JP7057653B2 - Detergent composition for removing resin mask - Google Patents
Detergent composition for removing resin mask Download PDFInfo
- Publication number
- JP7057653B2 JP7057653B2 JP2017236368A JP2017236368A JP7057653B2 JP 7057653 B2 JP7057653 B2 JP 7057653B2 JP 2017236368 A JP2017236368 A JP 2017236368A JP 2017236368 A JP2017236368 A JP 2017236368A JP 7057653 B2 JP7057653 B2 JP 7057653B2
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- 239000000203 mixture Substances 0.000 title claims description 179
- 239000003599 detergent Substances 0.000 title claims description 113
- 239000011347 resin Substances 0.000 title claims description 106
- 229920005989 resin Polymers 0.000 title claims description 106
- 239000012459 cleaning agent Substances 0.000 claims description 65
- 238000000034 method Methods 0.000 claims description 56
- 239000004094 surface-active agent Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 29
- 238000004140 cleaning Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 26
- -1 ethyleneoxy group Chemical group 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 239000002202 Polyethylene glycol Substances 0.000 description 21
- 229920001223 polyethylene glycol Polymers 0.000 description 21
- 239000012141 concentrate Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000004065 wastewater treatment Methods 0.000 description 15
- 239000000758 substrate Substances 0.000 description 11
- 238000007747 plating Methods 0.000 description 10
- 238000004904 shortening Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 238000011161 development Methods 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000693 micelle Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000012851 eutrophication Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- YHCCCMIWRBJYHG-UHFFFAOYSA-N 3-(2-ethylhexoxymethyl)heptane Chemical compound CCCCC(CC)COCC(CC)CCCC YHCCCMIWRBJYHG-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CSHOPPGMNYULAD-UHFFFAOYSA-N 1-tridecoxytridecane Chemical compound CCCCCCCCCCCCCOCCCCCCCCCCCCC CSHOPPGMNYULAD-UHFFFAOYSA-N 0.000 description 2
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 2
- MJELOWOAIAAUJT-UHFFFAOYSA-N 3,6,9,12,15-pentaoxatricosan-1-ol Chemical compound CCCCCCCCOCCOCCOCCOCCOCCO MJELOWOAIAAUJT-UHFFFAOYSA-N 0.000 description 2
- WIGIPJGWVLNDAF-UHFFFAOYSA-N 8-methyl-1-(8-methylnonoxy)nonane Chemical compound CC(C)CCCCCCCOCCCCCCCC(C)C WIGIPJGWVLNDAF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000282994 Cervidae Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229940043348 myristyl alcohol Drugs 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GUNFKDBVCDAULS-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-(2-ethylhexoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCC(CC)COCCOCCOCCOCCOCCOCCO GUNFKDBVCDAULS-UHFFFAOYSA-N 0.000 description 1
- 241000252095 Congridae Species 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000012964 benzotriazole Substances 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
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 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
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000543 intermediate Substances 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
- LAPRIVJANDLWOK-UHFFFAOYSA-N laureth-5 Polymers CCCCCCCCCCCCOCCOCCOCCOCCOCCO LAPRIVJANDLWOK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method 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
- 239000002904 solvent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
-
- 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
- G03F7/20—Exposure; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- 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
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
-
- 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
-
- C11D2111/22—
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
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洗浄方法及び電子部品の製造方法に関する。 The present disclosure relates to a detergent composition for removing a resin mask, a method for cleaning a resin mask using the detergent composition, and a method for manufacturing an electronic component.
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, power consumption has been reduced, processing speed has been increased, and miniaturization has progressed, and wiring such as package boards mounted on these has been miniaturized year by year. The metal mask method has been mainly used for the formation of such fine wiring and connection terminals such as pillars and bumps, but its versatility is low and it has become difficult to deal with miniaturization of wiring and the like. Is changing to other new methods.
新たな方法の一つとして、ドライフィルムレジストをメタルマスクに代えて厚膜樹脂マスクとして使用する方法が知られている。この樹脂マスクは最終的に剥離・除去されるが、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、（Ａ）窒素原子を１～４個有するアミン化合物、（Ｂ）分子量３０１～５０００の非イオン性界面活性剤、並びに（Ｃ）水を含有するレジスト用剥離剤組成物が記載されている。 As one of the new methods, a method of using a dry film resist as a thick film resin mask instead of a metal mask is known. This resin mask is finally peeled off and removed, and at that time, an alkaline cleaning agent for peeling is used. As such a detergent for peeling, for example, Patent Document 1 describes (A) an amine compound having 1 to 4 nitrogen atoms, (B) a nonionic surfactant having a molecular weight of 301 to 5000, and (C). Described are stripping agent compositions for resists containing water.
特許文献２には、還元剤および界面活性剤を含み、ｐＨが１０～１４である半導体デバイス用洗浄液が記載されている。 Patent Document 2 describes a cleaning liquid for a semiconductor device containing a reducing agent and a surfactant and having a pH of 10 to 14.
特許文献３には、（Ａ）界面活性剤を１質量％以上３０質量％以下、（Ｂ）防食剤を０．０５質量％以上１０質量％以下、（Ｃ）水を５質量％以上６０質量％以下、および（Ｄ）水溶性有機溶剤を３０質量％以上９５質量％以下含有するフォトレジスト用剥離液が記載されている。 In Patent Document 3, (A) a surfactant is 1% by mass or more and 30% by mass or less, (B) an anticorrosion agent is 0.05% by mass or more and 10% by mass or less, and (C) water is 5% by mass or more and 60% by mass. % Or less, and (D) a stripping solution for a photoresist containing 30% by mass or more and 95% by mass or less of a water-soluble organic solvent are described.
特許文献４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。 Patent Document 4 describes a) an inorganic alkaline compound 0 for removing resist, which is an unnecessary film component formed on the edge of a resist film coated on a substrate or the rear surface of a substrate, and preventing corrosion of equipment. .1 to 5% by weight, b) organic amine 0.1 to 5% by weight, c) organic solvent 0.1 to 30% by weight, d) anionic and nonionic surfactants 1: 5 to 25. Described is a resist removing thinner composition comprising 0.01 to 5% by weight of a surfactant 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。 In forming fine wiring on a printed circuit board, etc., not only the residual resin mask, but also the cleaning agent composition to reduce the residual auxiliary agents contained in the solder, plating solution, etc. used for fine wiring and bump formation. High detergency is required for objects. The resin mask is formed by using a resist whose physical properties such as solubility in a developing solution are changed by light, an electron beam, or the like. The resist is roughly classified into a negative type and a positive type according to the reaction method with light and electron beam. The negative resist has the property that its solubility in a developing solution decreases when exposed, and the layer containing the negative resist (hereinafter, also referred to as “negative resist layer”) is formed by the exposed portion after exposure and development processing. Used as a resin mask. The positive resist has the property of increasing its solubility in a developing solution when exposed, and the layer containing the positive resist (hereinafter, also referred to as “positive resist layer”) is exposed to the exposed portion after exposure and development processing. It is removed and the unexposed area is 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 treatment, heat treatment, and the like used when forming the connection portion, and it becomes difficult to remove the resin mask in the cleaning step of the next step. In particular, since a negative resist has a property of being cured by a reaction with light or an electron beam, a resin mask formed by using a negative resist is subjected to a plating treatment or a heat treatment used when forming a connection portion. Curing progresses more than necessary, and it cannot be completely removed in the cleaning process, or the time required for removal becomes very long, which damages the substrate and the metal surface. Since the resin mask thus plated and / or heat-treated is difficult to peel off, the detergent composition is required to have high resin mask removability.
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。 On the other hand, digitization is progressing in various fields, and the production volume of printed circuit boards and the like is increasing. Furthermore, in order to reduce the size of the equipment and devices used, increase the processing speed, and reduce power consumption, the wiring becomes finer and more multi-layered, the peeling / cleaning process increases, and the amount of cleaning agent composition used also increases. Tend to do. As the amount of the detergent composition used increases, the load of wastewater treatment of the detergent composition and waste liquid such as rinse water and the eutrophication of lakes and marshes due to the inflow of the waste liquid also increase, so that the wastewater treatment load is small. There is a strong demand for a detergent composition that does not contain nitrogen and phosphorus, which cause eutrophication of lakes and marshes, and can efficiently remove resin masks. However, it is difficult to achieve both high resin mask removability and low wastewater treatment load by the method described in the patent document.
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 cleaning agent composition for removing a resin mask, which has excellent resin mask removing property and a small wastewater treatment load, a method for removing a resin mask using the cleaning agent composition, and a method for manufacturing a substrate.
本開示は、一態様において、無機アルカリ（成分Ａ）、下記一般式（Ｉ）で表わされる界面活性剤（成分Ｂ）及び水（成分Ｃ）を含有し、成分Ｂのデイビス法によるＨＬＢが４．９以上７．９以下である、樹脂マスク剥離用洗浄剤組成物に関する。
Ｒ1－Ｏ－（ＥＯ）n（ＰＯ）m－Ｈ （Ｉ）
ただし、式（Ｉ）中、Ｒ1は炭素数８以上１４以下の直鎖又は分岐鎖のアルキル基及び炭素数８以上１４以下の直鎖又は分岐鎖のアルケニル基から選ばれる少なくとも１種を示し、ＥＯはエチレンオキシ基を示し、ｎはＥＯの平均付加モル数であって５以上１１以下の数であり、ＰＯはプロピレンオキシ基を示し、ｍはＰＯの平均付加モル数であって０以上４以下の数である。
In one embodiment, the present disclosure contains an inorganic alkali (component A), a surfactant (component B) represented by the following general formula (I), and water (component C), and the HLB of the component B according to the Davis method is 4. The present invention relates to a detergent composition for removing a resin mask, which is 9.9 or more and 7.9 or less.
R 1 -O- (EO) n (PO) m -H (I)
However, in the formula (I), R 1 represents at least one selected from a linear or branched alkyl group having 8 or more and 14 or less carbon atoms and a linear or branched alkenyl group having 8 or more and 14 or less carbon atoms. , EO indicates an ethyleneoxy group, n is the average number of added moles of EO, which is 5 or more and 11 or less, PO indicates a propyleneoxy group, and m is the average number of added moles of PO, which is 0 or more. It is a number of 4 or less.
本開示は、その他の態様において、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 relates to a method for removing a resin mask, which comprises a step of cleaning the object to be cleaned to which the resin mask is attached with the detergent composition according to the present disclosure in another aspect.
本開示は、その他の態様において、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 relates to a method for manufacturing an electronic component, which comprises a step of cleaning an object to be cleaned to which a resin mask is attached with the cleaning agent composition according to the present disclosure in another aspect.
本開示は、その他の態様において、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 relates, in other aspects, to the use of the cleaning agent composition according to the present disclosure in the manufacture of electronic components.
本開示は、その他の態様において、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成分Ａ～Ｃのうち、成分Ａを含有する第１液と、成分Ｂを含有する第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をさらに含有する、キットに関する。 The present disclosure is a kit for use in any of the removal methods according to the present disclosure and the method for manufacturing electronic components according to the present disclosure in other aspects, and is a component constituting the cleaning agent composition according to the present disclosure. Of A to C, the first liquid containing the component A and the second liquid containing the component B are contained in a state of not being mixed with each other, and at least one of the first liquid and the second liquid contains the component C. Further included, with respect to the kit.
本開示によれば、一態様において、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。 According to the present disclosure, in one embodiment, it is possible to provide a detergent composition for removing a resin mask, which is excellent in resin mask removability and has a small wastewater treatment load.
本開示は、無機アルカリ（成分Ａ）、所定の界面活性剤（成分Ｂ）及び水（成分Ｃ）を含有する、樹脂マスク剥離用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。さらに、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、湖沼等の富栄養化を抑制できるという知見に基づく。 The present disclosure provides a low wastewater treatment load by using a resin mask stripping detergent composition containing an inorganic alkali (component A), a predetermined surfactant (component B) and water (component C). Also based on the finding that resin masks, especially those that have been plated and / or heat treated, can be efficiently removed. Furthermore, it is based on the finding that eutrophication of lakes and marshes can be suppressed by not containing a nitrogen-containing compound and a phosphorus-containing compound in the detergent 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）、上記一般式（Ｉ）で表わされる界面活性剤（成分Ｂ）及び水（成分Ｃ）を含有し、成分Ｂのデイビス法によるＨＬＢが４．９以上７．９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。 That is, in one embodiment, the present disclosure contains an inorganic alkali (component A), a surfactant (component B) represented by the above general formula (I), and water (component C), and the HLB of the component B by the Davis method. The present invention relates to a detergent composition for removing a resin mask (hereinafter, also referred to as “detergent composition according to the present disclosure”), which has a value of 4.9 or more and 7.9 or less.
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。 According to the present disclosure, it is possible to provide a detergent composition having excellent resin mask removability and a small wastewater treatment load. Therefore, the cleaning agent composition according to the present disclosure can efficiently remove the resin mask, particularly the plating-treated and / or the heat-treated resin mask, even with a low wastewater treatment load. Then, by using the detergent composition according to the present disclosure, high quality electronic components can be obtained in high yield. Further, by using the cleaning agent composition according to the present disclosure, it is possible to efficiently manufacture an electronic component having a fine wiring pattern.
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、特定の構造を有し、ＨＬＢが所定の範囲内である界面活性剤（成分Ｂ）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、一般的に、ノニオン界面活性剤がアニオン界面活性剤等の電荷を有する界面活性剤よりも臨界ミセル濃度（ＣＭＣ）が低いことが知られている。本開示における成分Ｂは、臨界ミセル濃度（ＣＭＣ）が低いノニオン界面活性剤であることから、少ない添加量でも有効に作用し、成分Ａ（無機アルカリ）及び成分Ｃ（水）の樹脂マスクへの浸透を促進することで、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。
The details of the action mechanism of the effect in the detergent composition according to the present disclosure are unclear, but it is presumed as follows.
It is generally considered that the peeling of the resin mask is caused by the interfacial stress caused by the components of the cleaning agent composition permeating the resin mask and swelling the resin mask. In the cleaning agent composition according to the present disclosure, the component A (inorganic alkali) and the component C (water) permeate the resin mask to promote the dissociation of the alkali-soluble resin contained in the resin mask, and further charge repulsion. Promotes the peeling of the resin mask by causing. At this time, the surfactant (component B) having a specific structure and having an HLB within a predetermined range acts between the substrate surface and the resin mask, so that the adhesion between the substrate and the resin is reduced. It is presumed that the peeling of the resin mask is further promoted and the resin mask removability is significantly improved.
It is also generally known that nonionic surfactants have a lower critical micelle concentration (CMC) than charged surfactants such as anionic surfactants. Since the component B in the present disclosure is a nonionic surfactant having a low critical micelle concentration (CMC), it acts effectively even with a small addition amount, and the component A (inorganic alkali) and the component C (water) can be applied to the resin mask. It is presumed that by promoting the permeation, the organic substance content in the detergent composition can be reduced and the increase in the wastewater treatment load can be suppressed. It is considered that this makes it possible to form a fine circuit (wiring pattern) on the substrate efficiently and with high cleanliness.
However, the present disclosure may not be construed as being 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 the surface of a substance from treatments such as etching, plating, and heating, that is, a mask that functions as a protective film. In one or more embodiments, the resin mask is subjected to at least one treatment of a resist layer after an exposure or development step, exposure and development (hereinafter, also referred to as “exposure and / or development treatment”). Examples thereof include a resist layer and a cured resist layer. Examples of the resin material forming the resin mask include a film-shaped photosensitive resin or a resist film in one or more embodiments. 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 detergent composition according to the present disclosure contains an inorganic alkali (component A). The 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。 Examples of the component A include 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 a 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、そして、樹脂マスク除去性向上の観点から、１５質量％以下が好ましく、１０質量％以下がより好ましく、７．５質量％以下が更に好ましい。より具体的には、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、０．１質量％以上１５質量％以下が好ましく、０．３質量％以上１０質量％以下がより好ましく、０．５質量％以上７．５質量％以下が更に好ましい。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 at the time of use of the cleaning agent composition according to the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and more preferably 0.5, from the viewpoint of improving the resin mask removability. It is more preferably mass% or more, and from the viewpoint of improving the resin mask removability, it is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 7.5% by mass or less. More specifically, the content of the component A at the time of use of the cleaning agent composition according to the present disclosure is preferably 0.1% by mass or more and 15% by mass or less, and more preferably 0.3% by mass or more and 10% by mass or less. It is preferable, and more preferably 0.5% by mass or more and 7.5% by mass or less. When the component A is composed of two or more kinds of inorganic alkalis, the content of the component A means 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、洗浄剤組成物の洗浄への使用を開始する時点での各成分の含有量をいう。 In the present disclosure, the "content of each component at the time of use of the detergent composition" means the content of each component at the time of cleaning, that is, at the time when the use of the detergent composition for cleaning is started.
［成分Ｂ：界面活性剤］
本開示に係る洗浄剤組成物に含まれる界面活性剤（成分Ｂ）は、下記一般式（Ｉ）で表わされる界面活性剤であって、デイビス法によるＨＬＢが４．９以上７．９以下である界面活性剤である。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: Surfactant]
The surfactant (component B) contained in the detergent composition according to the present disclosure is a surfactant represented by the following general formula (I), and has an HLB of 4.9 or more and 7.9 or less by the Davis method. A surfactant. Component B can be used alone or in combination of two or more.
Ｒ1－Ｏ－（ＥＯ）n（ＰＯ）m－Ｈ （Ｉ）
ただし、式（Ｉ）中、Ｒ1は炭素数８以上１４以下の直鎖又は分岐鎖のアルキル基及び炭素数８以上１４以下の直鎖又は分岐鎖のアルケニル基から選ばれる少なくとも１種を示し、ＥＯはエチレンオキシ基を示し、ｎはＥＯの平均付加モル数であって５以上１１以下の数であり、ＰＯはプロピレンオキシ基を示し、ｍはＰＯの平均付加モル数であって０以上４以下の数である。
R 1 -O- (EO) n (PO) m -H (I)
However, in the formula (I), R 1 represents at least one selected from a linear or branched alkyl group having 8 or more and 14 or less carbon atoms and a linear or branched alkenyl group having 8 or more and 14 or less carbon atoms. , EO indicates an ethyleneoxy group, n is the average number of added moles of EO, which is 5 or more and 11 or less, PO indicates a propyleneoxy group, and m is the average number of added moles of PO, which is 0 or more. It is a number of 4 or less.
式（Ｉ）中、Ｒ1は、炭素数８以上１４以下の直鎖又は分岐鎖のアルキル基及び炭素数８以上１４以下の直鎖又は分岐鎖のアルケニル基から選ばれる少なくとも１種であって、樹脂マスク剥離性向上及び剥離時間を短くする観点から、炭素数８以上１４以下の直鎖アルキル基及び炭素数８以上１４以下の直鎖アルケニル基が好ましい。Ｒ1の炭素数は、同様の観点から、８以上であり、好ましくは９以上、より好ましくは１０以上であり、そして、１４以下であり、好ましくは１２以下、より好ましくは１１以下である。すなわち、Ｒ1の炭素数は、８以上１４以下であって、好ましくは９以上１２以下、より好ましくは１０以上１１以下、更に好ましくは１０である。Ｒ1の具体例としては、オクチル基、２－エチルヘキシル基、デシル基、イソデシル基、２－プロピルヘプチル基、ドデシル基、トリデシル基、及びテトラデシル基から選ばれる少なくも１種が挙げられる。 In formula (I), R 1 is at least one selected from a linear or branched alkyl group having 8 or more and 14 or less carbon atoms and a linear or branched alkenyl group having 8 or more and 14 or less carbon atoms. From the viewpoint of improving the peelability of the resin mask and shortening the peeling time, a linear alkyl group having 8 or more and 14 or less carbon atoms and a linear alkenyl group having 8 or more and 14 or less carbon atoms are preferable. From the same viewpoint, the carbon number of R 1 is 8 or more, preferably 9 or more, more preferably 10 or more, and 14 or less, preferably 12 or less, and more preferably 11 or less. That is, the carbon number of R 1 is 8 or more and 14 or less, preferably 9 or more and 12 or less, more preferably 10 or more and 11 or less, and further preferably 10. Specific examples of R 1 include at least one selected from an octyl group, a 2-ethylhexyl group, a decyl group, an isodecyl group, a 2-propylheptyl group, a dodecyl group, a tridecylic group, and a tetradecyl group.
式（Ｉ）中、（ＥＯ）n（ＰＯ）mは、エチレンオキシ基単独で構成されていてもよいし、エチレンオキシ基とプロピレンオキシ基とから構成されていてもよい。（ＥＯ）n（ＰＯ）mがエチレンオキシ基とプロピレンオキシ基とから構成される場合、ＰＯとＥＯの付加形態は、ランダム配列、ブロック配列のいずれでもよく、ＥＯとＰＯの付加順序は問わない。 In the formula (I), (EO) n (PO) m may be composed of an ethyleneoxy group alone or may be composed of an ethyleneoxy group and a propyleneoxy group. When (EO) n (PO) m is composed of an ethyleneoxy group and a propyleneoxy group, the addition form of PO and EO may be either a random sequence or a block sequence, and the addition order of EO and PO does not matter. ..
式（Ｉ）中、ｎは、樹脂マスク剥離性向上及び剥離時間を短くする観点から、５以上であり、好ましくは６以上、より好ましくは７以上であり、そして、１１以下であり、好ましくは１０以下、より好ましくは９以下である。すなわち、ｎは、５以上１１以下の数であって、好ましくは６以上１０以下、より好ましくは７以上９以下である。 In the formula (I), n is 5 or more, preferably 6 or more, more preferably 7 or more, and 11 or less, preferably 11 or less, from the viewpoint of improving the peelability of the resin mask and shortening the peeling time. It is 10 or less, more preferably 9 or less. That is, n is a number of 5 or more and 11 or less, preferably 6 or more and 10 or less, and more preferably 7 or more and 9 or less.
式（Ｉ）中、ｍは、剥離時間を短くする観点から、０以上であり、そして、４以下であり、好ましくは３以下、より好ましくは２以下である。すなわち、ｍは、０以上４以下の数であって、好ましくは０以上３以下、より好ましくは０以上２以下である。 In the formula (I), m is 0 or more and 4 or less, preferably 3 or less, and more preferably 2 or less, from the viewpoint of shortening the peeling time. That is, m is a number of 0 or more and 4 or less, preferably 0 or more and 3 or less, and more preferably 0 or more and 2 or less.
成分Ｂの具体例としては、ポリエチレングリコール（９）ラウリルエーテル、ポリエチレングリコール（８）２－エチルヘキシルエーテル、ポリエチレングリコール（６）２－エチルヘキシルエーテル、ポリエチレングリコール（７）デシルエーテル、ポリエチレングリコール（８．５）イソデシルエーテル、ポリエチレングリコール（１０）トリデシルエーテル、ポリエチレングリコール（９）デシルエーテル、ペンタエチレングリコールモノオクチルエーテル、ポリエチレングリコール（１２）アルキル（２級ドデシル及び２級テトラデシル混合）エーテル等が挙げられる。（ ）内の数値は平均付加モル数を表わす。 Specific examples of the component B include polyethylene glycol (9) lauryl ether, polyethylene glycol (8) 2-ethylhexyl ether, polyethylene glycol (6) 2-ethylhexyl ether, polyethylene glycol (7) decyl ether, and polyethylene glycol (8.5). ) Isodecyl ether, polyethylene glycol (10) tridecyl ether, polyethylene glycol (9) decyl ether, pentaethylene glycol monooctyl ether, polyethylene glycol (12) alkyl (secondary dodecyl and secondary tetradecyl mixed) ether and the like. .. The values in parentheses indicate the average number of added moles.
成分Ｂは、デイビス法によるＨＬＢが４．９以上７．９以下である。デイビス法によるＨＬＢとは、Davis, J. T.; Proc. Intern. Congr. Surface Activity, 2 nd, London, 1, 426 (1957)に記載の官能基によって決まる基数を用い、ＨＬＢ値を「７＋親水基の基数の総和－親油基の基数の総和」で定義する値であり、樹脂マスク剥離性向上及び剥離時間を短くする観点から、ＨＬＢは、４．９以上であり、好ましくは５．５以上、より好ましくは６以上、更に好ましくは６．１５以上であり、そして、７．９以下であり、好ましくは６．９以下、より好ましくは６．７以下、更に好ましくは６．５以下である。より具体的には、ＨＬＢは、４．９以上７．９以下であって、好ましくは５．５以上６．９以下、より好ましくは６以上６．７以下、更に好ましくは６．１５以上６．５以下である。 The component B has an HLB of 4.9 or more and 7.9 or less according to the Davis method. The HLB by the Davis method is a group number determined by the functional group described in Davis, J. T .; Proc. Intern. Congr. Surface Activity, 2nd, London, 1, 426 (1957), and the HLB value is "7 + hydrophilic group". It is a value defined by "total number of groups-total number of lipophilic groups", and the HLB is 4.9 or more, preferably 5.5 or more, from the viewpoint of improving the peelability of the resin mask and shortening the peeling time. It is more preferably 6 or more, further preferably 6.15 or more, and 7.9 or less, preferably 6.9 or less, more preferably 6.7 or less, still more preferably 6.5 or less. More specifically, the HLB is 4.9 or more and 7.9 or less, preferably 5.5 or more and 6.9 or less, more preferably 6 or more and 6.7 or less, and further preferably 6.15 or more and 6 It is less than 5.5.
成分Ｂの臨界ミセル濃度（ＣＭＣ）は、一又は複数の実施形態において、樹脂マスク剥離性向上及び剥離時間を短くする観点から、０．００００１質量％以上が好ましく、０．００００５質量％以上がより好ましく、０．０００１質量％以上が更に好ましく、そして、同様の観点から、０．１質量％以下が好ましく、０．０５質量％以下がより好ましく、０．０１質量％以下が更に好ましい。より具体的には、成分Ｂの臨界ミセル濃度（ＣＭＣ）は、０．００００１質量％以上０．１質量％以下が好ましく、０．００００５質量％以上０．０５質量％以下がより好ましく、０．０００１質量％以上０．０１質量％以下が更に好ましい。 The critical micelle concentration (CMC) of the component B is preferably 0.00001% by mass or more, more preferably 0.00005% by mass or more, from the viewpoint of improving the resin mask peelability and shortening the peeling time in one or more embodiments. Preferably, 0.0001% by mass or more is more preferable, and from the same viewpoint, 0.1% by mass or less is preferable, 0.05% by mass or less is more preferable, and 0.01% by mass or less is further preferable. More specifically, the critical micelle concentration (CMC) of the component B is preferably 0.00001% by mass or more and 0.1% by mass or less, more preferably 0.00005% by mass or more and 0.05% by mass or less, and 0. More preferably, it is 0001% by mass or more and 0.01% by mass or less.
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、樹脂マスク剥離性向上及び剥離時間を短くする観点から、０．０００１質量％以上が好ましく、０．００１質量％以上がより好ましく、０．０１質量％以上が更に好ましく、０．１質量％以上がより更に好ましく、そして、同様の観点から、１０質量％以下が好ましく、３質量％以下がより好ましく、２質量％以下が更に好ましく、１．２質量％以下がより更に好ましい。より具体的には、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、０．０００１質量％以上１０質量％以下が好ましく、０．００１質量％以上１０質量％以下がより好ましく、０．０１質量％以上１０質量％以下が更に好ましく、０．１質量％以上１０質量％以下がより更に好ましく、０．１質量％以上３質量％以下がより更に好ましく、０．１質量％以上２質量％以下がより更に好ましく、０．１質量％以上１．２質量％以下がより更に好ましい。成分Ｂが２種以上の界面活性剤からなる場合、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 at the time of use of the cleaning agent composition according to the present disclosure is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, from the viewpoint of improving the peelability of the resin mask and shortening the peeling time. Preferably, 0.01% by mass or more is further preferable, 0.1% by mass or more is further preferable, and from the same viewpoint, 10% by mass or less is preferable, 3% by mass or less is more preferable, and 2% by mass or less is preferable. Even more preferably, 1.2% by mass or less is even more preferable. More specifically, the content of component B at the time of use of the cleaning agent composition according to the present disclosure is preferably 0.0001% by mass or more and 10% by mass or less, and more preferably 0.001% by mass or more and 10% by mass or less. Preferably, it is more preferably 0.01% by mass or more and 10% by mass or less, further preferably 0.1% by mass or more and 10% by mass or less, still more preferably 0.1% by mass or more and 3% by mass or less, and 0.1% by mass. % Or more and 2% by mass or less are more preferable, and 0.1% by mass or more and 1.2% by mass or less are even more preferable. When the component B is composed of two or more kinds of surfactants, the content of the component B means 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、樹脂マスク剥離性向上及び剥離時間を短くする観点から、０．３以上が好ましく、０．４以上がより好ましく、０．５以上が更に好ましく、そして、同様の観点から、５００００以下が好ましく、１０００以下がより好ましく、１００以下が更に好ましく、８０以下がより更に好ましい。より具体的には、質量比（Ａ／Ｂ）は、０．３以上５００００以下が好ましく、０．４以上１０００以下がより好ましく、０．５以上１００以下が更に好ましく、０．５以上８０以下がより更に好ましい。 The mass ratio (A / B) of the component A to the component B in the detergent composition according to the present disclosure is preferably 0.3 or more, preferably 0.4 or more, from the viewpoint of improving the peelability of the resin mask and shortening the peeling time. More preferably, 0.5 or more is further preferable, and from the same viewpoint, 50,000 or less is preferable, 1000 or less is more preferable, 100 or less is further preferable, and 80 or less is further preferable. More specifically, the mass ratio (A / B) is preferably 0.3 or more and 50,000 or less, more preferably 0.4 or more and 1000 or less, further preferably 0.5 or more and 100 or less, and 0.5 or more and 80 or less. Is even more preferable.
［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 detergent composition according to the present disclosure contains water (component C). As the water of the component C, ion-exchanged water, RO water, distilled water, pure water, and ultrapure water can be used. The water content may be appropriately set according to the usage mode of the detergent composition according to the present disclosure.
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、樹脂マスク剥離性向上及び剥離時間を短くする観点から、８５質量％以上が好ましく、９０質量％以上がより好ましく、９５質量％以上が更に好ましく、そして、同様の観点から、９９．５質量％以下が好ましく、９９．４質量％以下がより好ましい。より具体的には、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９９．５質量％以下が好ましく、９０質量％以上９９．４質量％以下がより好ましく、９５質量％以上９９．４質量％以下が更に好ましい。 The content of component C at the time of use of the cleaning agent composition according to the present disclosure is preferably 85% by mass or more, more preferably 90% by mass or more, and more preferably 95% by mass from the viewpoint of improving the peelability of the resin mask and shortening the peeling time. % Or more is more preferable, and from the same viewpoint, 99.5% by mass or less is preferable, and 99.4% by mass or less is more preferable. More specifically, the content of the component C at the time of use of the detergent composition according to the present disclosure is preferably 85% by mass or more and 99.5% by mass or less, and more preferably 90% by mass or more and 99.4% by mass or less. It is preferable, and more preferably 95% by mass or more and 99.4% by mass or less.
［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さらに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、成分Ｂ以外の界面活性剤、キレート剤、増粘剤、分散剤、防錆剤、塩基性物質、有機溶剤、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。
[Arbitrary ingredient]
The detergent composition according to the present disclosure may further contain an arbitrary component, if necessary, in addition to the above-mentioned components A to C. Examples of the optional component include components that can be used in ordinary detergents, and examples thereof include surfactants other than component B, chelating agents, thickeners, dispersants, rust preventives, basic substances, and organic solvents. , Polymer compounds, solubilizers, antioxidants, preservatives, antifoaming agents, antibacterial agents and the like. The content of the optional component at the time of use of the cleaning agent 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 or more. It is more preferably 1.3% by mass or less, and even 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の使用時における成分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、１０質量％以下が好ましく、３質量％以下がより好ましく、２質量％以下が更に好ましく、１質量％以下がより更に好ましく、０．５質量％以下がより更に好ましく、そして、樹脂マスク剥離性向上及び剥離時間を短くする観点から、０．０００１質量％以上が好ましく、０．０１質量％以上がより好ましく、０．１質量％以上が更に好ましい。より具体的には、本開示に係る洗浄剤組成物の使用時における成分Ｂ及び任意成分由来の有機物の総含有量は、０．０００１質量％以上１０質量％以下が好ましく、０．０１質量％以上３質量％以下がより好ましく、０．０１質量％以上２質量％以下が更に好ましく、０．０１質量％以上１質量％以下がより更に好ましく、０．１質量％以上０．５質量％以下がより更に好ましい。 The total content of the organic substances derived from the component B and the optional component at the time of using the cleaning agent composition according to the present disclosure is preferably 10% by mass or less, more preferably 3% by mass or less, from the viewpoint of reducing the wastewater treatment load. 2% by mass or less is further preferable, 1% by mass or less is further preferable, 0.5% by mass or less is further preferable, and 0.0001% by mass or more from the viewpoint of improving the resin mask peelability and shortening the peeling time. Is preferable, 0.01% by mass or more is more preferable, and 0.1% by mass or more is further preferable. More specifically, the total content of the organic substances derived from the component B and the optional component at the time of using the cleaning agent composition according to the present disclosure is preferably 0.0001% by mass or more and 10% by mass or less, preferably 0.01% by mass. 3% by mass or more is more preferable, 0.01% by mass or more and 2% by mass or less is further preferable, 0.01% by mass or more and 1% by mass or less is further preferable, and 0.1% by mass or more and 0.5% by mass or less. Is even more preferable.
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「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」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 detergent composition according to the present disclosure preferably contains substantially no nitrogen-containing compound and phosphorus-containing compound from the viewpoint of reducing the wastewater treatment load and suppressing eutrophication of the wastewater area. In the present disclosure, "substantially free of nitrogen-containing compounds and phosphorus-containing compounds" means that the total content of nitrogen-containing compounds and phosphorus-containing compounds in the cleaning agent composition according to the present disclosure is less than 0.1% by mass. Say something. The total content of the nitrogen-containing compound and the phosphorus-containing compound in the cleaning agent composition according to the present disclosure is preferably 0.05% by mass or less from the viewpoint of reducing the wastewater treatment load and suppressing the eutrophication of the wastewater area. , 0.01% by mass or less is more preferable, and 0% by mass is further preferable. Examples of the nitrogen-containing compound include nitrogen-containing compounds that have been widely used as cleaning agent compositions, 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 the phosphorus-containing compound include phosphorus-containing compounds that have been widely used as cleaning agent compositions, and examples thereof include phosphoric acid and salts thereof, condensed phosphoric acid such as pyrophosphoric acid, polyphosphoric acid, and metaphosphoric acid and salts thereof. Inorganic phosphoric acid, as well as at least one or a combination of two or more selected from organic phosphoric acid and phosphoric acid esters.
本開示に係る洗浄剤組成物は、一実施形態において、還元剤をさらに含むものであってもよいし、その他の実施形態において、還元剤を実質的に含まないものであってもよい。本開示において「還元剤を実質的に含まない」とは、本開示に係る洗浄剤組成物の使用時における還元剤の含有量が０．０１質量％未満であることをいう。 The detergent composition according to the present disclosure may further contain a reducing agent in one embodiment, or may substantially contain no reducing agent in other embodiments. In the present disclosure, "substantially free of reducing agent" means that the content of the reducing agent at the time of use of the cleaning agent composition according to the present disclosure is less than 0.01% by mass.
［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。
[Manufacturing method of detergent composition]
The detergent composition according to the present disclosure can be produced by blending the above-mentioned components A to C and, if necessary, the above-mentioned optional components by a known method. For example, the detergent composition according to the present disclosure may be composed of at least the above-mentioned components A to C. Therefore, the present disclosure relates to a method for producing a detergent composition, which comprises at least a step of blending the components A to C. In the present disclosure, "blending" includes mixing components A to C and, if necessary, other components at the same time or in any order. In the method for producing a detergent composition according to the present disclosure, the preferable blending amount of each component can be the same as the preferable content of each component of the detergent composition according to the present disclosure described above.
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 detergent composition according to the present disclosure may be prepared as a concentrate in which the amount of water of the component C is reduced as long as the storage stability is not impaired by causing separation, precipitation or the like. The concentrate of the detergent composition is preferably a concentrate having a dilution ratio of 3 times or more from the viewpoint of transportation and storage, and preferably a concentrate having a dilution ratio of 10 times or less from the viewpoint of storage stability. .. The concentrate of the detergent composition can be diluted with water so that the components A to C have the above-mentioned contents (that is, the contents at the time of washing) at the time of use. Further, the concentrate of the detergent composition can be used by adding each component separately at the time of use. In the present disclosure, "at the time of use" or "at the time of cleaning" of the detergent composition of the concentrate means a state in which the concentrate of the detergent 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、樹脂マスク剥離性向上の観点から、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、１５質量％以下がより更に好ましい。より具体的には、本開示に係る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４０質量％以下が好ましく、２質量％以上３０質量％以下がより好ましく、５質量％以上２０質量％以下が更に好ましく、１０質量％以上１５質量％以下がより更に好ましい。 When the detergent composition according to the present disclosure is a concentrate, the content of the component A in the concentrate of the detergent composition is preferably 1% by mass or more, preferably 2% by mass, from the viewpoint of improving the resin mask peelability. The above is more preferable, 5% by mass or more is further preferable, 10% by mass or more is further preferable, and from the viewpoint of metal corrosion suppression and storage stability, 40% by mass or less is preferable, and 30% by mass or less is more preferable. 20% by mass or less is further preferable, and 15% by mass or less is even more preferable. More specifically, the content of component A in the concentrate of the detergent composition according to the present disclosure is preferably 1% by mass or more and 40% by mass or less, and more preferably 2% by mass or more and 30% by mass or less. More preferably, it is 10% by mass or more and 20% by mass or less, and even more preferably 10% by mass or more and 15% by mass or less.
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、樹脂マスク剥離性向上の観点から、０．０００３質量％以上が好ましく、０．０１質量％以上がより好ましく、０．１質量％以上が更に好ましく、０．５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、３０質量％以下が好ましく、１０質量％以下がより好ましく、５質量％以下が更に好ましく、２質量％以下がより更に好ましい。より具体的には、本開示に係る洗浄剤組成物の濃縮物中の成分Ｂの含有量は、０．０００３質量％以上３０質量％以下が好ましく、０．０１質量％以上１０質量％以下がより好ましく、０．１質量％以上５質量％以下が更に好ましく、０．５質量％以上２質量％以下がより更に好ましい。 When the detergent composition according to the present disclosure is a concentrate, the content of component B in the concentrate of the detergent composition is preferably 0.0003% by mass or more, preferably 0, from the viewpoint of improving the resin mask peelability. 0.01% by mass or more is more preferable, 0.1% by mass or more is further preferable, 0.5% by mass or more is further preferable, and 30% by mass or less is used from the viewpoint of reducing storage stability and wastewater treatment load. It is preferable, 10% by mass or less is more preferable, 5% by mass or less is further preferable, and 2% by mass or less is further preferable. More specifically, the content of component B in the concentrate of the detergent composition according to the present disclosure is preferably 0.0003% by mass or more and 30% by mass or less, preferably 0.01% by mass or more and 10% by mass or less. It is more preferably 0.1% by mass or more and 5% by mass or less, still more preferably 0.5% by mass or more and 2% by mass or less.
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、樹脂マスク剥離性向上、剥離時間を短くする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。より具体的には、本開示に係る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９５質量％以下が好ましく、６０質量％以上９０質量％以下がより好ましく、７０質量％以上８５質量％以下が更に好ましい。 When the detergent composition according to the present disclosure is a concentrate, the content of the component C in the concentrate of the detergent composition improves the resin mask peelability, shortens the peeling time, and stabilizes the detergent composition. From the viewpoint of the above, 50% by mass or more is preferable, 60% by mass or more is more preferable, 70% by mass or more is further preferable, and from the same viewpoint, 95% by mass or less is preferable, 90% by mass or less is more preferable, and 85 More preferably, it is by mass or less. More specifically, the content of component C in the concentrate of the detergent composition according to the present disclosure is preferably 50% by mass or more and 95% by mass or less, more preferably 60% by mass or more and 90% by mass or less, and 70% by mass. More preferably, it is by mass or more and 85% by mass or less.
［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。
[Item to be washed]
The cleaning agent composition according to the present disclosure can be used in one or more embodiments for cleaning an object to be cleaned to which a resin mask is attached. Examples of the object to be cleaned include electronic parts and their manufacturing intermediates. Examples of the electronic component include at least one component selected from a metal plate such as a printed circuit board, a wafer, a copper plate, and an aluminum plate. The manufacturing intermediate product is an intermediate product in the manufacturing process of the electronic component, and includes an intermediate product after the resin mask treatment. Specific examples of the object to be cleaned to which the resin mask is attached include wiring and wiring by undergoing a process such as soldering or plating (copper plating, aluminum plating, nickel plating, etc.) using the resin mask. Examples thereof include electronic components in which connection terminals and the like are formed on the surface of a 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。 The detergent composition according to the present disclosure is suitable for cleaning a resin mask or an object to be cleaned to which a plated and / or heat-treated resin mask is attached, in terms of cleaning effect, in one or more embodiments. Can be used for. As the resin mask, for example, a negative type resin mask or a positive type resin mask may be used, 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 resin mask include an exposed and / or developed negative dry film resist. In the present disclosure, the negative resin mask is formed by using a negative resist, and examples thereof include an exposed and / or developed negative resist layer. In the present disclosure, the positive resin mask is formed by using a positive resist, and examples thereof include an exposed and / or developed positive resist layer.
［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（以下、「本開示に係る除去方法」ともいう）に関する。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 embodiment, the present disclosure includes a method for removing a resin mask, which comprises contacting an object to be cleaned with a resin mask attached to the cleaning agent 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 the object to be cleaned to which the resin mask is attached with the detergent composition according to the present disclosure. Examples of the object to be cleaned include the above-mentioned object to be cleaned. As a method of bringing the cleaning agent composition according to the present disclosure into contact with the object to be cleaned, or a method of cleaning the object to be cleaned with the cleaning agent composition according to the present disclosure, for example, in a cleaning bath containing the cleaning agent composition. Examples thereof include a method of contacting by immersing in a cleaning agent composition, a method of injecting a cleaning agent composition into contact with a spray (shower method), and an ultrasonic cleaning method of irradiating ultrasonic waves during immersion. The detergent composition according to the present disclosure can be used as it is for cleaning without being diluted. The removal method according to the present disclosure preferably includes a step of contacting the cleaning agent composition with the object to be cleaned, rinsing with water, and drying. According to the removal method according to the present disclosure, a resin mask, particularly a resin mask that has been plated and / or heat-treated, can be efficiently removed. In the removal method according to the present disclosure, it is preferable to irradiate ultrasonic waves at the time of contact between the cleaning agent composition according to the present disclosure and the object to be cleaned because the cleaning power of the cleaning agent composition according to the present disclosure is easily exerted. It is more preferable that the ultrasonic wave has a relatively high frequency. From the same viewpoint, the ultrasonic irradiation conditions are preferably, for example, 26 to 72 kHz and 80 to 1500 W, and more preferably 36 to 72 kHz and 80 to 1500 W.
［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。
[Manufacturing method of electronic parts]
In one aspect, the method for manufacturing an electronic component according to the present disclosure includes a step of cleaning an object to be cleaned to which a resin mask is attached with the detergent composition according to the present disclosure. Examples of the object to be cleaned include the above-mentioned object to be cleaned. In the method for manufacturing an electronic component according to the present disclosure, by performing cleaning using the cleaning agent composition according to the present disclosure, it is possible to effectively remove the resin mask adhering to the electronic component while suppressing the corrosion of metal. , It becomes possible to manufacture highly reliable electronic parts. Further, by performing the removal method according to the present disclosure, the resin mask adhering to the electronic component can be easily removed, 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（以下、「本開示に係るキット」ともいう）に関する。
本開示に係るキットの一実施形態としては、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をさらに含有する、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液は、使用時に混合され、必要に応じて希釈されてもよい。第１液及び第２液の各々には、必要に応じて上述した任意成分が含まれていてもよい。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 relates to a kit for use in any of the removal method according to the present disclosure and the manufacturing method of the electronic component according to the present disclosure (hereinafter, also referred to as "kit according to the present disclosure").
As one embodiment of the kit according to the present disclosure, for example, a solution containing component A (liquid 1) and a solution containing component B (liquid 2) are contained in a state in which they are not mixed with each other. Examples of the kit (two-component detergent composition) further contain the component C in at least one of the first solution and the second solution. The first liquid and the second liquid may be mixed at the time of use and diluted if necessary. Each of the first liquid and the second liquid may contain the above-mentioned optional components, if necessary. According to the kit according to the present disclosure, a detergent composition having excellent resin mask removability and a small wastewater treatment load can be obtained.
本開示に係るキットとしては、入手性及び作業性の観点から、成分Ａを３０質量％以上５０質量％以下含有し、成分Ｃを残部として含む第１液と、成分Ｂのみからなる第２液と、を有するキット；成分Ａを３０質量％以上５０質量％以下含有し、成分Ｃを残部として含む第１液と、成分Ｂを１質量％以上９９質量％以下含有し、成分Ｃを残部として含む第２液と、を有するキット；又は、成分Ａを３０質量％以上５０質量％以下含有し、成分Ｃを残部として含む第１液と、成分Ｂを１質量％以上９９質量％以下含有し、任意成分及び成分Ｃを残部として含む第２液と、を有するキット；が好ましく挙げられる。これらのキットは、成分Ｃからなる第３液を更に有することができ、第３液を用いて、前記第１液と前記第２液との混合物を任意の濃度に希釈することがより好ましい。 From the viewpoint of availability and workability, the kit according to the present disclosure includes a first liquid containing 30% by mass or more and 50% by mass or less of component A and containing component C as a balance, and a second liquid consisting of only component B. A first liquid containing 30% by mass or more and 50% by mass or less of component A and containing component C as a balance, and 1% by mass or more and 99% by mass or less of component B containing component C as a balance. A kit containing a second liquid containing; or a first liquid containing 30% by mass or more and 50% by mass or less of component A and a component C as a balance and 1% by mass or more and 99% by mass or less of component B. , A kit having a second solution containing an optional component and a component C as a balance; These kits can further have a third liquid consisting of component C, and it is more preferable to use the third liquid to dilute the mixture of the first liquid and the second liquid to an arbitrary concentration.
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。
＜１＞ 無機アルカリ（成分Ａ）、下記一般式（Ｉ）で表わされる界面活性剤（成分Ｂ）及び水（成分Ｃ）を含有し、
成分Ｂのデイビス法によるＨＬＢが４．９以上７．９以下である、樹脂マスク剥離用洗浄剤組成物。
Ｒ1－Ｏ－（ＥＯ）n（ＰＯ）m－Ｈ （Ｉ）
ただし、式（Ｉ）中、Ｒ1は炭素数８以上１４以下の直鎖又は分岐鎖のアルキル基及び炭素数８以上１４以下の直鎖又は分岐鎖のアルケニル基から選ばれる少なくとも１種を示し、ＥＯはエチレンオキシ基を示し、ｎはＥＯの平均付加モル数であって５以上１１以下の数であり、ＰＯはプロピレンオキシ基を示し、ｍはＰＯの平均付加モル数であって０以上４以下の数である。
The present disclosure further relates to the following detergent compositions, removal methods, and manufacturing methods.
<1> Contains an inorganic alkali (component A), a surfactant (component B) represented by the following general formula (I), and water (component C).
A detergent composition for removing a resin mask, wherein the HLB of component B by the Davis method is 4.9 or more and 7.9 or less.
R 1 -O- (EO) n (PO) m -H (I)
However, in the formula (I), R 1 represents at least one selected from a linear or branched alkyl group having 8 or more and 14 or less carbon atoms and a linear or branched alkenyl group having 8 or more and 14 or less carbon atoms. , EO indicates an ethyleneoxy group, n is the average number of added moles of EO, which is 5 or more and 11 or less, PO indicates a propyleneoxy group, and m is the average number of added moles of PO, which is 0 or more. It is a number of 4 or less.
＜２＞ 式（Ｉ）中、Ｒ1は、炭素数８以上１４以下の直鎖又は分岐鎖のアルキル基及び炭素数８以上１４以下の直鎖又は分岐鎖のアルケニル基から選ばれる少なくとも１種であって、炭素数８以上１４以下の直鎖アルキル基及び炭素数８以上１４以下の直鎖アルケニル基が好ましい、＜１＞に記載の洗浄剤組成物。
＜３＞ 式（Ｉ）中、Ｒ1の炭素数は、８以上であって、好ましくは９以上、より好ましくは１０以上である、＜１＞又は＜２＞に記載の洗浄剤組成物。
＜４＞ 式（Ｉ）中、Ｒ1の炭素数は、１４以下であって、好ましくは１２以下、より好ましくは１１以下である、＜１＞から＜３＞のいずれかに記載の洗浄剤組成物。
＜５＞ 式（Ｉ）中、Ｒ1の炭素数は、８以上１４以下であって、好ましくは９以上１２以下、より好ましくは１０以上１１以下、更に好ましくは１０である、＜１＞から＜４＞のいずれかに記載の洗浄剤組成物。
＜６＞ 式（Ｉ）中のＲ1は、オクチル基、２－エチルヘキシル基、デシル基、イソデシル基、２－プロピルヘプチル基、ドデシル基、トリデシル基、及びテトラデシル基から選ばれる少なくも１種である、＜１＞から＜５＞のいずれかに記載の洗浄剤組成物。
＜７＞ 式（Ｉ）中、ＥＯとＰＯの付加形態は、ランダム配列、ブロック配列のいずれでもよく、ＥＯとＰＯの付加順序は問わない、＜１＞から＜６＞のいずれかに記載の洗浄剤組成物。
＜８＞ 式（Ｉ）中、ｎは、５以上であって、好ましくは６以上、より好ましくは７以上である、＜１＞から＜７＞のいずれかに記載の洗浄剤組成物。
＜９＞ 式（Ｉ）中、ｎは、１１以下であって、好ましくは１０以下、より好ましくは９以下である、＜１＞から＜８＞のいずれかに記載の洗浄剤組成物。
＜１０＞ 式（Ｉ）中、ｎは、５以上１１以下の数であって、好ましくは６以上１０以下、より好ましくは７以上９以下である、＜１＞から＜９＞のいずれかに記載の洗浄剤組成物。
＜１１＞ 式（Ｉ）中、ｍは、０以上４以下の数であって、好ましくは０以上３以下、より好ましくは０以上２以下である、＜１＞から＜１０＞のいずれかに記載の洗浄剤組成物。
＜１２＞ 成分ＢのＨＬＢは、４．９以上であって、好ましくは５．５以上、より好ましくは６以上、更に好ましくは６．１５以上である、＜１＞から＜１１＞のいずれかに記載の洗浄剤組成物。
＜１３＞ 成分ＢのＨＬＢは、７．９以下であって、好ましくは６．９以下、より好ましくは６．７以下、更に好ましくは６．５以下である、＜１＞から＜１２＞のいずれかに記載の洗浄剤組成物。
＜１４＞ 成分ＢのＨＬＢは、４．９以上７．９以下であって、好ましくは５．５以上６．９以下、より好ましくは６以上６．７以下、更に好ましくは６．１５以上６．５以下である、＜１＞から＜１３＞のいずれかに記載の洗浄剤組成物。
＜１５＞ 成分Ｂの臨界ミセル濃度（ＣＭＣ）は、０．００００１質量％以上が好ましく、０．００００５質量％以上がより好ましく、０．０００１質量％以上が更に好ましい、＜１＞から＜１４＞のいずれかに記載の洗浄剤組成物。
＜１６＞ 成分Ｂの臨界ミセル濃度（ＣＭＣ）は、０．１質量％以下が好ましく、０．０５質量％以下がより好ましく、０．０１質量％以下が更に好ましい、＜１＞から＜１５＞のいずれかに記載の洗浄剤組成物。
＜１７＞ 成分Ｂの臨界ミセル濃度（ＣＭＣ）は、０．００００１質量％以上０．１質量％以下が好ましく、０．００００５質量％以上０．０５質量％以下がより好ましく、０．０００１質量％以上０．０１質量％以下が更に好ましい、＜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、７．５質量％以下が更に好ましい、＜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における成分Ａの含有量は、０．１質量％以上１５質量％以下が好ましく、０．３質量％以上１０質量％以下がより好ましく、０．５質量％以上７．５質量％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＞ 洗浄剤組成物の使用時における成分Ｂの含有量は、０．０００１質量％以上が好ましく、０．００１質量％以上がより好ましく、０．０１質量％以上が更に好ましく、０．１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＞ 洗浄剤組成物の使用時における成分Ｂの含有量は、１０質量％以下が好ましく、３質量％以下がより好ましく、２質量％以下が更に好ましく、１．２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＞ 洗浄剤組成物の使用時における成分Ｂの含有量は、０．０００１質量％以上１０質量％以下が好ましく、０．００１質量％以上１０質量％以下がより好ましく、０．０１質量％以上１０質量％以下が更に好ましく、０．１質量％以上１０質量％以下がより更に好ましく、０．１質量％以上３質量％以下がより更に好ましく、０．１質量％以上２質量％以下がより更に好ましく、０．１質量％以上１．２質量％以下がより更に好ましい、＜１＞から＜２２＞のいずれかに記載の洗浄剤組成物。
＜２４＞ 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、０．０００１質量％以上１０質量％以下である、＜１＞から＜２３＞のいずれかに記載の洗浄剤組成物。
＜２５＞ 成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）は、０．３以上が好ましく、０．４以上がより好ましく、０．５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＞ 成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）は、５００００以下が好ましく、１０００以下がより好ましく、１００以下が更に好ましく、８０以下がより更に好ましい、＜１＞から＜２５＞のいずれかに記載の洗浄剤組成物。
＜２７＞ 成分Ｂに対する成分Ａの質量比（Ａ／Ｂ）は、０．３以上５００００以下が好ましく、０．４以上１０００以下がより好ましく、０．５以上１００以下が更に好ましく、０．５以上８０以下が更に好ましい、＜１＞から＜２６＞のいずれかに記載の洗浄剤組成物。
＜２８＞ 洗浄剤組成物の使用時における成分Ｃの含有量は、８５質量％以上が好ましく、９０質量％以上がより好ましく、９５質量％以上が更に好ましい、＜１＞から＜２７＞のいずれかに記載の洗浄剤組成物。
＜２９＞ 洗浄剤組成物の使用時における成分Ｃの含有量は、９９．５質量％以下が好ましく、９９．４質量％以下がより好ましい、＜１＞から＜２８＞のいずれかに記載の洗浄剤組成物。
＜３０＞ 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９９．５質量％以下が好ましく、９０質量％以上９９．４質量％以下がより好ましく、９５質量％以上９９．４質量％以下が更に好ましい、＜１＞から＜２９＞のいずれかに記載の洗浄剤組成物。
＜３１＞ 洗浄剤組成物の使用時における有機物の総含有量は、１０質量％以下が好ましく、３質量％以下がより好ましく、２質量％以下が更に好ましく、１質量％以下がより更に好ましく、０．５質量％以下がより更に好ましい、＜１＞から＜３０＞のいずれかに記載の洗浄剤組成物。
＜３２＞ 洗浄剤組成物の使用時における有機物の総含有量は、０．０００１質量％以上が好ましく、０．０１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＜３１＞のいずれかに記載の洗浄剤組成物。
＜３３＞ 洗浄剤組成物の使用時における有機物の総含有量は、０．０００１質量％以上１０質量％以下が好ましく、０．０１質量％以上３質量％以下がより好ましく、０．０１質量％以上２質量％以下が更に好ましく、０．０１質量％以上１質量％以下がより更に好ましく、０．１質量％以上０．５質量％以下がより更に好ましい、＜１＞から＜３２＞のいずれかに記載の洗浄剤組成物。
＜３４＞ 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＜３３＞のいずれかに記載の洗浄剤組成物。
＜３５＞ 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、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＜３４＞のいずれかに記載の洗浄剤組成物。
＜３６＞ 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＜３５＞のいずれかに記載の洗浄剤組成物。
＜３７＞ 樹脂マスクが付着した被洗浄物を＜１＞から＜３６＞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。
＜３８＞ 被洗浄物が、電子部品の製造中間物である、＜３７＞に記載の除去方法。
＜３９＞ 樹脂マスクが付着した被洗浄物を＜１＞から＜３６＞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。
＜４０＞ ＜１＞から＜３６＞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。
＜４１＞ ＜３７＞又は＜３８＞に記載の除去方法及び＜３９＞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＜３６＞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、成分Ａを含有する第１液と、成分Ｂを含有する第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をさらに含有する、キット。
<2> In the formula (I), R 1 is at least one selected from a linear or branched alkyl group having 8 or more and 14 or less carbon atoms and a linear or branched alkenyl group having 8 or more and 14 or less carbon atoms. The cleaning agent composition according to <1>, wherein a linear alkyl group having 8 to 14 carbon atoms and a linear alkenyl group having 8 to 14 carbon atoms are preferable.
<3> The detergent composition according to <1> or <2>, wherein R 1 has 8 or more carbon atoms, preferably 9 or more, and more preferably 10 or more carbon atoms in the formula (I).
<4> The cleaning agent according to any one of <1> to <3>, wherein the carbon number of R 1 in the formula (I) is 14 or less, preferably 12 or less, and more preferably 11 or less. Composition.
<5> In the formula (I), the carbon number of R 1 is 8 or more and 14 or less, preferably 9 or more and 12 or less, more preferably 10 or more and 11 or less, and further preferably 10 from <1>. The detergent composition according to any one of <4>.
<6> R 1 in the formula (I) is at least one selected from an octyl group, a 2-ethylhexyl group, a decyl group, an isodecyl group, a 2-propylheptyl group, a dodecyl group, a tridecyl group, and a tetradecyl group. The detergent composition according to any one of <1> to <5>.
<7> In the formula (I), the addition form of EO and PO may be either a random sequence or a block sequence, and the order of addition of EO and PO does not matter, according to any one of <1> to <6>. Detergent composition.
<8> The detergent composition according to any one of <1> to <7>, wherein n is 5 or more, preferably 6 or more, and more preferably 7 or more in the formula (I).
<9> The detergent composition according to any one of <1> to <8>, wherein n is 11 or less, preferably 10 or less, and more preferably 9 or less in the formula (I).
<10> In the formula (I), n is a number of 5 or more and 11 or less, preferably 6 or more and 10 or less, and more preferably 7 or more and 9 or less, any of <1> to <9>. Detergent composition according to description.
<11> In the formula (I), m is a number of 0 or more and 4 or less, preferably 0 or more and 3 or less, and more preferably 0 or more and 2 or less, any of <1> to <10>. Detergent composition according to description.
<12> The HLB of the component B is 4.9 or more, preferably 5.5 or more, more preferably 6 or more, still more preferably 6.15 or more, any of <1> to <11>. The cleaning agent composition according to.
<13> The HLB of the component B is 7.9 or less, preferably 6.9 or less, more preferably 6.7 or less, still more preferably 6.5 or less, from <1> to <12>. The detergent composition according to any one.
<14> The HLB of the component B is 4.9 or more and 7.9 or less, preferably 5.5 or more and 6.9 or less, more preferably 6 or more and 6.7 or less, and further preferably 6.15 or more and 6 or less. 5. The detergent composition according to any one of <1> to <13>, which is 5 or less.
<15> The critical micelle concentration (CMC) of the component B is preferably 0.00001% by mass or more, more preferably 0.00005% by mass or more, further preferably 0.0001% by mass or more, <1> to <14>. The cleaning agent composition according to any one of.
<16> The critical micelle concentration (CMC) of component B is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, still more preferably 0.01% by mass or less, <1> to <15>. The cleaning agent composition according to any one of.
<17> The critical micelle concentration (CMC) of component B is preferably 0.00001% by mass or more and 0.1% by mass or less, more preferably 0.00005% by mass or more and 0.05% by mass or less, and more preferably 0.0001% by mass. The cleaning agent composition according to any one of <1> to <16>, more preferably 0.01% by mass or less.
<18> The content of the component A at the time of using the detergent 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, <1>. The detergent composition according to any one of <17>.
<19> The content of the component A at the time of using the detergent composition is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 7.5% by mass or less, <1> to <18>. The detergent composition according to any one of.
<20> The content of the component A at the time of using the cleaning agent composition is preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.3% by mass or more and 10% by mass or less, and more preferably 0.5% by mass. The cleaning agent composition according to any one of <1> to <19>, more preferably 7.5% by mass or less.
<21> The content of component B at the time of use of the detergent composition is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, further preferably 0.01% by mass or more, and 0.1. The detergent composition according to any one of <1> to <20>, more preferably by mass or more.
<22> The content of component B at the time of use of the detergent composition is preferably 10% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, and further preferably 1.2% by mass or less. The detergent composition according to any one of <1> to <21>, which is preferable.
<23> The content of component B at the time of use of the cleaning agent composition is preferably 0.0001% by mass or more and 10% by mass or less, more preferably 0.001% by mass or more and 10% by mass or less, and more preferably 0.01% by mass. 10% by mass or more is further preferable, 0.1% by mass or more and 10% by mass or less is further preferable, 0.1% by mass or more and 3% by mass or less is further preferable, and 0.1% by mass or more and 2% by mass or less is more preferable. The cleaning agent composition according to any one of <1> to <22>, more preferably 0.1% by mass or more and 1.2% by mass or less.
<24> The content of component A at the time of use of the detergent composition is 0.1% by mass or more and 15% by mass or less.
The cleaning agent composition according to any one of <1> to <23>, wherein the content of component B at the time of using the cleaning agent composition is 0.0001% by mass or more and 10% by mass or less.
<25> The mass ratio (A / B) of the component A to the component B is preferably 0.3 or more, more preferably 0.4 or more, still more preferably 0.5 or more, any of <1> to <24>. Detergent composition according to crab.
<26> The mass ratio (A / B) of the component A to the component B is preferably 50,000 or less, more preferably 1000 or less, further preferably 100 or less, still more preferably 80 or less, of <1> to <25>. The detergent composition according to any one.
<27> The mass ratio (A / B) of the component A to the component B is preferably 0.3 or more and 50,000 or less, more preferably 0.4 or more and 1000 or less, further preferably 0.5 or more and 100 or less, and 0.5. The detergent composition according to any one of <1> to <26>, more preferably 80 or less.
<28> The content of the component C at the time of use of the detergent composition is preferably 85% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, any of <1> to <27>. Detergent composition according to crab.
<29> The content of the component C when the detergent composition is used is preferably 99.5% by mass or less, more preferably 99.4% by mass or less, according to any one of <1> to <28>. Detergent composition.
<30> The content of component C when the detergent composition is used is preferably 85% by mass or more and 99.5% by mass or less, more preferably 90% by mass or more and 99.4% by mass or less, and 95% by mass or more and 99. The detergent composition according to any one of <1> to <29>, more preferably 4% by mass or less.
<31> The total content of organic substances in use of the detergent composition is preferably 10% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, still more preferably 1% by mass or less. The detergent composition according to any one of <1> to <30>, more preferably 0.5% by mass or less.
<32> The total content of organic substances in use of the detergent composition is preferably 0.0001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.1% by mass or more, <1>. The detergent composition according to any one of <31>.
<33> The total content of organic substances in use of the cleaning agent composition is preferably 0.0001% by mass or more and 10% by mass or less, more preferably 0.01% by mass or more and 3% by mass or less, and more preferably 0.01% by mass. More preferably 2% by mass or less, further preferably 0.01% by mass or more and 1% by mass or less, still more preferably 0.1% by mass or more and 0.5% by mass or less, any of <1> to <32>. The cleaning agent composition described in Crab.
<34> The detergent composition according to any one of <1> to <33>, which does not substantially contain a nitrogen-containing compound and a phosphorus-containing compound.
<35> The total content of the nitrogen-containing compound and the phosphorus-containing compound in the detergent composition is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, still more preferably 0% by mass, <1. > To <34>. The detergent composition according to any one of.
<36> The cleaning agent composition according to any one of <1> to <35>, wherein the resin mask is a negative type dry film resist subjected to at least one treatment of exposure and development.
<37> A method for removing a resin mask, which comprises a step of cleaning the object to be cleaned to which a resin mask is attached with the detergent composition according to any one of <1> to <36>.
<38> The removal method according to <37>, wherein the object to be cleaned is an intermediate product for manufacturing electronic components.
<39> A method for manufacturing an electronic component, which comprises a step of cleaning an object to be cleaned to which a resin mask is attached with the detergent composition according to any one of <1> to <36>.
<40> Use of the cleaning agent composition according to any one of <1> to <36> for manufacturing electronic components.
<41> A kit for use in any of the removal method according to <37> or <38> and the method for manufacturing an electronic component according to <39>, and any one of <1> to <36>. Among the components A to C constituting the cleaning agent composition according to No. 1, the first solution containing the component A and the second solution containing the component B are contained in a state where they are not mixed with each other, and the first solution and the second solution are contained. A kit in which at least one of the second liquids further contains component C.
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 with reference to Examples, but the present disclosure is not limited to these Examples.
１．実施例１～１９及び比較例１～１４の洗浄剤組成物の調製
１００ｍＬ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）４．００ｇ、ポリエチレングリコール（９）ラウリルエーテル（成分Ｂ）１．００ｇ及び水（成分Ｃ）９５．００ｇを配合し、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２～１９及び比較例１～１４の洗浄剤組成物を、実施例１と同様の方法により、成分Ａ～Ｃ以外の成分を含む場合はそれらも同時に配合し、表１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％、有効分）を表１に示した。
1. 1. Preparation of Detergent Compositions of Examples 1 to 19 and Comparative Examples 1 to 14 Sodium hydroxide (component A) 4.00 g, polyethylene glycol (9) lauryl ether (component B) in a 100 mL glass beaker in terms of effective amount. The detergent composition of Example 1 was prepared by blending 00 g and 95.00 g of water (component C), stirring them and mixing them uniformly. Then, when the detergent compositions of Examples 2 to 19 and Comparative Examples 1 to 14 contain components other than the components A to C by the same method as in Example 1, they are also blended at the same time and are shown in Table 1. It was prepared with a composition ratio that would be an effective component. The content (mass%, effective content) of each component of each detergent composition is shown in Table 1.
実施例１～１９及び比較例１～１４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％）］
Ｂ１：ポリエチレングリコール（９）ラウリルエーテル（成分Ｂ）［青木油脂工業株式会社製、ブラウノン ＥＬ－１５０９Ｐ］
Ｂ３：ポリエチレングリコール（６）２－エチルヘキシルエーテル（成分Ｂ）［青木油脂工業株式会社製、ブラウノン ＥＨ－６］
Ｂ４：ポリエチレングリコール（７）デシルエーテル（成分Ｂ）［青木油脂工業株式会社製、ファインサーフ Ｄ－１３７０］
Ｂ５：ポリエチレングリコール（８．５）イソデシルエーテル（成分Ｂ）［青木油脂工業株式会社製、ファインサーフ Ｄ－８５］
Ｂ６：ポリエチレングリコール（１０）トリデシルエーテル（成分Ｂ）［青木油脂工業株式会社製、ファインサーフ ＴＤ－１００］
Ｂ８：ポリエチレングリコール（９）デシル（Ｇｕｅｒｂｅｔ）エーテル（成分Ｂ）［ＢＡＳＦ社製、ルテンゾール ＸＬ９０］
Ｂ９：ペンタエチレングリコールモノオクチルエーテル（成分Ｂ）［ＳＩＧＭＡ－ＡＬＤＲＩＣＨ社製］
Ｂ１０：ポリエチレングリコール（１２）アルキル（２級ドデシル及び２級テトラデシル混合）エーテル（成分Ｂ）［株式会社日本触媒製、ソフタノール １２０］
Ｂ１１：トリ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、ブチルトリグリコール（ＢＴＧ）］
Ｂ１２：ポリエチレングリコール（３）ラウリルエーテル（非成分Ｂ）［青木油脂工業株式会社製、ブラウノン ＥＬ－１５０３Ｐ］
Ｂ１３：ポリエチレングリコール（５）ラウリルエーテル（非成分Ｂ）［青木油脂工業株式会社製、ブラウノン ＥＬ－１５０５］
Ｂ１４：ポリエチレングリコール（４０）ラウリルエーテル（非成分Ｂ）［青木油脂工業株式会社製、ブラウノン ＥＬ－１５４０Ｐ］
Ｂ１５：ポリエチレングリコール（７）オレイルエーテル（非成分Ｂ）［青木油脂工業株式会社製、ブラウノン ＥＮ－１５０７］
Ｂ１６：ポリエチレングリコール（４）２－エチルヘキシルエーテル（非成分Ｂ）［青木油脂工業株式会社製、ブラウノン ＥＨ－４］
ベンゾトリアゾール［東京化成工業株式会社製、１，２，３－ベンゾトリアゾール］
２－エチルヘキサン酸［東京化成工業株式会社製］
ヒドロキシルアミン［和光純薬工業株式会社製、５０％ヒドロキシルアミン溶液］
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］
なお、化合物名中の（）内の数値は平均付加モル数を示す。
The following were used as the components of the detergent compositions of Examples 1 to 19 and Comparative Examples 1 to 14.
Sodium hydroxide (component A) [manufactured by Kanto Chemical Co., Inc., special grade deer, solid content 48% by mass]
Potassium hydroxide (ingredient A) [manufactured by Kanto Chemical Co., Inc., special grade deer, solid content 48% by mass]
Tetramethylammonium hydroxide (non-ingredient A) [manufactured by Showa Denko KK, TMAH (25%)]
B1: Polyethylene glycol (9) Lauryl ether (Component B) [Brownon EL-1509P, manufactured by Aoki Yushi Kogyo Co., Ltd.]
B3: Polyethylene glycol (6) 2-ethylhexyl ether (component B) [Brownon EH-6, manufactured by Aoki Oil & Fat Industry Co., Ltd.]
B4: Polyethylene glycol (7) decyl ether (component B) [Finesurf D-1370 manufactured by Aoki Yushi Kogyo Co., Ltd.]
B5: Polyethylene glycol (8.5) Isodecyl ether (component B) [Finesurf D-85, manufactured by Aoki Oil & Fat Industry Co., Ltd.]
B6: Polyethylene glycol (10) Tridecyl ether (component B) [Finesurf TD-100, manufactured by Aoki Yushi Kogyo Co., Ltd.]
B8: Polyethylene glycol (9) decyl (Guerbet) ether (component B) [BASF, Lutensol XL90]
B9: Pentaethylene glycol monooctyl ether (component B) [manufactured by SIGMA-ALDRICH]
B10: Polyethylene glycol (12) Alkyl (mixed with secondary dodecyl and secondary tetradecyl) ether (component B) [Nippon Shokubai Co., Ltd., Softanol 120]
B11: Triethylene glycol monobutyl ether (non-ingredient B) [Butyl Triglycol (BTG) manufactured by Nippon Embroidery Co., Ltd.]
B12: Polyethylene glycol (3) Lauryl ether (non-ingredient B) [Brownon EL-1503P, manufactured by Aoki Yushi Kogyo Co., Ltd.]
B13: Polyethylene glycol (5) Lauryl ether (non-ingredient B) [Brownon EL-1505, manufactured by Aoki Yushi Kogyo Co., Ltd.]
B14: Polyethylene glycol (40) Lauryl ether (non-ingredient B) [Brownon EL-1540P, manufactured by Aoki Yushi Kogyo Co., Ltd.]
B15: Polyethylene glycol (7) Oleyl ether (non-ingredient B) [Brownon EN-1507, manufactured by Aoki Oil & Fat Industry Co., Ltd.]
B16: Polyethylene glycol (4) 2-ethylhexyl ether (non-ingredient B) [Brownon EH-4, manufactured by Aoki Yushi Kogyo Co., Ltd.]
Benzotriazole [manufactured by Tokyo Chemical Industry Co., Ltd., 1,2,3-benzotriazole]
2-Ethylhexanoic acid [manufactured by Tokyo Chemical Industry Co., Ltd.]
Hydroxylamine [manufactured by Wako Pure Chemical Industries, Ltd., 50% hydroxylamine solution]
Water (component C) [Pure water of 1 μS / cm or less manufactured by the pure water device G-10DSTSET manufactured by Organo Corporation]
The value in parentheses in the compound name indicates the average number of moles added.
合成例１（界面活性剤Ｂ２（成分Ｂ））
ヘキサエチレングリコールモノ２－エチルヘキシルエ－テル（１モル、「ブラウノン ＥＨ－６」青木油脂工業株式会社製）と触媒量の水酸化カリウム（ナカライテスク株式会社製）をオートクレーブに仕込み、窒素置換後、減圧下で脱水を行い系内の水分を０．２％以下とし、エチレンオキシド（２モル）を１６０℃、０．３ＭＰａ以下で付加、熟成し、ＥＯ付加体（界面活性剤Ｂ２）を得た。得られた界面活性剤Ｂ２は、式（Ｉ）で表現すると、Ｒ1 ：２－エチルヘキシル基、ｎ：８、ｍ：０である。
Synthesis Example 1 (Surfactant B2 (Component B))
Hexaethylene glycol mono2-ethylhexyl ether (1 mol, "Brownon EH-6" manufactured by Aoki Yushi Kogyo Co., Ltd.) and a catalytic amount of potassium hydroxide (manufactured by Nakaraitesk Co., Ltd.) were charged into an autoclave, and after nitrogen substitution, Dehydration was carried out under reduced pressure to reduce the water content in the system to 0.2% or less, ethylene oxide (2 mol) was added and aged at 160 ° C. and 0.3 MPa or less to obtain an EO adduct (surfactant B2). The obtained surfactant B2 is represented by the formula (I) as R1 : 2-ethylhexyl group, n: 8, m: 0.
合成例２（界面活性剤Ｂ７（成分Ｂ））
ラウリルアルコール（０．７モル、「カルコール ２０９８」花王株式会社製）とミリスチルアルコール（０．３モル、「カルコール ４０９８」花王株式会社製）と触媒量の水酸化カリウム（ナカライテスク株式会社製）をオートクレーブに仕込み、窒素置換後、減圧下で脱水を行い系内の水分を０．２％以下とし、エチレンオキシド（５モル）を１６０℃、０．３ＭＰａ以下で付加、熟成し、ＥＯ付加体を得た。引き続きプロピレンオキシド（１．５モル）を１２５℃、０．３ＭＰａ以下で付加、熟成し、ＥＯ－ＰＯ付加体を得た。更にエチレンオキシド（５モル）を１６０℃、０．３ＭＰａ以下で付加、熟成し、ＥＯ－ＰＯ－ＥＯ付加体（界面活性剤Ｂ７）を得た。得られた界面活性剤Ｂ７は、式（Ｉ）で表現すると、Ｒ1：ドデシル基又はテトラデシル基、ｎ：１０、ｍ：１．５である。
Synthesis Example 2 (Surfactant B7 (Component B))
Lauryl alcohol (0.7 mol, "Calcol 2098" manufactured by Kao Co., Ltd.), myristyl alcohol (0.3 mol, manufactured by "Calcol 4098" Kao Co., Ltd.) and a catalytic amount of potassium hydroxide (manufactured by Nakaraitesk Co., Ltd.) It was charged in an autoclave, replaced with nitrogen, and dehydrated under reduced pressure to reduce the water content in the system to 0.2% or less, and ethylene oxide (5 mol) was added and aged at 160 ° C. and 0.3 MPa or less to obtain an EO adduct. rice field. Subsequently, propylene oxide (1.5 mol) was added and aged at 125 ° C. and 0.3 MPa or less to obtain an EO-PO adduct. Further, ethylene oxide (5 mol) was added and aged at 160 ° C. and 0.3 MPa or less to obtain an EO-PO-EO adduct (surfactant B7). The obtained surfactant B7 is represented by the formula (I) as R1 : dodecyl group or tetradecyl group, n: 10, m: 1.5.
合成例３（界面活性剤Ｂ１７（非成分Ｂ））
ポリエチレングリコール（９）アルキル（２級ドデシル及び２級テトラデシル混合）エーテル（１モル、「ソフタノール ９０」株式会社日本触媒製）と触媒量の水酸化カリウム（ナカライテスク株式会社製）をオートクレーブに仕込み、窒素置換後、減圧下で脱水を行い系内の水分を０．２％以下とし、プロピレンオキシド（５モル）を１２５℃、０．３ＭＰａ以下で付加、熟成し、ＥＯ－ＰＯ付加体（界面活性剤Ｂ１７）を得た。得られた界面活性剤Ｂ１７は、式（Ｉ）で表現すると、Ｒ1：ドデシル基又はテトラデシル基、ｎ：９、ｍ：５である。
Synthesis Example 3 (Surfactant B17 (Non-component B))
Polyethylene glycol (9) Alkyl (mixed with secondary dodecyl and secondary tetradecyl) ether (1 mol, "Sophthalol 90" manufactured by Nippon Catalyst Co., Ltd.) and a catalytic amount of potassium hydroxide (manufactured by Nakaraitesk Co., Ltd.) were charged into the autoclave. After substitution with nitrogen, dehydration is performed under reduced pressure to reduce the water content in the system to 0.2% or less, propylene oxide (5 mol) is added and aged at 125 ° C. and 0.3 MPa or less, and an EO-PO adduct (surfactant) is added. Agent B17) was obtained. The obtained surfactant B17 is represented by the formula (I) as R1 : dodecyl group or tetradecyl group, n: 9, m: 5.
合成例４（界面活性剤Ｂ１８（非成分Ｂ））
オクタノール（１モル、「カルコール ０８９８」花王株式会社製）と触媒量の水酸化カリウム（ナカライテスク株式会社製）をオートクレーブに仕込み、窒素置換後、減圧下で脱水を行い系内の水分を０．２％以下とし、プロピレンオキシド（３モル）を１２５℃、０．３ＭＰａ以下で付加、熟成し、ＰＯ付加体（界面活性剤Ｂ１８）を得た。得られた界面活性剤Ｂ１８は、式（Ｉ）で表現すると、Ｒ1：オクチル基、ｎ：０、ｍ：３である。
Synthesis Example 4 (Surfactant B18 (Non-component B))
Octanol (1 mol, "Calcol 0898" manufactured by Kao Co., Ltd.) and a catalytic amount of potassium hydroxide (manufactured by Nakaraitesk Co., Ltd.) are charged in an autoclave, and after nitrogen substitution, dehydration is performed under reduced pressure to remove water in the system. Propylene oxide (3 mol) was added at 125 ° C. and 0.3 MPa or less at 2% or less, and aged to obtain a PO adduct (surfactant B18). The obtained surfactant B18 is represented by the formula (I) as R1 : octyl group, n: 0, m: 3.
合成例５（界面活性剤Ｂ１９（非成分Ｂ））
ラウリルアルコール（０．７モル、「カルコール ２０９８」花王株式会社製）とミリスチルアルコール（０．３モル、「カルコール ４０９８」花王株式会社製）と触媒量の水酸化カリウム（ナカライテスク株式会社製）をオートクレーブに仕込み、窒素置換後、減圧下で脱水を行い系内の水分を０．２％以下とし、プロピレンオキシド（５モル）を１２５℃、０．３ＭＰａ以下で付加、熟成し、ＰＯ付加体（界面活性剤Ｂ１９）を得た。得られた界面活性剤Ｂ１９は、式（Ｉ）で表現すると、Ｒ1：ドデシル基又はテトラデシル基、ｎ：０、ｍ：５である。
Synthesis Example 5 (Surfactant B19 (Non-component B))
Lauryl alcohol (0.7 mol, "Calcol 2098" manufactured by Kao Co., Ltd.), myristyl alcohol (0.3 mol, manufactured by "Calcol 4098" Kao Co., Ltd.) and a catalytic amount of potassium hydroxide (manufactured by Nakaraitesk Co., Ltd.) It was charged in an autoclave, replaced with nitrogen, dehydrated under reduced pressure to reduce the water content in the system to 0.2% or less, and propylene oxide (5 mol) was added and aged at 125 ° C. and 0.3 MPa or less to obtain a PO adduct (PO adduct (PO adduct). Surfactant B19) was obtained. The obtained surfactant B19 is represented by the formula (I) as R1 : dodecyl group or tetradecyl group, n: 0, m: 5.
２．洗浄剤組成物の評価
調製した実施例１～１９及び比較例１～１４の洗浄剤組成物の樹脂マスク除去性を評価した。
2. 2. Evaluation of Detergent Composition The resin mask removability of the prepared detergent compositions of Examples 1 to 19 and Comparative Examples 1 to 14 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－１２２５、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５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５パターン
塗りつぶしパターン（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）＝３０μｍ／３０μｍの縞状パターン
縞状パターン２：Ｌ／Ｓ＝２５μｍ／２５μｍの縞状パターン
縞状パターン３：Ｌ／Ｓ＝２０μｍ／２０μｍの縞状パターン
縞状パターン４：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。
[Making test pieces]
A photosensitive film for direct imaging (direct drawing) (Hitachi Kasei Co., Ltd., Fotec RD-1225, negative type dry film resist) is placed on the surface of a glass epoxy multilayer substrate (Hitachi Kasei Co., Ltd., MCL-E-679FG) as follows. After laminating under the conditions and selectively exposing to cure the exposed part (exposure step), the unexposed part is removed by developing (development process), and the resist pattern (negative mold of the following five pattern shapes). A substrate having a resin mask) was obtained. Then, a test piece (4 cm × 4.5 cm) was obtained by copper-plating the region from which the unexposed portion was removed by the development treatment.
(1) Laminate: Using a clean roller (RY-505Z, manufactured by Leyon Industries, Ltd.) and a vacuum applicator (VA7024 / HP5, manufactured by ROHM & Haas), the roller temperature is 50 ° C., the roller pressure is 1.4 Bar, and the processing time is 30. Do it in seconds.
(2) Exposure: Using a direct drawing device for a printed circuit board (Mercurex LI-9500, manufactured by SCREEN Graphic and Precision Solutions Co., Ltd.), exposure is performed at an exposure amount of 15 mJ / cm 2 .
(3) Pattern shape: The following 5 patterns Fill pattern (solid): Partial striped pattern having an area of 30 μm × 30 μm or more 1: Ratio (L / S) of line width L and line spacing S = 30 μm / 30 μm Striped pattern Striped pattern 2: L / S = 25 μm / 25 μm striped pattern Striped pattern 3: L / S = 20 μm / 20 μm striped pattern Striped pattern 4: L / S = 15 μm / 15 μm striped pattern Pattern (4) Development: Using a substrate developer (LT-9803666 manufactured by Yanghuang Technology Co., Ltd.) and a 1% sodium carbonate aqueous solution at 30 ° C., a spray pressure of 0.2 MPa, 47 seconds, the resin of the unexposed portion. Remove the mask.
［洗浄試験１］
１００ｍＬガラスビーカーに、実施例１～１９及び比較例１～１４の各洗浄剤組成物を１００ｇ添加して５０℃に加温し、回転子（フッ素樹脂（ＰＴＦＥ）、φ８ｍｍ×２５ｍｍ）を用いて回転数３００ｒｐｍ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。
[Washing test 1]
To a 100 mL glass beaker, 100 g of each cleaning agent composition of Examples 1 to 19 and Comparative Examples 1 to 14 was added, heated to 50 ° C., and using a rotor (fluororesin (PTFE), φ8 mm × 25 mm). Immerse the test piece for 3 minutes with stirring at a rotation speed of 300 rpm. Then, it is immersed in a rinsing tank containing 100 g of water in a 100 mL glass beaker, rinsed, and then naturally dried.
［洗浄試験２］
１００ｍＬガラスビーカーに、実施例１～１９及び比較例１～１４の各洗浄剤組成物を１００ｇ添加して３０℃に加温し、攪拌及び搖動は行わず、テストピースを浸漬する。
[Washing test 2]
To a 100 mL glass beaker, 100 g of each detergent composition of Examples 1 to 19 and Comparative Examples 1 to 14 is added and heated to 30 ° C., and the test piece is immersed without stirring and shaking.
［樹脂マスク除去性評価１（剥離性）］
光学顕微鏡「デジタルマイクロスコープＶＨＸ－２０００」（株式会社キーエンス製）を用いて、洗浄試験１を行った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。各縞状パターン１～４の中で、完全に除去できた縞状パターンのＬ／Ｓの値を計測し、下記評価基準で評価した結果を表１に示す。
＜評価基準＞
１：すべての縞状パターンが完全剥離できた
２：縞状パターン１～３まで完全剥離できた
３：縞状パターン１～２まで完全剥離できた
４：縞状パターン１のみ完全剥離できた
５：いずれの縞状パターンも剥離できなかった
[Resin mask removability evaluation 1 (peeling property)]
Using an optical microscope "Digital Microscope VHX-2000" (manufactured by KEYENCE CORPORATION), visually check the presence or absence of the resin mask remaining in each part of the test piece after performing the cleaning test 1 by magnifying it 300 times. , Evaluate the resin mask removability. Table 1 shows the results of measuring the L / S value of the striped pattern that was completely removed from each of the striped patterns 1 to 4 and evaluating them according to the following evaluation criteria.
<Evaluation criteria>
1: All striped patterns could be completely peeled 2: Striped patterns 1 to 3 could be completely peeled 3: Striped patterns 1 to 2 could be completely peeled 4: Only striped pattern 1 could be completely peeled 5 : None of the striped patterns could be peeled off
［樹脂マスク除去性評価２（剥離時間）］
洗浄試験２を行い、目視にて、塗りつぶしパターン（ベタ）が完全にテストピースから剥離するまでの時間（秒）を測定する。結果を表１に示す。
[Resin mask removability evaluation 2 (peeling time)]
The cleaning test 2 is performed, and the time (seconds) until the fill pattern (solid) is completely peeled off from the test piece is visually measured. The results are shown in Table 1.
表１の結果から、無機アルカリ（成分Ａ）と所定の界面活性剤（成分Ｂ）とを含む実施例１～１９の洗浄剤組成物は、無機アルカリ（成分Ａ）又は所定の界面活性剤（成分Ｂ）を含まない比較例１～１４の洗浄剤組成物に比べて、効率よく樹脂マスクを除去できることがわかった。 From the results in Table 1, the detergent compositions of Examples 1 to 19 containing the inorganic alkali (component A) and the predetermined surfactant (component B) are the inorganic alkali (component A) or the predetermined surfactant ( It was found that the resin mask can be removed more efficiently than the detergent compositions of Comparative Examples 1 to 14 containing the component B).
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。 By using the present disclosure, the resin mask can be efficiently removed without increasing the wastewater treatment load. Therefore, the cleaning agent composition of the present disclosure is useful as a cleaning agent composition used in the manufacturing process of electronic parts, shortening the cleaning process of electronic parts to which a resin mask is attached, and the performance of manufactured electronic parts. Reliability can be improved, and the productivity of semiconductor devices can be improved.
Claims (10)
無機アルカリ（成分Ａ）、下記一般式（Ｉ）で表わされる界面活性剤（成分Ｂ）及び水（成分Ｃ）を含有し、
成分Ｂのデイビス法によるＨＬＢが６以上７．９以下である、樹脂マスク剥離用洗浄剤組成物。
Ｒ1－Ｏ－（ＥＯ）n（ＰＯ）m－Ｈ （Ｉ）
ただし、式（Ｉ）中、Ｒ1は炭素数８以上１４以下の直鎖又は分岐鎖のアルキル基及び炭素数８以上１４以下の直鎖又は分岐鎖のアルケニル基から選ばれる少なくとも１種を示し、ＥＯはエチレンオキシ基を示し、ｎはＥＯの平均付加モル数であって５以上１１以下の数であり、ＰＯはプロピレンオキシ基を示し、ｍはＰＯの平均付加モル数であって０以上１．５以下の数である。 A cleaning agent composition for peeling off a resin mask on which a cured negative-type dry film resist is plated.
It contains an inorganic alkali (component A), a surfactant (component B) represented by the following general formula (I), and water (component C).
A detergent composition for removing a resin mask, which has an HLB of component B of 6 or more and 7.9 or less by the Davis method.
R 1 -O- (EO) n (PO) m -H (I)
However, in the formula (I), R 1 represents at least one selected from a linear or branched alkyl group having 8 or more and 14 or less carbon atoms and a linear or branched alkenyl group having 8 or more and 14 or less carbon atoms. , EO indicates an ethyleneoxy group, n is the average number of added moles of EO, which is 5 or more and 11 or less, PO indicates a propyleneoxy group, and m is the average number of added moles of PO, which is 0 or more. The number is 1.5 or less.
洗浄剤組成物の使用時における成分Ｂの含有量が、０．０００１質量％以上１０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 at the time of use of the detergent composition is 0.1% by mass or more and 15% by mass or less.
The cleaning agent composition according to claim 1, wherein the content of the component B at the time of using the cleaning agent composition is 0.0001% by mass or more and 10% by mass or less.
請求項１から５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、成分Ａを含有する第１液と、成分Ｂを含有する第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をさらに含有する、キット。 A kit for use in any of the removal method according to claim 6 or 7 and the method for manufacturing electronic components according to claim 8 .
Of the components A to C constituting the cleaning agent composition according to any one of claims 1 to 5 , the first liquid containing the component A and the second liquid containing the component B are not mixed with each other. A kit comprising in a state, at least one of the first and second liquids further containing component C.
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| JP2017236368A JP7057653B2 (en) | 2017-12-08 | 2017-12-08 | Detergent composition for removing resin mask |
| CN201880079044.4A CN111448522A (en) | 2017-12-08 | 2018-11-07 | Cleaning agent composition for resin mask stripping |
| PCT/JP2018/041325 WO2019111625A1 (en) | 2017-12-08 | 2018-11-07 | Detergent composition for stripping resin mask |
| KR1020207016119A KR20200088365A (en) | 2017-12-08 | 2018-11-07 | Cleanser composition for resin mask peeling |
| TW107144127A TWI796397B (en) | 2017-12-08 | 2018-12-07 | Detergent composition for resin mask peeling |
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| CN117355798A (en) | 2021-06-24 | 2024-01-05 | 日油株式会社 | Release agent for resin film for circuit board and method for producing circuit board |
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| JPH07115048A (en) * | 1993-10-15 | 1995-05-02 | Sony Corp | Peeling method |
| JP4044215B2 (en) | 1998-02-25 | 2008-02-06 | 花王株式会社 | Release agent composition |
| JP2002016034A (en) * | 2000-06-30 | 2002-01-18 | Mitsubishi Electric Corp | Manufacturing method of semiconductor device, and the semiconductor device |
| KR100646793B1 (en) | 2001-11-13 | 2006-11-17 | 삼성전자주식회사 | Chemical rinse composition |
| US20050282093A1 (en) * | 2004-06-16 | 2005-12-22 | Dammel Ralph R | Aqueous edge bead remover |
| TWI413155B (en) * | 2005-11-22 | 2013-10-21 | Tokyo Ohka Kogyo Co Ltd | Cleaning liquid for photolithography and method of cleaning exposure equipment using the same |
| JP4884889B2 (en) | 2006-08-31 | 2012-02-29 | 東京応化工業株式会社 | Photoresist stripping solution and substrate processing method using the same |
| CN101802161B (en) * | 2007-09-14 | 2013-11-06 | 花王株式会社 | Alkaline nonionic surfactant composition |
| US20090229629A1 (en) * | 2008-03-14 | 2009-09-17 | Air Products And Chemicals, Inc. | Stripper For Copper/Low k BEOL Clean |
| JP5813280B2 (en) | 2008-03-19 | 2015-11-17 | 富士フイルム株式会社 | Semiconductor device cleaning liquid and cleaning method |
| CN101520612B (en) * | 2009-04-01 | 2011-12-21 | 苏州瑞红电子化学品有限公司 | Washing agent for color photoresist |
| TWI532834B (en) * | 2010-04-15 | 2016-05-11 | 富士軟片股份有限公司 | Method for cleaning semiconductor substrate, and two-component cleaning agent for semiconductor substrate |
| CN102486619A (en) * | 2010-12-02 | 2012-06-06 | 台湾永光化学工业股份有限公司 | Cleaning solution composition |
| US9275851B2 (en) * | 2011-03-21 | 2016-03-01 | Basf Se | Aqueous, nitrogen-free cleaning composition and its use for removing residues and contaminants from semiconductor substrates suitable for manufacturing microelectronic devices |
| FR2976290B1 (en) * | 2011-06-09 | 2014-08-15 | Jerome Daviot | COMPOSITION OF SOLUTIONS AND CONDITIONS OF USE FOR THE COMPLETE REMOVAL AND DISSOLUTION OF PHOTO-LITHOGRAPHIC RESINS |
| KR20170111411A (en) * | 2016-03-28 | 2017-10-12 | 동우 화인켐 주식회사 | Resist stripper composition, and method for manufacturing a plat panel for a display device and plat panel for a display device, and display device |
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