WO2022162972A1 - Resist redisue removal liquid and method for forming substrate with conductor pattern using same - Google Patents
Resist redisue removal liquid and method for forming substrate with conductor pattern using same Download PDFInfo
- Publication number
- WO2022162972A1 WO2022162972A1 PCT/JP2021/026008 JP2021026008W WO2022162972A1 WO 2022162972 A1 WO2022162972 A1 WO 2022162972A1 JP 2021026008 W JP2021026008 W JP 2021026008W WO 2022162972 A1 WO2022162972 A1 WO 2022162972A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resist
- resist residue
- residue remover
- substrate material
- pattern
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000004020 conductor Substances 0.000 title claims abstract description 23
- 239000007788 liquid Substances 0.000 title abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 18
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 229920000858 Cyclodextrin Polymers 0.000 claims description 33
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 238000011161 development Methods 0.000 claims description 18
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 11
- 229960004853 betadex Drugs 0.000 claims description 11
- 239000001116 FEMA 4028 Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims description 8
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 7
- 238000007772 electroless plating Methods 0.000 claims description 7
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims description 6
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims description 6
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims description 6
- BGYBONWLWSMGNV-UHFFFAOYSA-N 1,4,7,10,13,16,19,22-octaoxacyclotetracosane Chemical compound C1COCCOCCOCCOCCOCCOCCOCCO1 BGYBONWLWSMGNV-UHFFFAOYSA-N 0.000 claims description 3
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims description 3
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 3
- GQPLZGRPYWLBPW-UHFFFAOYSA-N calix[4]arene Chemical compound C1C(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC2=CC=CC1=C2 GQPLZGRPYWLBPW-UHFFFAOYSA-N 0.000 claims description 3
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- MMYYTPYDNCIFJU-UHFFFAOYSA-N calix[6]arene Chemical compound C1C(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC2=CC=CC1=C2 MMYYTPYDNCIFJU-UHFFFAOYSA-N 0.000 claims description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 2
- 241001120493 Arene Species 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000243 solution Substances 0.000 description 17
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 150000003983 crown ethers Chemical class 0.000 description 7
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000002075 main ingredient Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HDPRHRZFFPXZIL-UHFFFAOYSA-N calix[8]arene Chemical compound OC1=C(CC=2C(=C(CC=3C(=C(CC=4C(=C(CC=5C(=C(CC=6C(=C(CC=7C(=C(C8)C=CC=7)O)C=CC=6)O)C=CC=5)O)C=CC=4)O)C=CC=3)O)C=CC=2)O)C=CC=C1CC1=C(O)C8=CC=C1 HDPRHRZFFPXZIL-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical group OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- ZZTCCAPMZLDHFM-UHFFFAOYSA-N ammonium thioglycolate Chemical compound [NH4+].[O-]C(=O)CS ZZTCCAPMZLDHFM-UHFFFAOYSA-N 0.000 description 1
- 229940075861 ammonium thioglycolate Drugs 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Images
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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/268—Carbohydrates or derivatives thereof
-
- 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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
Definitions
- the invention pertaining to this application relates to a resist residue remover and a method for forming a substrate material with a conductive pattern using the same.
- dry film photoresist (hereinafter referred to as dry film resist) is placed on a substrate material, exposed and developed, a resist pattern is formed on the substrate material, A method of forming a conductor pattern using the resist pattern is performed.
- the photoresist material in the exposed area absorbs the developer and swells, sometimes forming bridges between the resist patterns. If the processing time of the developing step is shortened in order to avoid this problem, undeveloped portions of the photoresist material may remain undeveloped. As a result, resist residues (also referred to as scum) are generated, such as unintended resist trailing portions on the side surfaces of the resist pattern and photoresist material remaining in unexposed portions on the substrate material. If such a resist residue remains on the substrate material, the resolution of the photoresist is lowered, which hinders the improvement of the fineness of the conductor pattern.
- resist residues also referred to as scum
- a gap is generated between the bottom surface of the conductor pattern and the surface of the substrate material, which may reduce the adhesion of the conductor pattern and affect the reliability of the product.
- Patent Document 1 discloses a resist residue remover containing, as an active ingredient, a compound selected from the group consisting of a reducing agent having a mercapto group or a sulfite group and an anionic surfactant.
- Patent Document 1 when the resist residue removal solution of Patent Document 1 is used to remove the resist residue such as the resist skirting portion, the target portion may not be removed, resulting in a product that does not meet the market demand. There was a problem.
- the invention pertaining to the present application is a resist residue remover capable of stably and satisfactorily removing resist residues such as resist footings generated in the development process of a photoresist material for circuit formation, and the resist residue remover.
- An object of the present invention is to provide a method for forming a substrate material with a conductor pattern using
- Resist residue remover liquid according to the present application is used after development of a photoresist material for circuit formation, and contains 0.01% by mass or more of a cyclic oligomer and the balance is water. Prepare.
- the cyclic oligomer is preferably one or more selected from the group consisting of ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin.
- the cyclic oligomer includes 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, 24-crown-8-ether, calix[4 ]arene, calix[6]arene and calix[8]arene.
- the resist residue remover according to the present application preferably contains 0.001% by mass to 1% by mass of an alkaline component.
- the alkaline component is preferably one or more selected from the group consisting of sodium carbonate, tetramethylammonium and sodium hydroxide.
- the method for forming a substrate material with a conductive pattern using the resist residue remover according to the present application is a method using the above-described resist residue remover, and includes the following steps A to It is characterized by including step C.
- Process A A resist residue removing process in which a resist pattern is applied to the surface of a substrate material to obtain a substrate material with a resist pattern, and then the surface is brought into contact with the resist residue remover.
- Step B An electroless plating step of applying electroless plating to the surface of the substrate material with the resist pattern obtained in step A to obtain a substrate material with a metal film.
- Step C A resist removing step of removing the resist pattern from the surface of the substrate material with the metal film obtained in the step B to obtain a substrate material with a conductive pattern made of a metal film.
- the treatment with the resist residue remover is performed by spraying.
- a resist residue remover capable of stably and satisfactorily removing resist residues such as resist skirting portions generated in the development process of a photoresist material for circuit formation. can. Further, by using this resist residue remover, it is possible to provide a method of forming a substrate material with a conductive pattern in which an undercut portion is extremely unlikely to occur.
- (A) and (B) are electron microscope observation images of a resist pattern on a substrate material in Example 2 using the resist residue remover of the present application.
- (A) and (B) are electron microscope observation images of a resist pattern on a substrate material in Comparative Example 1 using no resist residue remover.
- (A) and (B) are electron microscope observation images of a resist pattern on a substrate material in Comparative Example 2 using a known bath as a resist residue remover.
- (A) to (E) are electron microscope observation images of conductor patterns on substrate materials in Example 2 and Examples 5 to 8 using the resist residue remover of the present application.
- (A) to (C) are electron microscope observations of conductor patterns on substrate materials in Comparative Example 1 that does not use a resist residue remover, and Comparative Examples 3 and 4 that use a known bath as a resist residue remover. is a statue. 4 is a graph showing the amount of skirting of dry film resists in Examples and Comparative Examples.
- the resist residue remover according to the present application basically comprises a cyclic oligomer and water.
- the resist residue remover will be described mainly assuming that a negative dry film resist is used.
- the resist residue means the resist trailing part on the side of the resist pattern, the uncured resist deposit on the resist pattern surface, and the substrate, which are generated in the development process of the photoresist material in the circuit formation process of the printed wiring board. This refers to unintended resist residue such as resist deposits on unexposed areas on a plate.
- the resist residue remover means a chemical solution for removing the resist residue remaining on the substrate material after the development process. When the resist residue remover contains the above components, it is possible to stably and satisfactorily remove the resist residue such as the resist skirting portion generated in the developing step of the photoresist material.
- Cyclic Oligomer The cyclic oligomer contained in the resist residue remover of the present application is a main ingredient for removing resist residue generated in the development process of a photoresist material for circuit formation. There are no particular restrictions on the type of this cyclic oligomer.
- the above-mentioned cyclic oligomers include cyclodextrins, crown ethers, and calixarenes.
- Cyclodextrin is a substance widely used industrially, and there are typically three types of ⁇ (hexamer), ⁇ (7mer), and ⁇ (octamer) depending on the number of bound glucose. do.
- the type of cyclodextrin used in the resist residue remover of the present application is not particularly limited. Therefore, the resist residue remover of the present application may contain at least one cyclodextrin such as ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin.
- the cyclic oligomer cyclodextrin contained in the resist residue removing solution of the present application is preferably ⁇ or ⁇ cyclodextrin, more preferably ⁇ -cyclodextrin.
- a resist residue remover containing ⁇ or ⁇ cyclodextrin can more stably remove resist residues with good reproducibility, and a resist residue remover containing ⁇ -cyclodextrin can This is because the effect can be obtained most stably.
- the content of this cyclodextrin is preferably 0.01% by mass or more. If the content of cyclodextrin is less than 0.01% by mass, it is not preferable because the resist residue generated in the development process tends to be unable to be stably removed. Although there is no particular upper limit for the content of cyclodextrin, exceeding the solubility in water, which is the solvent, does not improve the resist residue removal performance and is simply a waste of resources, which is undesirable. Therefore, experimentally, it can be understood that there is no point in containing more than 20% by mass of cyclodextrin in the resist residue remover of the present application. However, these numerical values are described assuming that they do not include unavoidable impurities.
- crown ether and calixarene are used as cyclic oligomers.
- types of crown ethers and calixarene used in the resist residue remover of the present application There are no particular restrictions on the types of crown ethers and calixarene used in the resist residue remover of the present application. Therefore, industrially easily available 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, 24-crown-8-ether, calix[4]arene, calix[6 ] at least one of compounds such as arene and calix [8] arene
- a crown ether when employed as the above-mentioned cyclic oligomer, it is preferably 18-crown-6-ether. This is because 18-crown-6-ether is relatively inexpensive and therefore excellent in terms of cost, and a resist residue remover containing the substance can more stably and reproducibly remove resist residues. be.
- the crown ether content is preferably 0.01% by mass to 5% by mass.
- a crown ether content of less than 0.01% by mass is not preferable because it tends to make it impossible to stably remove resist residues generated in the development process.
- the upper limit of the crown ether content is not particularly limited as in the case of the cyclodextrin described above. It is not desirable because it does not improve performance and is a mere waste of resources. However, these numerical values are described assuming that they do not include unavoidable impurities.
- the content of calixarene is preferably 0.01% by mass to 5% by mass. If the content of calixarene is less than 0.01% by mass, it tends to be difficult to stably remove resist residues generated in the development step, which is not preferable.
- the upper limit of the content of calixarene is not particularly limited as in the case of cyclodextrin described above. It is not desirable because it does not improve performance and is a mere waste of resources. However, these numerical values are described assuming that they do not include unavoidable impurities.
- the resist residue remover of the present application may contain an alkaline component.
- An alkali component such as sodium carbonate is used as a main component in a developer solution used in the development process of a photoresist material for forming a circuit board.
- the alkaline component is mixed in the processing solution in the process, and the pH of the resist residue removing solution, which is the processing solution, fluctuates. Therefore, it becomes difficult to perform stable processing. Therefore, if the resist residue remover contains the above-described alkaline component in advance, it is possible to suppress pH fluctuations of the resist residue remover during the resist residue removal step, and to obtain a more stable and favorable resist residue removal effect. can be done.
- examples of the above-mentioned alkaline component include sodium carbonate, tetramethylammonium, sodium hydroxide, etc., which are known as main ingredients of developer solutions.
- the resist residue remover of the present application contains an alkaline component, it may contain at least one of these alkaline compounds.
- the content of this alkaline component is preferably 0.001% by mass to 1% by mass. If the content of the alkali component is less than 0.001% by mass, the effect of suppressing pH fluctuation of the processing solution cannot be obtained, which is not preferable. On the other hand, if the content of the alkali component exceeds 1% by mass, the resist pattern tends to be unintentionally eroded, and the resist residue removal performance is not improved, which is not preferable.
- these numerical values are described assuming that they do not include unavoidable impurities.
- the resist residue remover of the present application may be prepared using a conventionally known method. For example, it can be obtained by bringing a cyclic oligomer such as cyclodextrin into contact with water, which is a solvent, and stirring it using a stirrer or the like to dissolve it.
- a cyclic oligomer such as cyclodextrin
- water which is a solvent
- an antifoaming agent or the like can be added in advance to the resist residue remover as necessary.
- the temperature of water in the resist residue remover can be room temperature or 60° C. or lower for the purpose of promoting dissolution of cyclic oligomers such as cyclodextrin.
- the method for forming a substrate material with a conductive pattern using the resist residue remover according to the present application is a method using the above-described resist residue remover, comprising the following steps: It includes steps A to C.
- Process A A resist residue removal process in which a resist pattern is applied to the surface of a substrate material to obtain a substrate material with a resist pattern, and then the surface is brought into contact with the resist residue remover for treatment.
- the method of treating the surface of the substrate material with the resist residue remover in the above-described step A includes spraying, immersion, and the like.
- spray spraying is more effective than the immersion method in which the surface of the substrate material is brought into contact with the resist residue remover and left stationary or shaken. It is preferable because it can be brought into contact.
- the nozzle of the spray device used for the spraying has a slit shape, since the resist residue removing liquid can be brought into contact with the surface of the substrate material more efficiently.
- the treatment time of the substrate material surface with the resist residue remover is preferably 5 seconds to 10 minutes. If the treatment time is shorter than 5 seconds, the effect of removing the resist residue tends not to be obtained, which is not preferable. On the other hand, even if the treatment time exceeds 10 minutes, the resist residue removing performance is not improved, and it is a factor in lowering the productivity of the product, which is not preferable. Furthermore, it is preferable that the liquid temperature of the resist residue remover in the above step A is 15.degree. C. to 40.degree. If the liquid temperature is lower than 15° C., the resist residue removing performance tends to be lowered, which is not preferable. On the other hand, if the liquid temperature exceeds 40° C., the resist pattern tends to be unintentionally corroded, and the resist residue removing performance is not improved, which is not preferable. Next, process B and process C will be described.
- Step B An electroless plating step of applying electroless plating to the surface of the substrate material with the resist pattern obtained in the above step A to obtain a substrate material with a metal film.
- Step C A resist removing step of removing the resist pattern from the surface of the substrate material with the metal film obtained in the step B to obtain a substrate material with a conductive pattern made of a metal film.
- the electroless plating treatment in step B may be performed by bringing a commercially available electroless copper plating solution or the like into contact with the surface of the substrate material by a method such as immersion.
- the resist pattern removing treatment in step C can be carried out by bringing a commercially available alkaline resist material removing liquid or the like into contact with the surface of the substrate material by spraying, immersion, or the like.
- Example 1 the following tests were carried out using a resist residue remover containing 0.1% by mass of ⁇ -cyclodextrin and the balance being deionized water (that is, an aqueous solution of ⁇ -cyclodextrin with a concentration of 0.1% by mass). gone.
- a substrate material having a copper layer provided on a resin plate made of epoxy resin is prepared, and a negative dry film resist (LDF525F manufactured by Nikko Materials Co., Ltd., film thickness 25 ⁇ m) is placed on the substrate material. was placed.
- LDF525F negative dry film resist manufactured by Nikko Materials Co., Ltd., film thickness 25 ⁇ m
- a mask substrate for forming a test circuit pattern is placed on the photoresist material, and a direct exposure device (FDi-3M manufactured by Oak Manufacturing Co., Ltd.) is used to emit h-line light from a mercury lamp (wavelength 405 nm, light intensity 95 mJ / cm). 2 ) was irradiated for exposure. Subsequently, a developer solution (aqueous solution of sodium carbonate having a concentration of 1% by mass) at 30° C. was sprayed onto the substrate material at 0.15 MPa for 38 seconds to remove the unexposed portion of the photoresist material for development.
- a direct exposure device FDi-3M manufactured by Oak Manufacturing Co., Ltd.
- the substrate material after the development was sprayed with a resist residue remover containing the above components at room temperature and 0.20 MPa for 60 seconds, and then washed with water to obtain a substrate material having a resist pattern on its surface.
- This water washing treatment was carried out by spraying deionized water at room temperature onto the substrate material at 0.10 MPa for 60 seconds.
- the spray device used in the above-described steps of development, resist residue removal, and water washing had a slit-shaped nozzle.
- the above substrate material with a resist pattern was immersed in an acidic degreasing agent (Melplate CL-2000 manufactured by Meltex Inc.), washed with water, and acid washed with sulfuric acid having a concentration of 10% by mass.
- This substrate material was immersed in a copper sulfate plating solution (Lucent Copper PVF manufactured by Meltex Co., Ltd.) and then washed with water to obtain a substrate material having a copper film on its surface.
- a resist material removing liquid (Melstrip DF-3850 manufactured by Meltex Co., Ltd.) to remove the resist pattern and then washed with water to obtain a substrate material having a conductor pattern on its surface.
- Example 2 a test was performed using a resist residue remover containing 0.1% by mass of ⁇ -cyclodextrin and the balance being deionized water instead of the resist residue remover of Example 1 described above. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
- Example 3 instead of the resist residue remover of Example 1, a test was performed using a resist residue remover containing 0.1% by mass of ⁇ -cyclodextrin and the balance being deionized water. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
- Example 4 instead of the resist residue remover of Example 1, a test was performed using a resist residue remover containing 0.1% by mass of 18-crown-6-ether and the balance being deionized water. rice field. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
- Example 5 instead of the resist residue remover of Example 1, a resist residue remover containing 0.1% by mass of ⁇ -cyclodextrin, 0.2% by mass of sodium carbonate, and the balance being deionized water was used. was tested using Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
- Example 6 instead of the resist residue remover of Example 1, a resist residue remover containing 0.1% by mass of ⁇ -cyclodextrin, 0.2% by mass of sodium carbonate, and the balance being deionized water was used. was tested using Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
- Example 7 instead of the resist residue remover of Example 1, a resist residue remover containing 0.1% by mass of ⁇ -cyclodextrin, 0.2% by mass of sodium carbonate, and the balance being deionized water was used. was tested using Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
- Example 8 instead of the resist residue removing solution of Example 1 described above, a resist containing 0.1% by mass of 18-crown-6-ether, 0.2% by mass of sodium carbonate, and the balance being deionized water was used. A test was performed using a residue remover. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
- Comparative Example 1 In Comparative Example 1, the test was performed by washing with water without performing the spraying treatment of the resist residue remover in Example 1 described above. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
- Comparative Example 2 In Comparative Example 2, instead of the resist residue remover of Example 1 described above, a resist residue remover consisting of an aqueous ammonium thioglycolate solution (concentration: 2 g/L) (removal described in Example 3 of Patent Document 1 described above) was used. liquid) was used for the test. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
- Comparative Example 3 In Comparative Example 3, instead of the resist residue remover of Example 1 described above, a resist residue remover consisting of an L-cysteine aqueous solution (concentration 1.3 g/L) (described in Example 7 of Patent Document 1 described above) was used. The test was performed using the removal liquid). Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
- Comparative Example 4 In Comparative Example 4, a test was performed using a resist residue remover consisting of an aqueous magnesium sulfate solution (concentration: 1 g/L) instead of the resist residue remover used in Example 1 described above. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
- Table 1 shows the content of the resist residue remover used in each test and the concentrations of its components.
- ⁇ Comparison between Examples and Comparative Examples> 1 to 3 show electron microscope observation images of resist patterns on substrate materials in Examples and Comparative Examples.
- the resist pattern of Example 2 shown in FIG. 1 has a desired shape and a smooth surface without resist residues such as resist skirting portions on the side surfaces and uncured resist deposits on the surface. there were.
- the resist patterns of Examples 1 and 3 to 8 also have good surfaces with no resist residue, as in Example 2, from electron microscope observation images. It could be confirmed.
- Comparative Example 1 shown in FIG. 2 and Comparative Example 2 shown in FIG. became a thing.
- FIGS. 4 and 5 show electron microscope observation images of the conductor patterns on the substrate materials in the example and the comparative example.
- the conductor patterns of Example 2 shown in FIG. 4A and Examples 5 to 8 shown in FIGS. There was almost no gap between them, and the adhesiveness and reliability of the product were excellent.
- the conductor patterns of Examples 1, 3, and 4, as well as Example 2 and Examples 5 to 8 exhibited adhesion and product quality with almost no undercuts. It was confirmed from an electron microscope observation image that it was excellent in reliability.
- Comparative Example 1 shown in FIG. 5A and Comparative Examples 3 and 4 shown in FIGS. Undercut portions, which are floats and gaps, were generated due to resist skirting portions remaining on the side surfaces of the pattern, and the adhesion and reliability of the product were low.
- the resist residue removal performance such as the resist skirting part possessed by the resist residue remover of the present application in more detail
- the conditions of Examples 1 to 8 and Comparative Examples 1 to 4 described above and the amount of skirting of the dry film resist and the variation in the numerical values were measured.
- the "footing amount of the dry film resist” is the length of the gap generated between the conductor pattern and the substrate material surface, measured from both sides of the conductor pattern based on the electron microscope observation image, that is, the conductor It is the length of the undercut part in the pattern.
- FIG. 6 shows excerpts of the evaluation results.
- the trailing amount of the dry film resist was as short as 0.2 ⁇ m or less, and the variation in numerical values for each test was small.
- the conductor patterns of Examples 1, 3, and 4 were as good as those of Examples 2 and 5 to 8.
- the amount of footing of the dry film resist was as short as 0.2 ⁇ m or less, and the variation in numerical values for each test was small.
- the conductor patterns formed under the conditions of Comparative Example 1, Comparative Example 3, and Comparative Example 4 had a long trailing amount of the dry film resist, and the variation in numerical values for each test was large.
- the resist residue remover of the present application was able to stably and satisfactorily remove the resist residue generated in the development process of the photoresist material. Then, by treating the substrate material after the development process using the resist residue remover of the present application, the conductor pattern is extremely unlikely to have an undercut portion, and the conductor has high adhesion to the surface of the substrate material and high product reliability. A substrate material with a pattern could be formed.
- the resist residue remover of the present application can stably and satisfactorily remove the resist residue remaining in unnecessary portions such as the resist skirting portion generated in the development process of the photoresist material, it is suitable for circuit formation of printed wiring boards. accuracy can be dramatically improved, making it possible to provide high-quality circuit boards.
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Abstract
The purpose of the invention according to the present application is to provide: a resist residue removal liquid that can stably and satisfactorily remove resist residues, such as resist trailing parts occurring in the side surface of a resist pattern in the step of developing a photoresist material for circuit formation, and uncured resist deposits on the front surface of the resist pattern; and a method for forming a substrate with a conductor pattern using the resist residue removal liquid. To accomplish this purpose, the resist residue removal liquid according to the present application is composed of at least 0.01% by mass of a cyclic oligomer and the rest water. The resist residue removal liquid preferably contains 0.001–1% by mass of an alkali component.
Description
本件出願に係る発明は、レジスト残渣除去液及びこれを用いる導体パターン付き基板材の形成方法に関する。
The invention pertaining to this application relates to a resist residue remover and a method for forming a substrate material with a conductive pattern using the same.
従来、プリント配線板の回路形成工程等において、基板材上にドライフィルムフォトレジスト（以下、ドライフィルムレジストと称する。）を配置して露光及び現像を行い、基板材上にレジストパターンを形成し、当該レジストパターンを用いて導体パターンを形成する方法が行われている。
Conventionally, in the circuit formation process of a printed wiring board, etc., a dry film photoresist (hereinafter referred to as dry film resist) is placed on a substrate material, exposed and developed, a resist pattern is formed on the substrate material, A method of forming a conductor pattern using the resist pattern is performed.
この現像工程において、ネガ型のドライフィルムレジストの場合、露光部のフォトレジスト材が現像液を吸収して膨潤し、レジストパターン間にブリッジ部ができることがある。そして、これを回避する目的で現像工程の処理時間を短くすると、フォトレジスト材の未露光部に現像残りが生じる場合がある。その結果、レジストパターンの側面に意図しないレジスト裾引き部が生じたり、基板材上の未露光部にフォトレジスト材が残存するなどして、レジスト残渣（スカムとも称される。）が発生する。基板材上にこのようなレジスト残渣があると、フォトレジストの解像度が低下して導体パターンの高精細化を妨げることになる。また、導体パターンの側面下部において、導体パターン底面と基板材表面との間に隙間（アンダーカット部）が生じて導体パターンの密着性が低下し、製品の信頼性に影響を与えるおそれがある。
In this development process, in the case of a negative dry film resist, the photoresist material in the exposed area absorbs the developer and swells, sometimes forming bridges between the resist patterns. If the processing time of the developing step is shortened in order to avoid this problem, undeveloped portions of the photoresist material may remain undeveloped. As a result, resist residues (also referred to as scum) are generated, such as unintended resist trailing portions on the side surfaces of the resist pattern and photoresist material remaining in unexposed portions on the substrate material. If such a resist residue remains on the substrate material, the resolution of the photoresist is lowered, which hinders the improvement of the fineness of the conductor pattern. In addition, at the lower part of the side surface of the conductor pattern, a gap (undercut portion) is generated between the bottom surface of the conductor pattern and the surface of the substrate material, which may reduce the adhesion of the conductor pattern and affect the reliability of the product.
そこで、基板材上からレジスト残渣を除去する簡便な方法として、レジスト残渣除去液を用いたウエットプロセスが提案されている。例えば、特許文献１には、メルカプト基又は亜硫酸基を有する還元剤及びアニオン性界面活性剤よりなる群から選ばれる化合物を有効成分として含有するレジスト残渣除去液が開示されている。
Therefore, a wet process using a resist residue remover has been proposed as a simple method for removing resist residues from substrate materials. For example, Patent Document 1 discloses a resist residue remover containing, as an active ingredient, a compound selected from the group consisting of a reducing agent having a mercapto group or a sulfite group and an anionic surfactant.
しかし、特許文献１のレジスト残渣除去液を用いてレジスト裾引き部等のレジスト残渣を除去する処理を行うと、目的とする部分が除去できていない場合があり、市場要求に合わない製品が生じるという不具合があった。
However, when the resist residue removal solution of Patent Document 1 is used to remove the resist residue such as the resist skirting portion, the target portion may not be removed, resulting in a product that does not meet the market demand. There was a problem.
本件出願に係る発明は、回路形成用のフォトレジスト材の現像工程で生じるレジスト裾引き部等のレジスト残渣を安定的かつ良好に除去することが可能なレジスト残渣除去液、及びこのレジスト残渣除去液を用いる導体パターン付き基板材の形成方法を提供することを目的とする。
The invention pertaining to the present application is a resist residue remover capable of stably and satisfactorily removing resist residues such as resist footings generated in the development process of a photoresist material for circuit formation, and the resist residue remover. An object of the present invention is to provide a method for forming a substrate material with a conductor pattern using
Ａ．本件出願に係るレジスト残渣除去液
本件出願に係るレジスト残渣除去液は、回路形成用のフォトレジスト材の現像後に用いるものであって、環状オリゴマーが０．０１質量％以上、残部は水の組成を備える。 A. Resist residue remover liquid according to the present application The resist residue remover liquid according to the present application is used after development of a photoresist material for circuit formation, and contains 0.01% by mass or more of a cyclic oligomer and the balance is water. Prepare.
本件出願に係るレジスト残渣除去液は、回路形成用のフォトレジスト材の現像後に用いるものであって、環状オリゴマーが０．０１質量％以上、残部は水の組成を備える。 A. Resist residue remover liquid according to the present application The resist residue remover liquid according to the present application is used after development of a photoresist material for circuit formation, and contains 0.01% by mass or more of a cyclic oligomer and the balance is water. Prepare.
本件出願に係るレジスト残渣除去液において、前記環状オリゴマーは、α－シクロデキストリン、β－シクロデキストリン及びγ－シクロデキストリンからなる群から選択される一種又は二種以上であることが好ましい。
In the resist residue remover according to the present application, the cyclic oligomer is preferably one or more selected from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.
本件出願に係るレジスト残渣除去液において、前記環状オリゴマーは、１２－クラウン－４－エーテル、１５－クラウン－５－エーテル、１８－クラウン－６－エーテル、２４－クラウン－８－エーテル、カリックス［４］アレーン、カリックス［６］アレーン及びカリックス［８］アレーンからなる群から選択される一種又は二種以上であることが好ましい。
In the resist residue remover according to the present application, the cyclic oligomer includes 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, 24-crown-8-ether, calix[4 ]arene, calix[6]arene and calix[8]arene.
本件出願に係るレジスト残渣除去液は、アルカリ成分を０．００１質量％～１質量％含むことが好ましい。
The resist residue remover according to the present application preferably contains 0.001% by mass to 1% by mass of an alkaline component.
本件出願に係るレジスト残渣除去液において、前記アルカリ成分は、炭酸ナトリウム、テトラメチルアンモニウム及び水酸化ナトリウムからなる群から選択される一種又は二種以上であることが好ましい。
In the resist residue remover according to the present application, the alkaline component is preferably one or more selected from the group consisting of sodium carbonate, tetramethylammonium and sodium hydroxide.
Ｂ．本件出願に係るレジスト残渣除去液を用いる導体パターン付き基板材の形成方法
本件出願に係る導体パターン付き基板材の形成方法は、上述のレジスト残渣除去液を用いる方法であって、以下の工程Ａ～工程Ｃを含むことを特徴とする。
工程Ａ： 基板材の表面にレジストパターンを施してレジストパターン付き基板材を得たのち、該表面を該レジスト残渣除去液と接触させて処理するレジスト残渣除去工程。
工程Ｂ： 工程Ａで得たレジストパターン付き基板材の表面に無電解めっきを施して金属皮膜付き基板材を得る無電解めっき工程。
工程Ｃ： 工程Ｂで得た金属皮膜付き基板材の表面からレジストパターンを除去して金属皮膜からなる導体パターン付き基板材を得るレジスト除去工程。 B. Method for forming a substrate material with a conductive pattern using the resist residue remover according to the present application The method for forming a substrate material with a conductive pattern according to the present application is a method using the above-described resist residue remover, and includes the following steps A to It is characterized by including step C.
Process A: A resist residue removing process in which a resist pattern is applied to the surface of a substrate material to obtain a substrate material with a resist pattern, and then the surface is brought into contact with the resist residue remover.
Step B: An electroless plating step of applying electroless plating to the surface of the substrate material with the resist pattern obtained in step A to obtain a substrate material with a metal film.
Step C: A resist removing step of removing the resist pattern from the surface of the substrate material with the metal film obtained in the step B to obtain a substrate material with a conductive pattern made of a metal film.
本件出願に係る導体パターン付き基板材の形成方法は、上述のレジスト残渣除去液を用いる方法であって、以下の工程Ａ～工程Ｃを含むことを特徴とする。
工程Ａ： 基板材の表面にレジストパターンを施してレジストパターン付き基板材を得たのち、該表面を該レジスト残渣除去液と接触させて処理するレジスト残渣除去工程。
工程Ｂ： 工程Ａで得たレジストパターン付き基板材の表面に無電解めっきを施して金属皮膜付き基板材を得る無電解めっき工程。
工程Ｃ： 工程Ｂで得た金属皮膜付き基板材の表面からレジストパターンを除去して金属皮膜からなる導体パターン付き基板材を得るレジスト除去工程。 B. Method for forming a substrate material with a conductive pattern using the resist residue remover according to the present application The method for forming a substrate material with a conductive pattern according to the present application is a method using the above-described resist residue remover, and includes the following steps A to It is characterized by including step C.
Process A: A resist residue removing process in which a resist pattern is applied to the surface of a substrate material to obtain a substrate material with a resist pattern, and then the surface is brought into contact with the resist residue remover.
Step B: An electroless plating step of applying electroless plating to the surface of the substrate material with the resist pattern obtained in step A to obtain a substrate material with a metal film.
Step C: A resist removing step of removing the resist pattern from the surface of the substrate material with the metal film obtained in the step B to obtain a substrate material with a conductive pattern made of a metal film.
本件出願に係る導体パターン付き基板材の形成方法において、前記工程Ａは、前記レジスト残渣除去液による処理をスプレー噴霧により行うことが好ましい。
In the method of forming a substrate material with a conductive pattern according to the present application, it is preferable that in the step A, the treatment with the resist residue remover is performed by spraying.
本件出願に係る発明によれば、回路形成用のフォトレジスト材の現像工程で生じるレジスト裾引き部等のレジスト残渣を安定的かつ良好に除去することが可能なレジスト残渣除去液を提供することができる。そして、このレジスト残渣除去液を用いることにより、アンダーカット部が極めて発生しにくい導体パターン付き基板材の形成方法を提供することができる。
According to the invention of the present application, it is possible to provide a resist residue remover capable of stably and satisfactorily removing resist residues such as resist skirting portions generated in the development process of a photoresist material for circuit formation. can. Further, by using this resist residue remover, it is possible to provide a method of forming a substrate material with a conductive pattern in which an undercut portion is extremely unlikely to occur.
Ａ．本件出願に係るレジスト残渣除去液の形態
本件出願に係るレジスト残渣除去液は、基本的に環状オリゴマー及び水の組成を備える。以下では、このレジスト残渣除去液について、主としてネガ型のドライフィルムレジストを用いた場合を想定して説明する。本件出願において、レジスト残渣とは、プリント配線板の回路形成工程等におけるフォトレジスト材の現像工程で生じる、レジストパターン側面のレジスト裾引き部、レジストパターン表面上の未硬化のレジスト付着物及び、基板材上の未露光部のレジスト付着物等の意図しないレジスト残存物等をいう。また、レジスト残渣除去液とは、現像工程後に基板材上に残存する当該レジスト残渣を除去するための薬液をいう。このレジスト残渣除去液が上述の成分を含むものであると、フォトレジスト材の現像工程で生じるレジスト裾引き部等のレジスト残渣を安定的かつ良好に除去することができる。 A. Form of resist residue remover according to the present application The resist residue remover according to the present application basically comprises a cyclic oligomer and water. In the following, the resist residue remover will be described mainly assuming that a negative dry film resist is used. In this application, the resist residue means the resist trailing part on the side of the resist pattern, the uncured resist deposit on the resist pattern surface, and the substrate, which are generated in the development process of the photoresist material in the circuit formation process of the printed wiring board. This refers to unintended resist residue such as resist deposits on unexposed areas on a plate. Further, the resist residue remover means a chemical solution for removing the resist residue remaining on the substrate material after the development process. When the resist residue remover contains the above components, it is possible to stably and satisfactorily remove the resist residue such as the resist skirting portion generated in the developing step of the photoresist material.
本件出願に係るレジスト残渣除去液は、基本的に環状オリゴマー及び水の組成を備える。以下では、このレジスト残渣除去液について、主としてネガ型のドライフィルムレジストを用いた場合を想定して説明する。本件出願において、レジスト残渣とは、プリント配線板の回路形成工程等におけるフォトレジスト材の現像工程で生じる、レジストパターン側面のレジスト裾引き部、レジストパターン表面上の未硬化のレジスト付着物及び、基板材上の未露光部のレジスト付着物等の意図しないレジスト残存物等をいう。また、レジスト残渣除去液とは、現像工程後に基板材上に残存する当該レジスト残渣を除去するための薬液をいう。このレジスト残渣除去液が上述の成分を含むものであると、フォトレジスト材の現像工程で生じるレジスト裾引き部等のレジスト残渣を安定的かつ良好に除去することができる。 A. Form of resist residue remover according to the present application The resist residue remover according to the present application basically comprises a cyclic oligomer and water. In the following, the resist residue remover will be described mainly assuming that a negative dry film resist is used. In this application, the resist residue means the resist trailing part on the side of the resist pattern, the uncured resist deposit on the resist pattern surface, and the substrate, which are generated in the development process of the photoresist material in the circuit formation process of the printed wiring board. This refers to unintended resist residue such as resist deposits on unexposed areas on a plate. Further, the resist residue remover means a chemical solution for removing the resist residue remaining on the substrate material after the development process. When the resist residue remover contains the above components, it is possible to stably and satisfactorily remove the resist residue such as the resist skirting portion generated in the developing step of the photoresist material.
Ａ－１．環状オリゴマー
本件出願のレジスト残渣除去液が含有する環状オリゴマーは、回路形成用のフォトレジスト材の現像工程で生じるレジスト残渣を除去するための主剤である。この環状オリゴマーの種類に特段の制限はない。 A-1. Cyclic Oligomer The cyclic oligomer contained in the resist residue remover of the present application is a main ingredient for removing resist residue generated in the development process of a photoresist material for circuit formation. There are no particular restrictions on the type of this cyclic oligomer.
本件出願のレジスト残渣除去液が含有する環状オリゴマーは、回路形成用のフォトレジスト材の現像工程で生じるレジスト残渣を除去するための主剤である。この環状オリゴマーの種類に特段の制限はない。 A-1. Cyclic Oligomer The cyclic oligomer contained in the resist residue remover of the present application is a main ingredient for removing resist residue generated in the development process of a photoresist material for circuit formation. There are no particular restrictions on the type of this cyclic oligomer.
ここで、上述の環状オリゴマーとして、シクロデキストリン類、クラウンエーテル類、カリックスアレーン類が挙げられる。以下ではまず、環状オリゴマーにシクロデキストリンを用いる場合について説明する。シクロデキストリンは、工業的に広く用いられる物質であって、代表的には結合するブドウ糖の数によってα（６量体）、β（７量体）、γ（８量体）の三種類が存在する。本件出願のレジスト残渣除去液に用いるシクロデキストリンの種類には、特段の制限はない。そのため、本件出願のレジスト残渣除去液は、α－シクロデキストリン、β－シクロデキストリン及びγ－シクロデキストリン等のいずれかのシクロデキストリンのうち少なくとも一つを含有していればよい。
Here, the above-mentioned cyclic oligomers include cyclodextrins, crown ethers, and calixarenes. First, the case where cyclodextrin is used as the cyclic oligomer will be described below. Cyclodextrin is a substance widely used industrially, and there are typically three types of α (hexamer), β (7mer), and γ (octamer) depending on the number of bound glucose. do. The type of cyclodextrin used in the resist residue remover of the present application is not particularly limited. Therefore, the resist residue remover of the present application may contain at least one cyclodextrin such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.
また、本件出願のレジスト残渣除去液が含有する環状オリゴマーであるシクロデキストリンは、β又はγのシクロデキストリンであることが好ましく、β－シクロデキストリンであることがより好ましい。β又はγのシクロデキストリンを含有するレジスト残渣除去液であれば、より安定的に再現性良くレジスト残渣を除去することができ、また、β－シクロデキストリンを含有するレジスト残渣除去液であれば、最も安定的に当該効果を得ることができるためである。
In addition, the cyclic oligomer cyclodextrin contained in the resist residue removing solution of the present application is preferably β or γ cyclodextrin, more preferably β-cyclodextrin. A resist residue remover containing β or γ cyclodextrin can more stably remove resist residues with good reproducibility, and a resist residue remover containing β-cyclodextrin can This is because the effect can be obtained most stably.
そして、このシクロデキストリンの含有量は、０．０１質量％以上であることが好ましい。シクロデキストリンの含有量が０．０１質量％未満であると、現像工程で生じるレジスト残渣を安定的に除去できない傾向にあるため好ましくない。シクロデキストリンの含有量の上限値に特段の制限はないが、溶媒である水への溶解度を超えても、レジスト残渣除去性能が向上するものでもなく、単なる資源の無駄となるため好ましくない。そのため、実験的にみれば、本件出願のレジスト残渣除去液が、シクロデキストリンを２０質量％を超えて含有していても仕方がないと理解できる。ただし、これらの数値は、不可避不純物を含まないものとして記載している。
And the content of this cyclodextrin is preferably 0.01% by mass or more. If the content of cyclodextrin is less than 0.01% by mass, it is not preferable because the resist residue generated in the development process tends to be unable to be stably removed. Although there is no particular upper limit for the content of cyclodextrin, exceeding the solubility in water, which is the solvent, does not improve the resist residue removal performance and is simply a waste of resources, which is undesirable. Therefore, experimentally, it can be understood that there is no point in containing more than 20% by mass of cyclodextrin in the resist residue remover of the present application. However, these numerical values are described assuming that they do not include unavoidable impurities.
次に、環状オリゴマーにクラウンエーテル、カリックスアレーンを用いる場合について説明する。本件出願のレジスト残渣除去液に用いるクラウンエーテル、カリックスアレーンの種類には、特段の制限はない。そのため、工業的に入手が容易な１２－クラウン－４－エーテル、１５－クラウン－５－エーテル、１８－クラウン－６－エーテル、２４－クラウン－８－エーテル、カリックス［４］アレーン、カリックス［６］アレーン及びカリックス［８］アレーン等の化合物のうち少なくとも一つを含有していればよい
Next, the case where crown ether and calixarene are used as cyclic oligomers will be explained. There are no particular restrictions on the types of crown ethers and calixarene used in the resist residue remover of the present application. Therefore, industrially easily available 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, 24-crown-8-ether, calix[4]arene, calix[6 ] at least one of compounds such as arene and calix [8] arene
また、上述の環状オリゴマーとしてクラウンエーテルを採用する場合は、１８－クラウン－６－エーテルであることが好ましい。１８－クラウン－６－エーテルは比較的安価であるためコスト面で優れていると共に、当該物質を含有するレジスト残渣除去液は、より安定的に再現性良くレジスト残渣を除去することができるためである。
Also, when a crown ether is employed as the above-mentioned cyclic oligomer, it is preferably 18-crown-6-ether. This is because 18-crown-6-ether is relatively inexpensive and therefore excellent in terms of cost, and a resist residue remover containing the substance can more stably and reproducibly remove resist residues. be.
そして、クラウンエーテルの含有量は、０．０１質量％～５質量％であることが好ましい。クラウンエーテルの含有量が０．０１質量％未満であると、現像工程で生じるレジスト残渣を安定的に除去できない傾向にあるため好ましくない。クラウンエーテルの含有量の上限値については、上述のシクロデキストリンと同様に特段の制限はないものの、含有量が５質量％を超えると、溶媒である水に対する溶解度を超過する一方でレジスト残渣除去性能が向上するものでもなく、単なる資源の無駄となるため好ましくない。ただし、これらの数値は、不可避不純物を含まないものとして記載している。
The crown ether content is preferably 0.01% by mass to 5% by mass. A crown ether content of less than 0.01% by mass is not preferable because it tends to make it impossible to stably remove resist residues generated in the development process. The upper limit of the crown ether content is not particularly limited as in the case of the cyclodextrin described above. It is not desirable because it does not improve performance and is a mere waste of resources. However, these numerical values are described assuming that they do not include unavoidable impurities.
カリックスアレーンの含有量は、０．０１質量％～５質量％であることが好ましい。カリックスアレーンの含有量が０．０１質量％未満であると、現像工程で生じるレジスト残渣を安定的に除去できない傾向にあるため好ましくない。カリックスアレーンの含有量の上限値については、上述のシクロデキストリンと同様に特段の制限はないものの、含有量が５質量％を超えると、溶媒である水に対する溶解度を超過する一方でレジスト残渣除去性能が向上するものでもなく、単なる資源の無駄となるため好ましくない。ただし、これらの数値は、不可避不純物を含まないものとして記載している。
The content of calixarene is preferably 0.01% by mass to 5% by mass. If the content of calixarene is less than 0.01% by mass, it tends to be difficult to stably remove resist residues generated in the development step, which is not preferable. The upper limit of the content of calixarene is not particularly limited as in the case of cyclodextrin described above. It is not desirable because it does not improve performance and is a mere waste of resources. However, these numerical values are described assuming that they do not include unavoidable impurities.
Ａ－２．アルカリ成分
本件出願のレジスト残渣除去液は、アルカリ成分を含有してもよい。回路基板形成用のフォトレジスト材の現像工程で用いる現像剤液には、炭酸ナトリウム等のアルカリ成分が主剤として用いられている。このアルカリ成分が、基板材上に残存するなどしてレジスト残渣除去工程に持ち込まれると、当該工程の処理溶液中に、このアルカリ成分が混入し、処理溶液であるレジスト残渣除去液のｐＨが変動して安定的に処理を行うことが困難になる。そのため、レジスト残渣除去液が上述のアルカリ成分を予め含むものであると、レジスト残渣除去工程時に、レジスト残渣除去液のｐＨ変動を抑制することができ、より安定的かつ良好にレジスト残渣除去効果を得ることができる。 A-2. Alkaline component The resist residue remover of the present application may contain an alkaline component. An alkali component such as sodium carbonate is used as a main component in a developer solution used in the development process of a photoresist material for forming a circuit board. When this alkaline component remains on the substrate material and is brought into the resist residue removing process, the alkaline component is mixed in the processing solution in the process, and the pH of the resist residue removing solution, which is the processing solution, fluctuates. Therefore, it becomes difficult to perform stable processing. Therefore, if the resist residue remover contains the above-described alkaline component in advance, it is possible to suppress pH fluctuations of the resist residue remover during the resist residue removal step, and to obtain a more stable and favorable resist residue removal effect. can be done.
本件出願のレジスト残渣除去液は、アルカリ成分を含有してもよい。回路基板形成用のフォトレジスト材の現像工程で用いる現像剤液には、炭酸ナトリウム等のアルカリ成分が主剤として用いられている。このアルカリ成分が、基板材上に残存するなどしてレジスト残渣除去工程に持ち込まれると、当該工程の処理溶液中に、このアルカリ成分が混入し、処理溶液であるレジスト残渣除去液のｐＨが変動して安定的に処理を行うことが困難になる。そのため、レジスト残渣除去液が上述のアルカリ成分を予め含むものであると、レジスト残渣除去工程時に、レジスト残渣除去液のｐＨ変動を抑制することができ、より安定的かつ良好にレジスト残渣除去効果を得ることができる。 A-2. Alkaline component The resist residue remover of the present application may contain an alkaline component. An alkali component such as sodium carbonate is used as a main component in a developer solution used in the development process of a photoresist material for forming a circuit board. When this alkaline component remains on the substrate material and is brought into the resist residue removing process, the alkaline component is mixed in the processing solution in the process, and the pH of the resist residue removing solution, which is the processing solution, fluctuates. Therefore, it becomes difficult to perform stable processing. Therefore, if the resist residue remover contains the above-described alkaline component in advance, it is possible to suppress pH fluctuations of the resist residue remover during the resist residue removal step, and to obtain a more stable and favorable resist residue removal effect. can be done.
ここで、上述のアルカリ成分として、現像剤液の主剤として公知である炭酸ナトリウム、テトラメチルアンモニウム、水酸化ナトリウム等が挙げられる。本件出願のレジスト残渣除去液がアルカリ成分を含有する場合、これらのアルカリ化合物のうち少なくとも一種を含有していればよい。そして、このアルカリ成分の含有量は、０．００１質量％～１質量％であることが好ましい。アルカリ成分の含有量が０．００１質量％未満であると、処理溶液のｐＨ変動を抑制する効果が得られないため好ましくない。一方、アルカリ成分の含有量が１質量％を超えると、レジストパターンに対する意図しない浸食がおこる傾向にあり、レジスト残渣除去性能も向上しないため好ましくない。ただし、これらの数値は、不可避不純物を含まないものとして記載している。
Here, examples of the above-mentioned alkaline component include sodium carbonate, tetramethylammonium, sodium hydroxide, etc., which are known as main ingredients of developer solutions. When the resist residue remover of the present application contains an alkaline component, it may contain at least one of these alkaline compounds. The content of this alkaline component is preferably 0.001% by mass to 1% by mass. If the content of the alkali component is less than 0.001% by mass, the effect of suppressing pH fluctuation of the processing solution cannot be obtained, which is not preferable. On the other hand, if the content of the alkali component exceeds 1% by mass, the resist pattern tends to be unintentionally eroded, and the resist residue removal performance is not improved, which is not preferable. However, these numerical values are described assuming that they do not include unavoidable impurities.
Ａ－３．レジスト残渣除去液の調製方法
本件出願に係るレジスト残渣除去液の調製方法について、簡単に説明する。本件出願のレジスト残渣除去液は、従来公知の方法を用いて調製すればよい。例えば、溶媒である水にシクロデキストリン等の環状オリゴマーを接触させ、攪拌器等を用いて攪拌を行い溶解して得ることができる。ここで、レジスト残渣除去液の調製に際し、必要に応じて予め当該レジスト残渣除去液に消泡剤等を加えることもできる。また、当該レジスト残渣除去液における水の温度は、シクロデキストリン等の環状オリゴマーの溶解促進等の目的で、室温又は６０℃以下の温度とすることができる。 A-3. Method for Preparing Resist Residue Remover Solution A method for preparing the resist residue remover solution according to the present application will be briefly described. The resist residue remover of the present application may be prepared using a conventionally known method. For example, it can be obtained by bringing a cyclic oligomer such as cyclodextrin into contact with water, which is a solvent, and stirring it using a stirrer or the like to dissolve it. Here, when preparing the resist residue remover, an antifoaming agent or the like can be added in advance to the resist residue remover as necessary. The temperature of water in the resist residue remover can be room temperature or 60° C. or lower for the purpose of promoting dissolution of cyclic oligomers such as cyclodextrin.
本件出願に係るレジスト残渣除去液の調製方法について、簡単に説明する。本件出願のレジスト残渣除去液は、従来公知の方法を用いて調製すればよい。例えば、溶媒である水にシクロデキストリン等の環状オリゴマーを接触させ、攪拌器等を用いて攪拌を行い溶解して得ることができる。ここで、レジスト残渣除去液の調製に際し、必要に応じて予め当該レジスト残渣除去液に消泡剤等を加えることもできる。また、当該レジスト残渣除去液における水の温度は、シクロデキストリン等の環状オリゴマーの溶解促進等の目的で、室温又は６０℃以下の温度とすることができる。 A-3. Method for Preparing Resist Residue Remover Solution A method for preparing the resist residue remover solution according to the present application will be briefly described. The resist residue remover of the present application may be prepared using a conventionally known method. For example, it can be obtained by bringing a cyclic oligomer such as cyclodextrin into contact with water, which is a solvent, and stirring it using a stirrer or the like to dissolve it. Here, when preparing the resist residue remover, an antifoaming agent or the like can be added in advance to the resist residue remover as necessary. The temperature of water in the resist residue remover can be room temperature or 60° C. or lower for the purpose of promoting dissolution of cyclic oligomers such as cyclodextrin.
Ｂ．本件出願に係るレジスト残渣除去液を用いる導体パターン付き基板材の形成方法の形態
本件出願に係る導体パターン付き基板材の形成方法は、上述のレジスト残渣除去液を用いる方法であって、以下の工程Ａ～工程Ｃを含むものである。 B. Form of method for forming a substrate material with a conductive pattern using the resist residue remover according to the present application The method for forming a substrate material with a conductive pattern according to the present application is a method using the above-described resist residue remover, comprising the following steps: It includes steps A to C.
本件出願に係る導体パターン付き基板材の形成方法は、上述のレジスト残渣除去液を用いる方法であって、以下の工程Ａ～工程Ｃを含むものである。 B. Form of method for forming a substrate material with a conductive pattern using the resist residue remover according to the present application The method for forming a substrate material with a conductive pattern according to the present application is a method using the above-described resist residue remover, comprising the following steps: It includes steps A to C.
工程Ａ： 基板材の表面にレジストパターンを施してレジストパターン付き基板材を得たのち、該表面を該レジスト残渣除去液と接触させて処理するレジスト残渣除去工程。
Process A: A resist residue removal process in which a resist pattern is applied to the surface of a substrate material to obtain a substrate material with a resist pattern, and then the surface is brought into contact with the resist residue remover for treatment.
ここで、上述の工程Ａにおける、レジスト残渣除去液による基板材表面の処理方法としては、スプレー噴霧、浸漬等が挙げられる。このうちスプレー噴霧は、レジスト残渣除去液に基板材表面を接触させて静置又は揺動させる浸漬法と比べて、より精密なレジストパターン付き基板材表面に対しても隅々まで当該除去液を接触させることができるため好ましい。また、噴霧に用いるスプレー装置のノズルがスリット形状であると、より効率的に基板材表面にレジスト残渣除去液を接触させることができるため好ましい。
Here, the method of treating the surface of the substrate material with the resist residue remover in the above-described step A includes spraying, immersion, and the like. Among these methods, spray spraying is more effective than the immersion method in which the surface of the substrate material is brought into contact with the resist residue remover and left stationary or shaken. It is preferable because it can be brought into contact. Further, it is preferable that the nozzle of the spray device used for the spraying has a slit shape, since the resist residue removing liquid can be brought into contact with the surface of the substrate material more efficiently.
そして、上述の工程Ａにおける、レジスト残渣除去液による基板材表面の処理時間は、５秒間～１０分間であることが好ましい。処理時間が５秒間より短いと、レジスト残渣除去効果が得られない傾向にあるため好ましくない。一方、処理時間が１０分間を超えても、レジスト残渣除去性能が向上するものでもなく、製品の生産性を低下させる要因となるため好ましくない。更に、上述の工程Ａにおけるレジスト残渣除去液の液温は、１５℃～４０℃であることが好ましい。液温が１５℃より低いと、レジスト残渣除去性能が低下する傾向にあるため好ましくない。一方、液温が４０℃を超えると、レジストパターンに対する意図しない浸食がおこる傾向にあり、レジスト残渣除去性能も向上しないため好ましくない。次に、工程Ｂ及び工程Ｃについて説明する。
In the above step A, the treatment time of the substrate material surface with the resist residue remover is preferably 5 seconds to 10 minutes. If the treatment time is shorter than 5 seconds, the effect of removing the resist residue tends not to be obtained, which is not preferable. On the other hand, even if the treatment time exceeds 10 minutes, the resist residue removing performance is not improved, and it is a factor in lowering the productivity of the product, which is not preferable. Furthermore, it is preferable that the liquid temperature of the resist residue remover in the above step A is 15.degree. C. to 40.degree. If the liquid temperature is lower than 15° C., the resist residue removing performance tends to be lowered, which is not preferable. On the other hand, if the liquid temperature exceeds 40° C., the resist pattern tends to be unintentionally corroded, and the resist residue removing performance is not improved, which is not preferable. Next, process B and process C will be described.
工程Ｂ： 上述の工程Ａで得たレジストパターン付き基板材の表面に無電解めっきを施して金属皮膜付き基板材を得る無電解めっき工程。
工程Ｃ： 工程Ｂで得た金属皮膜付き基板材の表面からレジストパターンを除去して金属皮膜からなる導体パターン付き基板材を得るレジスト除去工程。 Step B: An electroless plating step of applying electroless plating to the surface of the substrate material with the resist pattern obtained in the above step A to obtain a substrate material with a metal film.
Step C: A resist removing step of removing the resist pattern from the surface of the substrate material with the metal film obtained in the step B to obtain a substrate material with a conductive pattern made of a metal film.
工程Ｃ： 工程Ｂで得た金属皮膜付き基板材の表面からレジストパターンを除去して金属皮膜からなる導体パターン付き基板材を得るレジスト除去工程。 Step B: An electroless plating step of applying electroless plating to the surface of the substrate material with the resist pattern obtained in the above step A to obtain a substrate material with a metal film.
Step C: A resist removing step of removing the resist pattern from the surface of the substrate material with the metal film obtained in the step B to obtain a substrate material with a conductive pattern made of a metal film.
上述の工程Ｂ及び工程Ｃには、公知の方法を採用すればよく、処理条件等に特段の制限はない。そのため、工程Ｂの無電解めっき処理は、基板材表面に市販の無電解銅めっき液等を浸漬等の方法で接触させて行えばよい。また、工程Ｃのレジストパターン除去処理は、基板材表面に市販のアルカリ性レジスト材除去液等をスプレー噴霧、浸漬等により接触させて行うことができる。
A known method may be adopted for the above-mentioned steps B and C, and there are no particular restrictions on the treatment conditions. Therefore, the electroless plating treatment in step B may be performed by bringing a commercially available electroless copper plating solution or the like into contact with the surface of the substrate material by a method such as immersion. In addition, the resist pattern removing treatment in step C can be carried out by bringing a commercially available alkaline resist material removing liquid or the like into contact with the surface of the substrate material by spraying, immersion, or the like.
以下に、本件出願に係る発明について、実施例を示して具体的に説明する。ただし、本件出願に係る発明は、これらの実施例に限定されるものではない。
Below, the invention pertaining to this application will be specifically explained with examples. However, the invention according to the present application is not limited to these examples.
実施例１では、α－シクロデキストリンが０．１質量％、残部がイオン交換水であるレジスト残渣除去液（即ち、濃度０．１質量％のα－シクロデキストリン水溶液）を用いて以下の試験を行った。まず、エポキシ系樹脂からなる樹脂板の上に銅層を設けた基板材を用意し、当該基板材の上にネガ型のドライフィルムレジスト（ニッコー・マテリアルズ株式会社製のＬＤＦ５２５Ｆ、膜厚２５μｍ）を配置した。このフォトレジスト材の上に試験回路パターン形成用のマスク基板を配置し、ダイレクト露光装置（株式会社オーク製作所製のＦＤｉ－３Ｍ）により水銀ランプのｈ線の光（波長４０５ｎｍ、光強度９５ｍＪ／ｃｍ２）を照射して露光を行った。次いで、この基板材上に３０℃の現像剤液（濃度１質量％の炭酸ナトリウム水溶液）を０．１５ＭＰａで３８秒間スプレー噴霧し、未露光部のフォトレジスト材を除去して現像を行った。
In Example 1, the following tests were carried out using a resist residue remover containing 0.1% by mass of α-cyclodextrin and the balance being deionized water (that is, an aqueous solution of α-cyclodextrin with a concentration of 0.1% by mass). gone. First, a substrate material having a copper layer provided on a resin plate made of epoxy resin is prepared, and a negative dry film resist (LDF525F manufactured by Nikko Materials Co., Ltd., film thickness 25 μm) is placed on the substrate material. was placed. A mask substrate for forming a test circuit pattern is placed on the photoresist material, and a direct exposure device (FDi-3M manufactured by Oak Manufacturing Co., Ltd.) is used to emit h-line light from a mercury lamp (wavelength 405 nm, light intensity 95 mJ / cm). 2 ) was irradiated for exposure. Subsequently, a developer solution (aqueous solution of sodium carbonate having a concentration of 1% by mass) at 30° C. was sprayed onto the substrate material at 0.15 MPa for 38 seconds to remove the unexposed portion of the photoresist material for development.
次に、この現像後の基板材に対して、上述の成分を有するレジスト残渣除去液を室温且つ０．２０ＭＰａで６０秒間スプレー噴霧した後水洗し、レジストパターンを表面に有する基板材を得た。なお、この水洗処理は、室温のイオン交換水を基板材に対して０．１０ＭＰａで６０秒間スプレー噴霧して行った。また、上述の現像、レジスト残渣除去及び水洗の各工程で用いたスプレー装置には、スリット形状のノズルを有するものを使用した。
Next, the substrate material after the development was sprayed with a resist residue remover containing the above components at room temperature and 0.20 MPa for 60 seconds, and then washed with water to obtain a substrate material having a resist pattern on its surface. This water washing treatment was carried out by spraying deionized water at room temperature onto the substrate material at 0.10 MPa for 60 seconds. The spray device used in the above-described steps of development, resist residue removal, and water washing had a slit-shaped nozzle.
続いて、上述のレジストパターン付き基板材を酸性脱脂剤（メルテックス株式会社製のメルプレートＣＬ－２０００）に浸漬した後水洗し、濃度１０質量％の硫酸により酸洗浄を行った。この基板材を硫酸銅めっき液（メルテックス株式会社製のルーセントカパーＰＶＦ）に浸漬した後水洗し、銅皮膜を表面に有する基板材を得た。そして、この基板材をレジスト材除去液（メルテックス株式会社製のメルストリップＤＦ－３８５０）に浸漬してレジストパターンを除去した後水洗し、導体パターンを表面に有する基板材を得た。
Subsequently, the above substrate material with a resist pattern was immersed in an acidic degreasing agent (Melplate CL-2000 manufactured by Meltex Inc.), washed with water, and acid washed with sulfuric acid having a concentration of 10% by mass. This substrate material was immersed in a copper sulfate plating solution (Lucent Copper PVF manufactured by Meltex Co., Ltd.) and then washed with water to obtain a substrate material having a copper film on its surface. Then, this substrate material was immersed in a resist material removing liquid (Melstrip DF-3850 manufactured by Meltex Co., Ltd.) to remove the resist pattern and then washed with water to obtain a substrate material having a conductor pattern on its surface.
実施例２では、上述の実施例１のレジスト残渣除去液に替えて、β－シクロデキストリンが０．１質量％、残部がイオン交換水であるレジスト残渣除去液を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。
In Example 2, a test was performed using a resist residue remover containing 0.1% by mass of β-cyclodextrin and the balance being deionized water instead of the resist residue remover of Example 1 described above. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
実施例３では、上述の実施例１のレジスト残渣除去液に替えて、γ－シクロデキストリンが０．１質量％、残部がイオン交換水であるレジスト残渣除去液を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。
In Example 3, instead of the resist residue remover of Example 1, a test was performed using a resist residue remover containing 0.1% by mass of γ-cyclodextrin and the balance being deionized water. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
実施例４では、上述の実施例１のレジスト残渣除去液に替えて、１８－クラウン－６－エーテルが０．１質量％、残部がイオン交換水であるレジスト残渣除去液を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。
In Example 4, instead of the resist residue remover of Example 1, a test was performed using a resist residue remover containing 0.1% by mass of 18-crown-6-ether and the balance being deionized water. rice field. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
実施例５では、上述の実施例１のレジスト残渣除去液に替えて、α－シクロデキストリンが０．１質量％、炭酸ナトリウムが０．２質量％、残部がイオン交換水であるレジスト残渣除去液を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。
In Example 5, instead of the resist residue remover of Example 1, a resist residue remover containing 0.1% by mass of α-cyclodextrin, 0.2% by mass of sodium carbonate, and the balance being deionized water was used. was tested using Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
実施例６では、上述の実施例１のレジスト残渣除去液に替えて、β－シクロデキストリンが０．１質量％、炭酸ナトリウムが０．２質量％、残部がイオン交換水であるレジスト残渣除去液を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。
In Example 6, instead of the resist residue remover of Example 1, a resist residue remover containing 0.1% by mass of β-cyclodextrin, 0.2% by mass of sodium carbonate, and the balance being deionized water was used. was tested using Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
実施例７では、上述の実施例１のレジスト残渣除去液に替えて、γ－シクロデキストリンが０．１質量％、炭酸ナトリウムが０．２質量％、残部がイオン交換水であるレジスト残渣除去液を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。
In Example 7, instead of the resist residue remover of Example 1, a resist residue remover containing 0.1% by mass of γ-cyclodextrin, 0.2% by mass of sodium carbonate, and the balance being deionized water was used. was tested using Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
実施例８では、上述の実施例１のレジスト残渣除去液に替えて、１８－クラウン－６－エーテルが０．１質量％、炭酸ナトリウムが０．２質量％、残部がイオン交換水であるレジスト残渣除去液を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。
In Example 8, instead of the resist residue removing solution of Example 1 described above, a resist containing 0.1% by mass of 18-crown-6-ether, 0.2% by mass of sodium carbonate, and the balance being deionized water was used. A test was performed using a residue remover. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
［比較例１］
比較例１では、上述の実施例１における、レジスト残渣除去液の噴霧処理は実施せずに水洗し、試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。 [Comparative Example 1]
In Comparative Example 1, the test was performed by washing with water without performing the spraying treatment of the resist residue remover in Example 1 described above. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
比較例１では、上述の実施例１における、レジスト残渣除去液の噴霧処理は実施せずに水洗し、試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。 [Comparative Example 1]
In Comparative Example 1, the test was performed by washing with water without performing the spraying treatment of the resist residue remover in Example 1 described above. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
［比較例２］
比較例２では、上述の実施例１のレジスト残渣除去液に替えて、チオグリコール酸アンモニウム水溶液（濃度２ｇ／Ｌ）からなるレジスト残渣除去液（上述の特許文献１の実施例３に記載の除去液）を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。 [Comparative Example 2]
In Comparative Example 2, instead of the resist residue remover of Example 1 described above, a resist residue remover consisting of an aqueous ammonium thioglycolate solution (concentration: 2 g/L) (removal described in Example 3 ofPatent Document 1 described above) was used. liquid) was used for the test. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
比較例２では、上述の実施例１のレジスト残渣除去液に替えて、チオグリコール酸アンモニウム水溶液（濃度２ｇ／Ｌ）からなるレジスト残渣除去液（上述の特許文献１の実施例３に記載の除去液）を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。 [Comparative Example 2]
In Comparative Example 2, instead of the resist residue remover of Example 1 described above, a resist residue remover consisting of an aqueous ammonium thioglycolate solution (concentration: 2 g/L) (removal described in Example 3 of
［比較例３］
比較例３では、上述の実施例１のレジスト残渣除去液に替えて、Ｌ－システイン水溶液（濃度１．３ｇ／Ｌ）からなるレジスト残渣除去液（上述の特許文献１の実施例７に記載の除去液）を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。 [Comparative Example 3]
In Comparative Example 3, instead of the resist residue remover of Example 1 described above, a resist residue remover consisting of an L-cysteine aqueous solution (concentration 1.3 g/L) (described in Example 7 ofPatent Document 1 described above) was used. The test was performed using the removal liquid). Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
比較例３では、上述の実施例１のレジスト残渣除去液に替えて、Ｌ－システイン水溶液（濃度１．３ｇ／Ｌ）からなるレジスト残渣除去液（上述の特許文献１の実施例７に記載の除去液）を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。 [Comparative Example 3]
In Comparative Example 3, instead of the resist residue remover of Example 1 described above, a resist residue remover consisting of an L-cysteine aqueous solution (concentration 1.3 g/L) (described in Example 7 of
［比較例４］
比較例４では、上述の実施例１のレジスト残渣除去液に替えて、硫酸マグネシウム水溶液（濃度１ｇ／Ｌ）からなるレジスト残渣除去液を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。 [Comparative Example 4]
In Comparative Example 4, a test was performed using a resist residue remover consisting of an aqueous magnesium sulfate solution (concentration: 1 g/L) instead of the resist residue remover used in Example 1 described above. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
比較例４では、上述の実施例１のレジスト残渣除去液に替えて、硫酸マグネシウム水溶液（濃度１ｇ／Ｌ）からなるレジスト残渣除去液を用いて試験を行った。その他の試験条件は、実施例１と同様であるため記載を省略する。 [Comparative Example 4]
In Comparative Example 4, a test was performed using a resist residue remover consisting of an aqueous magnesium sulfate solution (concentration: 1 g/L) instead of the resist residue remover used in Example 1 described above. Other test conditions are the same as in Example 1, and therefore descriptions thereof are omitted.
実施例及び比較例の試験条件について、理解を容易にするために、表１に各試験で用いたレジスト残渣除去液の内容及びその含有成分の濃度を示す。
In order to facilitate understanding of the test conditions of Examples and Comparative Examples, Table 1 shows the content of the resist residue remover used in each test and the concentrations of its components.
＜実施例と比較例との対比＞
図１～図３に、実施例及び比較例における基板材上のレジストパターンの電子顕微鏡観察像を示す。結果として、図１に示す実施例２のレジストパターンは、側面のレジスト裾引き部や表面上の未硬化のレジスト付着物等のレジスト残渣がなく、目的とする形状かつ滑らかな表面を有するものであった。図示は省略するが、実施例１及び実施例３～実施例８のレジストパターンについても、実施例２と同様に、レジスト残渣のない良好な表面を有するものであることが、電子顕微鏡観察像から確認できた。一方、図２に示す比較例１と、図３に示す比較例２とは、レジスト裾引き部等のレジスト残渣が生じており、特に、比較例２は、レジストパターンの表面に凹凸部を有するものとなった。 <Comparison between Examples and Comparative Examples>
1 to 3 show electron microscope observation images of resist patterns on substrate materials in Examples and Comparative Examples. As a result, the resist pattern of Example 2 shown in FIG. 1 has a desired shape and a smooth surface without resist residues such as resist skirting portions on the side surfaces and uncured resist deposits on the surface. there were. Although not shown, the resist patterns of Examples 1 and 3 to 8 also have good surfaces with no resist residue, as in Example 2, from electron microscope observation images. It could be confirmed. On the other hand, in Comparative Example 1 shown in FIG. 2 and Comparative Example 2 shown in FIG. became a thing.
図１～図３に、実施例及び比較例における基板材上のレジストパターンの電子顕微鏡観察像を示す。結果として、図１に示す実施例２のレジストパターンは、側面のレジスト裾引き部や表面上の未硬化のレジスト付着物等のレジスト残渣がなく、目的とする形状かつ滑らかな表面を有するものであった。図示は省略するが、実施例１及び実施例３～実施例８のレジストパターンについても、実施例２と同様に、レジスト残渣のない良好な表面を有するものであることが、電子顕微鏡観察像から確認できた。一方、図２に示す比較例１と、図３に示す比較例２とは、レジスト裾引き部等のレジスト残渣が生じており、特に、比較例２は、レジストパターンの表面に凹凸部を有するものとなった。 <Comparison between Examples and Comparative Examples>
1 to 3 show electron microscope observation images of resist patterns on substrate materials in Examples and Comparative Examples. As a result, the resist pattern of Example 2 shown in FIG. 1 has a desired shape and a smooth surface without resist residues such as resist skirting portions on the side surfaces and uncured resist deposits on the surface. there were. Although not shown, the resist patterns of Examples 1 and 3 to 8 also have good surfaces with no resist residue, as in Example 2, from electron microscope observation images. It could be confirmed. On the other hand, in Comparative Example 1 shown in FIG. 2 and Comparative Example 2 shown in FIG. became a thing.
次に、図４及び図５として、実施例及び比較例における基板材上の導体パターンの電子顕微鏡観察像を示す。結果として、図４の（Ａ）に示す実施例２と、同図の（Ｂ）～（Ｅ）に示す実施例５～実施例８との導体パターンは、基板材表面と導体パターン底面との間に殆ど隙間が生じておらず、密着性及び製品の信頼性に優れるものであった。図示は省略するが、実施例１、実施例３及び実施例４の導体パターンについても、実施例２及び実施例５～実施例８と同様に、アンダーカット部が殆ど生じない密着性及び製品の信頼性に優れるものであることが、電子顕微鏡観察像から確認できた。一方、図５の（Ａ）に示す比較例１と、同図の（Ｂ）及び（Ｃ）に示す比較例３及び比較例４とは、基板材表面と導体パターン底面との間に、レジストパターンの側面に残存したレジスト裾引き部等に起因する浮きや隙間であるアンダーカット部が生じており、密着性及び製品の信頼性が低いものとなった。
Next, FIGS. 4 and 5 show electron microscope observation images of the conductor patterns on the substrate materials in the example and the comparative example. As a result, the conductor patterns of Example 2 shown in FIG. 4A and Examples 5 to 8 shown in FIGS. There was almost no gap between them, and the adhesiveness and reliability of the product were excellent. Although illustration is omitted, the conductor patterns of Examples 1, 3, and 4, as well as Example 2 and Examples 5 to 8, exhibited adhesion and product quality with almost no undercuts. It was confirmed from an electron microscope observation image that it was excellent in reliability. On the other hand, in Comparative Example 1 shown in FIG. 5A and Comparative Examples 3 and 4 shown in FIGS. Undercut portions, which are floats and gaps, were generated due to resist skirting portions remaining on the side surfaces of the pattern, and the adhesion and reliability of the product were low.
続いて、本件出願のレジスト残渣除去液が有するレジスト裾引き部等のレジスト残渣除去性能をより詳細に評価するために、上述の実施例１～実施例８及び比較例１～比較例４の条件で各３回試験を行い、ドライフィルムレジストの裾引き量及びその数値のばらつきを測定した。ここで、「ドライフィルムレジストの裾引き量」とは、電子顕微鏡観察像に基づき導体パターンの両側面から各々測定した、導体パターンと基板材表面との間に生じた隙間の長さ、即ち導体パターンにおけるアンダーカット部の長さである。図６に、抜粋してその評価結果を示す。実施例２及び実施例５～実施例８の条件で形成した基板材上の導体パターンは、いずれもドライフィルムレジストの裾引き量が０．２μｍ以下と短く、試験ごとの数値のばらつきも小さかった。また、同様に行った上述の他の各試験で得た測定結果によれば、実施例１、実施例３及び実施例４の導体パターンについても、実施例２及び実施例５～実施例８と同様に、ドライフィルムレジストの裾引き量が０．２μｍ以下と短く、試験ごとの数値のばらつきも小さかった。一方、比較例１、比較例３及び比較例４の条件で形成した導体パターンは、ドライフィルムレジストの裾引き量が長く、試験ごとの数値のばらつきも大きかった。
Subsequently, in order to evaluate the resist residue removal performance such as the resist skirting part possessed by the resist residue remover of the present application in more detail, the conditions of Examples 1 to 8 and Comparative Examples 1 to 4 described above , and the amount of skirting of the dry film resist and the variation in the numerical values were measured. Here, the "footing amount of the dry film resist" is the length of the gap generated between the conductor pattern and the substrate material surface, measured from both sides of the conductor pattern based on the electron microscope observation image, that is, the conductor It is the length of the undercut part in the pattern. FIG. 6 shows excerpts of the evaluation results. In the conductor patterns formed on the substrate material under the conditions of Example 2 and Examples 5 to 8, the trailing amount of the dry film resist was as short as 0.2 μm or less, and the variation in numerical values for each test was small. . Further, according to the measurement results obtained in the other tests performed in the same manner, the conductor patterns of Examples 1, 3, and 4 were as good as those of Examples 2 and 5 to 8. Similarly, the amount of footing of the dry film resist was as short as 0.2 μm or less, and the variation in numerical values for each test was small. On the other hand, the conductor patterns formed under the conditions of Comparative Example 1, Comparative Example 3, and Comparative Example 4 had a long trailing amount of the dry film resist, and the variation in numerical values for each test was large.
これらの結果から理解できるように、本件出願のレジスト残渣除去液は、フォトレジスト材の現像工程で生じるレジスト残渣を安定的かつ良好に除去することができた。そして、本件出願のレジスト残渣除去液を用いて現像工程後の基板材を処理することにより、導体パターンにアンダーカット部が極めて発生しにくく基板材表面との密着性及び製品の信頼性が高い導体パターン付き基板材を形成することができた。特に、β－シクロデキストリン又はγ－シクロデキストリンを主剤とするレジスト残渣除去液を採用した実施例２、実施例３、実施例６及び実施例７は、レジスト残渣の除去と、密着性及び製品の信頼性が高い導体パターン付き基板材の形成とにおいて、より優れた効果を奏し、β－シクロデキストリンを主剤とするレジスト残渣除去液を採用した実施例２及び実施例６は、これらの点において最も優れた効果を奏するものであった。
As can be understood from these results, the resist residue remover of the present application was able to stably and satisfactorily remove the resist residue generated in the development process of the photoresist material. Then, by treating the substrate material after the development process using the resist residue remover of the present application, the conductor pattern is extremely unlikely to have an undercut portion, and the conductor has high adhesion to the surface of the substrate material and high product reliability. A substrate material with a pattern could be formed. In particular, Examples 2, 3, 6, and 7, in which a resist residue remover containing β-cyclodextrin or γ-cyclodextrin as a main ingredient, was used for removal of resist residue, adhesion, and product quality. Examples 2 and 6, in which a resist residue remover containing β-cyclodextrin as a main component, is used, exhibiting superior effects in forming a substrate material with a highly reliable conductive pattern, are the most excellent in these respects. It was an excellent effect.
本件出願のレジスト残渣除去液は、フォトレジスト材の現像工程で生じるレジスト裾引き部等、不要な部分に残存するレジスト残渣を安定的かつ良好に除去することができるため、プリント配線基板の回路形成の精度を飛躍的に高めることができ、高品質の回路基板の提供を可能とする。
Since the resist residue remover of the present application can stably and satisfactorily remove the resist residue remaining in unnecessary portions such as the resist skirting portion generated in the development process of the photoresist material, it is suitable for circuit formation of printed wiring boards. accuracy can be dramatically improved, making it possible to provide high-quality circuit boards.
Claims (7)
- 回路形成用のフォトレジスト材の現像後に用いるレジスト残渣除去液であって、
当該レジスト残渣除去液の成分は、環状オリゴマーが０．０１質量％以上、残部は水であることを特徴とするレジスト残渣除去液。 A resist residue remover used after development of a photoresist material for circuit formation,
A resist residue remover comprising a cyclic oligomer of 0.01% by mass or more and a balance of water as a component of the resist residue remover. - 前記環状オリゴマーは、α－シクロデキストリン、β－シクロデキストリン及びγ－シクロデキストリンからなる群から選択される一種又は二種以上である請求項１に記載のレジスト残渣除去液。 The resist residue remover according to claim 1, wherein the cyclic oligomer is one or more selected from the group consisting of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.
- 前記環状オリゴマーは、１２－クラウン－４－エーテル、１５－クラウン－５エーテル、１８－クラウン－６－エーテル、２４－クラウン－８－エーテル、カリックス［４］アレーン、カリックス［６］アレーン及びカリックス［８］アレーンからなる群から選択される一種又は二種以上である請求項１に記載のレジスト残渣除去液。 Said cyclic oligomers are 12-crown-4-ether, 15-crown-5 ether, 18-crown-6-ether, 24-crown-8-ether, calix[4]arene, calix[6]arene and calix[ 8) The resist residue remover according to claim 1, which is one or more selected from the group consisting of arenes.
- アルカリ成分を０．００１質量％～１質量％含む請求項１～請求項３のいずれか一項に記載のレジスト残渣除去液。 The resist residue remover according to any one of claims 1 to 3, which contains 0.001% by mass to 1% by mass of an alkaline component.
- 前記アルカリ成分は、炭酸ナトリウム、テトラメチルアンモニウム及び水酸化ナトリウムからなる群から選択される一種又は二種以上である請求項４に記載のレジスト残渣除去液。 The resist residue remover according to claim 4, wherein the alkali component is one or more selected from the group consisting of sodium carbonate, tetramethylammonium and sodium hydroxide.
- 請求項１～請求項５のいずれかに記載のレジスト残渣除去液を用いる導体パターン付き基板材の形成方法であって、
以下の工程Ａ～工程Ｃを含むことを特徴とする導体パターン付き基板材の形成方法。
工程Ａ： 基板材の表面にレジストパターンを施してレジストパターン付き基板材を得たのち、該表面を該レジスト残渣除去液と接触させて処理するレジスト残渣除去工程。
工程Ｂ： 工程Ａで得たレジストパターン付き基板材の表面に無電解めっきを施して金属皮膜付き基板材を得る無電解めっき工程。
工程Ｃ： 工程Ｂで得た金属皮膜付き基板材の表面からレジストパターンを除去して金属皮膜からなる導体パターン付き基板材を得るレジスト除去工程。 A method for forming a substrate material with a conductive pattern using the resist residue remover according to any one of claims 1 to 5,
A method for forming a substrate material with a conductor pattern, comprising the following steps A to C.
Process A: A resist residue removing process in which a resist pattern is applied to the surface of a substrate material to obtain a substrate material with a resist pattern, and then the surface is brought into contact with the resist residue remover.
Step B: An electroless plating step of applying electroless plating to the surface of the substrate material with the resist pattern obtained in step A to obtain a substrate material with a metal film.
Step C: A resist removing step of removing the resist pattern from the surface of the substrate material with the metal film obtained in the step B to obtain a substrate material with a conductive pattern made of a metal film. - 前記工程Ａは、前記レジスト残渣除去液による処理をスプレー噴霧により行う請求項６に記載の導体パターン形成方法。 The method of forming a conductive pattern according to claim 6, wherein in said step A, the treatment with said resist residue remover is carried out by spraying.
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| KR1020237024623A KR20230122109A (en) | 2021-01-29 | 2021-07-09 | Resist residue removal solution and method for forming a substrate material with a conductor pattern using the same |
| JP2022524038A JP7407479B2 (en) | 2021-01-29 | 2021-07-09 | Resist residue removal solution and method for forming substrate material with conductor pattern using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0194342A (en) * | 1987-10-06 | 1989-04-13 | Mitsubishi Electric Corp | Resist pattern forming method |
| JP2004246107A (en) * | 2003-02-14 | 2004-09-02 | Toppan Printing Co Ltd | Developing liquid for photosensitive resin composition and printed wiring board using the same |
| JP2005181814A (en) * | 2003-12-22 | 2005-07-07 | Matsushita Electric Ind Co Ltd | Method for forming pattern |
| WO2020170632A1 (en) * | 2019-02-21 | 2020-08-27 | 富士フイルム株式会社 | Chemical solution, chemical solution container, method for manufacturing chemical solution, and method for manufacturing semiconductor chip |
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| JP5624753B2 (en) * | 2009-03-31 | 2014-11-12 | 東京応化工業株式会社 | Lithographic cleaning liquid and resist pattern forming method using the same |
| JP7049051B2 (en) | 2016-05-30 | 2022-04-06 | 株式会社Jcu | Resist residue remover, conductor pattern forming method using it, and substrate manufacturing method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0194342A (en) * | 1987-10-06 | 1989-04-13 | Mitsubishi Electric Corp | Resist pattern forming method |
| JP2004246107A (en) * | 2003-02-14 | 2004-09-02 | Toppan Printing Co Ltd | Developing liquid for photosensitive resin composition and printed wiring board using the same |
| JP2005181814A (en) * | 2003-12-22 | 2005-07-07 | Matsushita Electric Ind Co Ltd | Method for forming pattern |
| WO2020170632A1 (en) * | 2019-02-21 | 2020-08-27 | 富士フイルム株式会社 | Chemical solution, chemical solution container, method for manufacturing chemical solution, and method for manufacturing semiconductor chip |
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