask removability. Therefore, the cleaning composition of the present disclosure is useful as a cleaning composition used in the manufacturing process of electronic components, and can shorten the cleaning process for electronic components to which resin masks are attached, and improve the performance and performance of electronic components manufactured. It is possible to improve reliability and improve productivity of semiconductor devices.
Claims (9)
成分Ｂが、グリコールエーテル及び芳香族ケトンから選ばれる少なくとも１種の溶剤であり、
成分Ｃが、カルボキシ基及びホスホン酸基から選ばれる少なくとも１種の酸基を２以上有する化合物であり、
使用時における成分Ｂの含有量が、１質量％以上１２質量％以下、
使用時における成分Ｄの含有量が、６５質量％以上９５質量％以下である、樹脂マスク剥離用洗浄剤組成物。 Contains an alkaline agent (component A), an organic solvent (component B), a chelating agent (component C) and water (component D),
Component B is at least one solvent selected from glycol ethers and aromatic ketones,
Component C is a compound having two or more at least one acid group selected from a carboxy group and a phosphonic acid group,
The content of component B during use is 1% by mass or more and 12% by mass or less,
A detergent composition for removing a resin mask, in which the content of component D during use is 65% by mass or more and 95% by mass or less.
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| JP2004325918A (en) | 2003-03-06 | 2004-11-18 | Kao Corp | Remover composition |
| JP2005217116A (en) | 2004-01-29 | 2005-08-11 | Kao Corp | Non-fluorine based residue cleaning agent for copper wiring |
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| JP2002075993A (en) * | 2000-06-15 | 2002-03-15 | Mitsubishi Electric Corp | Method of manufacturing semiconductor device |
| JP4159944B2 (en) * | 2003-07-31 | 2008-10-01 | 花王株式会社 | Resist stripping composition |
| CN104427781B (en) * | 2013-09-11 | 2019-05-17 | 花王株式会社 | The manufacturing method of resin mask layer detergent composition and circuit substrate |
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| JP2005217116A (en) | 2004-01-29 | 2005-08-11 | Kao Corp | Non-fluorine based residue cleaning agent for copper wiring |
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