WO2018047631A1 - Cleaning agent composition for resin mask detachment - Google Patents
Cleaning agent composition for resin mask detachment Download PDFInfo
- Publication number
- WO2018047631A1 WO2018047631A1 PCT/JP2017/030352 JP2017030352W WO2018047631A1 WO 2018047631 A1 WO2018047631 A1 WO 2018047631A1 JP 2017030352 W JP2017030352 W JP 2017030352W WO 2018047631 A1 WO2018047631 A1 WO 2018047631A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- cleaning composition
- mass
- resin mask
- composition according
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 219
- 239000011347 resin Substances 0.000 title claims abstract description 123
- 229920005989 resin Polymers 0.000 title claims abstract description 123
- 239000012459 cleaning agent Substances 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims description 217
- 238000000034 method Methods 0.000 claims description 52
- 238000004519 manufacturing process Methods 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 18
- -1 nitrogen-containing compound Chemical class 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 238000011161 development Methods 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 18
- 239000012141 concentrate Substances 0.000 description 30
- 239000003599 detergent Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 239000007788 liquid Substances 0.000 description 17
- 238000007747 plating Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- CUZKCNWZBXLAJX-UHFFFAOYSA-N 2-phenylmethoxyethanol Chemical compound OCCOCC1=CC=CC=C1 CUZKCNWZBXLAJX-UHFFFAOYSA-N 0.000 description 9
- 238000007654 immersion Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 7
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- RNDNSYIPLPAXAZ-UHFFFAOYSA-N 2-Phenyl-1-propanol Chemical compound OCC(C)C1=CC=CC=C1 RNDNSYIPLPAXAZ-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 230000007103 stamina Effects 0.000 description 6
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000012851 eutrophication Methods 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- VTBOTOBFGSVRMA-UHFFFAOYSA-N 1-Methylcyclohexanol Chemical compound CC1(O)CCCCC1 VTBOTOBFGSVRMA-UHFFFAOYSA-N 0.000 description 4
- HTSABYAWKQAHBT-UHFFFAOYSA-N 3-methylcyclohexanol Chemical group CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 241000282994 Cervidae Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004380 ashing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- MZQZXSHFWDHNOW-UHFFFAOYSA-N 1-phenylpropane-1,2-diol Chemical compound CC(O)C(O)C1=CC=CC=C1 MZQZXSHFWDHNOW-UHFFFAOYSA-N 0.000 description 1
- OHJYHAOODFPJOD-UHFFFAOYSA-N 2-(2-ethylhexoxy)ethanol Chemical compound CCCCC(CC)COCCO OHJYHAOODFPJOD-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion 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
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- VUVZASHBYYMLRC-UHFFFAOYSA-N heptane-2,3-diol Chemical compound CCCCC(O)C(C)O VUVZASHBYYMLRC-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 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
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/08—Liquid soap, e.g. for dispensers; capsuled
-
- 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
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
-
- 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
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Definitions
- the present disclosure relates to a resin mask peeling cleaning composition, a resin mask removing method using the cleaning composition, and an electronic component manufacturing method.
- Patent Document 1 contains 0.5 to 3.0 parts by mass of quaternary ammonium hydroxide in 100 parts by mass of the cleaning composition, Containing 3.0 parts by weight or more and 10.0 parts by weight or less of an acidic amine, 0.3 parts by weight or more and 2.5 parts by weight or less of an acid or an ammonium salt thereof, and 50.0 parts by weight or more and 95.0 parts by weight of water.
- the cleaning composition for resin mask layers used for manufacture of the circuit board containing below mass part is described.
- Patent Document 2 discloses that about 2 to 55% by weight of the total weight of the composition of at least one alkanolamine, at least one morpholine, or a mixture thereof and about 20 to 94% by weight of at least one organic.
- a composition for removing a film resist comprising a solvent and about 0.5-60% by weight water is described.
- Patent Document 3 discloses that (a) a fluorine compound, (b) an intramolecular molecule used for removal of residues generated after etching and ashing (ashing) in the manufacture of semiconductor elements such as IC and LSI and liquid crystal panel elements. Describes a resist stripping solution containing a divalent alcohol compound having an ether bond, (c) an organic acid compound, and (d) water.
- Patent Document 4 is a stripping solution for stripping an unexposed portion of an epoxy resin photosolder resist as a so-called resist developing solution, and is characterized in that an additive of propylene glycol ether is added to an alkaline solution. A stripping solution is described.
- Patent Document 5 a) inorganic alkali compound 0 for removing the resist of unnecessary film components formed on the edge of the resist film coated on the substrate or on the rear surface of the substrate and preventing the corrosion of the equipment. 1 to 5% by weight, b) 0.1 to 5% by weight of organic amine, c) 0.1 to 30% by weight of organic solvent, d) 1: 5 to 25 of anionic surfactant and nonionic surfactant.
- a thinner composition for resist removal characterized by containing 0.01 to 5% by weight of a surfactant in a weight ratio of e) and 60 to 99% by weight of water.
- the resin mask is formed using a resist whose physical properties such as solubility in a developing solution are changed by light, electron beam, or the like. Resists are roughly classified into negative types and positive types according to the method of reaction with light or electron beams. A negative resist has a characteristic that the solubility in a developing solution is lowered when exposed. A layer containing a negative resist (hereinafter also referred to as a “negative resist layer”) has an exposed portion after exposure and development processing. Used as a resin mask.
- a positive resist has a property of increasing the solubility in a developer when exposed to light.
- a layer containing a positive resist (hereinafter also referred to as a “positive resist layer”) has an exposed portion after exposure and development processing. The unexposed part is removed and used as a resin mask.
- a resin mask having such characteristics, it is possible to form fine connection portions of a circuit board such as metal wiring, metal pillars, and solder bumps.
- the characteristics of the resin mask change due to the plating process or the heat treatment used when these connection parts are formed, and it becomes difficult to remove the resin mask in the next cleaning process.
- negative resists have the property of being cured by reaction with light or electron beams
- resin masks formed using negative resists can be obtained by plating or heat treatment used at the time of forming connection parts. Curing progresses more than necessary and cannot be completely removed in the cleaning process, or the time required for removal becomes very long, thereby damaging the substrate and the metal surface. Since the resin mask that has been plated and / or heat-treated in this manner is difficult to peel off, the cleaning composition is required to have high resin mask removability. On the other hand, digitization has progressed in various fields, and the production volume of printed circuit boards and the like has increased.
- the present disclosure provides a resin mask peeling cleaning composition having excellent resin mask removability and a small wastewater treatment load, a resin mask removing method and a substrate manufacturing method using the cleaning composition.
- the present disclosure contains an inorganic alkali (component A), an organic solvent (component B), and water (component C).
- component A an organic solvent
- component B an organic solvent
- component C water
- the content of Component C when using the cleaning composition is 85% by mass or more, It is related with the cleaning composition for resin mask peeling whose mass ratio (A / B) of component A with respect to component B is 1 or more and 60 or less.
- the present disclosure in one aspect, relates to a method for removing a resin mask, including a step of cleaning an object to be cleaned to which the resin mask is attached with the cleaning composition according to the present disclosure.
- the present disclosure in one aspect, relates to a method for manufacturing an electronic component including a step of cleaning an object to be cleaned to which a resin mask is attached with the cleaning composition according to the present disclosure.
- the present disclosure in one aspect, relates to the use of the cleaning composition according to the present disclosure for the manufacture of electronic components.
- the present disclosure it is possible to provide a resin mask peeling cleaning composition having excellent resin mask removability and a small wastewater treatment load. And by using the cleaning composition according to the present disclosure, a high-quality electronic component can be obtained with a high yield. Furthermore, an electronic component having a fine wiring pattern can be efficiently manufactured by using the cleaning composition according to the present disclosure.
- the present disclosure includes an inorganic alkali (component A), an organic solvent (component B) having a specific Hansen solubility parameter, and water (component C), the content of component C, and the mass ratio of component A and component B Is based on the knowledge that the resin mask, in particular, the plating mask and / or the heat-treated resin mask can be efficiently removed even with a low wastewater treatment load. Moreover, it is based on the knowledge that eutrophication of a lake can be suppressed by not including a nitrogen-containing compound and a phosphorus-containing compound in a cleaning composition.
- the present invention relates to a resin mask peeling cleaning composition (hereinafter, also referred to as “cleaning composition according to the present disclosure”) in which the mass ratio (A / B) of component A to B is 1 or more and 60 or less.
- the cleaning composition according to the present disclosure can efficiently remove a resin mask, in particular, a plating mask and / or a heat-treated resin mask, even at a low wastewater treatment load. And by using the cleaning composition according to the present disclosure, a high-quality electronic component can be obtained with a high yield. Furthermore, an electronic component having a fine wiring pattern can be efficiently manufactured by using the cleaning composition according to the present disclosure.
- the peeling of the resin mask is caused by interfacial stress due to the components of the cleaning composition penetrating into the resin mask and swelling of the resin mask.
- component A inorganic alkali
- component C water
- penetrate into the resin mask thereby promoting dissociation of the alkali-soluble resin blended in the resin mask and further charge repulsion. This promotes the peeling of the resin mask.
- the component B organic solvent having a specific Hansen solubility parameter acts between the substrate surface and the resin mask, so that the adhesion between the substrate and the resin is reduced, and further the peeling of the resin mask is promoted. It is estimated that the resin mask removability is remarkably improved.
- the content of the water of component C at the time of use of the cleaning composition according to the present disclosure is as high as 85% by mass or more, the content of organic matter in the cleaning composition can be reduced, and the wastewater treatment load is increased. It is estimated that it can be suppressed. Thereby, it is considered that a fine circuit (wiring pattern) can be formed on the substrate efficiently and with high cleanliness.
- the present disclosure is not limited to this mechanism.
- the resin mask is a mask for protecting a material surface from processing such as etching, plating, and heating, that is, a mask that functions as a protective film.
- the resin mask in one or a plurality of embodiments, the resist layer after the exposure or development step, and at least one treatment of exposure and development (hereinafter, also referred to as “exposure and / or development treatment”) are performed.
- a resist layer or a cured resist layer may be mentioned.
- a resin material for forming the resin mask in one or a plurality of embodiments, a film-like photosensitive resin or a resist film may be used.
- a general-purpose resist film can be used.
- composition according to the present disclosure includes an inorganic alkali (component A).
- Component A can be used alone or in combination of two or more.
- Component A includes, for example, one or a combination of two or more selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium silicate and potassium silicate, and resin. From the viewpoint of improving mask removability, one or a combination of two or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate is preferable, and at least one of sodium hydroxide and potassium hydroxide is more preferable.
- the content of Component A during use of the cleaning composition according to the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, from the viewpoint of improving resin mask removability. More preferably 1% by weight or more, still more preferably 1% by weight or more, still more preferably 2% by weight or more, and preferably 15% by weight or less from the viewpoint of improving resin mask removability and suppressing metal corrosion. The following is more preferable, 7% by mass or less is further preferable, and 5% by mass or less is more preferable.
- component A is composed of two or more inorganic alkalis
- the content of component A refers to the total content thereof.
- the “content of each component when using the cleaning composition” refers to the content of each component at the time of cleaning, that is, when the cleaning composition is used for cleaning.
- Component B Organic solvent
- the cleaning composition according to the present disclosure includes an organic solvent (component B).
- Component B can be used alone or in combination of two or more.
- the cleaning composition according to the present disclosure contains two or more kinds of organic solvents (hereinafter also referred to as “mixed organic solvents”), the Hansen solubility parameter of the entire mixed organic solvent may not be within the above range. If the solvent contains at least one organic solvent having a Hansen solubility parameter within the above range, the effects of the present disclosure can be exhibited.
- HSP Hansen solubility parameter
- the component B is not particularly limited as long as the distance between the HSP coordinates of the component B and the component coordinates X satisfies the above formula.
- propylene glycol phenyl ether (distance: 0.32 MPa 0.5 )
- Glycol ethers such as ethylene glycol monobenzyl ether (distance: 1.18 MPa 0.5 ) and ethylene glycol mono n-hexyl ether (distance: 1.50 MPa 0.5 ); 1-methylcyclohexanol (distance: 1.19 MPa 0.5 ), 3 Monoalkyl alcohols such as methylcyclohexanol (distance: 1.08 MPa 0.5 ) and 4-methylcyclohexanol (distance: 0.59 MPa 0.5 ); 1-phenyl-1-propanol (distance: 1.39 MPa 0.5 ), 2- Phenyl-1-propanol (distance: 1.37 MPa 0.5 ), etc.
- Examples thereof include one or a combination of two or more selected from aromatic alcohols and the like.
- one or more selected from propylene glycol phenyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono n-hexyl ether, 1-phenyl-1-propanol and 2-phenyl-1-propanol The combination of these is preferable, and at least one of propylene glycol phenyl ether and ethylene glycol monobenzyl ether is more preferable.
- ethylene glycol monobenzyl ether ethylene glycol mono n-hexyl ether, 1-methylcyclohexanol, 2-phenyl-1-propanol and 1-phenyl-1-
- propanol are preferable, and one or more combinations selected from ethylene glycol monobenzyl ether, 2-phenyl-1-propanol and 1-phenyl-1-propanol are more preferable.
- the numerical value in parentheses indicates the distance (unit: MPa 0.5 ) between the HSP coordinate of component B and the component coordinate X.
- stamina means that good cleaning properties are ensured even when the cleaning composition is used for a long time (recycle cleaning).
- Component B in the present disclosure preferably has a high boiling point from the viewpoint of fire risk reduction due to ignition and stamina properties.
- the boiling point of Component B is preferably 160 ° C. or higher, more preferably 250 ° C. or higher.
- component B preferably has high water solubility from the viewpoint of concentration.
- the solubility of component B in 100 mL of water is preferably 0.3 g or more.
- the content of Component B when using the cleaning composition according to the present disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of improving the resin mask removability. 1% by mass or more is more preferable, from the viewpoint of stamina, 0.2% by mass or more is more preferable, and from the viewpoint of reducing wastewater treatment load, 3% by mass or less is preferable, and 2% by mass or less is more preferable. Preferably, 1 mass% or less is still more preferable, and 0.5 mass% or less is still more preferable.
- component B consists of two or more organic solvents
- the content of component B refers to the total content thereof.
- the mass ratio (A / B) of component A to component B in the cleaning composition according to the present disclosure is 1 or more and 60 or less, preferably 1.1 or more from the viewpoint of improving the resin mask removability. 2 or more is more preferable, 1.5 or more is still more preferable, 2 or more is more preferable, 3 or more is more preferable, 5 or more is still more preferable, 10 or more is still more preferable, 15 or more is still more preferable, and From the viewpoint of reducing storage stability and wastewater treatment load, it is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, and even more preferably 20 or less.
- the cleaning composition according to the present disclosure includes water (component C).
- water of component C ion exchange water, RO water, distilled water, pure water, and ultrapure water can be used. What is necessary is just to set content of water suitably according to the usage condition of the cleaning composition which concerns on this indication.
- Content of the component C at the time of use of the cleaning composition which concerns on this indication is 85 mass% or more, and 90 mass% or more is preferable from a viewpoint of a resin mask removability improvement, and 95 mass% or more is more preferable. And from the same viewpoint, 99 mass% or less is preferable, 98 mass% or less is more preferable, 97 mass% or less is still more preferable.
- the cleaning composition according to the present disclosure may contain an optional component as necessary in addition to the components A to C.
- optional components include components that can be used in ordinary cleaning agents, such as chelating agents, thickeners, dispersants, rust inhibitors, basic substances, surfactants, polymer compounds, and solubilization. Agents, antioxidants, antiseptics, antifoaming agents, antibacterial agents and the like.
- the total content of optional components during use of the cleaning composition according to the present disclosure is preferably 0% by mass or more and 2.0% by mass or less, more preferably 0% by mass or more and 1.5% by mass or less, and 0% by mass. The content is more preferably 1.3% by mass or less and still more preferably 0% by mass or more and 1.0% by mass or less.
- the total content of Component B and the organic matter derived from the optional component in the cleaning composition according to the present disclosure is preferably 3% by mass or less, more preferably 2% by mass or less. % Or less is more preferable, 0.5% by mass or less is more preferable, and from the viewpoint of improving resin mask removability, 0.01% by mass or more is preferable, 0.05% by mass or more is more preferable, and 0.1% More preferably, it is more than mass%.
- the cleaning composition according to the present disclosure preferably contains substantially no nitrogen-containing compound and phosphorus-containing compound from the viewpoint of reducing wastewater treatment load and suppressing eutrophication of the drainage area.
- substantially free means that the total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning composition according to the present disclosure is less than 0.1 mass%.
- the total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning composition according to the present disclosure is preferably 0.05% by mass or less from the viewpoint of reducing wastewater treatment load and suppressing eutrophication of the drainage area. 0.01 mass% or less is more preferable, and 0 mass% is still more preferable.
- nitrogen-containing compound examples include nitrogen-containing compounds that have been widely used as a cleaning composition, and examples thereof include at least one or a combination of two or more selected from amines and salts thereof, ammonia, and ammonium salts.
- amine examples include amino alcohols such as monoethanolamine and diethanolamine.
- ammonium salt examples include quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH).
- phosphorus-containing compounds include phosphorus-containing compounds that have been widely used in the past as cleaning compositions, such as phosphoric acid and salts thereof, condensed phosphoric acid such as pyrophosphoric acid, polyphosphoric acid, and metaphosphoric acid, and salts thereof. Inorganic phosphoric acid, organic phosphoric acid, and a combination of two or more selected from phosphoric esters.
- the cleaning composition according to the present disclosure can be produced by blending the components A to C and, if necessary, the above-mentioned optional components by a known method.
- the cleaning composition according to the present disclosure can be formed by blending at least the components A to C.
- the present disclosure relates to a method for producing a cleaning composition comprising a step of blending at least the components A to C.
- “compounding” includes mixing the components A to C and other components as necessary at the same time or in any order.
- the preferable blending amount of each component may be the same as the preferable content of each component of the cleaning composition according to the present disclosure described above.
- the pH at the time of use of the cleaning composition according to the present disclosure is preferably 10.0 or more, more preferably 10.5 or more from the viewpoint of improving the resin mask removability, and 14 or less from the viewpoint of suppressing metal corrosion. Is preferable, 13.9 or less is more preferable, and 13.7 or less is still more preferable.
- the pH is the pH of the cleaning composition at 25 ° C., and can be measured using, for example, a pH meter (A Denki Kogyo Co., Ltd., HM-30G).
- the pH is adjusted with inorganic acids such as nitric acid and sulfuric acid; organic acids such as oxycarboxylic acid, polyvalent carboxylic acid, aminopolycarboxylic acid and amino acid; and metal salts, ammonium salts, ammonia, amines and the like thereof. It can adjust by mix
- the cleaning composition according to the present disclosure may be prepared as a concentrate in which the amount of water of component C is reduced within a range that does not impair storage stability by causing separation or precipitation.
- the concentrate of the cleaning composition is preferably a concentrate having a dilution ratio of 3 times or more from the viewpoint of transportation and storage, and is preferably a concentrate having a dilution ratio of 10 times or less from the viewpoint of storage stability. .
- the concentrate of the cleaning composition can be used by diluting with water so that the components A to C have the above-described content (that is, the content at the time of cleaning) at the time of use.
- the concentrate of a cleaning composition can also be used by adding each component separately at the time of use.
- “when using” or “when cleaning” the cleaning composition of the concentrated solution refers to a state in which the concentrate of the cleaning composition is diluted.
- the content of the component A in the cleaning composition concentrate is preferably 1% by mass or more from the viewpoint of improving the resin mask removability, and is 2% by mass.
- the above is more preferable, 5% by mass or more is further preferable, 10% by mass or more is more preferable, and 40% by mass or less is preferable, and 30% by mass or less is more preferable from the viewpoint of metal corrosion inhibition and storage stability. 20 mass% or less is still more preferable, and 10 mass% or less is still more preferable.
- the content of Component B in the cleaning composition concentrate is preferably 0.1% by mass or more from the viewpoint of improving resin mask removability. .2% by mass or more is more preferable, 0.5% by mass or more is more preferable, 1% by mass or more is more preferable, and 10% by mass or less is preferable from the viewpoint of reducing storage stability and wastewater treatment load. 5 mass% or less is more preferable, 2 mass% or less is still more preferable, and 1.5 mass% or less is still more preferable.
- the content of the component C in the cleaning composition concentrate is 50 mass from the viewpoint of improving the resin mask removability and stabilizing the cleaning composition.
- % Or more preferably 60% by weight or more, more preferably 70% by weight or more, and from the same viewpoint, 95% by weight or less is preferable, 90% by weight or less is more preferable, and 85% by weight or less is more preferable.
- the pH of the concentrate of the cleaning composition according to the present disclosure is preferably 10.0 or more, more preferably 10.5 or more, from the viewpoint of improving the removability of the resin mask after dilution, and during storage and handling. From the viewpoint of safety, 14 or less is preferable.
- the cleaning composition according to the present disclosure can be used for cleaning an object to be cleaned to which a resin mask is attached.
- the objects to be cleaned include electronic components and production intermediates thereof.
- the electronic component include at least one component selected from metal plates such as a printed board, a wafer, a copper plate, and an aluminum plate.
- the said manufacturing intermediate is an intermediate product in the manufacturing process of an electronic component, Comprising: The intermediate product after a resin mask process is included.
- the object to be cleaned to which the resin mask is attached for example, by performing a process such as soldering using a resin mask or a plating process (copper plating, aluminum plating, nickel plating, etc.), wiring or Examples thereof include an electronic component having a connection terminal or the like formed on the surface of the substrate.
- the cleaning composition according to the present disclosure is suitable for cleaning an object to be cleaned to which a resin mask or a plating and / or heat-treated resin mask is attached in terms of cleaning effect.
- the resin mask may be, for example, a negative type resin mask or a positive type resin mask, and a negative type resin mask is preferable from the viewpoint that the effects of the present disclosure are easily exhibited.
- the negative type resin mask include negative dry film resists that have been exposed and / or developed.
- the negative type resin mask is formed using a negative type resist, and examples thereof include a negative type resist layer that has been exposed and / or developed.
- the positive resin mask is formed using a positive resist, and examples thereof include a positive resist layer that has been exposed and / or developed.
- the present disclosure relates to a method for removing a resin mask, which includes contacting an object to be cleaned to which the resin mask is attached with the cleaning composition according to the present disclosure (hereinafter, also referred to as a removal method according to the present disclosure).
- the removal method according to the present disclosure includes a step of cleaning an object to be cleaned to which a resin mask is attached with the cleaning composition according to the present disclosure. Examples of the objects to be cleaned include the objects to be cleaned described above.
- Examples of a method of bringing the cleaning composition according to the present disclosure into contact with an object to be cleaned or a method of cleaning the object to be cleaned with the cleaning composition according to the present disclosure include, for example, in a cleaning bath containing the cleaning composition Examples include a method of contacting by dipping, a method of injecting a cleaning composition into a spray form (shower method), an ultrasonic cleaning method of irradiating ultrasonically during immersion, and the like.
- the cleaning composition according to the present disclosure can be used for cleaning as it is without being diluted.
- the removal method according to the present disclosure preferably includes a step of bringing a cleaning object into contact with the cleaning composition, rinsing with water, and drying.
- the removal method according to the present disclosure it is possible to efficiently remove a resin mask, particularly a resin mask that has been subjected to plating treatment and / or heat treatment.
- the ultrasonic wave has a relatively high frequency.
- the ultrasonic irradiation conditions are preferably 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.
- the manufacturing method of the electronic component which concerns on this indication includes the process of wash
- the objects to be cleaned include the objects to be cleaned described above.
- the method for manufacturing an electronic component according to the present disclosure can effectively remove the resin mask attached to the electronic component while performing the cleaning using the cleaning composition according to the present disclosure while suppressing corrosion of the metal. This makes it possible to manufacture highly reliable electronic components. Furthermore, by performing the removal method according to the present disclosure, it becomes easy to remove the resin mask attached to the electronic component, so that the cleaning time can be shortened and the manufacturing efficiency of the electronic component can be improved.
- the present disclosure is a kit for use in any one of the removal method according to the present disclosure and the method for manufacturing an electronic component according to the present disclosure, and includes the components A to C constituting the cleaning composition according to the present disclosure.
- the present invention relates to a kit containing at least one of the components in a state where it is not mixed with other components. According to the kit according to the present disclosure, it is possible to obtain a cleaning composition having excellent resin mask removability and a small wastewater treatment load.
- the kit according to the present disclosure includes, for example, a solution containing the component A (first liquid) and a solution containing the component B (second liquid) in a state where they are not mixed with each other. At least one of the two liquids further contains a component C, and a kit (two-component detergent composition) in which the first liquid and the second liquid are mixed at the time of use can be mentioned.
- a kit two-component detergent composition in which the first liquid and the second liquid are mixed at the time of use can be mentioned.
- Each of the first liquid and the second liquid may contain the above-described optional components as necessary.
- the present disclosure further relates to the following detergent composition, removal method, and production method.
- ⁇ 1> Contains an inorganic alkali (component A), an organic solvent (component B) and water (component C),
- the content of Component C when using the cleaning composition is 85% by mass or more,
- the cleaning composition for resin mask peeling whose mass ratio (A / B) of the component A with respect to the component B is 1-60.
- Component B is propylene glycol phenyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono n-hexyl ether, 1-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 1-phenyl-1-
- the cleaning composition according to ⁇ 1> which is one or a combination of two or more selected from propanol and 2-phenyl-1-propanol.
- the content of the component A at the time of use of the cleaning composition is 0.1% by mass or more and 15% by mass or less
- the cleaning composition according to ⁇ 1> or ⁇ 2>, wherein the content of component B when the cleaning composition is used is 0.01% by mass or more and 3% by mass or less.
- the content of component A when using the cleaning composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and 1% by mass.
- the content of component A when using the cleaning composition is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7% by mass or less, and further more preferably 5% by mass or less.
- ⁇ 6> The cleaning composition according to any one of ⁇ 1> to ⁇ 5>, wherein the boiling point of component B is preferably 160 ° C. or higher, and more preferably 250 ° C. or higher.
- ⁇ 7> The cleaning composition according to any one of ⁇ 1> to ⁇ 6>, wherein the solubility of Component B in 100 mL of water is 0.3 g or more.
- the content of Component B during use of the cleaning composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and 0.2%
- the content of Component B during use of the cleaning composition is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.
- the cleaning composition according to any one of ⁇ 1> to ⁇ 8> is 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and 0.2%
- the cleaning composition according to any one of ⁇ 1> to ⁇ 8> is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and 0.2%
- the mass ratio (A / B) of component A to component B in the cleaning composition is 1 or more and 60 or less, preferably 1.1 or more, more preferably 1.2 or more, and 1.5 or more. Is more preferably, 2 or more is still more preferable, 3 or more is more preferable, 5 or more is still more preferable, 10 or more is still more preferable, and 15 or more is still more preferable, ⁇ 1> to ⁇ 9>
- the mass ratio (A / B) of component A to component B in the cleaning composition is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, and even more preferably 20 or less, ⁇ 1> To ⁇ 10>.
- the content of Component C during use of the cleaning composition is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less, any one of ⁇ 1> to ⁇ 12>
- the total content of optional components during use of the cleaning composition is preferably 0% by mass or more and 2.0% by mass or less, more preferably 0% by mass or more and 1.5% by mass or less, and more preferably 0% by mass or more.
- the cleaning composition according to any one of ⁇ 1> to ⁇ 13> which is more preferably 1.3% by mass or less, and still more preferably 0% by mass or more and 1.0% by mass or less.
- the total content of organic substances in the cleaning composition is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.
- the total content of organic substances in the cleaning composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more, from ⁇ 1> to ⁇
- the cleaning composition according to any one of 15> is more preferably 1.3% by mass or less, and still more preferably 0% by mass or more and 1.0% by mass or less.
- the total content of organic substances in the cleaning composition is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably
- the cleaning composition according to any one of ⁇ 1> to ⁇ 16> which is substantially free of a nitrogen-containing compound and a phosphorus-containing compound.
- the total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning composition is less than 0.1 mass%, preferably 0.05 mass% or less, more preferably 0.01 mass% or less,
- the cleaning composition according to any one of ⁇ 1> to ⁇ 18>, wherein the pH during use of the cleaning composition is preferably 10.0 or more, and more preferably 10.5 or more.
- the pH in use of the cleaning composition is preferably 14 or less, more preferably 13.9 or less, and even more preferably 13.7 or less, the cleaning agent according to any one of ⁇ 1> to ⁇ 19> Composition.
- the content of component A in the concentrate of the detergent composition is preferably 1% by mass or more, more preferably 2% by mass or more, and more preferably 5% by mass or more.
- the content of component A in the concentrate of the detergent composition is preferably 40% by mass or less, more preferably 30% by mass or less, and 20% by mass or less.
- the content of Component B in the concentrate of the detergent composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0
- the content of component B in the concentrate of the detergent composition is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 2% by mass or less.
- the content of component C in the concentrate of the detergent composition is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more.
- the content of component C in the concentrate of the detergent composition is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less.
- the cleaning composition according to any one of ⁇ 1> to ⁇ 25> which is more preferable.
- the pH of the cleaning composition concentrate is preferably 10.0 or more, more preferably 10.5 or more, any one of ⁇ 1> to ⁇ 26> The cleaning composition described in 1.
- the cleaning composition is a concentrate, the cleaning composition according to any one of ⁇ 1> to ⁇ 27>, wherein the pH of the cleaning composition is preferably 14 or less.
- the resin mask is a negative dry film resist subjected to at least one of exposure and development.
- ⁇ 30> A method for removing a resin mask, comprising a step of cleaning an object to be cleaned to which a resin mask is adhered with the cleaning composition according to any one of ⁇ 1> to ⁇ 29>.
- the removal method according to ⁇ 30>, wherein the object to be cleaned is a manufacturing intermediate for electronic components.
- ⁇ 32> A method for manufacturing an electronic component, comprising a step of cleaning an object to be cleaned to which a resin mask is attached with the cleaning composition according to any one of ⁇ 1> or ⁇ 29>.
- ⁇ 33> Use of the cleaning composition according to any one of ⁇ 1> to ⁇ 29> for manufacturing an electronic component.
- a kit comprising at least one of the components A to C constituting the detergent composition in a state where it is not mixed with other components.
- a solution containing component A (first liquid) and a solution containing component B (second liquid) are included in a state where they are not mixed with each other, and at least one of the first liquid and the second liquid is The kit according to ⁇ 34>, further comprising component C, wherein the first liquid and the second liquid are mixed at the time of use.
- ⁇ 36> Use of the cleaning composition according to any one of ⁇ 1> to ⁇ 29> for removing a resin mask from an object to be cleaned.
- ⁇ 37> Use of the cleaning composition according to any one of ⁇ 1> to ⁇ 29> for cleaning an electronic component.
- a photosensitive film for direct imaging (direct drawing) (manufactured by Hitachi Chemical Co., Ltd., Photec RD-1215, negative dry film resist) is applied to the surface of a glass epoxy multilayer substrate (manufactured by Hitachi Chemical Co., Ltd., MCL-E-679FG) as follows. After laminating under conditions, selectively exposing to cure the exposed area (exposure process), developing to remove the unexposed area (developing process), resist pattern (negative pattern of the following three pattern shapes) A substrate having a resin mask) was obtained. And the test piece (4 cm x 4.5 cm) was obtained by carrying out the copper plating process to the area
- Examples 27 to 29 and Comparative Examples 20 to 22 Add 10 kg of each of the detergent compositions of Examples 27 to 29 and Comparative Examples 20 to 22 to a 10 L stainless beaker, heat to 60 ° C., and spray 1 fluid nozzle (full cone) JJXP030 (manufactured by Ikeuchi Co., Ltd.) The test piece is sprayed for 3 minutes (pressure: 0.2 MPa, spray distance: 8 cm) while circulating at a flow rate of 3 L / min with a box type spray washing machine attached as a nozzle. And after immersing and immersing in the rinse tank which added 100g of water to a 100 mL glass beaker, it dries with a nitrogen blow.
- solid peelability indicates the peelability of the resin mask when the resist pattern is solid
- the cleaning compositions of Examples 1 to 29 are comparative examples 1 to 16, which do not contain a predetermined solvent (component B), inorganic alkalis Compared with Comparative Examples 17 to 22 not containing (Component A), the plated resin mask could be removed efficiently. That is, the cleaning compositions of Examples 1 to 29 were excellent in resin mask removability as compared with Comparative Examples 1 to 22.
- the cleaning composition of the present disclosure is useful as a cleaning composition used in the manufacturing process of an electronic component, shortening the cleaning process of the electronic component to which the resin mask is adhered, and the performance of the manufactured electronic component. Reliability can be improved and productivity of the semiconductor device can be improved.
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Abstract
The purpose of the present invention is to provide a cleaning agent composition for resin mask detachment having superior resin mask removal properties and little waste water treatment burden. This disclosure relates to a cleaning agent composition for resin mask detachment wherein, in an embodiment: the cleaning agent composition includes an inorganic alkali (component A), an organic solvent (component B), and water (component C); the coordinates of the Hansen solubility parameter for component B are within a range of a 1.5 MPa0.5 sphere centered on δd = 17.5, δp = 5.0, and δh = 11.5; the component C content during use of the cleaning agent composition is 85% by mass or greater; and the mass ratio (A/B) of component A to component B is 1 - 60.
Description
本開示は、樹脂マスク剥離用洗浄剤組成物、該洗浄剤組成物を用いた樹脂マスクの除去方法及び電子部品の製造方法に関する。
The present disclosure relates to a resin mask peeling cleaning composition, a resin mask removing method using the cleaning composition, and an electronic component manufacturing method.
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, in personal computers and various electronic devices, low power consumption, high processing speed, and miniaturization have progressed, and the wiring of package boards and the like mounted thereon has been miniaturized year by year. The metal mask method has been mainly used to form such fine wiring and connection terminals such as pillars and bumps. However, it is difficult to respond to miniaturization of wiring etc. because of its low versatility. 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、その際にアルカリ性の剥離用洗浄剤が使用される。このような剥離用洗浄剤として、例えば、特許文献１には、洗浄剤組成物１００質量部中、第四級アンモニウム水酸化物を０．５質量部以上３．０質量部以下含有し、水溶性アミンを３．０質量部以上１０．０質量部以下含有し、酸又はそのアンモニウム塩を０．３質量部以上２．５質量部以下含有し、水を５０．０質量部以上９５．０質量部以下含有する回路基板の製造に用いる樹脂マスク層用洗浄剤組成物が記載されている。
As a new method, a method of using a dry film resist as a thick film resin mask instead of a metal mask is known. The resin mask is finally peeled and removed, and an alkaline peeling cleaning agent is used at that time. As such a cleaning agent for peeling, for example, Patent Document 1 contains 0.5 to 3.0 parts by mass of quaternary ammonium hydroxide in 100 parts by mass of the cleaning composition, Containing 3.0 parts by weight or more and 10.0 parts by weight or less of an acidic amine, 0.3 parts by weight or more and 2.5 parts by weight or less of an acid or an ammonium salt thereof, and 50.0 parts by weight or more and 95.0 parts by weight of water. The cleaning composition for resin mask layers used for manufacture of the circuit board containing below mass part is described.
特許文献２には、組成物の全重量の約２～５５重量％の少なくとも１種類のアルカノールアミン、少なくとも１種類のモルホリン、又はこれらの混合物と、約２０～９４重量％の少なくとも１種類の有機溶媒と、約０．５～６０重量％の水とを含むフィルム・レジストを除去するための組成物が記載されている。
Patent Document 2 discloses that about 2 to 55% by weight of the total weight of the composition of at least one alkanolamine, at least one morpholine, or a mixture thereof and about 20 to 94% by weight of at least one organic. A composition for removing a film resist comprising a solvent and about 0.5-60% by weight water is described.
特許文献３には、ＩＣやＬＳＩ等の半導体素子や液晶パネル素子製造時のエッチングやアッシング（灰化）の後に発生する残渣物の除去に使用する、（ａ）フッ素化合物、（ｂ）分子内にエーテル結合を有する２価のアルコール化合物、（ｃ）有機酸化合物、及び（ｄ）水を含有してなるレジスト剥離液が記載されている。
Patent Document 3 discloses that (a) a fluorine compound, (b) an intramolecular molecule used for removal of residues generated after etching and ashing (ashing) in the manufacture of semiconductor elements such as IC and LSI and liquid crystal panel elements. Describes a resist stripping solution containing a divalent alcohol compound having an ether bond, (c) an organic acid compound, and (d) water.
特許文献４には、いわゆるレジスト用現像液として、エポキシ樹脂系フォトソルダーレジストの未感光部分を剥離する剥離液であって、アルカリ溶液にプロピレン系グリコールエーテルの添加剤を添加したことを特徴とする剥離液が記載されている。
Patent Document 4 is a stripping solution for stripping an unexposed portion of an epoxy resin photosolder resist as a so-called resist developing solution, and is characterized in that an additive of propylene glycol ether is added to an alkaline solution. A stripping solution is described.
特許文献５には、基板上にコーティングされるレジスト膜の縁部または基板の後面に形成される不要な膜成分のレジストを除去し、装備の腐蝕を防止するための、ａ）無機アルカリ化合物０．１乃至５重量％、ｂ）有機アミン０．１乃至５重量％、ｃ）有機溶剤０．１乃至３０重量％、ｄ）アニオン系界面活性剤及びノニオン系界面活性剤を１:５乃至２５の重量比で含む界面活性剤０．０１乃至５重量％、及びｅ）水６０乃至９９重量％、を含むことを特徴とするレジスト除去用シンナー組成物が記載されている。
In Patent Document 5, a) inorganic alkali compound 0 for removing the resist of unnecessary film components formed on the edge of the resist film coated on the substrate or on the rear surface of the substrate and preventing the corrosion of the equipment. 1 to 5% by weight, b) 0.1 to 5% by weight of organic amine, c) 0.1 to 30% by weight of organic solvent, d) 1: 5 to 25 of anionic surfactant and nonionic surfactant There is described a thinner composition for resist removal characterized by containing 0.01 to 5% by weight of a surfactant in a weight ratio of e) and 60 to 99% by weight of 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メッキ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。樹脂マスクは、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。そして、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。しかし、これら接続部形成時に使用されるメッキ処理や加熱処理等によって樹脂マスクの特性が変化し、次工程の洗浄工程において樹脂マスクを除去しにくくなってしまう。特に、ネガ型レジストは、光や電子線との反応により硬化する特性を有することから、ネガ型レジストを用いて形成された樹脂マスクは、接続部形成時に使用されるメッキ処理や加熱処理等によって必要以上に硬化が進み、洗浄工程で完全に除去できないか、あるいは、除去にかかる時間が非常に長くなることで基板や金属表面にダメージを与えてしまう。このようにメッキ処理及び／又は加熱処理された樹脂マスクは剥離しにくいため、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、様々な分野において電子化が進みプリント基板等の生産量が増加している。さらに、利用される機器や装置の小型化、処理速度の高速化、消費電力を低減するため、配線が微細化、多層化し、剥離・洗浄工程が増加し、洗浄剤組成物の使用量も増加する傾向にある。この洗浄剤組成物の使用量の増加に伴い、洗浄剤組成物やリンス水等の廃液の排水処理負荷や廃液流入による湖沼の富栄養化も増大していることから、排水処理負荷が小さく、湖沼の富栄養化の原因となる窒素及びリンを含有せず、樹脂マスクを効率よく除去できる洗浄剤組成物が強く要望されている。しかし、前記特許文献に記載の方法では、高い樹脂マスク除去性と低い排水処理負荷の両立が難しい。 In forming fine wiring on a printed circuit board, etc., not only the resin mask remains, but also the cleaning agent composition to reduce the residual of auxiliary agents contained in solder and plating solution used for fine wiring and bump formation. Goods are required to have high cleanability. The resin mask is formed using a resist whose physical properties such as solubility in a developing solution are changed by light, electron beam, or the like. Resists are roughly classified into negative types and positive types according to the method of reaction with light or electron beams. A negative resist has a characteristic that the solubility in a developing solution is lowered when exposed. A layer containing a negative resist (hereinafter also referred to as a “negative resist layer”) has an exposed portion after exposure and development processing. Used as a resin mask. A positive resist has a property of increasing the solubility in a developer when exposed to light. A layer containing a positive resist (hereinafter also referred to as a “positive resist layer”) has an exposed portion after exposure and development processing. The unexposed part is removed and used as a resin mask. By using a resin mask having such characteristics, it is possible to form fine connection portions of a circuit board such as metal wiring, metal pillars, and solder bumps. However, the characteristics of the resin mask change due to the plating process or the heat treatment used when these connection parts are formed, and it becomes difficult to remove the resin mask in the next cleaning process. In particular, since negative resists have the property of being cured by reaction with light or electron beams, resin masks formed using negative resists can be obtained by plating or heat treatment used at the time of forming connection parts. Curing progresses more than necessary and cannot be completely removed in the cleaning process, or the time required for removal becomes very long, thereby damaging the substrate and the metal surface. Since the resin mask that has been plated and / or heat-treated in this manner is difficult to peel off, the cleaning composition is required to have high resin mask removability.
On the other hand, digitization has progressed in various fields, and the production volume of printed circuit boards and the like has increased. Furthermore, in order to reduce the size of equipment and devices used, increase the processing speed, and reduce power consumption, wiring is miniaturized and multilayered, peeling and cleaning processes increase, and the amount of cleaning composition used also increases. Tend to. With the increase in the amount of use of this detergent composition, wastewater treatment load of waste liquid such as detergent composition and rinse water and eutrophication of lakes due to inflow of waste liquid are increasing, so the wastewater treatment load is small, There is a strong demand for a cleaning composition that does not contain nitrogen and phosphorus that cause eutrophication of lakes and can efficiently remove the resin mask. However, in the method described in the patent document, it is difficult to achieve both high resin mask removability and low wastewater treatment load.
一方、様々な分野において電子化が進みプリント基板等の生産量が増加している。さらに、利用される機器や装置の小型化、処理速度の高速化、消費電力を低減するため、配線が微細化、多層化し、剥離・洗浄工程が増加し、洗浄剤組成物の使用量も増加する傾向にある。この洗浄剤組成物の使用量の増加に伴い、洗浄剤組成物やリンス水等の廃液の排水処理負荷や廃液流入による湖沼の富栄養化も増大していることから、排水処理負荷が小さく、湖沼の富栄養化の原因となる窒素及びリンを含有せず、樹脂マスクを効率よく除去できる洗浄剤組成物が強く要望されている。しかし、前記特許文献に記載の方法では、高い樹脂マスク除去性と低い排水処理負荷の両立が難しい。 In forming fine wiring on a printed circuit board, etc., not only the resin mask remains, but also the cleaning agent composition to reduce the residual of auxiliary agents contained in solder and plating solution used for fine wiring and bump formation. Goods are required to have high cleanability. The resin mask is formed using a resist whose physical properties such as solubility in a developing solution are changed by light, electron beam, or the like. Resists are roughly classified into negative types and positive types according to the method of reaction with light or electron beams. A negative resist has a characteristic that the solubility in a developing solution is lowered when exposed. A layer containing a negative resist (hereinafter also referred to as a “negative resist layer”) has an exposed portion after exposure and development processing. Used as a resin mask. A positive resist has a property of increasing the solubility in a developer when exposed to light. A layer containing a positive resist (hereinafter also referred to as a “positive resist layer”) has an exposed portion after exposure and development processing. The unexposed part is removed and used as a resin mask. By using a resin mask having such characteristics, it is possible to form fine connection portions of a circuit board such as metal wiring, metal pillars, and solder bumps. However, the characteristics of the resin mask change due to the plating process or the heat treatment used when these connection parts are formed, and it becomes difficult to remove the resin mask in the next cleaning process. In particular, since negative resists have the property of being cured by reaction with light or electron beams, resin masks formed using negative resists can be obtained by plating or heat treatment used at the time of forming connection parts. Curing progresses more than necessary and cannot be completely removed in the cleaning process, or the time required for removal becomes very long, thereby damaging the substrate and the metal surface. Since the resin mask that has been plated and / or heat-treated in this manner is difficult to peel off, the cleaning composition is required to have high resin mask removability.
On the other hand, digitization has progressed in various fields, and the production volume of printed circuit boards and the like has increased. Furthermore, in order to reduce the size of equipment and devices used, increase the processing speed, and reduce power consumption, wiring is miniaturized and multilayered, peeling and cleaning processes increase, and the amount of cleaning composition used also increases. Tend to. With the increase in the amount of use of this detergent composition, wastewater treatment load of waste liquid such as detergent composition and rinse water and eutrophication of lakes due to inflow of waste liquid are increasing, so the wastewater treatment load is small, There is a strong demand for a cleaning composition that does not contain nitrogen and phosphorus that cause eutrophication of lakes and can efficiently remove the resin mask. However, in the method described in the patent document, it is difficult to achieve both high resin mask removability and low wastewater treatment load.
そこで、本開示は、樹脂マスク除去性に優れ、排水処理負荷の小さい樹脂マスク剥離用洗浄剤組成物、該洗浄剤組成物を用いた樹脂マスクの除去方法及び基板の製造方法を提供する。
Therefore, the present disclosure provides a resin mask peeling cleaning composition having excellent resin mask removability and a small wastewater treatment load, a resin mask removing method and a substrate manufacturing method using the cleaning composition.
本開示は、一態様において、無機アルカリ（成分Ａ）、有機溶剤（成分Ｂ）及び水（成分Ｃ）を含有し、
成分Ｂのハンセン溶解度パラメータの座標が、δｄ＝１７．５、δｐ＝５．０、δｈ＝１１．５を中心とする半径１．５ＭＰａ0.5の球の範囲内であり、
洗浄剤組成物の使用時における成分Ｃの含有量が、８５質量％以上であり、
成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）が、１以上６０以下である、樹脂マスク剥離用洗浄剤組成物に関する。 In one aspect, the present disclosure contains an inorganic alkali (component A), an organic solvent (component B), and water (component C).
The Hansen solubility parameter coordinates of component B are within the range of a sphere with a radius of 1.5 MPa 0.5 centered at δd = 17.5, δp = 5.0, δh = 11.5,
The content of Component C when using the cleaning composition is 85% by mass or more,
It is related with the cleaning composition for resin mask peeling whose mass ratio (A / B) of component A with respect to component B is 1 or more and 60 or less.
成分Ｂのハンセン溶解度パラメータの座標が、δｄ＝１７．５、δｐ＝５．０、δｈ＝１１．５を中心とする半径１．５ＭＰａ0.5の球の範囲内であり、
洗浄剤組成物の使用時における成分Ｃの含有量が、８５質量％以上であり、
成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）が、１以上６０以下である、樹脂マスク剥離用洗浄剤組成物に関する。 In one aspect, the present disclosure contains an inorganic alkali (component A), an organic solvent (component B), and water (component C).
The Hansen solubility parameter coordinates of component B are within the range of a sphere with a radius of 1.5 MPa 0.5 centered at δd = 17.5, δp = 5.0, δh = 11.5,
The content of Component C when using the cleaning composition is 85% by mass or more,
It is related with the cleaning composition for resin mask peeling whose mass ratio (A / B) of component A with respect to component B is 1 or more and 60 or less.
本開示は、一態様において、樹脂マスクが付着した被洗浄物を本開示に係る洗浄剤組成物で洗浄する工程を含む、樹脂マスクの除去方法に関する。
The present disclosure, in one aspect, relates to a method for removing a resin mask, including a step of cleaning an object to be cleaned to which the resin mask is attached with the cleaning composition according to the present disclosure.
本開示は、一態様において、樹脂マスクが付着した被洗浄物を本開示に係る洗浄剤組成物で洗浄する工程を含む、電子部品の製造方法に関する。
The present disclosure, in one aspect, relates to a method for manufacturing an electronic component including a step of cleaning an object to be cleaned to which a resin mask is attached with the cleaning composition according to the present disclosure.
本開示は、一態様において、本開示に係る洗浄剤組成物の、電子部品の製造への使用に関する。
The present disclosure, in one aspect, relates to the use of the cleaning composition according to the present disclosure for the manufacture of electronic components.
本開示によれば、樹脂マスク除去性に優れ、排水処理負荷の小さい樹脂マスク剥離用洗浄剤組成物を提供できる。そして、本開示に係る洗浄剤組成物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。さらに、本開示に係る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, it is possible to provide a resin mask peeling cleaning composition having excellent resin mask removability and a small wastewater treatment load. And by using the cleaning composition according to the present disclosure, a high-quality electronic component can be obtained with a high yield. Furthermore, an electronic component having a fine wiring pattern can be efficiently manufactured by using the cleaning composition according to the present disclosure.
本開示は、無機アルカリ（成分Ａ）、特定のハンセン溶解度パラメータを有する有機溶剤（成分Ｂ）及び水（成分Ｃ）を含有し、成分Ｃの含有量、及び成分Ａと成分Ｂとの質量比が特定された洗浄剤組成物を用いることで、低い排水処理負荷であっても、樹脂マスク、特にメッキ処理及び／又は加熱処理された樹脂マスクを効率よく除去できるという知見に基づく。また、洗浄剤組成物中に窒素含有化合物及びリン含有化合物を含有させないことで、湖沼の富栄養化を抑制できるという知見に基づく。
The present disclosure includes an inorganic alkali (component A), an organic solvent (component B) having a specific Hansen solubility parameter, and water (component C), the content of component C, and the mass ratio of component A and component B Is based on the knowledge that the resin mask, in particular, the plating mask and / or the heat-treated resin mask can be efficiently removed even with a low wastewater treatment load. Moreover, it is based on the knowledge that eutrophication of a lake can be suppressed by not including a nitrogen-containing compound and a phosphorus-containing compound in a cleaning composition.
すなわち、本開示は、一態様において、無機アルカリ（成分Ａ）、有機溶剤（成分Ｂ）及び水（成分Ｃ）を含有し、成分Ｂのハンセン溶解度パラメータの座標が、δｄ＝１７．５、δｐ＝５．０、δｈ＝１１．５を中心とする半径１．５ＭＰａ0.5の球の範囲内であり、洗浄剤組成物の使用時における成分Ｃの含有量が、８５質量％以上であり、成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）が、１以上６０以下である、樹脂マスク剥離用洗浄剤組成物（以下、「本開示に係る洗浄剤組成物」ともいう）に関する。本開示によれば、樹脂マスク除去性に優れ、排水処理負荷の小さい洗浄剤組成物を提供できる。よって、本開示に係る洗浄剤組成物は、低い排水処理負荷であっても、樹脂マスク、特に、メッキ処理及び／又は加熱処理された樹脂マスクを効率よく除去できる。そして、本開示に係る洗浄剤組成物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。さらに、本開示に係る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。
That is, in one aspect, the present disclosure contains an inorganic alkali (component A), an organic solvent (component B), and water (component C), and the coordinates of the Hansen solubility parameter of component B are δd = 17.5, δp = 5.0, δh = 11.5 in the range of a sphere having a radius of 1.5 MPa 0.5 , the content of component C when using the cleaning composition is 85% by mass or more, The present invention relates to a resin mask peeling cleaning composition (hereinafter, also referred to as “cleaning composition according to the present disclosure”) in which the mass ratio (A / B) of component A to B is 1 or more and 60 or less. According to the present disclosure, it is possible to provide a cleaning composition having excellent resin mask removability and a small wastewater treatment load. Therefore, the cleaning composition according to the present disclosure can efficiently remove a resin mask, in particular, a plating mask and / or a heat-treated resin mask, even at a low wastewater treatment load. And by using the cleaning composition according to the present disclosure, a high-quality electronic component can be obtained with a high yield. Furthermore, an electronic component having a fine wiring pattern can be efficiently manufactured by using the cleaning composition according to the present disclosure.
本開示に係る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。
一般に、樹脂マスクの剥離は、洗浄剤組成物の成分が樹脂マスクに浸透し、樹脂マスクが膨潤することによる界面ストレスに起因すると考えられている。本開示に係る洗浄剤組成物では、成分Ａ（無機アルカリ）と成分Ｃ（水）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、さら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。このとき、特定のハンセン溶解度パラメータを有する成分Ｂ（有機溶剤）が基板表面と樹脂マスクとの間に作用することで、基板－樹脂間の密着力が低下してさらに樹脂マスクの剥離を促進し、樹脂マスク除去性が格段に向上するものと推定される。
また、本開示に係る洗浄剤組成物は、特定のハンセン溶解度パラメータを有する成分Ｂを、特定の質量比（Ａ／Ｂ＝１～６０）で含有することで、成分Ｂと樹脂マスクの樹脂成分との相溶性が高くなり、樹脂マスクと水との界面において効果的な剥離作用が発揮され、樹脂マスク除去性がより向上すると推定される。
さらに、本開示に係る洗浄剤組成物の使用時における成分Ｃの水の含有量は８５質量％以上と多いことから、洗浄剤組成物中の有機物含有量を低減でき、排水処理負荷の増大を抑制できると推定される。これにより、効率よくかつ高い清浄度で基板上に微細な回路（配線パターン）の形成が可能になると考えられる。
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 action mechanism of the effect in the cleaning composition according to the present disclosure are unclear, it is estimated as follows.
In general, it is considered that the peeling of the resin mask is caused by interfacial stress due to the components of the cleaning composition penetrating into the resin mask and swelling of the resin mask. In the cleaning composition according to the present disclosure, component A (inorganic alkali) and component C (water) penetrate into the resin mask, thereby promoting dissociation of the alkali-soluble resin blended in the resin mask and further charge repulsion. This promotes the peeling of the resin mask. At this time, the component B (organic solvent) having a specific Hansen solubility parameter acts between the substrate surface and the resin mask, so that the adhesion between the substrate and the resin is reduced, and further the peeling of the resin mask is promoted. It is estimated that the resin mask removability is remarkably improved.
Further, the cleaning composition according to the present disclosure contains component B having a specific Hansen solubility parameter at a specific mass ratio (A / B = 1 to 60), so that the resin component of component B and the resin mask can be obtained. It is presumed that the compatibility with the resin mask increases, an effective peeling action is exhibited at the interface between the resin mask and water, and the resin mask removability is further improved.
Furthermore, since the content of the water of component C at the time of use of the cleaning composition according to the present disclosure is as high as 85% by mass or more, the content of organic matter in the cleaning composition can be reduced, and the wastewater treatment load is increased. It is estimated that it can be suppressed. Thereby, it is considered that a fine circuit (wiring pattern) can be formed on the substrate efficiently and with high cleanliness.
However, the present disclosure is not limited to this mechanism.
一般に、樹脂マスクの剥離は、洗浄剤組成物の成分が樹脂マスクに浸透し、樹脂マスクが膨潤することによる界面ストレスに起因すると考えられている。本開示に係る洗浄剤組成物では、成分Ａ（無機アルカリ）と成分Ｃ（水）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、さら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。このとき、特定のハンセン溶解度パラメータを有する成分Ｂ（有機溶剤）が基板表面と樹脂マスクとの間に作用することで、基板－樹脂間の密着力が低下してさらに樹脂マスクの剥離を促進し、樹脂マスク除去性が格段に向上するものと推定される。
また、本開示に係る洗浄剤組成物は、特定のハンセン溶解度パラメータを有する成分Ｂを、特定の質量比（Ａ／Ｂ＝１～６０）で含有することで、成分Ｂと樹脂マスクの樹脂成分との相溶性が高くなり、樹脂マスクと水との界面において効果的な剥離作用が発揮され、樹脂マスク除去性がより向上すると推定される。
さらに、本開示に係る洗浄剤組成物の使用時における成分Ｃの水の含有量は８５質量％以上と多いことから、洗浄剤組成物中の有機物含有量を低減でき、排水処理負荷の増大を抑制できると推定される。これにより、効率よくかつ高い清浄度で基板上に微細な回路（配線パターン）の形成が可能になると考えられる。
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 action mechanism of the effect in the cleaning composition according to the present disclosure are unclear, it is estimated as follows.
In general, it is considered that the peeling of the resin mask is caused by interfacial stress due to the components of the cleaning composition penetrating into the resin mask and swelling of the resin mask. In the cleaning composition according to the present disclosure, component A (inorganic alkali) and component C (water) penetrate into the resin mask, thereby promoting dissociation of the alkali-soluble resin blended in the resin mask and further charge repulsion. This promotes the peeling of the resin mask. At this time, the component B (organic solvent) having a specific Hansen solubility parameter acts between the substrate surface and the resin mask, so that the adhesion between the substrate and the resin is reduced, and further the peeling of the resin mask is promoted. It is estimated that the resin mask removability is remarkably improved.
Further, the cleaning composition according to the present disclosure contains component B having a specific Hansen solubility parameter at a specific mass ratio (A / B = 1 to 60), so that the resin component of component B and the resin mask can be obtained. It is presumed that the compatibility with the resin mask increases, an effective peeling action is exhibited at the interface between the resin mask and water, and the resin mask removability is further improved.
Furthermore, since the content of the water of component C at the time of use of the cleaning composition according to the present disclosure is as high as 85% by mass or more, the content of organic matter in the cleaning composition can be reduced, and the wastewater treatment load is increased. It is estimated that it can be suppressed. Thereby, it is considered that a fine circuit (wiring pattern) can be formed on the substrate efficiently and with high cleanliness.
However, the present disclosure is not limited to this mechanism.
本開示において樹脂マスクとは、エッチング、メッキ、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、露光又は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、又は、レジストフィルムが挙げられる。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 is a mask for protecting a material surface from processing such as etching, plating, and heating, that is, a mask that functions as a protective film. As the resin mask, in one or a plurality of embodiments, the resist layer after the exposure or development step, and at least one treatment of exposure and development (hereinafter, also referred to as “exposure and / or development treatment”) are performed. A resist layer or a cured resist layer may be mentioned. As a resin material for forming the resin mask, in one or a plurality of embodiments, a film-like photosensitive resin or a resist film may be used. A general-purpose resist film can be used.
［成分Ａ：無機アルカリ］
本開示に係る洗浄剤組成物は、無機アルカリ（成分Ａ）を含む。成分Ａは、１種又は２種以上を併用して用いることができる。 [Component A: Inorganic alkali]
The cleaning composition according to the present disclosure includes an inorganic alkali (component A). Component A can be used alone or in combination of two or more.
本開示に係る洗浄剤組成物は、無機アルカリ（成分Ａ）を含む。成分Ａは、１種又は２種以上を併用して用いることができる。 [Component A: Inorganic alkali]
The cleaning composition according to the present disclosure includes an inorganic alkali (component A). Component A can be used alone or in combination of two or more.
成分Ａとしては、例えば、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１種又は２種以上の組合せが挙げられ、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い。
Component A includes, for example, one or a combination of two or more selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium silicate and potassium silicate, and resin. From the viewpoint of improving mask removability, one or a combination of two or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate is preferable, and at least one of sodium hydroxide and potassium hydroxide is more preferable.
本開示に係る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、０．１質量％以上が好ましく、０．３質量％以上がより好ましく、０．５質量％以上が更に好ましく、１質量％以上がより更に好ましく、２質量％以上がより更に好ましく、そして、樹脂マスク除去性向上及び金属腐食抑制の観点から、１５質量％以下が好ましく、１０質量％以下がより好ましく、７質量％以下が更に好ましく、５質量％以下がより更に好ましい。成分Ａが２種以上の無機アルカリからなる場合、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 during use of the cleaning composition according to the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, from the viewpoint of improving resin mask removability. More preferably 1% by weight or more, still more preferably 1% by weight or more, still more preferably 2% by weight or more, and preferably 15% by weight or less from the viewpoint of improving resin mask removability and suppressing metal corrosion. The following is more preferable, 7% by mass or less is further preferable, and 5% by mass or less is more preferable. When component A is composed of two or more inorganic alkalis, the content of component A refers to the total content thereof.
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、洗浄剤組成物を洗浄に使用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 when using the cleaning composition” refers to the content of each component at the time of cleaning, that is, when the cleaning composition is used for cleaning.
［成分Ｂ：有機溶剤］
本開示に係る洗浄剤組成物は、有機溶剤（成分Ｂ）を含む。成分Ｂは、１種又は２種以上を併用して用いることができる。 [Component B: Organic solvent]
The cleaning composition according to the present disclosure includes an organic solvent (component B). Component B can be used alone or in combination of two or more.
本開示に係る洗浄剤組成物は、有機溶剤（成分Ｂ）を含む。成分Ｂは、１種又は２種以上を併用して用いることができる。 [Component B: Organic solvent]
The cleaning composition according to the present disclosure includes an organic solvent (component B). Component B can be used alone or in combination of two or more.
本開示において、成分Ｂのハンセン溶解度パラメータの座標は、δｄ＝１７．５、δｐ＝５．０、δｈ＝１１．５を中心とする半径１．５ＭＰａ0.5の球の範囲内である。本開示に係る洗浄剤組成物が２種以上の有機溶剤（以下、「混合有機溶剤」ともいう）を含む場合、混合有機溶剤全体のハンセン溶解度パラメータは上記範囲内でなくてもよく、混合有機溶剤中に上記範囲内のハンセン溶解度パラメータを有する有機溶剤が少なくとも１種含まれていれば、本開示の効果は発揮されうる。
In the present disclosure, the coordinates of the Hansen solubility parameter of component B are within the range of a sphere with a radius of 1.5 MPa 0.5 centered at δd = 17.5, δp = 5.0, and δh = 11.5. When the cleaning composition according to the present disclosure contains two or more kinds of organic solvents (hereinafter also referred to as “mixed organic solvents”), the Hansen solubility parameter of the entire mixed organic solvent may not be within the above range. If the solvent contains at least one organic solvent having a Hansen solubility parameter within the above range, the effects of the present disclosure can be exhibited.
ここで、ハンセン溶解度パラメータ (Hansen solubility parameter)（以下、「ＨＳＰ」ともいう)とは、Charles M. Hansenが１９６７年に発表した、物質の溶解性の予測に用いられる値であって、「分子間の相互作用が似ている２つの物質は、互いに溶解しやすい」との考えに基づくパラメータである。ＨＳＰは以下の３つのパラメータ（単位：ＭＰａ0.5）で構成されている。
δｄ：分子間の分散力によるエネルギー
δｐ：分子間の双極子相互作用によるエネルギー
δｈ：分子間の水素結合によるエネルギー
これら３つのパラメータは３次元空間（ハンセン空間）における座標とみなすことができ、２つの物質のＨＳＰをハンセン空間内に置いたとき、２点間の距離が近ければ近いほど互いに溶解しやすいことを示している。化学工業２０１０年３月号（化学工業社）等に詳細な説明があり、パソコン用ソフト「HSPiP：Hansen Solubility Parameters in Practice」等を用いることで各種物質のハンセン溶解度パラメータを得ることができる。本開示は、このパソコン用ソフト「HSPiP：Hansen Solubility Parameters in Practice」を用いて得られたハンセン溶解度パラメータを用いている。 Here, the Hansen solubility parameter (hereinafter also referred to as “HSP”) is a value used to predict the solubility of a substance, published in 1967 by Charles M. Hansen. It is a parameter based on the idea that two substances having similar interactions between each other are easily dissolved. The HSP is composed of the following three parameters (unit: MPa 0.5 ).
δd: energy due to intermolecular dispersion force δp: energy due to dipolar interaction between molecules δh: energy due to hydrogen bonds between molecules These three parameters can be regarded as coordinates in a three-dimensional space (Hansen space). When the HSPs of two substances are placed in the Hansen space, the closer the distance between the two points is, the easier it is to dissolve each other. There is a detailed explanation in the March, 2010 issue of Chemical Industry (Chemical Industry Co., Ltd.), and Hansen Solubility Parameters of various substances can be obtained by using PC software “HSPiP: Hansen Solubility Parameters in Practice”. The present disclosure uses Hansen solubility parameters obtained using the personal computer software “HSPiP: Hansen Solubility Parameters in Practice”.
δｄ：分子間の分散力によるエネルギー
δｐ：分子間の双極子相互作用によるエネルギー
δｈ：分子間の水素結合によるエネルギー
これら３つのパラメータは３次元空間（ハンセン空間）における座標とみなすことができ、２つの物質のＨＳＰをハンセン空間内に置いたとき、２点間の距離が近ければ近いほど互いに溶解しやすいことを示している。化学工業２０１０年３月号（化学工業社）等に詳細な説明があり、パソコン用ソフト「HSPiP：Hansen Solubility Parameters in Practice」等を用いることで各種物質のハンセン溶解度パラメータを得ることができる。本開示は、このパソコン用ソフト「HSPiP：Hansen Solubility Parameters in Practice」を用いて得られたハンセン溶解度パラメータを用いている。 Here, the Hansen solubility parameter (hereinafter also referred to as “HSP”) is a value used to predict the solubility of a substance, published in 1967 by Charles M. Hansen. It is a parameter based on the idea that two substances having similar interactions between each other are easily dissolved. The HSP is composed of the following three parameters (unit: MPa 0.5 ).
δd: energy due to intermolecular dispersion force δp: energy due to dipolar interaction between molecules δh: energy due to hydrogen bonds between molecules These three parameters can be regarded as coordinates in a three-dimensional space (Hansen space). When the HSPs of two substances are placed in the Hansen space, the closer the distance between the two points is, the easier it is to dissolve each other. There is a detailed explanation in the March, 2010 issue of Chemical Industry (Chemical Industry Co., Ltd.), and Hansen Solubility Parameters of various substances can be obtained by using PC software “HSPiP: Hansen Solubility Parameters in Practice”. The present disclosure uses Hansen solubility parameters obtained using the personal computer software “HSPiP: Hansen Solubility Parameters in Practice”.
本開示における成分ＢのＨＳＰの座標は、下記のように表現することもできる。すなわち、成分ＢのＨＳＰの座標を（δｄB、δｐB、δｈB）としたとき、該成分ＢのＨＳＰの座標（δｄB、δｐB、δｈB）と成分座標Ｘ（δｄ＝１７．５、δｐ＝５．０、δｈ＝１１．５）との距離（単位：ＭＰａ0.5）が下記式を満たすものとすることができる。
距離＝［（δｄB－１７．５）2＋（δｐB－５．０）2＋（δｈB－１１．５）2］0.5
≦１．５ＭＰａ0.5 The HSP coordinates of component B in the present disclosure can also be expressed as follows. That is, assuming that the HSP coordinates of the component B are (δd B , δp B , δh B ), the HSP coordinates (δd B , δp B , δh B ) of the component B and the component coordinates X (δd = 17.5) , Δp = 5.0, δh = 11.5) (unit: MPa 0.5 ) can satisfy the following formula.
Distance = [(δd B −17.5) 2 + (δp B −5.0) 2 + (δh B −11.5) 2 ] 0.5
≦ 1.5 MPa 0.5
距離＝［（δｄB－１７．５）2＋（δｐB－５．０）2＋（δｈB－１１．５）2］0.5
≦１．５ＭＰａ0.5 The HSP coordinates of component B in the present disclosure can also be expressed as follows. That is, assuming that the HSP coordinates of the component B are (δd B , δp B , δh B ), the HSP coordinates (δd B , δp B , δh B ) of the component B and the component coordinates X (δd = 17.5) , Δp = 5.0, δh = 11.5) (unit: MPa 0.5 ) can satisfy the following formula.
Distance = [(δd B −17.5) 2 + (δp B −5.0) 2 + (δh B −11.5) 2 ] 0.5
≦ 1.5 MPa 0.5
成分Ｂとしては、成分ＢのＨＳＰの座標と成分座標Ｘとの距離が上記式を満たす有機溶剤であれば特に限定されなくてもよく、例えば、プロピレングリコールフェニルエーテル（距離：０．３２ＭＰａ0.5）、エチレングリコールモノベンジルエーテル（距離：１．１８ＭＰａ0.5）、エチレングリコールモノｎ－ヘキシルエーテル（距離：１．５０ＭＰａ0.5）等のグリコールエーテル；１－メチルシクロヘキサノール（距離：１．１９ＭＰａ0.5）、３－メチルシクロヘキサノール（距離：１．０８ＭＰａ0.5）、４－メチルシクロヘキサノール（距離：０．５９ＭＰａ0.5）等のモノアルキルアルコール；１－フェニル－１－プロパノール（距離：１．３９ＭＰａ0.5）、２－フェニル－１－プロパノール（距離：１．３７ＭＰａ0.5）等の芳香族アルコール；等から選ばれる１種又は２種以上の組合せが挙げられる。スタミナ性の観点からは、プロピレングリコールフェニルエーテル、エチレングリコールモノベンジルエーテル、エチレングリコールモノｎ－ヘキシルエーテル、１－フェニル－１－プロパノール及び２－フェニル－１－プロパノールから選ばれる１種又は２種以上の組合せが好ましく、プロピレングリコールフェニルエーテル及びエチレングリコールモノベンジルエーテルの少なくとも一方がより好ましい。洗浄剤組成物の濃縮物の保存安定性の観点からは、エチレングリコールモノベンジルエーテル、エチレングリコールモノｎ－ヘキシルエーテル、１－メチルシクロヘキサノール、２－フェニル－１－プロパノール及び１－フェニル－１－プロパノールから選ばれる１種又は２種以上の組合せが好ましく、エチレングリコールモノベンジルエーテル、２－フェニル－１－プロパノール及び１－フェニル－１－プロパノールから選ばれる１種又は２種以上の組合せがより好ましい。括弧内の数値は、成分ＢのＨＳＰの座標と成分座標Ｘとの距離（単位：ＭＰａ0.5）を示す。本開示において、スタミナ性とは、洗浄剤組成物を長時間使用（リサイクル洗浄）しても、良好な洗浄性が確保されていることをいう。
The component B is not particularly limited as long as the distance between the HSP coordinates of the component B and the component coordinates X satisfies the above formula. For example, propylene glycol phenyl ether (distance: 0.32 MPa 0.5 ) Glycol ethers such as ethylene glycol monobenzyl ether (distance: 1.18 MPa 0.5 ) and ethylene glycol mono n-hexyl ether (distance: 1.50 MPa 0.5 ); 1-methylcyclohexanol (distance: 1.19 MPa 0.5 ), 3 Monoalkyl alcohols such as methylcyclohexanol (distance: 1.08 MPa 0.5 ) and 4-methylcyclohexanol (distance: 0.59 MPa 0.5 ); 1-phenyl-1-propanol (distance: 1.39 MPa 0.5 ), 2- Phenyl-1-propanol (distance: 1.37 MPa 0.5 ), etc. Examples thereof include one or a combination of two or more selected from aromatic alcohols and the like. From the viewpoint of stamina, one or more selected from propylene glycol phenyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono n-hexyl ether, 1-phenyl-1-propanol and 2-phenyl-1-propanol The combination of these is preferable, and at least one of propylene glycol phenyl ether and ethylene glycol monobenzyl ether is more preferable. From the viewpoint of the storage stability of the concentrate of the detergent composition, ethylene glycol monobenzyl ether, ethylene glycol mono n-hexyl ether, 1-methylcyclohexanol, 2-phenyl-1-propanol and 1-phenyl-1- One or more combinations selected from propanol are preferable, and one or more combinations selected from ethylene glycol monobenzyl ether, 2-phenyl-1-propanol and 1-phenyl-1-propanol are more preferable. . The numerical value in parentheses indicates the distance (unit: MPa 0.5 ) between the HSP coordinate of component B and the component coordinate X. In the present disclosure, the term “stamina” means that good cleaning properties are ensured even when the cleaning composition is used for a long time (recycle cleaning).
本開示における成分Ｂは、引火による火災リスク低減及びスタミナ性の観点から、沸点が高いことが好ましく、例えば、成分Ｂの沸点は、１６０℃以上が好ましく、２５０℃以上がより好ましい。本開示において成分Ｂは、濃縮性の観点から、水への溶解度が高いことが好ましく、例えば、成分Ｂの水１００ｍＬに対する溶解度は、０．３ｇ以上が好ましい。
Component B in the present disclosure preferably has a high boiling point from the viewpoint of fire risk reduction due to ignition and stamina properties. For example, the boiling point of Component B is preferably 160 ° C. or higher, more preferably 250 ° C. or higher. In the present disclosure, component B preferably has high water solubility from the viewpoint of concentration. For example, the solubility of component B in 100 mL of water is preferably 0.3 g or more.
本開示に係る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、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましく、スタミナ性の観点からは、０．２質量％以上がより更に好ましく、そして、排水処理負荷を低減する観点から、３質量％以下が好ましく、２質量％以下がより好ましく、１質量％以下が更に好ましく、０．５質量％以下がより更に好ましい。成分Ｂが２種以上の有機溶剤からなる場合、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 according to the present disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of improving the resin mask removability. 1% by mass or more is more preferable, from the viewpoint of stamina, 0.2% by mass or more is more preferable, and from the viewpoint of reducing wastewater treatment load, 3% by mass or less is preferable, and 2% by mass or less is more preferable. Preferably, 1 mass% or less is still more preferable, and 0.5 mass% or less is still more preferable. When component B consists of two or more organic solvents, the content of component B refers to the total content thereof.
本開示に係る洗浄剤組成物における成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）は、１以上６０以下であって、樹脂マスク除去性向上の観点から、１．１以上が好ましく、１．２以上がより好ましく、１．５以上が更に好ましく、２以上がより更に好ましく、３以上がより更に好ましく、５以上がより更に好ましく、１０以上がより更に好ましく、１５以上がより更に好ましく、そして、保存安定性及び排水処理負荷を低減する観点から、５０以下が好ましく、４０以下がより好ましく、３０以下が更に好ましく、２０以下がより更に好ましい。
The mass ratio (A / B) of component A to component B in the cleaning composition according to the present disclosure is 1 or more and 60 or less, preferably 1.1 or more from the viewpoint of improving the resin mask removability. 2 or more is more preferable, 1.5 or more is still more preferable, 2 or more is more preferable, 3 or more is more preferable, 5 or more is still more preferable, 10 or more is still more preferable, 15 or more is still more preferable, and From the viewpoint of reducing storage stability and wastewater treatment load, it is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, and even more preferably 20 or less.
［成分Ｃ：水］
本開示に係る洗浄剤組成物は、水（成分Ｃ）を含む。成分Ｃの水としては、イオン交換水、ＲＯ水、蒸留水、純水、超純水が使用されうる。水の含有量は、本開示に係る洗浄剤組成物の使用態様にあわせて適宜設定すればよい。 [Component C: Water]
The cleaning composition according to the present disclosure includes water (component C). As the water of component C, ion exchange water, RO water, distilled water, pure water, and ultrapure water can be used. What is necessary is just to set content of water suitably according to the usage condition of the cleaning composition which concerns on this indication.
本開示に係る洗浄剤組成物は、水（成分Ｃ）を含む。成分Ｃの水としては、イオン交換水、ＲＯ水、蒸留水、純水、超純水が使用されうる。水の含有量は、本開示に係る洗浄剤組成物の使用態様にあわせて適宜設定すればよい。 [Component C: Water]
The cleaning composition according to the present disclosure includes water (component C). As the water of component C, ion exchange water, RO water, distilled water, pure water, and ultrapure water can be used. What is necessary is just to set content of water suitably according to the usage condition of the cleaning composition which concerns on this indication.
本開示に係る洗浄剤組成物の使用時における成分Ｃの含有量は、８５質量％以上であって、樹脂マスク除去性向上の観点から、９０質量％以上が好ましく、９５質量％以上がより好ましく、そして、同様の観点から、９９質量％以下が好ましく、９８質量％以下がより好ましく、９７質量％以下が更に好ましい。
Content of the component C at the time of use of the cleaning composition which concerns on this indication is 85 mass% or more, and 90 mass% or more is preferable from a viewpoint of a resin mask removability improvement, and 95 mass% or more is more preferable. And from the same viewpoint, 99 mass% or less is preferable, 98 mass% or less is more preferable, 97 mass% or less is still more preferable.
［任意成分］
本開示に係る洗浄剤組成物は、前記成分Ａ～Ｃ以外に、必要に応じて任意成分を含有することができる。任意成分としては、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、キレート剤、増粘剤、分散剤、防錆剤、塩基性物質、界面活性剤、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。本開示に係る洗浄剤組成物の使用時における任意成分の合計含有量は、０質量％以上２．０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１．０質量％以下がより更に好ましい。 [Optional ingredients]
The cleaning composition according to the present disclosure may contain an optional component as necessary in addition to the components A to C. Examples of optional components include components that can be used in ordinary cleaning agents, such as chelating agents, thickeners, dispersants, rust inhibitors, basic substances, surfactants, polymer compounds, and solubilization. Agents, antioxidants, antiseptics, antifoaming agents, antibacterial agents and the like. The total content of optional components during use of the cleaning composition according to the present disclosure is preferably 0% by mass or more and 2.0% by mass or less, more preferably 0% by mass or more and 1.5% by mass or less, and 0% by mass. The content is more preferably 1.3% by mass or less and still more preferably 0% by mass or more and 1.0% by mass or less.
本開示に係る洗浄剤組成物は、前記成分Ａ～Ｃ以外に、必要に応じて任意成分を含有することができる。任意成分としては、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、キレート剤、増粘剤、分散剤、防錆剤、塩基性物質、界面活性剤、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。本開示に係る洗浄剤組成物の使用時における任意成分の合計含有量は、０質量％以上２．０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１．０質量％以下がより更に好ましい。 [Optional ingredients]
The cleaning composition according to the present disclosure may contain an optional component as necessary in addition to the components A to C. Examples of optional components include components that can be used in ordinary cleaning agents, such as chelating agents, thickeners, dispersants, rust inhibitors, basic substances, surfactants, polymer compounds, and solubilization. Agents, antioxidants, antiseptics, antifoaming agents, antibacterial agents and the like. The total content of optional components during use of the cleaning composition according to the present disclosure is preferably 0% by mass or more and 2.0% by mass or less, more preferably 0% by mass or more and 1.5% by mass or less, and 0% by mass. The content is more preferably 1.3% by mass or less and still more preferably 0% by mass or more and 1.0% by mass or less.
本開示に係る洗浄剤組成物中の成分Ｂ及び任意成分由来の有機物の総含有量は、排水処理負荷を低減する観点から、３質量％以下が好ましく、２質量％以下がより好ましく、１質量％以下が更に好ましく、０．５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、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましい。
From the viewpoint of reducing the wastewater treatment load, the total content of Component B and the organic matter derived from the optional component in the cleaning composition according to the present disclosure is preferably 3% by mass or less, more preferably 2% by mass or less. % Or less is more preferable, 0.5% by mass or less is more preferable, and from the viewpoint of improving resin mask removability, 0.01% by mass or more is preferable, 0.05% by mass or more is more preferable, and 0.1% More preferably, it is more than mass%.
本開示に係る洗浄剤組成物は、排水処理負荷を低減し、排水域の富栄養化を抑制する観点から、窒素含有化合物及びリン含有化合物を実質的に含まないことが好ましい。本開示において「実質的に含まない」とは、本開示に係る洗浄剤組成物中の窒素含有化合物及びリン含有化合物の合計含有量が０．１質量％未満であることをいう。本開示に係る洗浄剤組成物中の窒素含有化合物及びリン含有化合物の合計含有量は、排水処理負荷を低減し、排水域の富栄養化を抑制する観点から、０．０５質量％以下が好ましく、０．０１質量％以下がより好ましく、０質量％が更に好ましい。窒素含有化合物としては、洗浄剤組成物として従来から広く用いられている窒素含有化合物が挙げられ、例えば、アミン及びその塩、アンモニア、並びにアンモニウム塩から選ばれる少なくとも１種又は２種以上の組合せが挙げられる。前記アミンとしては、例えば、モノエタノールアミン、ジエタノールアミン等のアミノアルコールが挙げられる。前記アンモニウム塩としては、例えば、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）等の４級アンモニウム塩を挙げることができる。リン含有化合物としては、洗浄剤組成物として従来から広く用いられているリン含有化合物が挙げられ、例えば、リン酸及びその塩、ピロリン酸、ポリリン酸、メタリン酸等の縮合リン酸及びその塩などの無機リン酸、並びに有機リン酸、リン酸エステルから選ばれる少なくとも１種又は２種以上の組合せが挙げられる。
The cleaning composition according to the present disclosure preferably contains substantially no nitrogen-containing compound and phosphorus-containing compound from the viewpoint of reducing wastewater treatment load and suppressing eutrophication of the drainage area. In the present disclosure, “substantially free” means that the total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning composition according to the present disclosure is less than 0.1 mass%. The total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning composition according to the present disclosure is preferably 0.05% by mass or less from the viewpoint of reducing wastewater treatment load and suppressing eutrophication of the drainage area. 0.01 mass% or less is more preferable, and 0 mass% is still more preferable. Examples of the nitrogen-containing compound include nitrogen-containing compounds that have been widely used as a cleaning composition, and examples thereof include at least one or a combination of two or more selected from amines and salts thereof, ammonia, and ammonium salts. Can be mentioned. Examples of the amine include amino alcohols such as monoethanolamine and diethanolamine. Examples of the ammonium salt include quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH). Examples of phosphorus-containing compounds include phosphorus-containing compounds that have been widely used in the past as cleaning compositions, such as phosphoric acid and salts thereof, condensed phosphoric acid such as pyrophosphoric acid, polyphosphoric acid, and metaphosphoric acid, and salts thereof. Inorganic phosphoric acid, organic phosphoric acid, and a combination of two or more selected from phosphoric esters.
［洗浄剤組成物の製造方法］
本開示に係る洗浄剤組成物は、前記成分Ａ～Ｃ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、本開示に係る洗浄剤組成物は、少なくとも前記成分Ａ～Ｃ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～Ｃ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～Ｃ及び必要に応じてその他の成分を同時に又は任意の順に混合することを含む。本開示に係る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、上述した本開示に係る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。 [Production method of cleaning composition]
The cleaning composition according to the present disclosure can be produced by blending the components A to C and, if necessary, the above-mentioned optional components by a known method. For example, the cleaning composition according to the present disclosure can be formed by blending at least the components A to C. Accordingly, the present disclosure relates to a method for producing a cleaning composition comprising a step of blending at least the components A to C. In the present disclosure, “compounding” includes mixing the components A to C and other components as necessary at the same time or in any order. In the manufacturing method of the cleaning composition according to the present disclosure, the preferable blending amount of each component may be the same as the preferable content of each component of the cleaning composition according to the present disclosure described above.
本開示に係る洗浄剤組成物は、前記成分Ａ～Ｃ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、本開示に係る洗浄剤組成物は、少なくとも前記成分Ａ～Ｃ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～Ｃ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～Ｃ及び必要に応じてその他の成分を同時に又は任意の順に混合することを含む。本開示に係る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、上述した本開示に係る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。 [Production method of cleaning composition]
The cleaning composition according to the present disclosure can be produced by blending the components A to C and, if necessary, the above-mentioned optional components by a known method. For example, the cleaning composition according to the present disclosure can be formed by blending at least the components A to C. Accordingly, the present disclosure relates to a method for producing a cleaning composition comprising a step of blending at least the components A to C. In the present disclosure, “compounding” includes mixing the components A to C and other components as necessary at the same time or in any order. In the manufacturing method of the cleaning composition according to the present disclosure, the preferable blending amount of each component may be the same as the preferable content of each component of the cleaning composition according to the present disclosure described above.
本開示に係る洗浄剤組成物の使用時のｐＨは、樹脂マスク除去性向上の観点から、１０．０以上が好ましく、１０．５以上がより好ましく、そして、金属腐食抑制の観点から、１４以下が好ましく、１３．９以下がより好ましく、１３．７以下が更に好ましい。ｐＨは、２５℃における洗浄剤組成物のｐＨであり、例えば、ｐＨメータ（亜電波工業株式会社、ＨＭ－３０Ｇ）を用いて測定できる。
The pH at the time of use of the cleaning composition according to the present disclosure is preferably 10.0 or more, more preferably 10.5 or more from the viewpoint of improving the resin mask removability, and 14 or less from the viewpoint of suppressing metal corrosion. Is preferable, 13.9 or less is more preferable, and 13.7 or less is still more preferable. The pH is the pH of the cleaning composition at 25 ° C., and can be measured using, for example, a pH meter (A Denki Kogyo Co., Ltd., HM-30G).
本開示においてｐＨは、必要により、硝酸、硫酸等の無機酸；オキシカルボン酸、多価カルボン酸、アミノポリカルボン酸、アミノ酸等の有機酸；及びそれらの金属塩やアンモニウム塩、アンモニア、アミン等の成分Ａ以外の塩基性物質を適宜、所望量で配合することで調整することができる。
In the present disclosure, if necessary, the pH is adjusted with inorganic acids such as nitric acid and sulfuric acid; organic acids such as oxycarboxylic acid, polyvalent carboxylic acid, aminopolycarboxylic acid and amino acid; and metal salts, ammonium salts, ammonia, amines and the like thereof. It can adjust by mix | blending basic substances other than the component A of this in a desired quantity suitably.
本開示に係る洗浄剤組成物は、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成分Ｃの水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１０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～Ｃが上述した含有量（すなわち、洗浄時の含有量）になるよう水で希釈して使用することができる。さら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 according to the present disclosure may be prepared as a concentrate in which the amount of water of component C is reduced within a range that does not impair storage stability by causing separation or precipitation. The concentrate of the cleaning composition is preferably a concentrate having a dilution ratio of 3 times or more from the viewpoint of transportation and storage, and is preferably a concentrate having a dilution ratio of 10 times or less from the viewpoint of storage stability. . The concentrate of the cleaning composition can be used by diluting with water so that the components A to C have the above-described content (that is, the content at the time of cleaning) at the time of use. Furthermore, the concentrate of a cleaning composition can also be used by adding each component separately at the time of use. In the present disclosure, “when using” or “when cleaning” the cleaning composition of the concentrated solution refers to a state in which the concentrate of the cleaning composition is diluted.
本開示に係る洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分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、２質量％以上がより好ましく、５質量％以上が更に好ましく、１０質量％以上がより更に好ましく、そして、金属腐食抑制及び保存安定性の観点から、４０質量％以下が好ましく、３０質量％以下がより好ましく、２０質量％以下が更に好ましく、１０質量％以下がより更に好ましい。
When the cleaning composition according to the present disclosure is a concentrate, the content of the component A in the cleaning composition concentrate is preferably 1% by mass or more from the viewpoint of improving the resin mask removability, and is 2% by mass. The above is more preferable, 5% by mass or more is further preferable, 10% by mass or more is more preferable, and 40% by mass or less is preferable, and 30% by mass or less is more preferable from the viewpoint of metal corrosion inhibition and storage stability. 20 mass% or less is still more preferable, and 10 mass% or less is still more preferable.
本開示に係る洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ｂの含有量は、樹脂マスク除去性向上の観点から、０．１質量％以上が好ましく、０．２質量％以上がより好ましく、０．５質量％以上が更に好ましく、１質量％以上がより更に好ましく、そして、保存安定性及び排水処理負荷を低減する観点から、１０質量％以下が好ましく、５質量％以下がより好ましく、２質量％以下が更に好ましく、１．５質量％以下がより更に好ましい。
When the cleaning composition according to the present disclosure is a concentrate, the content of Component B in the cleaning composition concentrate is preferably 0.1% by mass or more from the viewpoint of improving resin mask removability. .2% by mass or more is more preferable, 0.5% by mass or more is more preferable, 1% by mass or more is more preferable, and 10% by mass or less is preferable from the viewpoint of reducing storage stability and wastewater treatment load. 5 mass% or less is more preferable, 2 mass% or less is still more preferable, and 1.5 mass% or less is still more preferable.
本開示に係る洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ｃの含有量は、樹脂マスク除去性向上及び洗浄剤組成物を安定化する観点から、５０質量％以上が好ましく、６０質量％以上がより好ましく、７０質量％以上が更に好ましく、そして、同様の観点から、９５質量％以下が好ましく、９０質量％以下がより好ましく、８５質量％以下が更に好ましい。
When the cleaning composition according to the present disclosure is a concentrate, the content of the component C in the cleaning composition concentrate is 50 mass from the viewpoint of improving the resin mask removability and stabilizing the cleaning composition. % Or more, preferably 60% by weight or more, more preferably 70% by weight or more, and from the same viewpoint, 95% by weight or less is preferable, 90% by weight or less is more preferable, and 85% by weight or less is more preferable. .
本開示に係る洗浄剤組成物の濃縮物のｐＨは、希釈後の樹脂マスク除去性向上の観点から、１０．０以上が好ましく、１０．５以上がより好ましく、そして、保管時及び取扱い時の安全性の観点から、１４以下が好ましい。
The pH of the concentrate of the cleaning composition according to the present disclosure is preferably 10.0 or more, more preferably 10.5 or more, from the viewpoint of improving the removability of the resin mask after dilution, and during storage and handling. From the viewpoint of safety, 14 or less is preferable.
［被洗浄物］
本開示に係る洗浄剤組成物は、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、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やメッキ処理（銅メッキ、アルミニウムメッキ、ニッケルメッキ等）等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。 [To be cleaned]
In one or a plurality of embodiments, the cleaning composition according to the present disclosure can be used for cleaning an object to be cleaned to which a resin mask is attached. Examples of the objects to be cleaned include electronic components and production intermediates thereof. Examples of the electronic component include at least one component selected from metal plates such as a printed board, a wafer, a copper plate, and an aluminum plate. The said manufacturing intermediate is an intermediate product in the manufacturing process of an electronic component, Comprising: The intermediate product after a resin mask process is included. As a specific example of the object to be cleaned to which the resin mask is attached, for example, by performing a process such as soldering using a resin mask or a plating process (copper plating, aluminum plating, nickel plating, etc.), wiring or Examples thereof include an electronic component having a connection terminal or the like formed on the surface of the substrate.
本開示に係る洗浄剤組成物は、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、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やメッキ処理（銅メッキ、アルミニウムメッキ、ニッケルメッキ等）等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。 [To be cleaned]
In one or a plurality of embodiments, the cleaning composition according to the present disclosure can be used for cleaning an object to be cleaned to which a resin mask is attached. Examples of the objects to be cleaned include electronic components and production intermediates thereof. Examples of the electronic component include at least one component selected from metal plates such as a printed board, a wafer, a copper plate, and an aluminum plate. The said manufacturing intermediate is an intermediate product in the manufacturing process of an electronic component, Comprising: The intermediate product after a resin mask process is included. As a specific example of the object to be cleaned to which the resin mask is attached, for example, by performing a process such as soldering using a resin mask or a plating process (copper plating, aluminum plating, nickel plating, etc.), wiring or Examples thereof include an electronic component having a connection terminal or the like formed on the surface of the substrate.
本開示に係る洗浄剤組成物は、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、メッキ処理及び／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く、本開示の効果が発揮されやすい点からは、ネガ型樹脂マスクが好ましい。ネガ型樹脂マスクとしては、例えば、露光及び／又は現像処理されたネガ型ドライフィルムレジストが挙げられる。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 a plurality of embodiments, the cleaning composition according to the present disclosure is suitable for cleaning an object to be cleaned to which a resin mask or a plating and / or heat-treated resin mask is attached in terms of cleaning effect. Can be used. The resin mask may be, for example, a negative type resin mask or a positive type resin mask, and a negative type resin mask is preferable from the viewpoint that the effects of the present disclosure are easily exhibited. Examples of the negative type resin mask include negative dry film resists that have been exposed and / or developed. In the present disclosure, the negative type resin mask is formed using a negative type resist, and examples thereof include a negative type resist layer that has been exposed and / or developed. In the present disclosure, the positive resin mask is formed using a positive resist, and examples thereof include a positive resist layer that has been exposed and / or developed.
［樹脂マスク除去方法］
本開示は、一態様において、樹脂マスクが付着した被洗浄物を本開示に係る洗浄剤組成物に接触させることを含む、樹脂マスクの除去方法に関する（以下、本開示に係る除去方法ともいう）。本開示に係る除去方法は、樹脂マスクが付着した被洗浄物を本開示に係る洗浄剤組成物で洗浄する工程を有する。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。被洗浄物に本開示に係る洗浄剤組成物を接触させる方法、又は、被洗浄物を本開示に係る洗浄剤組成物で洗浄する方法としては、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や、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。本開示に係る洗浄剤組成物は、希釈することなくそのまま洗浄に使用できる。本開示に係る除去方法は、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好ましい。本開示に係る除去方法であれば、樹脂マスク、特にメッキ処理及び／又は加熱処理された樹脂マスクを効率よく除去できる。本開示に係る除去方法は、本開示に係る洗浄剤組成物の洗浄力が発揮されやすい点から、本開示に係る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。 [Resin mask removal method]
In one aspect, the present disclosure relates to a method for removing a resin mask, which includes contacting an object to be cleaned to which the resin mask is attached with the cleaning composition according to the present disclosure (hereinafter, also referred to as a removal method according to the present disclosure). . The removal method according to the present disclosure includes a step of cleaning an object to be cleaned to which a resin mask is attached with the cleaning composition according to the present disclosure. Examples of the objects to be cleaned include the objects to be cleaned described above. Examples of a method of bringing the cleaning composition according to the present disclosure into contact with an object to be cleaned or a method of cleaning the object to be cleaned with the cleaning composition according to the present disclosure include, for example, in a cleaning bath containing the cleaning composition Examples include a method of contacting by dipping, a method of injecting a cleaning composition into a spray form (shower method), an ultrasonic cleaning method of irradiating ultrasonically during immersion, and the like. The cleaning composition according to the present disclosure can be used for cleaning as it is without being diluted. The removal method according to the present disclosure preferably includes a step of bringing a cleaning object into contact with the cleaning composition, rinsing with water, and drying. With the removal method according to the present disclosure, it is possible to efficiently remove a resin mask, particularly a resin mask that has been subjected to plating treatment and / or heat treatment. In the removal method according to the present disclosure, it is preferable to irradiate ultrasonic waves when the cleaning composition according to the present disclosure is in contact with the object to be cleaned from the viewpoint that the cleaning power of the cleaning composition according to the present disclosure is easily exhibited. More preferably, the ultrasonic wave has a relatively high frequency. From the same viewpoint, for example, the ultrasonic irradiation conditions are preferably 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.
本開示は、一態様において、樹脂マスクが付着した被洗浄物を本開示に係る洗浄剤組成物に接触させることを含む、樹脂マスクの除去方法に関する（以下、本開示に係る除去方法ともいう）。本開示に係る除去方法は、樹脂マスクが付着した被洗浄物を本開示に係る洗浄剤組成物で洗浄する工程を有する。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。被洗浄物に本開示に係る洗浄剤組成物を接触させる方法、又は、被洗浄物を本開示に係る洗浄剤組成物で洗浄する方法としては、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や、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。本開示に係る洗浄剤組成物は、希釈することなくそのまま洗浄に使用できる。本開示に係る除去方法は、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好ましい。本開示に係る除去方法であれば、樹脂マスク、特にメッキ処理及び／又は加熱処理された樹脂マスクを効率よく除去できる。本開示に係る除去方法は、本開示に係る洗浄剤組成物の洗浄力が発揮されやすい点から、本開示に係る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。 [Resin mask removal method]
In one aspect, the present disclosure relates to a method for removing a resin mask, which includes contacting an object to be cleaned to which the resin mask is attached with the cleaning composition according to the present disclosure (hereinafter, also referred to as a removal method according to the present disclosure). . The removal method according to the present disclosure includes a step of cleaning an object to be cleaned to which a resin mask is attached with the cleaning composition according to the present disclosure. Examples of the objects to be cleaned include the objects to be cleaned described above. Examples of a method of bringing the cleaning composition according to the present disclosure into contact with an object to be cleaned or a method of cleaning the object to be cleaned with the cleaning composition according to the present disclosure include, for example, in a cleaning bath containing the cleaning composition Examples include a method of contacting by dipping, a method of injecting a cleaning composition into a spray form (shower method), an ultrasonic cleaning method of irradiating ultrasonically during immersion, and the like. The cleaning composition according to the present disclosure can be used for cleaning as it is without being diluted. The removal method according to the present disclosure preferably includes a step of bringing a cleaning object into contact with the cleaning composition, rinsing with water, and drying. With the removal method according to the present disclosure, it is possible to efficiently remove a resin mask, particularly a resin mask that has been subjected to plating treatment and / or heat treatment. In the removal method according to the present disclosure, it is preferable to irradiate ultrasonic waves when the cleaning composition according to the present disclosure is in contact with the object to be cleaned from the viewpoint that the cleaning power of the cleaning composition according to the present disclosure is easily exhibited. More preferably, the ultrasonic wave has a relatively high frequency. From the same viewpoint, for example, the ultrasonic irradiation conditions are preferably 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.
［電子部品の製造方法］
本開示に係る電子部品の製造方法は、一態様において、樹脂マスクが付着した被洗浄物を本開示に係る洗浄剤組成物で洗浄する工程を含む。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。本開示に係る電子部品の製造方法は、本開示に係る洗浄剤組成物を用いて洗浄を行うことにより、金属の腐食を抑制しながら、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。さらに、本開示に係る除去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。 [Method of manufacturing electronic parts]
The manufacturing method of the electronic component which concerns on this indication includes the process of wash | cleaning the to-be-cleaned object which the resin mask adhered to the cleaning composition which concerns on this indication in one aspect | mode. Examples of the objects to be cleaned include the objects to be cleaned described above. The method for manufacturing an electronic component according to the present disclosure can effectively remove the resin mask attached to the electronic component while performing the cleaning using the cleaning composition according to the present disclosure while suppressing corrosion of the metal. This makes it possible to manufacture highly reliable electronic components. Furthermore, by performing the removal method according to the present disclosure, it becomes easy to remove the resin mask attached to the electronic component, so that the cleaning time can be shortened and the manufacturing efficiency of the electronic component can be improved.
本開示に係る電子部品の製造方法は、一態様において、樹脂マスクが付着した被洗浄物を本開示に係る洗浄剤組成物で洗浄する工程を含む。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。本開示に係る電子部品の製造方法は、本開示に係る洗浄剤組成物を用いて洗浄を行うことにより、金属の腐食を抑制しながら、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。さらに、本開示に係る除去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。 [Method of manufacturing electronic parts]
The manufacturing method of the electronic component which concerns on this indication includes the process of wash | cleaning the to-be-cleaned object which the resin mask adhered to the cleaning composition which concerns on this indication in one aspect | mode. Examples of the objects to be cleaned include the objects to be cleaned described above. The method for manufacturing an electronic component according to the present disclosure can effectively remove the resin mask attached to the electronic component while performing the cleaning using the cleaning composition according to the present disclosure while suppressing corrosion of the metal. This makes it possible to manufacture highly reliable electronic components. Furthermore, by performing the removal method according to the present disclosure, it becomes easy to remove the resin mask attached to the electronic component, so that the cleaning time can be shortened and the manufacturing efficiency of the electronic component can be improved.
［キット］
本開示は、本開示に係る除去方法及び本開示に係る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であって、本開示に係る洗浄剤組成物を構成する前記成分Ａ～Ｃのうちの少なくとも１成分を他の成分と混合されない状態で含む、キットに関する。本開示に係るキットによれば、樹脂マスク除去性に優れ、排水処理負荷の小さい洗浄剤組成物が得られうる。 [kit]
The present disclosure is a kit for use in any one of the removal method according to the present disclosure and the method for manufacturing an electronic component according to the present disclosure, and includes the components A to C constituting the cleaning composition according to the present disclosure. The present invention relates to a kit containing at least one of the components in a state where it is not mixed with other components. According to the kit according to the present disclosure, it is possible to obtain a cleaning composition having excellent resin mask removability and a small wastewater treatment load.
本開示は、本開示に係る除去方法及び本開示に係る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であって、本開示に係る洗浄剤組成物を構成する前記成分Ａ～Ｃのうちの少なくとも１成分を他の成分と混合されない状態で含む、キットに関する。本開示に係るキットによれば、樹脂マスク除去性に優れ、排水処理負荷の小さい洗浄剤組成物が得られうる。 [kit]
The present disclosure is a kit for use in any one of the removal method according to the present disclosure and the method for manufacturing an electronic component according to the present disclosure, and includes the components A to C constituting the cleaning composition according to the present disclosure. The present invention relates to a kit containing at least one of the components in a state where it is not mixed with other components. According to the kit according to the present disclosure, it is possible to obtain a cleaning composition having excellent resin mask removability and a small wastewater treatment load.
本開示に係るキットとしては、例えば、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Ｃをさらに含有し、第１液及び第２液が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。
The kit according to the present disclosure includes, for example, a solution containing the component A (first liquid) and a solution containing the component B (second liquid) in a state where they are not mixed with each other. At least one of the two liquids further contains a component C, and a kit (two-component detergent composition) in which the first liquid and the second liquid are mixed at the time of use can be mentioned. Each of the first liquid and the second liquid may contain the above-described optional components as necessary.
本開示はさらに以下の洗浄剤組成物、除去方法、製造方法に関する。
The present disclosure further relates to the following detergent composition, removal method, and production method.
＜１＞ 無機アルカリ（成分Ａ）、有機溶剤（成分Ｂ）及び水（成分Ｃ）を含有し、
成分Ｂのハンセン溶解度パラメータの座標が、δｄ＝１７．５、δｐ＝５．０、δｈ＝１１．５を中心とする半径１．５ＭＰａ0.5の球の範囲内であり、
洗浄剤組成物の使用時における成分Ｃの含有量が、８５質量％以上であり、
成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）が、１以上６０以下である、樹脂マスク剥離用洗浄剤組成物。 <1> Contains an inorganic alkali (component A), an organic solvent (component B) and water (component C),
The Hansen solubility parameter coordinates of component B are within the range of a sphere with a radius of 1.5 MPa 0.5 centered at δd = 17.5, δp = 5.0, δh = 11.5,
The content of Component C when using the cleaning composition is 85% by mass or more,
The cleaning composition for resin mask peeling whose mass ratio (A / B) of the component A with respect to the component B is 1-60.
成分Ｂのハンセン溶解度パラメータの座標が、δｄ＝１７．５、δｐ＝５．０、δｈ＝１１．５を中心とする半径１．５ＭＰａ0.5の球の範囲内であり、
洗浄剤組成物の使用時における成分Ｃの含有量が、８５質量％以上であり、
成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）が、１以上６０以下である、樹脂マスク剥離用洗浄剤組成物。 <1> Contains an inorganic alkali (component A), an organic solvent (component B) and water (component C),
The Hansen solubility parameter coordinates of component B are within the range of a sphere with a radius of 1.5 MPa 0.5 centered at δd = 17.5, δp = 5.0, δh = 11.5,
The content of Component C when using the cleaning composition is 85% by mass or more,
The cleaning composition for resin mask peeling whose mass ratio (A / B) of the component A with respect to the component B is 1-60.
＜２＞ 成分Ｂが、プロピレングリコールフェニルエーテル、エチレングリコールモノベンジルエーテル、エチレングリコールモノｎ－ヘキシルエーテル、１－メチルシクロヘキサノール、３－メチルシクロヘキサノール、４－メチルシクロヘキサノール、１－フェニル－１－プロパノール及び２－フェニル－１－プロパノールから選ばれる１種又は２種以上の組合せである、＜１＞に記載の洗浄剤組成物。
＜３＞ 洗浄剤組成物の使用時における成分Ａの含有量が、０．１質量％以上１５質量％以下であり、
洗浄剤組成物の使用時における成分Ｂの含有量が、０．０１質量％以上３質量％以下である、＜１＞又は＜２＞に記載の洗浄剤組成物。
＜４＞ 洗浄剤組成物の使用時における成分Ａの含有量は、０．１質量％以上が好ましく、０．３質量％以上がより好ましく、０．５質量％以上が更に好ましく、１質量％以上がより更に好ましく、２質量％以上がより更に好ましい、＜１＞から＜３＞のいずれかに記載の洗浄剤組成物。
＜５＞ 洗浄剤組成物の使用時における成分Ａの含有量は、１５質量％以下が好ましく、１０質量％以下がより好ましく、７質量％以下が更に好ましく、５質量％以下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の沸点は、１６０℃以上が好ましく、２５０℃以上がより好ましい、＜１＞から＜５＞のいずれかに記載の洗浄剤組成物。
＜７＞ 成分Ｂの水１００ｍＬに対する溶解度は、０．３ｇ以上である、＜１＞から＜６＞のいずれかに記載の洗浄剤組成物。
＜８＞ 洗浄剤組成物の使用時における成分Ｂの含有量は、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましく、０．２質量％以上がより更に好ましい、＜１＞から＜７＞のいずれかに記載の洗浄剤組成物。
＜９＞ 洗浄剤組成物の使用時における成分Ｂの含有量は、３質量％以下が好ましく、２質量％以下がより好ましく、１質量％以下が更に好ましく、０．５質量％以下がより更に好ましい、＜１＞から＜８＞のいずれかに記載の洗浄剤組成物。
＜１０＞ 洗浄剤組成物における成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）は、１以上６０以下であって、１．１以上が好ましく、１．２以上がより好ましく、１．５以上が更に好ましく、２以上がより更に好ましく、３以上がより更に好ましく、５以上がより更に好ましく、１０以上がより更に好ましく、１５以上がより更に好ましい、＜１＞から＜９＞のいずれかに記載の洗浄剤組成物。
＜１１＞ 洗浄剤組成物における成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）は、５０以下が好ましく、４０以下がより好ましく、３０以下が更に好ましく、２０以下がより更に好ましい、＜１＞から＜１０＞のいずれかに記載の洗浄剤組成物。
＜１２＞ 洗浄剤組成物の使用時における成分Ｃの含有量は、９０質量％以上が好ましく、９５質量％以上がより好ましい、＜１＞から＜１１＞のいずれか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Ｃの含有量は、９９質量％以下が好ましく、９８質量％以下がより好ましく、９７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＞ 洗浄剤組成物の使用時における任意成分の合計含有量は、０質量％以上２．０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１．０質量％以下がより更に好ましい、＜１＞から＜１３＞のいずれかに記載の洗浄剤組成物。
＜１５＞ 洗浄剤組成物中の有機物の総含有量は、３質量％以下が好ましく、２質量％以下がより好ましく、１質量％以下が更に好ましく、０．５質量％以下がより更に好ましい、＜１＞から＜１４＞のいずれかに記載の洗浄剤組成物。
＜１６＞ 洗浄剤組成物中の有機物の総含有量は、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましい、＜１＞から＜１５＞のいずれかに記載の洗浄剤組成物。
＜１７＞ 窒素含有化合物及びリン含有化合物を実質的に含まない、＜１＞から＜１６＞のいずれかに記載の洗浄剤組成物。
＜１８＞ 洗浄剤組成物中の窒素含有化合物及びリン含有化合物の合計含有量が、０．１質量％未満であり、０．０５質量％以下が好ましく、０．０１質量％以下がより好ましく、０質量％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＞ 洗浄剤組成物の使用時のｐＨは、１０．０以上が好ましく、１０．５以上がより好ましい、＜１＞から＜１８＞のいずれかに記載の洗浄剤組成物。
＜２０＞ 洗浄剤組成物の使用時のｐＨは、１４以下が好ましく、１３．９以下がより好ましく、１３．７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＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ａの含有量は、１質量％以上が好ましく、２質量％以上がより好ましく、５質量％以上が更に好ましく、１０質量％以上がより更に好ましい、＜１＞から＜２０＞のいずれかに記載の洗浄剤組成物。
＜２２＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ａの含有量は、４０質量％以下が好ましく、３０質量％以下がより好ましく、２０質量％以下が更に好ましく、１０質量％以下がより更に好ましい、＜１＞から＜２１＞のいずれかに記載の洗浄剤組成物。
＜２３＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ｂの含有量は、０．１質量％以上が好ましく、０．２質量％以上がより好ましく、０．５質量％以上が更に好ましく、１質量％以上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＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ｂの含有量は、１０質量％以下が好ましく、５質量％以下がより好ましく、２質量％以下が更に好ましく、１．５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＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ｃの含有量は、５０質量％以上が好ましく、６０質量％以上がより好ましく、７０質量％以上が更に好ましい、＜１＞から＜２４＞のいずれかに記載の洗浄剤組成物。
＜２６＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ｃの含有量は、９５質量％以下が好ましく、９０質量％以下がより好ましく、８５質量％以下が更に好ましい、＜１＞から＜２５＞のいずれかに記載の洗浄剤組成物。
＜２７＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物のｐＨは、１０．０以上が好ましく、１０．５以上がより好ましい、＜１＞から＜２６＞のいずれかに記載の洗浄剤組成物。
＜２８＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物のｐＨは、１４以下が好ましい、＜１＞から＜２７＞のいずれかに記載の洗浄剤組成物。
＜２９＞ 樹脂マスクが、露光及び現像の少なくとも一方の処理が施されたネガ型ドライフィルムレジストである、＜１＞から＜２８＞のいずれかに記載の洗浄剤組成物。
＜３０＞ 樹脂マスクが付着した被洗浄物を＜１＞から＜２９＞のいずれかに記載の洗浄剤組成物で洗浄する工程を含む、樹脂マスクの除去方法。
＜３１＞ 被洗浄物が、電子部品の製造中間物である、＜３０＞に記載の除去方法。
＜３２＞ 樹脂マスクが付着した被洗浄物を＜１＞又は＜２９＞のいずれかに記載の洗浄剤組成物で洗浄する工程を含む、電子部品の製造方法。
＜３３＞ ＜１＞から＜２９＞のいずれかに記載の洗浄剤組成物の、電子部品の製造への使用。
＜３４＞ ＜３０＞又は＜３１＞の除去方法及び＜３２＞に記載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であって、＜１＞から＜２９＞のいずれかに記載の洗浄剤組成物を構成する成分Ａ～Ｃのうちの少なくとも１成分を他の成分と混合されない状態で含む、キット。
＜３５＞ 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Ｃをさらに含有し、第１液及び第２液が使用時に混合される、＜３４＞に記載のキット。
＜３６＞ 被洗浄物から樹脂マスクを除去するための、＜１＞から＜２９＞のいずれかに記載の洗浄剤組成物の使用。
＜３７＞ 電子部品を洗浄するための、＜１＞から＜２９＞のいずれかに記載の洗浄剤組成物の使用。 <2> Component B is propylene glycol phenyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono n-hexyl ether, 1-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 1-phenyl-1- The cleaning composition according to <1>, which is one or a combination of two or more selected from propanol and 2-phenyl-1-propanol.
<3> The content of the component A at the time of use of the cleaning composition is 0.1% by mass or more and 15% by mass or less,
The cleaning composition according to <1> or <2>, wherein the content of component B when the cleaning composition is used is 0.01% by mass or more and 3% by mass or less.
<4> The content of component A when using the cleaning composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and 1% by mass. The cleaning composition according to any one of <1> to <3>, wherein the above is more preferable, and 2% by mass or more is even more preferable.
<5> The content of component A when using the cleaning composition is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7% by mass or less, and further more preferably 5% by mass or less. The cleaning composition according to any one of <1> to <4>.
<6> The cleaning composition according to any one of <1> to <5>, wherein the boiling point of component B is preferably 160 ° C. or higher, and more preferably 250 ° C. or higher.
<7> The cleaning composition according to any one of <1> to <6>, wherein the solubility of Component B in 100 mL of water is 0.3 g or more.
<8> The content of Component B during use of the cleaning composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and 0.2% The cleaning composition according to any one of <1> to <7>, wherein the content is more preferably at least% by mass.
<9> The content of Component B during use of the cleaning composition is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. The cleaning composition according to any one of <1> to <8>.
<10> The mass ratio (A / B) of component A to component B in the cleaning composition is 1 or more and 60 or less, preferably 1.1 or more, more preferably 1.2 or more, and 1.5 or more. Is more preferably, 2 or more is still more preferable, 3 or more is more preferable, 5 or more is still more preferable, 10 or more is still more preferable, and 15 or more is still more preferable, <1> to <9> The cleaning composition as described.
<11> The mass ratio (A / B) of component A to component B in the cleaning composition is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, and even more preferably 20 or less, <1> To <10>.
<12> The cleaning composition according to any one of <1> to <11>, wherein the content of the component C when using the cleaning composition is preferably 90% by mass or more, more preferably 95% by mass or more. .
<13> The content of Component C during use of the cleaning composition is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less, any one of <1> to <12> A cleaning composition according to claim 1.
<14> The total content of optional components during use of the cleaning composition is preferably 0% by mass or more and 2.0% by mass or less, more preferably 0% by mass or more and 1.5% by mass or less, and more preferably 0% by mass or more. The cleaning composition according to any one of <1> to <13>, which is more preferably 1.3% by mass or less, and still more preferably 0% by mass or more and 1.0% by mass or less.
<15> The total content of organic substances in the cleaning composition is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. The cleaning composition according to any one of <1> to <14>.
<16> The total content of organic substances in the cleaning composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more, from <1> to < The cleaning composition according to any one of 15>.
<17> The cleaning composition according to any one of <1> to <16>, which is substantially free of a nitrogen-containing compound and a phosphorus-containing compound.
<18> The total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning composition is less than 0.1 mass%, preferably 0.05 mass% or less, more preferably 0.01 mass% or less, The cleaning composition according to any one of <1> to <17>, further preferably 0% by mass.
<19> The cleaning composition according to any one of <1> to <18>, wherein the pH during use of the cleaning composition is preferably 10.0 or more, and more preferably 10.5 or more.
<20> The pH in use of the cleaning composition is preferably 14 or less, more preferably 13.9 or less, and even more preferably 13.7 or less, the cleaning agent according to any one of <1> to <19> Composition.
<21> When the detergent composition is a concentrate, the content of component A in the concentrate of the detergent composition is preferably 1% by mass or more, more preferably 2% by mass or more, and more preferably 5% by mass or more. The cleaning composition according to any one of <1> to <20>, further preferably 10% by mass or more.
<22> When the detergent composition is a concentrate, the content of component A in the concentrate of the detergent composition is preferably 40% by mass or less, more preferably 30% by mass or less, and 20% by mass or less. The cleaning composition according to any one of <1> to <21>, further preferably 10% by mass or less.
<23> When the detergent composition is a concentrate, the content of Component B in the concentrate of the detergent composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0 The cleaning composition according to any one of <1> to <22>, more preferably 5% by mass or more, and still more preferably 1% by mass or more.
<24> When the detergent composition is a concentrate, the content of component B in the concentrate of the detergent composition is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 2% by mass or less. The cleaning composition according to any one of <1> to <23>, further preferably 1.5% by mass or less.
<25> When the detergent composition is a concentrate, the content of component C in the concentrate of the detergent composition is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. The cleaning composition according to any one of <1> to <24>, which is more preferable.
<26> When the detergent composition is a concentrate, the content of component C in the concentrate of the detergent composition is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less. The cleaning composition according to any one of <1> to <25>, which is more preferable.
<27> When the cleaning composition is a concentrate, the pH of the cleaning composition concentrate is preferably 10.0 or more, more preferably 10.5 or more, any one of <1> to <26> The cleaning composition described in 1.
<28> When the cleaning composition is a concentrate, the cleaning composition according to any one of <1> to <27>, wherein the pH of the cleaning composition is preferably 14 or less.
<29> The cleaning composition according to any one of <1> to <28>, wherein the resin mask is a negative dry film resist subjected to at least one of exposure and development.
<30> A method for removing a resin mask, comprising a step of cleaning an object to be cleaned to which a resin mask is adhered with the cleaning composition according to any one of <1> to <29>.
<31> The removal method according to <30>, wherein the object to be cleaned is a manufacturing intermediate for electronic components.
<32> A method for manufacturing an electronic component, comprising a step of cleaning an object to be cleaned to which a resin mask is attached with the cleaning composition according to any one of <1> or <29>.
<33> Use of the cleaning composition according to any one of <1> to <29> for manufacturing an electronic component.
<34> A kit for use in any one of the method for removing <30> or <31> and the method for producing an electronic component according to <32>, wherein the kit is described in any one of <1> to <29> A kit comprising at least one of the components A to C constituting the detergent composition in a state where it is not mixed with other components.
<35> A solution containing component A (first liquid) and a solution containing component B (second liquid) are included in a state where they are not mixed with each other, and at least one of the first liquid and the second liquid is The kit according to <34>, further comprising component C, wherein the first liquid and the second liquid are mixed at the time of use.
<36> Use of the cleaning composition according to any one of <1> to <29> for removing a resin mask from an object to be cleaned.
<37> Use of the cleaning composition according to any one of <1> to <29> for cleaning an electronic component.
＜３＞ 洗浄剤組成物の使用時における成分Ａの含有量が、０．１質量％以上１５質量％以下であり、
洗浄剤組成物の使用時における成分Ｂの含有量が、０．０１質量％以上３質量％以下である、＜１＞又は＜２＞に記載の洗浄剤組成物。
＜４＞ 洗浄剤組成物の使用時における成分Ａの含有量は、０．１質量％以上が好ましく、０．３質量％以上がより好ましく、０．５質量％以上が更に好ましく、１質量％以上がより更に好ましく、２質量％以上がより更に好ましい、＜１＞から＜３＞のいずれかに記載の洗浄剤組成物。
＜５＞ 洗浄剤組成物の使用時における成分Ａの含有量は、１５質量％以下が好ましく、１０質量％以下がより好ましく、７質量％以下が更に好ましく、５質量％以下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の沸点は、１６０℃以上が好ましく、２５０℃以上がより好ましい、＜１＞から＜５＞のいずれかに記載の洗浄剤組成物。
＜７＞ 成分Ｂの水１００ｍＬに対する溶解度は、０．３ｇ以上である、＜１＞から＜６＞のいずれかに記載の洗浄剤組成物。
＜８＞ 洗浄剤組成物の使用時における成分Ｂの含有量は、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましく、０．２質量％以上がより更に好ましい、＜１＞から＜７＞のいずれかに記載の洗浄剤組成物。
＜９＞ 洗浄剤組成物の使用時における成分Ｂの含有量は、３質量％以下が好ましく、２質量％以下がより好ましく、１質量％以下が更に好ましく、０．５質量％以下がより更に好ましい、＜１＞から＜８＞のいずれかに記載の洗浄剤組成物。
＜１０＞ 洗浄剤組成物における成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）は、１以上６０以下であって、１．１以上が好ましく、１．２以上がより好ましく、１．５以上が更に好ましく、２以上がより更に好ましく、３以上がより更に好ましく、５以上がより更に好ましく、１０以上がより更に好ましく、１５以上がより更に好ましい、＜１＞から＜９＞のいずれかに記載の洗浄剤組成物。
＜１１＞ 洗浄剤組成物における成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）は、５０以下が好ましく、４０以下がより好ましく、３０以下が更に好ましく、２０以下がより更に好ましい、＜１＞から＜１０＞のいずれかに記載の洗浄剤組成物。
＜１２＞ 洗浄剤組成物の使用時における成分Ｃの含有量は、９０質量％以上が好ましく、９５質量％以上がより好ましい、＜１＞から＜１１＞のいずれか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Ｃの含有量は、９９質量％以下が好ましく、９８質量％以下がより好ましく、９７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＞ 洗浄剤組成物の使用時における任意成分の合計含有量は、０質量％以上２．０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１．０質量％以下がより更に好ましい、＜１＞から＜１３＞のいずれかに記載の洗浄剤組成物。
＜１５＞ 洗浄剤組成物中の有機物の総含有量は、３質量％以下が好ましく、２質量％以下がより好ましく、１質量％以下が更に好ましく、０．５質量％以下がより更に好ましい、＜１＞から＜１４＞のいずれかに記載の洗浄剤組成物。
＜１６＞ 洗浄剤組成物中の有機物の総含有量は、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましい、＜１＞から＜１５＞のいずれかに記載の洗浄剤組成物。
＜１７＞ 窒素含有化合物及びリン含有化合物を実質的に含まない、＜１＞から＜１６＞のいずれかに記載の洗浄剤組成物。
＜１８＞ 洗浄剤組成物中の窒素含有化合物及びリン含有化合物の合計含有量が、０．１質量％未満であり、０．０５質量％以下が好ましく、０．０１質量％以下がより好ましく、０質量％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＞ 洗浄剤組成物の使用時のｐＨは、１０．０以上が好ましく、１０．５以上がより好ましい、＜１＞から＜１８＞のいずれかに記載の洗浄剤組成物。
＜２０＞ 洗浄剤組成物の使用時のｐＨは、１４以下が好ましく、１３．９以下がより好ましく、１３．７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＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ａの含有量は、１質量％以上が好ましく、２質量％以上がより好ましく、５質量％以上が更に好ましく、１０質量％以上がより更に好ましい、＜１＞から＜２０＞のいずれかに記載の洗浄剤組成物。
＜２２＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ａの含有量は、４０質量％以下が好ましく、３０質量％以下がより好ましく、２０質量％以下が更に好ましく、１０質量％以下がより更に好ましい、＜１＞から＜２１＞のいずれかに記載の洗浄剤組成物。
＜２３＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ｂの含有量は、０．１質量％以上が好ましく、０．２質量％以上がより好ましく、０．５質量％以上が更に好ましく、１質量％以上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＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ｂの含有量は、１０質量％以下が好ましく、５質量％以下がより好ましく、２質量％以下が更に好ましく、１．５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＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ｃの含有量は、５０質量％以上が好ましく、６０質量％以上がより好ましく、７０質量％以上が更に好ましい、＜１＞から＜２４＞のいずれかに記載の洗浄剤組成物。
＜２６＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物中の成分Ｃの含有量は、９５質量％以下が好ましく、９０質量％以下がより好ましく、８５質量％以下が更に好ましい、＜１＞から＜２５＞のいずれかに記載の洗浄剤組成物。
＜２７＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物のｐＨは、１０．０以上が好ましく、１０．５以上がより好ましい、＜１＞から＜２６＞のいずれかに記載の洗浄剤組成物。
＜２８＞ 洗浄剤組成物が濃縮物である場合、洗浄剤組成物の濃縮物のｐＨは、１４以下が好ましい、＜１＞から＜２７＞のいずれかに記載の洗浄剤組成物。
＜２９＞ 樹脂マスクが、露光及び現像の少なくとも一方の処理が施されたネガ型ドライフィルムレジストである、＜１＞から＜２８＞のいずれかに記載の洗浄剤組成物。
＜３０＞ 樹脂マスクが付着した被洗浄物を＜１＞から＜２９＞のいずれかに記載の洗浄剤組成物で洗浄する工程を含む、樹脂マスクの除去方法。
＜３１＞ 被洗浄物が、電子部品の製造中間物である、＜３０＞に記載の除去方法。
＜３２＞ 樹脂マスクが付着した被洗浄物を＜１＞又は＜２９＞のいずれかに記載の洗浄剤組成物で洗浄する工程を含む、電子部品の製造方法。
＜３３＞ ＜１＞から＜２９＞のいずれかに記載の洗浄剤組成物の、電子部品の製造への使用。
＜３４＞ ＜３０＞又は＜３１＞の除去方法及び＜３２＞に記載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であって、＜１＞から＜２９＞のいずれかに記載の洗浄剤組成物を構成する成分Ａ～Ｃのうちの少なくとも１成分を他の成分と混合されない状態で含む、キット。
＜３５＞ 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Ｃをさらに含有し、第１液及び第２液が使用時に混合される、＜３４＞に記載のキット。
＜３６＞ 被洗浄物から樹脂マスクを除去するための、＜１＞から＜２９＞のいずれかに記載の洗浄剤組成物の使用。
＜３７＞ 電子部品を洗浄するための、＜１＞から＜２９＞のいずれかに記載の洗浄剤組成物の使用。 <2> Component B is propylene glycol phenyl ether, ethylene glycol monobenzyl ether, ethylene glycol mono n-hexyl ether, 1-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, 1-phenyl-1- The cleaning composition according to <1>, which is one or a combination of two or more selected from propanol and 2-phenyl-1-propanol.
<3> The content of the component A at the time of use of the cleaning composition is 0.1% by mass or more and 15% by mass or less,
The cleaning composition according to <1> or <2>, wherein the content of component B when the cleaning composition is used is 0.01% by mass or more and 3% by mass or less.
<4> The content of component A when using the cleaning composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and 1% by mass. The cleaning composition according to any one of <1> to <3>, wherein the above is more preferable, and 2% by mass or more is even more preferable.
<5> The content of component A when using the cleaning composition is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7% by mass or less, and further more preferably 5% by mass or less. The cleaning composition according to any one of <1> to <4>.
<6> The cleaning composition according to any one of <1> to <5>, wherein the boiling point of component B is preferably 160 ° C. or higher, and more preferably 250 ° C. or higher.
<7> The cleaning composition according to any one of <1> to <6>, wherein the solubility of Component B in 100 mL of water is 0.3 g or more.
<8> The content of Component B during use of the cleaning composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and 0.2% The cleaning composition according to any one of <1> to <7>, wherein the content is more preferably at least% by mass.
<9> The content of Component B during use of the cleaning composition is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. The cleaning composition according to any one of <1> to <8>.
<10> The mass ratio (A / B) of component A to component B in the cleaning composition is 1 or more and 60 or less, preferably 1.1 or more, more preferably 1.2 or more, and 1.5 or more. Is more preferably, 2 or more is still more preferable, 3 or more is more preferable, 5 or more is still more preferable, 10 or more is still more preferable, and 15 or more is still more preferable, <1> to <9> The cleaning composition as described.
<11> The mass ratio (A / B) of component A to component B in the cleaning composition is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, and even more preferably 20 or less, <1> To <10>.
<12> The cleaning composition according to any one of <1> to <11>, wherein the content of the component C when using the cleaning composition is preferably 90% by mass or more, more preferably 95% by mass or more. .
<13> The content of Component C during use of the cleaning composition is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less, any one of <1> to <12> A cleaning composition according to claim 1.
<14> The total content of optional components during use of the cleaning composition is preferably 0% by mass or more and 2.0% by mass or less, more preferably 0% by mass or more and 1.5% by mass or less, and more preferably 0% by mass or more. The cleaning composition according to any one of <1> to <13>, which is more preferably 1.3% by mass or less, and still more preferably 0% by mass or more and 1.0% by mass or less.
<15> The total content of organic substances in the cleaning composition is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. The cleaning composition according to any one of <1> to <14>.
<16> The total content of organic substances in the cleaning composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more, from <1> to < The cleaning composition according to any one of 15>.
<17> The cleaning composition according to any one of <1> to <16>, which is substantially free of a nitrogen-containing compound and a phosphorus-containing compound.
<18> The total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning composition is less than 0.1 mass%, preferably 0.05 mass% or less, more preferably 0.01 mass% or less, The cleaning composition according to any one of <1> to <17>, further preferably 0% by mass.
<19> The cleaning composition according to any one of <1> to <18>, wherein the pH during use of the cleaning composition is preferably 10.0 or more, and more preferably 10.5 or more.
<20> The pH in use of the cleaning composition is preferably 14 or less, more preferably 13.9 or less, and even more preferably 13.7 or less, the cleaning agent according to any one of <1> to <19> Composition.
<21> When the detergent composition is a concentrate, the content of component A in the concentrate of the detergent composition is preferably 1% by mass or more, more preferably 2% by mass or more, and more preferably 5% by mass or more. The cleaning composition according to any one of <1> to <20>, further preferably 10% by mass or more.
<22> When the detergent composition is a concentrate, the content of component A in the concentrate of the detergent composition is preferably 40% by mass or less, more preferably 30% by mass or less, and 20% by mass or less. The cleaning composition according to any one of <1> to <21>, further preferably 10% by mass or less.
<23> When the detergent composition is a concentrate, the content of Component B in the concentrate of the detergent composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0 The cleaning composition according to any one of <1> to <22>, more preferably 5% by mass or more, and still more preferably 1% by mass or more.
<24> When the detergent composition is a concentrate, the content of component B in the concentrate of the detergent composition is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 2% by mass or less. The cleaning composition according to any one of <1> to <23>, further preferably 1.5% by mass or less.
<25> When the detergent composition is a concentrate, the content of component C in the concentrate of the detergent composition is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. The cleaning composition according to any one of <1> to <24>, which is more preferable.
<26> When the detergent composition is a concentrate, the content of component C in the concentrate of the detergent composition is preferably 95% by mass or less, more preferably 90% by mass or less, and 85% by mass or less. The cleaning composition according to any one of <1> to <25>, which is more preferable.
<27> When the cleaning composition is a concentrate, the pH of the cleaning composition concentrate is preferably 10.0 or more, more preferably 10.5 or more, any one of <1> to <26> The cleaning composition described in 1.
<28> When the cleaning composition is a concentrate, the cleaning composition according to any one of <1> to <27>, wherein the pH of the cleaning composition is preferably 14 or less.
<29> The cleaning composition according to any one of <1> to <28>, wherein the resin mask is a negative dry film resist subjected to at least one of exposure and development.
<30> A method for removing a resin mask, comprising a step of cleaning an object to be cleaned to which a resin mask is adhered with the cleaning composition according to any one of <1> to <29>.
<31> The removal method according to <30>, wherein the object to be cleaned is a manufacturing intermediate for electronic components.
<32> A method for manufacturing an electronic component, comprising a step of cleaning an object to be cleaned to which a resin mask is attached with the cleaning composition according to any one of <1> or <29>.
<33> Use of the cleaning composition according to any one of <1> to <29> for manufacturing an electronic component.
<34> A kit for use in any one of the method for removing <30> or <31> and the method for producing an electronic component according to <32>, wherein the kit is described in any one of <1> to <29> A kit comprising at least one of the components A to C constituting the detergent composition in a state where it is not mixed with other components.
<35> A solution containing component A (first liquid) and a solution containing component B (second liquid) are included in a state where they are not mixed with each other, and at least one of the first liquid and the second liquid is The kit according to <34>, further comprising component C, wherein the first liquid and the second liquid are mixed at the time of use.
<36> Use of the cleaning composition according to any one of <1> to <29> for removing a resin mask from an object to be cleaned.
<37> Use of the cleaning composition according to any one of <1> to <29> for cleaning an electronic component.
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。
Hereinafter, the present disclosure will be specifically described by way of examples. However, the present disclosure is not limited to these examples.
１．溶剤（成分Ｂ）の物性（ＨＳＰの座標及び距離）について
各溶媒Ｂ１～２０のＨＳＰの座標（δｄ1、δｐ1、δｈ1）は、パソコン用ソフトウエア「HSPiP：Hansen Solubility Parameters in Practice」を用いて算出した。そして、成分ＢのＨＳＰの座標（δｄ1、δｐ1、δｈ1）と成分座標Ｘ（δｄ＝１７．５、δｐ＝５．０、δｈ＝１１．５）との距離を下記式により算出した。算出結果を表１に示す。
距離＝［（δｄ1－１７．５）2＋（δｐ1－５．０）2＋（δｈ1－１１．５）2］0.5 1. About the physical properties (HSP coordinates and distance) of the solvent (component B) The HSP coordinates (δd 1 , δp 1 , δh 1 ) of each solvent B1 to 20 are the software for personal computers “HSPiP: Hansen Solubility Parameters in Practice”. Used to calculate. Then, the distance between the HSP coordinates (δd 1 , δp 1 , δh 1 ) of the component B and the component coordinates X (δd = 17.5, δp = 5.0, δh = 11.5) was calculated by the following formula. . The calculation results are shown in Table 1.
Distance = [(δd 1 −17.5) 2 + (δp 1 −5.0) 2 + (δh 1 −11.5) 2 ] 0.5
各溶媒Ｂ１～２０のＨＳＰの座標（δｄ1、δｐ1、δｈ1）は、パソコン用ソフトウエア「HSPiP：Hansen Solubility Parameters in Practice」を用いて算出した。そして、成分ＢのＨＳＰの座標（δｄ1、δｐ1、δｈ1）と成分座標Ｘ（δｄ＝１７．５、δｐ＝５．０、δｈ＝１１．５）との距離を下記式により算出した。算出結果を表１に示す。
距離＝［（δｄ1－１７．５）2＋（δｐ1－５．０）2＋（δｈ1－１１．５）2］0.5 1. About the physical properties (HSP coordinates and distance) of the solvent (component B) The HSP coordinates (δd 1 , δp 1 , δh 1 ) of each solvent B1 to 20 are the software for personal computers “HSPiP: Hansen Solubility Parameters in Practice”. Used to calculate. Then, the distance between the HSP coordinates (δd 1 , δp 1 , δh 1 ) of the component B and the component coordinates X (δd = 17.5, δp = 5.0, δh = 11.5) was calculated by the following formula. . The calculation results are shown in Table 1.
Distance = [(δd 1 −17.5) 2 + (δp 1 −5.0) 2 + (δh 1 −11.5) 2 ] 0.5
２．洗浄剤組成物の調製（実施例１～２９及び比較例１～２２）
［実施例１～２６及び比較例１～１９の洗浄剤組成物の調製］
５００ｍＬガラスビーカーに有効分換算で水酸化ナトリウム（成分Ａ）１７．５ｇ、プロピレングリコールフェニルエーテル（成分Ｂ）１．０ｇ及び水（成分Ｃ）４８１．５ｇを添加し、それを攪拌して均一に混合することにより、実施例１の洗浄剤組成物を調製した。そして、実施例２～２６及び比較例１～１９の洗浄剤組成物を、実施例１と同様の方法により、表２－１、表２－２及び表３に示す有効分になる組成比で調製した。各洗浄剤組成物の各成分の含有量（質量％）及び質量比Ａ／Ｂを表２－１、表２－２及び表３に示した。表２－１及び表２－２中、混合有機溶剤としてのＨＳＰの距離については、「HSPiP：Hansen Solubility Parameters in Practice」の混合有機溶剤のＨＳＰ算出機能を用いて算出した。 2. Preparation of cleaning composition (Examples 1 to 29 and Comparative Examples 1 to 22)
[Preparation of cleaning compositions of Examples 1 to 26 and Comparative Examples 1 to 19]
In a 500 mL glass beaker, 17.5 g of sodium hydroxide (component A), 1.0 g of propylene glycol phenyl ether (component B) and 481.5 g of water (component C) are added in terms of effective amount, and the mixture is stirred uniformly. The detergent composition of Example 1 was prepared by mixing. Then, the cleaning compositions of Examples 2 to 26 and Comparative Examples 1 to 19 were prepared by the same method as in Example 1 with the composition ratios for effective components shown in Table 2-1, Table 2-2, and Table 3. Prepared. The contents (mass%) and mass ratio A / B of each component of each cleaning composition are shown in Table 2-1, Table 2-2, and Table 3. In Tables 2-1 and 2-2, the HSP distance as the mixed organic solvent was calculated using the HSP calculation function of the mixed organic solvent in “HSPiP: Hansen Solubility Parameters in Practice”.
［実施例１～２６及び比較例１～１９の洗浄剤組成物の調製］
５００ｍＬガラスビーカーに有効分換算で水酸化ナトリウム（成分Ａ）１７．５ｇ、プロピレングリコールフェニルエーテル（成分Ｂ）１．０ｇ及び水（成分Ｃ）４８１．５ｇを添加し、それを攪拌して均一に混合することにより、実施例１の洗浄剤組成物を調製した。そして、実施例２～２６及び比較例１～１９の洗浄剤組成物を、実施例１と同様の方法により、表２－１、表２－２及び表３に示す有効分になる組成比で調製した。各洗浄剤組成物の各成分の含有量（質量％）及び質量比Ａ／Ｂを表２－１、表２－２及び表３に示した。表２－１及び表２－２中、混合有機溶剤としてのＨＳＰの距離については、「HSPiP：Hansen Solubility Parameters in Practice」の混合有機溶剤のＨＳＰ算出機能を用いて算出した。 2. Preparation of cleaning composition (Examples 1 to 29 and Comparative Examples 1 to 22)
[Preparation of cleaning compositions of Examples 1 to 26 and Comparative Examples 1 to 19]
In a 500 mL glass beaker, 17.5 g of sodium hydroxide (component A), 1.0 g of propylene glycol phenyl ether (component B) and 481.5 g of water (component C) are added in terms of effective amount, and the mixture is stirred uniformly. The detergent composition of Example 1 was prepared by mixing. Then, the cleaning compositions of Examples 2 to 26 and Comparative Examples 1 to 19 were prepared by the same method as in Example 1 with the composition ratios for effective components shown in Table 2-1, Table 2-2, and Table 3. Prepared. The contents (mass%) and mass ratio A / B of each component of each cleaning composition are shown in Table 2-1, Table 2-2, and Table 3. In Tables 2-1 and 2-2, the HSP distance as the mixed organic solvent was calculated using the HSP calculation function of the mixed organic solvent in “HSPiP: Hansen Solubility Parameters in Practice”.
［実施例２７～２９及び比較例２０～２２の洗浄剤組成物］
１０Ｌステンレスビーカーに有効分換算で水酸化ナトリウム（成分Ａ）１７５ｇ、プロピレングリコールフェニルエーテル（成分Ｂ）１０ｇ及び水（成分Ｃ）４８１５ｇを添加し、それを攪拌して均一に混合することにより、実施例２７の洗浄剤組成物を調製した。そして、実施例２８～２９及び比較例２０～２２の洗浄剤組成物を、実施例２７と同様の方法により、表４に示す有効分になる組成比で調製した。各洗浄剤組成物の各成分の含有量（質量％）を表４に示した。 [Detergent compositions of Examples 27 to 29 and Comparative Examples 20 to 22]
It is carried out by adding 175 g of sodium hydroxide (component A), 10 g of propylene glycol phenyl ether (component B) and 4815 g of water (component C) in an equivalent amount to a 10 L stainless beaker, and stirring and mixing them uniformly. The detergent composition of Example 27 was prepared. Then, the cleaning compositions of Examples 28 to 29 and Comparative Examples 20 to 22 were prepared by the same method as in Example 27 at the composition ratios having the effective components shown in Table 4. Table 4 shows the content (% by mass) of each component of each cleaning composition.
１０Ｌステンレスビーカーに有効分換算で水酸化ナトリウム（成分Ａ）１７５ｇ、プロピレングリコールフェニルエーテル（成分Ｂ）１０ｇ及び水（成分Ｃ）４８１５ｇを添加し、それを攪拌して均一に混合することにより、実施例２７の洗浄剤組成物を調製した。そして、実施例２８～２９及び比較例２０～２２の洗浄剤組成物を、実施例２７と同様の方法により、表４に示す有効分になる組成比で調製した。各洗浄剤組成物の各成分の含有量（質量％）を表４に示した。 [Detergent compositions of Examples 27 to 29 and Comparative Examples 20 to 22]
It is carried out by adding 175 g of sodium hydroxide (component A), 10 g of propylene glycol phenyl ether (component B) and 4815 g of water (component C) in an equivalent amount to a 10 L stainless beaker, and stirring and mixing them uniformly. The detergent composition of Example 27 was prepared. Then, the cleaning compositions of Examples 28 to 29 and Comparative Examples 20 to 22 were prepared by the same method as in Example 27 at the composition ratios having the effective components shown in Table 4. Table 4 shows the content (% by mass) of each component of each cleaning composition.
実施例１～２９及び比較例１～２２の洗浄剤組成物の成分としては下記のものを使用した。
・水酸化ナトリウム（成分Ａ）（関東化学株式会社製、鹿特級、固形分４８質量％）
・水酸化カリウム（成分Ａ）（関東化学株式会社製、鹿特級、固形分４８質量％）
・テトラメチルアンモニウムヒドロキシド（非成分Ａ）（昭和電工株式会社製、ＴＭＡＨ（２５％））
・プロピレングリコールフェニルエーテル（成分Ｂ）（日本乳化剤株式会社製、フェニルプロピレングリコール（ＰｈＦＧ））
・１－メチルシクロヘキサノール（成分Ｂ）（東京化成工業株式会社製）
・３－メチルシクロヘキサノール（成分Ｂ）（メルク株式会社製）
・４－メチルシクロヘキサノール（成分Ｂ）（東京化成工業株式会社製）
・エチレングリコールモノベンジルエーテル（成分Ｂ）（日本乳化剤株式会社製、ベンジルグリコール（ＢｚＧ））
・１－フェニル－１－プロパノール（成分Ｂ）（東京化成工業株式会社製）
・２－フェニル－１－プロパノール（成分Ｂ）（東京化成工業株式会社製）
・エチレングリコールモノｎ－ヘキシルエーテル（成分Ｂ）（日本乳化剤株式会社製、ヘキシルグリコール（ＨｅＧ））
・エチレングリコールモノブチルエーテル（非成分Ｂ）（日本乳化剤株式会社製、ブチルグリコール（ＢＧ））
・エチレングリコールモノ２－エチルヘキシルエーテル（非成分Ｂ）（日本乳化剤株式会社製、２エチルヘキシルグリコール（ＥＨＧ））
・ｏ－メトキシフェノール（非成分Ｂ）（東京化成工業株式会社製、グアヤコール）
・シクロヘキサノール（非成分Ｂ）（和光純薬工業株式会社製）
・ジエチレングリコールモノブチルエーテル（非成分Ｂ）（日本乳化剤株式会社製、ブチルジグリコール（ＢＤＧ））
・ベンジルアルコール（非成分Ｂ）（ランクセス株式会社製）
・２－フェノキシエタノール（非成分Ｂ）（東京化成工業株式会社製）
・プロピレングリコールモノブチルエーテル（非成分Ｂ）（日本乳化剤株式会社製、ブチルプロピレングリコール（ＢＦＧ））
・モノエタノールアミン（非成分Ｂ）（株式会社日本触媒製）
・プロピレングリコールモノメチルエーテル（非成分Ｂ）（日本乳化剤株式会社製、メチルプロピレングリコール（ＭＦＧ））
・プロピレングリコールモノメチルエーテルアセテート（非成分Ｂ）（日本乳化剤株式会社製、メチルプロピレングリコールアセテート（ＭＦＧ－ＡＣ））
・ジメチルスホキシド（非成分Ｂ）（ナカライテスク株式会社製）
・水（成分Ｃ）（オルガノ株式会社製純水装置Ｇ－１０ＤＳＴＳＥＴで製造した１μＳ/ｃｍ以下の純水） As the components of the detergent compositions of Examples 1 to 29 and Comparative Examples 1 to 22, the following were used.
・ Sodium hydroxide (component A) (Kanto Chemical Co., Ltd., deer special grade, solid content 48% by mass)
Potassium hydroxide (component A) (manufactured by Kanto Chemical Co., Ltd., deer special grade, solid content 48% by mass)
Tetramethylammonium hydroxide (non-component A) (manufactured by Showa Denko KK, TMAH (25%))
Propylene glycol phenyl ether (component B) (manufactured by Nippon Emulsifier Co., Ltd., phenylpropylene glycol (PhFG))
1-methylcyclohexanol (component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 3-Methylcyclohexanol (component B) (Merck Co., Ltd.)
・ 4-Methylcyclohexanol (component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ethylene glycol monobenzyl ether (component B) (Nippon Emulsifier Co., Ltd., benzyl glycol (BzG))
・ 1-Phenyl-1-propanol (component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 2-Phenyl-1-propanol (component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
Ethylene glycol mono n-hexyl ether (component B) (manufactured by Nippon Emulsifier Co., Ltd., hexyl glycol (HeG))
・ Ethylene glycol monobutyl ether (non-component B) (Nippon Emulsifier Co., Ltd., butyl glycol (BG))
・ Ethylene glycol mono 2-ethylhexyl ether (non-component B) (manufactured by Nippon Emulsifier Co., Ltd., 2-ethylhexyl glycol (EHG))
O-Methoxyphenol (non-component B) (Tokyo Chemical Industry Co., Ltd., guaiacol)
・ Cyclohexanol (non-component B) (Wako Pure Chemical Industries, Ltd.)
・ Diethylene glycol monobutyl ether (non-component B) (Nippon Emulsifier Co., Ltd., butyl diglycol (BDG))
・ Benzyl alcohol (non-component B) (manufactured by LANXESS)
・ 2-phenoxyethanol (non-component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
Propylene glycol monobutyl ether (non-component B) (Nippon Emulsifier Co., Ltd., butyl propylene glycol (BFG))
・ Monoethanolamine (non-component B) (manufactured by Nippon Shokubai Co., Ltd.)
・ Propylene glycol monomethyl ether (non-component B) (manufactured by Nippon Emulsifier Co., Ltd., methyl propylene glycol (MFG))
・ Propylene glycol monomethyl ether acetate (non-component B) (manufactured by Nippon Emulsifier Co., Ltd., methyl propylene glycol acetate (MFG-AC))
・ Dimethyl sulfoxide (non-component B) (manufactured by Nacalai Tesque)
Water (component C) (pure water of 1 μS / cm or less produced with a pure water apparatus G-10DSTSET manufactured by Organo Corporation)
・水酸化ナトリウム（成分Ａ）（関東化学株式会社製、鹿特級、固形分４８質量％）
・水酸化カリウム（成分Ａ）（関東化学株式会社製、鹿特級、固形分４８質量％）
・テトラメチルアンモニウムヒドロキシド（非成分Ａ）（昭和電工株式会社製、ＴＭＡＨ（２５％））
・プロピレングリコールフェニルエーテル（成分Ｂ）（日本乳化剤株式会社製、フェニルプロピレングリコール（ＰｈＦＧ））
・１－メチルシクロヘキサノール（成分Ｂ）（東京化成工業株式会社製）
・３－メチルシクロヘキサノール（成分Ｂ）（メルク株式会社製）
・４－メチルシクロヘキサノール（成分Ｂ）（東京化成工業株式会社製）
・エチレングリコールモノベンジルエーテル（成分Ｂ）（日本乳化剤株式会社製、ベンジルグリコール（ＢｚＧ））
・１－フェニル－１－プロパノール（成分Ｂ）（東京化成工業株式会社製）
・２－フェニル－１－プロパノール（成分Ｂ）（東京化成工業株式会社製）
・エチレングリコールモノｎ－ヘキシルエーテル（成分Ｂ）（日本乳化剤株式会社製、ヘキシルグリコール（ＨｅＧ））
・エチレングリコールモノブチルエーテル（非成分Ｂ）（日本乳化剤株式会社製、ブチルグリコール（ＢＧ））
・エチレングリコールモノ２－エチルヘキシルエーテル（非成分Ｂ）（日本乳化剤株式会社製、２エチルヘキシルグリコール（ＥＨＧ））
・ｏ－メトキシフェノール（非成分Ｂ）（東京化成工業株式会社製、グアヤコール）
・シクロヘキサノール（非成分Ｂ）（和光純薬工業株式会社製）
・ジエチレングリコールモノブチルエーテル（非成分Ｂ）（日本乳化剤株式会社製、ブチルジグリコール（ＢＤＧ））
・ベンジルアルコール（非成分Ｂ）（ランクセス株式会社製）
・２－フェノキシエタノール（非成分Ｂ）（東京化成工業株式会社製）
・プロピレングリコールモノブチルエーテル（非成分Ｂ）（日本乳化剤株式会社製、ブチルプロピレングリコール（ＢＦＧ））
・モノエタノールアミン（非成分Ｂ）（株式会社日本触媒製）
・プロピレングリコールモノメチルエーテル（非成分Ｂ）（日本乳化剤株式会社製、メチルプロピレングリコール（ＭＦＧ））
・プロピレングリコールモノメチルエーテルアセテート（非成分Ｂ）（日本乳化剤株式会社製、メチルプロピレングリコールアセテート（ＭＦＧ－ＡＣ））
・ジメチルスホキシド（非成分Ｂ）（ナカライテスク株式会社製）
・水（成分Ｃ）（オルガノ株式会社製純水装置Ｇ－１０ＤＳＴＳＥＴで製造した１μＳ/ｃｍ以下の純水） As the components of the detergent compositions of Examples 1 to 29 and Comparative Examples 1 to 22, the following were used.
・ Sodium hydroxide (component A) (Kanto Chemical Co., Ltd., deer special grade, solid content 48% by mass)
Potassium hydroxide (component A) (manufactured by Kanto Chemical Co., Ltd., deer special grade, solid content 48% by mass)
Tetramethylammonium hydroxide (non-component A) (manufactured by Showa Denko KK, TMAH (25%))
Propylene glycol phenyl ether (component B) (manufactured by Nippon Emulsifier Co., Ltd., phenylpropylene glycol (PhFG))
1-methylcyclohexanol (component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 3-Methylcyclohexanol (component B) (Merck Co., Ltd.)
・ 4-Methylcyclohexanol (component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ethylene glycol monobenzyl ether (component B) (Nippon Emulsifier Co., Ltd., benzyl glycol (BzG))
・ 1-Phenyl-1-propanol (component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 2-Phenyl-1-propanol (component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
Ethylene glycol mono n-hexyl ether (component B) (manufactured by Nippon Emulsifier Co., Ltd., hexyl glycol (HeG))
・ Ethylene glycol monobutyl ether (non-component B) (Nippon Emulsifier Co., Ltd., butyl glycol (BG))
・ Ethylene glycol mono 2-ethylhexyl ether (non-component B) (manufactured by Nippon Emulsifier Co., Ltd., 2-ethylhexyl glycol (EHG))
O-Methoxyphenol (non-component B) (Tokyo Chemical Industry Co., Ltd., guaiacol)
・ Cyclohexanol (non-component B) (Wako Pure Chemical Industries, Ltd.)
・ Diethylene glycol monobutyl ether (non-component B) (Nippon Emulsifier Co., Ltd., butyl diglycol (BDG))
・ Benzyl alcohol (non-component B) (manufactured by LANXESS)
・ 2-phenoxyethanol (non-component B) (manufactured by Tokyo Chemical Industry Co., Ltd.)
Propylene glycol monobutyl ether (non-component B) (Nippon Emulsifier Co., Ltd., butyl propylene glycol (BFG))
・ Monoethanolamine (non-component B) (manufactured by Nippon Shokubai Co., Ltd.)
・ Propylene glycol monomethyl ether (non-component B) (manufactured by Nippon Emulsifier Co., Ltd., methyl propylene glycol (MFG))
・ Propylene glycol monomethyl ether acetate (non-component B) (manufactured by Nippon Emulsifier Co., Ltd., methyl propylene glycol acetate (MFG-AC))
・ Dimethyl sulfoxide (non-component B) (manufactured by Nacalai Tesque)
Water (component C) (pure water of 1 μS / cm or less produced with a pure water apparatus G-10DSTSET manufactured by Organo Corporation)
３．洗浄剤組成物の評価
調製した実施例１～２９及び比較例１～２２の洗浄剤組成物の樹脂マスク除去性を評価した。 3. Evaluation of Cleaning Composition The resin mask removability of the prepared cleaning compositions of Examples 1 to 29 and Comparative Examples 1 to 22 was evaluated.
調製した実施例１～２９及び比較例１～２２の洗浄剤組成物の樹脂マスク除去性を評価した。 3. Evaluation of Cleaning Composition The resin mask removability of the prepared cleaning compositions of Examples 1 to 29 and Comparative Examples 1 to 22 was evaluated.
［テストピースの作製］
ダイレクトイメージング（直接描画）用感光性フィルム（日立化成株式会社製、フォテック ＲＤ－１２１５、ネガ型ドライフィルムレジスト）をガラスエポキシ多層基板（日立化成株式会社製、ＭＣＬ－Ｅ－６７９ＦＧ)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（下記３つの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メッキ処理することで、テストピース（４ｃｍ×４．５ｃｍ）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、処理時間３０秒で行う。
（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：下記の３パターン
・ベタ：３０μｍ×３０μｍ以上の面積を有する部分
・縞状パターン１：ライン幅Ｌとライン間隔Ｓとの比（Ｌ／Ｓ）＝２０μｍ／２０μｍの縞状パターン
・縞状パターン２：Ｌ／Ｓ＝１５μｍ／１５μｍ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、４７秒間で、未露光部の樹脂マスクを除去する。 [Production of test pieces]
A photosensitive film for direct imaging (direct drawing) (manufactured by Hitachi Chemical Co., Ltd., Photec RD-1215, negative dry film resist) is applied to the surface of a glass epoxy multilayer substrate (manufactured by Hitachi Chemical Co., Ltd., MCL-E-679FG) as follows. After laminating under conditions, selectively exposing to cure the exposed area (exposure process), developing to remove the unexposed area (developing process), resist pattern (negative pattern of the following three pattern shapes) A substrate having a resin mask) was obtained. And the test piece (4 cm x 4.5 cm) was obtained by carrying out the copper plating process to the area | region from which the unexposed part was removed by the said development process.
(1) Lamination: Using a clean roller (Rayon Industries, Ltd., RY-505Z) and a vacuum applicator (Rohm & Haas, VA7024 / HP5), a roller temperature of 50 ° C., a roller pressure of 1.4 Bar, and a processing time of 30 In seconds.
(2) Exposure: Exposure is performed at an exposure amount of 15 mJ / cm 2 using a direct drawing apparatus for printed circuit boards (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions, Inc.).
(3) Pattern shape: The following three patterns Solid: Part having an area of 30 μm × 30 μm or more Striped pattern 1: Striped pattern with a ratio of line width L to line interval S (L / S) = 20 μm / 20 μm Pattern / striped pattern 2: Striped pattern of L / S = 15 μm / 15 μm (4) Development: Substrate developing device (manufactured by Hohiro Kagaku Co., Ltd., LT-980366), 1% sodium carbonate aqueous solution at 30 ° C. Then, the unexposed portion of the resin mask is removed at a spray pressure of 0.2 MPa for 47 seconds.
ダイレクトイメージング（直接描画）用感光性フィルム（日立化成株式会社製、フォテック ＲＤ－１２１５、ネガ型ドライフィルムレジスト）をガラスエポキシ多層基板（日立化成株式会社製、ＭＣＬ－Ｅ－６７９ＦＧ)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（下記３つの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メッキ処理することで、テストピース（４ｃｍ×４．５ｃｍ）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、処理時間３０秒で行う。
（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：下記の３パターン
・ベタ：３０μｍ×３０μｍ以上の面積を有する部分
・縞状パターン１：ライン幅Ｌとライン間隔Ｓとの比（Ｌ／Ｓ）＝２０μｍ／２０μｍの縞状パターン
・縞状パターン２：Ｌ／Ｓ＝１５μｍ／１５μｍ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、４７秒間で、未露光部の樹脂マスクを除去する。 [Production of test pieces]
A photosensitive film for direct imaging (direct drawing) (manufactured by Hitachi Chemical Co., Ltd., Photec RD-1215, negative dry film resist) is applied to the surface of a glass epoxy multilayer substrate (manufactured by Hitachi Chemical Co., Ltd., MCL-E-679FG) as follows. After laminating under conditions, selectively exposing to cure the exposed area (exposure process), developing to remove the unexposed area (developing process), resist pattern (negative pattern of the following three pattern shapes) A substrate having a resin mask) was obtained. And the test piece (4 cm x 4.5 cm) was obtained by carrying out the copper plating process to the area | region from which the unexposed part was removed by the said development process.
(1) Lamination: Using a clean roller (Rayon Industries, Ltd., RY-505Z) and a vacuum applicator (Rohm & Haas, VA7024 / HP5), a roller temperature of 50 ° C., a roller pressure of 1.4 Bar, and a processing time of 30 In seconds.
(2) Exposure: Exposure is performed at an exposure amount of 15 mJ / cm 2 using a direct drawing apparatus for printed circuit boards (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions, Inc.).
(3) Pattern shape: The following three patterns Solid: Part having an area of 30 μm × 30 μm or more Striped pattern 1: Striped pattern with a ratio of line width L to line interval S (L / S) = 20 μm / 20 μm Pattern / striped pattern 2: Striped pattern of L / S = 15 μm / 15 μm (4) Development: Substrate developing device (manufactured by Hohiro Kagaku Co., Ltd., LT-980366), 1% sodium carbonate aqueous solution at 30 ° C. Then, the unexposed portion of the resin mask is removed at a spray pressure of 0.2 MPa for 47 seconds.
［洗浄試験１（浸漬洗浄）］（実施例１～２６及び比較例１～１９）
１００ｍＬガラスビーカーに、実施例１～２６及び比較例１～１９の各洗浄剤組成物を１００ｇ添加して６０℃に加温し、回転子（フッ素樹脂（ＰＴＦＥ）、φ８ｍｍ×２５ｍｍ）を用いて回転数４００ｒｐｍで撹拌した状態で、テストピースを３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、自然乾燥する。さらに、実施例１８～２６及び比較例１７～１９の洗浄剤組成物については、浸漬時間を３分間、６分間、２５分間、３０分間とした洗浄試験を行った。 [Cleaning Test 1 (Immersion Cleaning)] (Examples 1 to 26 and Comparative Examples 1 to 19)
In a 100 mL glass beaker, 100 g of each of the cleaning compositions of Examples 1 to 26 and Comparative Examples 1 to 19 was added and heated to 60 ° C., using a rotor (fluororesin (PTFE), φ8 mm × 25 mm). The test piece is immersed for 3 minutes with stirring at a rotational speed of 400 rpm. And after immersing in the rinse tank which added 100g of water to the 100mL glass beaker, it rinses naturally. Further, the cleaning compositions of Examples 18 to 26 and Comparative Examples 17 to 19 were subjected to cleaning tests with immersion times of 3 minutes, 6 minutes, 25 minutes, and 30 minutes.
１００ｍＬガラスビーカーに、実施例１～２６及び比較例１～１９の各洗浄剤組成物を１００ｇ添加して６０℃に加温し、回転子（フッ素樹脂（ＰＴＦＥ）、φ８ｍｍ×２５ｍｍ）を用いて回転数４００ｒｐｍで撹拌した状態で、テストピースを３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、自然乾燥する。さらに、実施例１８～２６及び比較例１７～１９の洗浄剤組成物については、浸漬時間を３分間、６分間、２５分間、３０分間とした洗浄試験を行った。 [Cleaning Test 1 (Immersion Cleaning)] (Examples 1 to 26 and Comparative Examples 1 to 19)
In a 100 mL glass beaker, 100 g of each of the cleaning compositions of Examples 1 to 26 and Comparative Examples 1 to 19 was added and heated to 60 ° C., using a rotor (fluororesin (PTFE), φ8 mm × 25 mm). The test piece is immersed for 3 minutes with stirring at a rotational speed of 400 rpm. And after immersing in the rinse tank which added 100g of water to the 100mL glass beaker, it rinses naturally. Further, the cleaning compositions of Examples 18 to 26 and Comparative Examples 17 to 19 were subjected to cleaning tests with immersion times of 3 minutes, 6 minutes, 25 minutes, and 30 minutes.
［洗浄試験２（スプレー洗浄）］（実施例２７～２９及び比較例２０～２２）
１０Ｌステンレスビーカーに、実施例２７～２９及び比較例２０～２２の各洗浄剤組成物を１０ｋｇ添加して６０℃に加温し、１流体ノズル（充円錐）ＪＪＸＰ０３０（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流量３Ｌ／分で循環しながら、テストピースを３分間スプレー（圧力：０．２ＭＰａ、スプレー距離：８ｃｍ）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。 [Cleaning Test 2 (Spray Cleaning)] (Examples 27 to 29 and Comparative Examples 20 to 22)
Add 10 kg of each of the detergent compositions of Examples 27 to 29 and Comparative Examples 20 to 22 to a 10 L stainless beaker, heat to 60 ° C., and spray 1 fluid nozzle (full cone) JJXP030 (manufactured by Ikeuchi Co., Ltd.) The test piece is sprayed for 3 minutes (pressure: 0.2 MPa, spray distance: 8 cm) while circulating at a flow rate of 3 L / min with a box type spray washing machine attached as a nozzle. And after immersing and immersing in the rinse tank which added 100g of water to a 100 mL glass beaker, it dries with a nitrogen blow.
１０Ｌステンレスビーカーに、実施例２７～２９及び比較例２０～２２の各洗浄剤組成物を１０ｋｇ添加して６０℃に加温し、１流体ノズル（充円錐）ＪＪＸＰ０３０（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流量３Ｌ／分で循環しながら、テストピースを３分間スプレー（圧力：０．２ＭＰａ、スプレー距離：８ｃｍ）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。 [Cleaning Test 2 (Spray Cleaning)] (Examples 27 to 29 and Comparative Examples 20 to 22)
Add 10 kg of each of the detergent compositions of Examples 27 to 29 and Comparative Examples 20 to 22 to a 10 L stainless beaker, heat to 60 ° C., and spray 1 fluid nozzle (full cone) JJXP030 (manufactured by Ikeuchi Co., Ltd.) The test piece is sprayed for 3 minutes (pressure: 0.2 MPa, spray distance: 8 cm) while circulating at a flow rate of 3 L / min with a box type spray washing machine attached as a nozzle. And after immersing and immersing in the rinse tank which added 100g of water to a 100 mL glass beaker, it dries with a nitrogen blow.
［樹脂マスク除去性評価１］（実施例１～１７、２７～２９及び比較例１～１６、２０～２２）
実施例１～１７、２７～２９及び比較例１～１６、２０～２２の洗浄剤組成物を用いて洗浄した後のテストピースの樹脂マスク除去性について下記条件で評価した。
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、乾燥後のテストピースの各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、樹脂マスク除去性を評価する。完全に除去できた場合は「１」、わずかでも残存する場合は「２」とし、表２－１、表２－２及び表４に結果を示す。
表２－１、表２－２及び表４中、「ベタの剥離性」とは、レジストパターンがベタである場合の樹脂マスクの剥離性を示し、「縞状パターン１の剥離性」は、レジストパターンが縞状パターン１（Ｌ／Ｓ＝２０μｍ／２０μｍ）の場合の樹脂マスクの剥離性を示し、「縞状パターン２の剥離性」は、レジストパターンが縞状パターン２（Ｌ／Ｓ＝１５μｍ／１５μｍ）の場合の剥離性を示す。 [Resin Mask Removability Evaluation 1] (Examples 1 to 17, 27 to 29 and Comparative Examples 1 to 16, 20 to 22)
The resin mask removability of the test pieces after cleaning using the cleaning compositions of Examples 1 to 17, 27 to 29 and Comparative Examples 1 to 16 and 20 to 22 was evaluated under the following conditions.
Using an optical microscope “Digital Microscope VHX-2000” (manufactured by Keyence Corporation), the presence or absence of the resin mask remaining on each part of the test piece after drying is magnified 300 times and visually confirmed, and the resin mask is removed. To evaluate. The results are shown in Table 2-1, Table 2-2, and Table 4 with “1” when completely removed and “2” when even a little remains.
In Table 2-1, Table 2-2, and Table 4, “solid peelability” indicates the peelability of the resin mask when the resist pattern is solid, and “stripe pattern 1 peelability” The releasability of the resin mask when the resist pattern is a striped pattern 1 (L / S = 20 μm / 20 μm) is shown. “Removability of the striped pattern 2” indicates that the resist pattern is a striped pattern 2 (L / S = The peelability in the case of 15 μm / 15 μm) is shown.
実施例１～１７、２７～２９及び比較例１～１６、２０～２２の洗浄剤組成物を用いて洗浄した後のテストピースの樹脂マスク除去性について下記条件で評価した。
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、乾燥後のテストピースの各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、樹脂マスク除去性を評価する。完全に除去できた場合は「１」、わずかでも残存する場合は「２」とし、表２－１、表２－２及び表４に結果を示す。
表２－１、表２－２及び表４中、「ベタの剥離性」とは、レジストパターンがベタである場合の樹脂マスクの剥離性を示し、「縞状パターン１の剥離性」は、レジストパターンが縞状パターン１（Ｌ／Ｓ＝２０μｍ／２０μｍ）の場合の樹脂マスクの剥離性を示し、「縞状パターン２の剥離性」は、レジストパターンが縞状パターン２（Ｌ／Ｓ＝１５μｍ／１５μｍ）の場合の剥離性を示す。 [Resin Mask Removability Evaluation 1] (Examples 1 to 17, 27 to 29 and Comparative Examples 1 to 16, 20 to 22)
The resin mask removability of the test pieces after cleaning using the cleaning compositions of Examples 1 to 17, 27 to 29 and Comparative Examples 1 to 16 and 20 to 22 was evaluated under the following conditions.
Using an optical microscope “Digital Microscope VHX-2000” (manufactured by Keyence Corporation), the presence or absence of the resin mask remaining on each part of the test piece after drying is magnified 300 times and visually confirmed, and the resin mask is removed. To evaluate. The results are shown in Table 2-1, Table 2-2, and Table 4 with “1” when completely removed and “2” when even a little remains.
In Table 2-1, Table 2-2, and Table 4, “solid peelability” indicates the peelability of the resin mask when the resist pattern is solid, and “stripe pattern 1 peelability” The releasability of the resin mask when the resist pattern is a striped pattern 1 (L / S = 20 μm / 20 μm) is shown. “Removability of the striped pattern 2” indicates that the resist pattern is a striped pattern 2 (L / S = The peelability in the case of 15 μm / 15 μm) is shown.
［樹脂マスク除去性評価２］（実施例１、４、８、１８～２６及び比較例１７～１９）
実施例１、４、８、１８～２６及び比較例１７～１９の洗浄剤組成物を用いて洗浄した後のテストピースの樹脂マスク除去性について下記条件で評価した。
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、乾燥後のテストピースの各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、樹脂マスク除去性を評価する。樹脂マスクが完全に剥離するまでに要した洗浄剤組成物への浸漬時間の最短時間を下記のように評価し、表３に結果を示す。浸漬時間が短いほど、樹脂マスク除去性が高いことを示す。
表３中、「ベタの剥離性」とは、レジストパターンがベタである場合の樹脂マスクの剥離性を示し、「縞状パターン１の剥離性」は、レジストパターンが縞状パターン１（Ｌ／Ｓ＝２０μｍ／２０μｍ）の場合の樹脂マスクの剥離性を示し、「縞状パターン２の剥離性」は、レジストパターンが縞状パターン２（Ｌ／Ｓ＝１５μｍ／１５μｍ）の場合の剥離性を示す。
＜評価基準＞
１：浸漬時間３分間で完全剥離達成
２：浸漬時間６分間で完全剥離達成
３：浸漬時間２５分間で完全剥離達成
４：浸漬時間３０分間であっても剥離残あり [Resin Mask Removability Evaluation 2] (Examples 1, 4, 8, 18 to 26 and Comparative Examples 17 to 19)
The resin mask removability of the test pieces after being cleaned using the cleaning compositions of Examples 1, 4, 8, 18 to 26 and Comparative Examples 17 to 19 was evaluated under the following conditions.
Using an optical microscope “Digital Microscope VHX-2000” (manufactured by Keyence Corporation), the presence or absence of the resin mask remaining on each part of the test piece after drying is magnified 300 times and visually confirmed, and the resin mask is removed. To evaluate. The shortest immersion time in the cleaning composition required until the resin mask completely peeled was evaluated as follows, and the results are shown in Table 3. It shows that resin mask removability is so high that immersion time is short.
In Table 3, “solid peelability” indicates the peelability of the resin mask when the resist pattern is solid, and “stripe pattern 1 peelability” indicates that the resist pattern is a stripe pattern 1 (L / The releasability of the resin mask in the case of S = 20 μm / 20 μm) is shown, and the “peelability of striped pattern 2” is the peelability when the resist pattern is striped pattern 2 (L / S = 15 μm / 15 μm). Show.
<Evaluation criteria>
1: Complete peeling achieved in immersion time of 3 minutes 2: Complete peeling achieved in immersion time of 6 minutes 3: Complete peeling achieved in immersion time of 25 minutes 4: Peeling remaining even in immersion time of 30 minutes
実施例１、４、８、１８～２６及び比較例１７～１９の洗浄剤組成物を用いて洗浄した後のテストピースの樹脂マスク除去性について下記条件で評価した。
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、乾燥後のテストピースの各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、樹脂マスク除去性を評価する。樹脂マスクが完全に剥離するまでに要した洗浄剤組成物への浸漬時間の最短時間を下記のように評価し、表３に結果を示す。浸漬時間が短いほど、樹脂マスク除去性が高いことを示す。
表３中、「ベタの剥離性」とは、レジストパターンがベタである場合の樹脂マスクの剥離性を示し、「縞状パターン１の剥離性」は、レジストパターンが縞状パターン１（Ｌ／Ｓ＝２０μｍ／２０μｍ）の場合の樹脂マスクの剥離性を示し、「縞状パターン２の剥離性」は、レジストパターンが縞状パターン２（Ｌ／Ｓ＝１５μｍ／１５μｍ）の場合の剥離性を示す。
＜評価基準＞
１：浸漬時間３分間で完全剥離達成
２：浸漬時間６分間で完全剥離達成
３：浸漬時間２５分間で完全剥離達成
４：浸漬時間３０分間であっても剥離残あり [Resin Mask Removability Evaluation 2] (Examples 1, 4, 8, 18 to 26 and Comparative Examples 17 to 19)
The resin mask removability of the test pieces after being cleaned using the cleaning compositions of Examples 1, 4, 8, 18 to 26 and Comparative Examples 17 to 19 was evaluated under the following conditions.
Using an optical microscope “Digital Microscope VHX-2000” (manufactured by Keyence Corporation), the presence or absence of the resin mask remaining on each part of the test piece after drying is magnified 300 times and visually confirmed, and the resin mask is removed. To evaluate. The shortest immersion time in the cleaning composition required until the resin mask completely peeled was evaluated as follows, and the results are shown in Table 3. It shows that resin mask removability is so high that immersion time is short.
In Table 3, “solid peelability” indicates the peelability of the resin mask when the resist pattern is solid, and “stripe pattern 1 peelability” indicates that the resist pattern is a stripe pattern 1 (L / The releasability of the resin mask in the case of S = 20 μm / 20 μm) is shown, and the “peelability of striped pattern 2” is the peelability when the resist pattern is striped pattern 2 (L / S = 15 μm / 15 μm). Show.
<Evaluation criteria>
1: Complete peeling achieved in immersion time of 3 minutes 2: Complete peeling achieved in immersion time of 6 minutes 3: Complete peeling achieved in immersion time of 25 minutes 4: Peeling remaining even in immersion time of 30 minutes
［スタミナ性評価］（実施例１、３及び４）
３００ｍＬガラスビーカーに、実施例１、３及び４の各洗浄液組成物３００ｇを入れ、６０℃のウォーターバスで保温し、回転子（フッ素樹脂（ＰＴＦＥ）、φ８ｍｍ×４０ｍｍ）を用いて回転数３００ｒｐｍで撹拌する。蒸発により低下した液量を水の添加で補い、５時間後の各洗浄剤組成物の全有機炭素（ＴＯＣ）を平沼全有機炭素測定装置ＴＯＣ－２０００（平沼産業株式会社製）で測定し、ＴＯＣの変化を下記式にて算出する。残存有機炭素率が１００％に近いほど、有効成分（成分Ｂ）の変化が少なくスタミナ性が良いと評価できる。ここで、「有効成分の変化」とは、洗浄剤組成物の長時間使用中に成分Ｂが飛散、揮発又は蒸発することにより、洗浄剤組成物中の成分Ｂの含有量が減少することをいう。
残存有機炭素率（％）＝試験後のＴＯＣ÷試験前のＴＯＣ×１００ [Stamina evaluation] (Examples 1, 3 and 4)
Into a 300 mL glass beaker, 300 g of each of the cleaning liquid compositions of Examples 1, 3 and 4 was placed, kept warm in a water bath at 60 ° C., and rotated at 300 rpm using a rotor (fluororesin (PTFE), φ8 mm × 40 mm). Stir. The amount of liquid reduced by evaporation was supplemented with water, and the total organic carbon (TOC) of each cleaning composition after 5 hours was measured with Hiranuma Total Organic Carbon Measuring Device TOC-2000 (manufactured by Hiranuma Sangyo Co., Ltd.) The change in TOC is calculated by the following formula. It can be evaluated that the closer the residual organic carbon ratio is to 100%, the less the change in the active ingredient (component B) and the better the stamina. Here, “change in active ingredient” means that the content of component B in the cleaning composition is reduced by scattering, volatilization or evaporation of component B during long-term use of the cleaning composition. Say.
Residual organic carbon ratio (%) = TOC after test / TOC before test × 100
３００ｍＬガラスビーカーに、実施例１、３及び４の各洗浄液組成物３００ｇを入れ、６０℃のウォーターバスで保温し、回転子（フッ素樹脂（ＰＴＦＥ）、φ８ｍｍ×４０ｍｍ）を用いて回転数３００ｒｐｍで撹拌する。蒸発により低下した液量を水の添加で補い、５時間後の各洗浄剤組成物の全有機炭素（ＴＯＣ）を平沼全有機炭素測定装置ＴＯＣ－２０００（平沼産業株式会社製）で測定し、ＴＯＣの変化を下記式にて算出する。残存有機炭素率が１００％に近いほど、有効成分（成分Ｂ）の変化が少なくスタミナ性が良いと評価できる。ここで、「有効成分の変化」とは、洗浄剤組成物の長時間使用中に成分Ｂが飛散、揮発又は蒸発することにより、洗浄剤組成物中の成分Ｂの含有量が減少することをいう。
残存有機炭素率（％）＝試験後のＴＯＣ÷試験前のＴＯＣ×１００ [Stamina evaluation] (Examples 1, 3 and 4)
Into a 300 mL glass beaker, 300 g of each of the cleaning liquid compositions of Examples 1, 3 and 4 was placed, kept warm in a water bath at 60 ° C., and rotated at 300 rpm using a rotor (fluororesin (PTFE), φ8 mm × 40 mm). Stir. The amount of liquid reduced by evaporation was supplemented with water, and the total organic carbon (TOC) of each cleaning composition after 5 hours was measured with Hiranuma Total Organic Carbon Measuring Device TOC-2000 (manufactured by Hiranuma Sangyo Co., Ltd.) The change in TOC is calculated by the following formula. It can be evaluated that the closer the residual organic carbon ratio is to 100%, the less the change in the active ingredient (component B) and the better the stamina. Here, “change in active ingredient” means that the content of component B in the cleaning composition is reduced by scattering, volatilization or evaporation of component B during long-term use of the cleaning composition. Say.
Residual organic carbon ratio (%) = TOC after test / TOC before test × 100
［濃縮性評価］（実施例１～８）
実施例１～８の各洗浄剤組成物の水以外の成分に水を添加し、目視にて濁りや析出物がなく均一透明になるまでの濃縮倍率を測定する。測定は１０倍濃縮から開始した。
＜濃縮倍率の測定方法＞
１００ｍＬビーカー（空重量測定）に４８％ＮａＯＨ（７．２９ｇ＝有効分で３．５０ｇ）及び各溶剤（０．２０ｇ）を添加し、そこへ均一透明になるまで水を添加して、重量測定（最終重量）し、濃縮倍率を算出する。
濃縮倍率＝１００÷（最終重量－ビーカー空重量） [Evaluation of concentration] (Examples 1 to 8)
Water is added to components other than water in each of the cleaning compositions of Examples 1 to 8, and the concentration ratio until the film becomes uniform and transparent with no turbidity or precipitate is measured. The measurement started with 10-fold concentration.
<Measurement method of concentration ratio>
48% NaOH (7.29 g = 3.50 g in effective amount) and each solvent (0.20 g) are added to a 100 mL beaker (empty weight measurement), and water is added thereto until uniform transparency, and weight measurement is performed. (Final weight) and calculate the concentration factor.
Concentration factor = 100 ÷ (final weight-empty beaker weight)
実施例１～８の各洗浄剤組成物の水以外の成分に水を添加し、目視にて濁りや析出物がなく均一透明になるまでの濃縮倍率を測定する。測定は１０倍濃縮から開始した。
＜濃縮倍率の測定方法＞
１００ｍＬビーカー（空重量測定）に４８％ＮａＯＨ（７．２９ｇ＝有効分で３．５０ｇ）及び各溶剤（０．２０ｇ）を添加し、そこへ均一透明になるまで水を添加して、重量測定（最終重量）し、濃縮倍率を算出する。
濃縮倍率＝１００÷（最終重量－ビーカー空重量） [Evaluation of concentration] (Examples 1 to 8)
Water is added to components other than water in each of the cleaning compositions of Examples 1 to 8, and the concentration ratio until the film becomes uniform and transparent with no turbidity or precipitate is measured. The measurement started with 10-fold concentration.
<Measurement method of concentration ratio>
48% NaOH (7.29 g = 3.50 g in effective amount) and each solvent (0.20 g) are added to a 100 mL beaker (empty weight measurement), and water is added thereto until uniform transparency, and weight measurement is performed. (Final weight) and calculate the concentration factor.
Concentration factor = 100 ÷ (final weight-empty beaker weight)
上記表２－１、表２－２、表３及び表４に示すとおり、実施例１～２９の洗浄剤組成物は、所定の溶媒（成分Ｂ）を含まない比較例１～１６、無機アルカリ（成分Ａ）を含まない比較例１７～２２に比べて、メッキ処理された樹脂マスクを効率よく除去できていた。すなわち、実施例１～２９の洗浄剤組成物は、比較例１～２２に比べて、樹脂マスク除去性に優れていた。
As shown in the above Table 2-1, Table 2-2, Table 3 and Table 4, the cleaning compositions of Examples 1 to 29 are comparative examples 1 to 16, which do not contain a predetermined solvent (component B), inorganic alkalis Compared with Comparative Examples 17 to 22 not containing (Component A), the plated resin mask could be removed efficiently. That is, the cleaning compositions of Examples 1 to 29 were excellent in resin mask removability as compared with Comparative Examples 1 to 22.
本開示を用いることにより、排水処理負荷を大きくすることなく、樹脂マスクを効率よく除去できる。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。
</ RTI> By using the present disclosure, the resin mask can be efficiently removed without increasing the wastewater treatment load. Therefore, the cleaning composition of the present disclosure is useful as a cleaning composition used in the manufacturing process of an electronic component, shortening the cleaning process of the electronic component to which the resin mask is adhered, and the performance of the manufactured electronic component. Reliability can be improved and productivity of the semiconductor device can be improved.
Claims (14)
- 無機アルカリ（成分Ａ）、有機溶剤（成分Ｂ）及び水（成分Ｃ）を含有し、
成分Ｂのハンセン溶解度パラメータの座標が、δｄ＝１７．５、δｐ＝５．０、δｈ＝１１．５を中心とする半径１．５ＭＰａ0.5の球の範囲内であり、
洗浄剤組成物の使用時における成分Ｃの含有量が、８５質量％以上であり、
成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）が、１以上６０以下である、樹脂マスク剥離用洗浄剤組成物。 Contains inorganic alkali (component A), organic solvent (component B) and water (component C),
The Hansen solubility parameter coordinates of component B are within the range of a sphere with a radius of 1.5 MPa 0.5 centered at δd = 17.5, δp = 5.0, δh = 11.5,
The content of Component C when using the cleaning composition is 85% by mass or more,
The cleaning composition for resin mask peeling whose mass ratio (A / B) of the component A with respect to the component B is 1-60. - 洗浄剤組成物の使用時における成分Ａの含有量が、０．１質量％以上１５質量％以下であり、
洗浄剤組成物の使用時における成分Ｂの含有量が、０．０１質量％以上３質量％以下である、請求項１に記載の洗浄剤組成物。 The content of component A during use of the cleaning composition is 0.1% by mass or more and 15% by mass or less,
The cleaning composition of Claim 1 whose content of the component B at the time of use of a cleaning composition is 0.01 mass% or more and 3 mass% or less. - 成分Ｂの沸点が、１６０℃以上である、請求項１又は２に記載の洗浄剤組成物。 The cleaning composition of Claim 1 or 2 whose boiling point of the component B is 160 degreeC or more.
- 成分Ｂの２５℃の水１００ｍＬに対する溶解度が、０．３ｇ以上である、請求項１から３のいずれかに記載の洗浄剤組成物。 The cleaning composition according to any one of claims 1 to 3, wherein the solubility of Component B in 100 mL of water at 25 ° C is 0.3 g or more.
- 洗浄剤組成物中の有機物の総含有量が、３質量％以下である、請求項１から４のいずれかに記載の洗浄剤組成物。 The cleaning composition according to any one of claims 1 to 4, wherein the total content of organic substances in the cleaning composition is 3% by mass or less.
- 窒素含有化合物及びリン含有化合物を実質的に含まない、請求項１から５のいずれかに記載の洗浄剤組成物。 The cleaning composition according to any one of claims 1 to 5, which is substantially free of a nitrogen-containing compound and a phosphorus-containing compound.
- 樹脂マスクが、露光及び現像の少なくとも一方の処理が施されたネガ型ドライフィルムレジストである、請求項１から６のいずれかに記載の洗浄剤組成物。 The cleaning composition according to any one of claims 1 to 6, wherein the resin mask is a negative dry film resist subjected to at least one of exposure and development.
- 樹脂マスクが付着した被洗浄物を請求項１から７のいずれかに記載の洗浄剤組成物で洗浄する工程を含む、樹脂マスクの除去方法。 A method for removing a resin mask, comprising a step of cleaning an object to be cleaned to which the resin mask is adhered with the cleaning composition according to any one of claims 1 to 7.
- 被洗浄物が、電子部品の製造中間物である、請求項８に記載の除去方法。 The removal method according to claim 8, wherein the object to be cleaned is an intermediate for manufacturing an electronic component.
- 樹脂マスクが付着した被洗浄物を請求項１から７のいずれかに記載の洗浄剤組成物で洗浄する工程を含む、電子部品の製造方法。 A method for manufacturing an electronic component, comprising a step of cleaning an object to be cleaned to which a resin mask is adhered with the cleaning composition according to any one of claims 1 to 7.
- 請求項１から７のいずれかに記載の洗浄剤組成物の、電子部品の製造への使用。 Use of the cleaning composition according to any one of claims 1 to 7 for the production of electronic parts.
- 請求項８又は９の除去方法及び請求項１０に記載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であって、
請求項１から７のいずれかに記載の洗浄剤組成物を構成する成分Ａ～Ｃのうちの少なくとも１成分を、他の成分と混合されない状態で含む、キット。 A kit for use in any of the removal method of claim 8 or 9 and the electronic component manufacturing method of claim 10,
A kit comprising at least one of the components A to C constituting the cleaning composition according to any one of claims 1 to 7 in a state where it is not mixed with other components. - 被洗浄物から樹脂マスクを除去するための、請求項１から７のいずれかに記載の洗浄剤組成物の使用。 Use of the cleaning composition according to any one of claims 1 to 7 for removing a resin mask from an object to be cleaned.
- 電子部品を洗浄するための、請求項１から７のいずれかに記載の洗浄剤組成物の使用。 Use of the cleaning composition according to any one of claims 1 to 7 for cleaning electronic parts.
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| KR1020197006640A KR102455657B1 (en) | 2016-09-09 | 2017-08-24 | Detergent composition for resin mask peeling |
| CN201780054413.XA CN109791377B (en) | 2016-09-09 | 2017-08-24 | Detergent composition for resin mask stripping |
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| JP7020905B2 (en) * | 2017-12-27 | 2022-02-16 | 花王株式会社 | Detergent composition for removing resin mask |
| WO2019172377A1 (en) | 2018-03-07 | 2019-09-12 | 株式会社小糸製作所 | Vehicle cleaner system |
| JP7290194B1 (en) | 2022-10-19 | 2023-06-13 | Jsr株式会社 | Semiconductor processing composition and method |
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| CN109791377A (en) | 2019-05-21 |
| KR20190051965A (en) | 2019-05-15 |
| JP2018041033A (en) | 2018-03-15 |
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| CN109791377B (en) | 2023-03-28 |
| KR102455657B1 (en) | 2022-10-17 |
| TW201817864A (en) | 2018-05-16 |
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