WO2021152709A1 - 感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法 - Google Patents
感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法 Download PDFInfo
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- WO2021152709A1 WO2021152709A1 PCT/JP2020/003045 JP2020003045W WO2021152709A1 WO 2021152709 A1 WO2021152709 A1 WO 2021152709A1 JP 2020003045 W JP2020003045 W JP 2020003045W WO 2021152709 A1 WO2021152709 A1 WO 2021152709A1
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- layer
- support film
- meth
- photosensitive
- photosensitive element
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012216 imaging agent Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IRDCEJVOXCGYAV-UHFFFAOYSA-M lithium;2-dodecylbenzenesulfonate Chemical compound [Li+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O IRDCEJVOXCGYAV-UHFFFAOYSA-M 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- RUAIJHHRCIHFEV-UHFFFAOYSA-N methyl 4-amino-5-chlorothiophene-2-carboxylate Chemical compound COC(=O)C1=CC(N)=C(Cl)S1 RUAIJHHRCIHFEV-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/093—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antistatic means, e.g. for charge depletion
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
Definitions
- the present disclosure relates to a method for forming a photosensitive element and a resist pattern, and a method for manufacturing a printed wiring board.
- a layer formed on a support film using a photosensitive resin composition (hereinafter, also referred to as “sensitive layer”) is used.
- the photosensitive element provided is widely used.
- the printed wiring board is manufactured by the following procedure, for example, using a photosensitive element. That is, first, the photosensitive layer of the photosensitive element is laminated on a circuit-forming substrate such as a copper-clad laminate. Next, the photosensitive layer is exposed through a mask film or the like to form a photocurable portion. At this time, the support film is peeled off before or after the exposure. Then, the region other than the photocurable portion of the photosensitive layer is removed with a developing solution to form a resist pattern. Next, using the resist pattern as a resist, an etching treatment or a plating treatment is performed to form a conductor pattern, and finally the photocurable portion (resist pattern) of the photosensitive layer is peeled off (removed).
- a support film having a specified haze value, a support film having a limited lubricant particle size, or the like may be used (see, for example, Patent Documents 1 and 2).
- the resolution required for the photosensitive element and the exposure apparatus used for the circuit formation has increased, and the resist defect (for example, resist chipping) derived from the lubricant of the support film of the photosensitive element or its agglomerate has increased.
- the increase in defects such as) has become a problem. Further, if foreign matter or the like in the air adheres to the surface of the support film on which the photosensitive layer is not formed, resist defect due to the foreign matter or the like adhering to the support film when the photosensitive layer is exposed without peeling off the support film. Is likely to occur.
- An object of the present disclosure is to provide a photosensitive element capable of reducing the occurrence of resist defects, a method for forming a resist pattern using the photosensitive element, and a method for manufacturing a printed wiring board.
- the photosensitive element according to the present disclosure includes a support film and a photosensitive layer formed on the first surface of the support film, and the surface resistivity of the first surface of the support film is 1 ⁇ 10 13 to It is 1 ⁇ 10 17 ⁇ , and the surface resistivity of the second surface opposite to the first surface is 1 ⁇ 10 8 to 1 ⁇ 10 12 ⁇ .
- the method for forming a resist pattern according to the present disclosure includes a laminating step of laminating the photosensitive element on a substrate in this order of a photosensitive layer and a supporting film, and irradiating a predetermined portion of the photosensitive layer with active light through the supporting film to obtain light. It includes an exposure step of forming a cured portion and a developing step of removing a region other than the photocured portion in the photosensitive layer.
- the method for manufacturing a printed wiring board according to the present disclosure includes a step of forming a conductor pattern by etching or plating a substrate having a resist pattern formed by the method for forming a resist pattern.
- a photosensitive element capable of reducing the number of resist defects, a method for forming a resist pattern using the photosensitive element, and a method for manufacturing a printed wiring board.
- the numerical range indicated by using “-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
- the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step.
- the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
- (meth) acrylic acid means at least one of "acrylic acid” and the corresponding "methacrylic acid”, and the same applies to other similar expressions such as (meth) acrylate.
- the "solid content” is a non-volatile component excluding volatile substances such as water and solvent contained in the photosensitive resin composition, and is volatile when the resin composition is dried. It shows the components that remain without being used, and also includes liquid, starch syrup, and wax-like substances at room temperature around 25 ° C.
- the photosensitive element of the present embodiment includes a support film and a photosensitive layer formed on the first surface of the support film.
- FIG. 1 is a schematic cross-sectional view showing an embodiment of a photosensitive element. As shown in FIG. 1, the photosensitive element 1 according to the present embodiment includes a support film 10 and a photosensitive layer 20.
- the photosensitive layer 20 is provided on the first surface 10a of the support film 10.
- the support film 10 has a second surface 10b on the side opposite to the first surface 10a.
- the surface resistivity of the first surface 10a in the support film is larger than the surface resistivity of the second surface 10b.
- the surface resistivity of the first surface is 1 ⁇ 10 13 to 1 ⁇ 10 17 ⁇
- the surface resistivity of the second surface is 1 ⁇ 10 8 to 1 ⁇ 10 12 ⁇ .
- the surface resistivity of the first surface may be 1 ⁇ 10 14 to 1 ⁇ 10 16 ⁇
- the surface resistivity of the second surface may be 1 ⁇ 10 9 to 1 ⁇ 10 11.
- the support film according to the present embodiment has a first layer containing a lubricant on the first surface side, and a second layer containing an antistatic agent and a lubricant on the second surface side.
- the support film may have a two-layer structure having a first layer and a second layer, or a three-layer structure having a base material layer between the first layer and the second layer. May be good.
- FIG. 2 is a schematic cross-sectional view showing an embodiment of a support film having a three-layer structure.
- the support film 10 has a first layer 12, a base material layer 16, and a second layer 14.
- the first layer 12 is located on the first surface 10a side of the support film on which the photosensitive layer 20 is provided.
- the second layer 14 is provided on the side of the base material layer 16 opposite to the first layer 12, and is located on the second surface 10b side of the support film 10.
- the support film may be a biaxially oriented polyester film having a three-layer structure.
- the first layer 12 is a layer containing a lubricant.
- the thickness of the first layer 12 may be 0.05 to 3.0 ⁇ m, 0.1 to 2.0 ⁇ m, or 0.2 to 1.0 ⁇ m.
- the second layer 14 is a layer containing an antistatic agent and a lubricant.
- the thickness of the second layer 14 may be 0.05 to 3.0 ⁇ m, 0.1 to 2.0 ⁇ m, or 0.2 to 1.0 ⁇ m.
- the antistatic agent does not have to be uniformly dispersed in the second layer 14, and may be present on the side of the second layer 14 that does not come into contact with the base material layer 16 (the second surface 10b side).
- the base material layer 16 is a layer that does not contain a lubricant and an antistatic agent.
- the base material layer may be composed of, for example, a polyester film containing polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene-2,6-naphthalate (PEN).
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PEN polyethylene-2,6-naphthalate
- the thickness of the base material layer 16 may be 5 to 40 ⁇ m, 8 to 30 ⁇ m, or 10 to 25 ⁇ m.
- the three-layer structure support film has a first layer and a second layer on the base material layer by using known methods such as roll coating, flow coating, spray coating, curtain flow coating, dip coating, and slit die coating. It can be produced by forming each of the layers.
- FIG. 3 is a schematic cross-sectional view showing an embodiment of a support film having a two-layer structure.
- the support film 10 has a first layer 22 and a second layer 24.
- the first layer 22 is located on the first surface 10a side of the support film on which the photosensitive layer 20 is provided.
- the second layer 24 is located on the second surface 10b side.
- the support film may be a biaxially oriented polyester film having a two-layer structure.
- the first layer 22 is a layer containing a lubricant.
- the thickness of the first layer 22 may be 6-50 ⁇ m, 8-40 ⁇ m, or 10-25 ⁇ m.
- the first layer may be formed by kneading a lubricant into polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene-2,6-naphthalate (PEN).
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PEN polyethylene-2,6-naphthalate
- the second layer 24 is a layer containing an antistatic agent and a lubricant.
- the thickness of the second layer 24 may be 0.05 to 3.0 ⁇ m, 0.1 to 2.0 ⁇ m, or 0.2 to 1.0 ⁇ m.
- the antistatic agent does not have to be uniformly dispersed in the second layer 24, and may be present on the side of the second layer 24 that does not come into contact with the first layer 22 (the second surface 10b side). ..
- the support film having a two-layer structure is known, for example, after forming the first layer 22, a roll coat, a flow coat, a spray coat, a curtain flow coat, a dip coat, a slit die coat and the like are known on the first layer 22.
- the method can be used to form the second layer 24.
- the average particle size of the lubricant contained in the first layer and the second layer is preferably 1 ⁇ m or less, preferably 0.1 to 1 ⁇ m, 0.1 to 0.8 ⁇ m, or 0.2 to 0.5 ⁇ m. There may be. From the viewpoint of improving the smoothness of the first surface 10a of the support film, the average particle size of the lubricant contained in the first layer is preferably smaller than the average particle size of the lubricant contained in the second layer.
- the average particle size of the lubricant can be measured by observing the surface of the support film using a scanning electron microscope.
- the number of lubricants contained in the first layer is preferably smaller than the number of lubricants contained in the second layer.
- the number of lubricants contained in the first layer is preferably 150 or less per 15 ⁇ m ⁇ 15 ⁇ m, and may be 10 to 120 or 15 to 100.
- the number of lubricants contained in the second layer is preferably 500 or less per 150 ⁇ m ⁇ 150 ⁇ m square, and may be 200 to 480 or 300 to 460.
- the number of lubricants can be measured by observing the surface of the support film using a confocal laser scanning microscope.
- the lubricant is not particularly limited as long as it does not hinder the light transmission of the support film and is a component used for producing a polyester film, and may be an inorganic lubricant or an organic lubricant.
- the inorganic lubricant include silica, calcium carbonate, alumina, wallastonite, kaolin, zinc oxide, barium sulfate, calcium phosphate, calcium, barium, zinc or a salt of manganese and terephthalic acid.
- the organic lubricant include crosslinked polymers such as polystyrene and polymethylmethacrylate.
- the antistatic agent can be selected within a range that does not impair the light transmission of the support film.
- examples of the antistatic agent include a hydroxyl group-containing compound such as polyoxyalkylene glycol, a ⁇ -conjugated polymer such as alkoxypolythiophene, a polyhydric alcohol having three or more hydroxyl groups such as glycerin tristearate, and a polyhydric alcohol having 12 or more carbon atoms.
- Examples include ester products with aliphatic monocarboxylic acids, lithium metal-containing compounds such as lithium dodecylbenzenesulfonate, organic sulfonic acid metal salts such as sodium dodecylbenzenesulfonate, and lithium metal-containing compounds such as lithium trifluoromethanesulfonate. Be done.
- Haze refers to a value measured using a commercially available turbidity meter (turbidity meter) in accordance with the method specified in JIS K7105.
- the haze can be measured with a commercially available turbidity meter such as NDH-5000 (manufactured by Nippon Denshoku Industries Co., Ltd., trade name).
- the thickness of the support film may be 5 to 50 ⁇ m, 8 to 40 ⁇ m, 10 to 30 ⁇ m, or 10 to 25 ⁇ m.
- the photosensitive layer 20 is a layer formed from the photosensitive resin composition.
- the photosensitive resin composition used for forming the photosensitive layer 20 is not particularly limited.
- the photosensitive resin composition may contain (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator.
- the (A) binder polymer (hereinafter, also referred to as “(A) component”) can be produced, for example, by radically polymerizing a polymerizable monomer.
- the polymerizable monomer include styrene or a styrene derivative, acrylamide such as diacetoneacrylamide, ethers of vinyl alcohol such as acrylonitrile and vinyl-n-butyl ether, (meth) acrylic acid alkyl ester, and (meth) acrylic acid.
- Benzyl ester (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl ( Meta) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, ⁇ -bromoacrylic acid, ⁇ -chloroacrylic acid, ⁇ -frill (meth) acrylic acid, ⁇ -styryl (Meta) Acrylic acid, maleic acid, maleic acid anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate and other maleic acid monoesters, fumaric acid, silicic acid, ⁇ -cyanosilicic acid, itaconic acid, croton Acrylic and propioleic acid can be mentioned.
- the component (A) may have a carboxy group from the viewpoint of alkali developability.
- the component (A) having a carboxy group can be produced, for example, by radically polymerizing a polymerizable monomer having a carboxy group and another polymerizable monomer.
- the polymerizable monomer having a carboxy group may be (meth) acrylic acid or methacrylic acid.
- the content of the structural unit based on the polymerizable monomer having a carboxy group is 10 to 50% by mass based on the total amount of the component (A). It may be 15 to 40% by mass, or 20 to 35% by mass.
- the carboxy group content is 10% by mass or more, the alkali developability tends to be improved, and when the carboxy group content is 50% by mass or less, the alkali resistance tends to be excellent.
- the acid value of the component (A) having a carboxy group may be 50 to 250 mgKOH / g, 50 to 200 mgKOH / g, or 100 to 200 mgKOH / g.
- the component (A) may have a structural unit based on styrene or a styrene derivative from the viewpoint of adhesion and peeling characteristics.
- the styrene derivative is a polymerizable compound in which the hydrogen atom in the ⁇ -position or aromatic ring of styrene such as vinyltoluene and ⁇ -methylstyrene is substituted.
- the content of the structural unit based on styrene or styrene derivative in the component (A) may be 10 to 60% by mass, 15 to 50% by mass, 35 to 50% by mass, or 40 to 50% by mass. When this content is 10% by mass or more, the adhesion tends to be improved, and when it is 60% by mass or less, it is possible to suppress the peeling piece from becoming large during development, and the time required for peeling tends to be long. be.
- the component (A) may have a structural unit based on the (meth) acrylic acid benzyl ester from the viewpoint of improving the resolution.
- the content of the structural unit derived from the (meth) acrylic acid benzyl ester in the component (A) may be 10 to 40% by mass, 15 to 35% by mass, or 20 to 30% by mass.
- the component (A) may have a structural unit based on the (meth) acrylic acid alkyl ester from the viewpoint of improving plasticity.
- the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, and (meth) acrylic acid pentyl.
- Esters (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl Examples include esters, (meth) acrylic acid undecyl esters, and (meth) acrylic acid dodecyl esters.
- the weight average molecular weight (Mw) of the component (A) may be 10,000 to 300,000, 150,000 to 150,000, 200,000 to 100,000, or 25,000 to 80,000.
- Mw of the component (A) is 10,000 or more, the developer resistance tends to be excellent, and when the Mw of the component (A) is 300,000 or less, the development time tends to be suppressed from becoming long.
- the component (A) may have a dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 3.0 or 1.0 to 2.0. The resolution tends to improve as the degree of dispersion decreases.
- the weight average molecular weight and the number average molecular weight in the present specification are values measured by gel permeation chromatography (GPC) and converted using standard polystyrene as a standard sample.
- the component (A) one type can be used alone or two or more types can be used in combination.
- the component (A) includes, for example, two or more kinds of binder polymers composed of different polymerizable monomers, two or more kinds of binder polymers having different Mw, and different dispersities. Two or more binder polymers can be mentioned.
- the content of the component (A) is 30 to 80 parts by mass, 40 to 75 parts by mass, 50 to 70 parts by mass, or 50 to 50 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) described later. It may be 60 parts by mass. When the content of the component (A) is within this range, the strength of the photocurable portion of the photosensitive layer becomes better.
- (B) photopolymerizable compound (hereinafter, also referred to as "(B) component")
- a compound having at least one ethylenically unsaturated bond in the molecule can be used.
- the component (B) one type can be used alone or two or more types can be used in combination.
- the ethylenically unsaturated bond contained in the component (B) is not particularly limited as long as photopolymerization is possible.
- Examples of the ethylenically unsaturated bond include an ⁇ , ⁇ -unsaturated carbonyl group such as a (meth) acryloyl group.
- Examples of the photopolymerizable compound having an ⁇ , ⁇ -unsaturated carbonyl group include ⁇ , ⁇ -unsaturated carboxylic acid ester of a polyhydric alcohol, bisphenol type (meth) acrylate, and ⁇ , ⁇ -unmodified of a glycidyl group-containing compound.
- Examples include saturated carboxylic acid adducts, (meth) acrylates with urethane bonds, nonylphenoxypolyethyleneoxyacrylates, (meth) acrylates with a phthalic acid skeleton, and (meth) acrylic acid alkyl esters.
- Examples of the ⁇ , ⁇ -unsaturated carboxylic acid ester of the polyhydric alcohol include polyethylene glycol di (meth) acrylate having an ethylene group number of 2 to 14, and polypropylene glycol di (meth) acrylate having a propylene group number of 2 to 14. Meta) acrylate, polyethylene / polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) having 2 to 14 ethylene groups and 2 to 14 propylene groups.
- EO-modified trimethylolpropane tri (meth) acrylate PO-modified trimethylolpropane tri (meth) acrylate
- EO PO-modified trimethylolpropane tri (meth) acrylate
- PO PO-modified trimethylolpropane tri (meth) acrylate
- tetramethylolmethanetri (meth) acrylate tetramethylolmethanetetra
- examples include (meth) acrylates and (meth) acrylate compounds having a skeleton derived from dipentaerythritol or pentaerythritol.
- EO modification means having a block structure of an ethylene oxide (EO) group
- PO modification means having a block structure of a propylene oxide (PO) group.
- the component (B) may contain a polyalkylene glycol di (meth) acrylate from the viewpoint of improving the flexibility of the resist pattern.
- the polyalkylene glycol di (meth) acrylate may have at least one of an EO group and a PO group, and may have both an EO group and a PO group.
- the EO group and the PO group may be continuously present in blocks or randomly.
- the PO group may be either an oxy-n-propylene group or an oxyisopropylene group.
- the secondary carbon of the propylene group may be bonded to the oxygen atom, or the primary carbon may be bonded to the oxygen atom.
- polyalkylene glycol di (meth) acrylate examples include, for example, FA-023M (manufactured by Hitachi Kasei Co., Ltd.), FA-024M (manufactured by Hitachi Kasei Co., Ltd.), and NK Ester HEMA-9P (Shin-Nakamura Chemical Industry Co., Ltd.). (Made by company).
- the component (B) may contain a (meth) acrylate having a urethane bond from the viewpoint of improving the flexibility of the resist pattern.
- a (meth) acrylate having a urethane bond examples include a (meth) acrylic monomer having an OH group at the ⁇ -position and a diisocyanate (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexa).
- Examples thereof include addition reactants with methylene diisocyanate and the like, tris ((meth) acryloxitetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, and EO and PO-modified urethane di (meth) acrylate.
- Examples of commercially available EO-modified urethane di (meth) acrylate products include “UA-11” and “UA-21EB” (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
- Examples of commercially available products of EO and PO-modified urethane di (meth) acrylate include “UA-13” (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
- the component (B) may contain dipentaerythritol or a (meth) acrylate compound having a skeleton derived from pentaerythritol from the viewpoint of easily forming a thick-film resist pattern and improving resolution and adhesion in a well-balanced manner.
- the (meth) acrylate compound having a skeleton derived from dipentaerythritol or pentaerythritol preferably has four or more (meth) acryloyl groups, and is preferably dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate. It may be.
- a polyfunctional (meth) acrylate compound obtained by reacting a polyhydric alcohol with an ⁇ , ⁇ -unsaturated carboxylic acid may be contained.
- the polyfunctional (meth) acrylate compound may have at least one of an EO group and a PO group, and may have both an EO group and a PO group.
- dipentaerythritol (meth) acrylate having an EO group or the like can be used. Examples of commercially available products of dipentaerythritol (meth) acrylate having an EO group include DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.).
- the component (B) may contain a bisphenol type (meth) acrylate, and may contain a bisphenol A type (meth) acrylate among the bisphenol type (meth) acrylates.
- the bisphenol A type (meth) acrylate include 2,2-bis (4-((meth) acryloxipolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypolypropoxy)). Phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, and 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane. Be done.
- nonylphenoxypolyethyleneoxyacrylate examples include nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, and nonylphenoxynonaethyleneoxy.
- examples thereof include acrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate.
- Examples of the (meth) acrylate having a phthalate skeleton include ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate and ⁇ -hydroxyethyl- ⁇ '-(meth) acryloyloxy.
- Ethyl-o-phthalate and ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate can be mentioned.
- ⁇ -Chloro- ⁇ -hydroxypropyl- ⁇ '-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (Hitachi Kasei Co., Ltd.).
- the (C) photopolymerization initiator (hereinafter, also referred to as “component (C)”) is not particularly limited as long as the component (B) can be polymerized, and the photopolymerization initiator that is usually used is used. It can be selected as appropriate. As the component (C), one type can be used alone or two or more types can be used in combination.
- the component (C) examples include photopolymerization initiators such as acylphosphine oxide-based, oxime ester-based, aromatic ketone-based, quinone-based, alkylphenone-based, imidazole-based, acridine-based, phenylglycine-based, and coumarin-based. ..
- the component (C) may contain an acridine-based photopolymerization initiator, a phenylglycine-based photopolymerization initiator, or an imidazole-based photopolymerization initiator in terms of improving sensitivity and resolution in a well-balanced manner.
- acrydin-based photopolymerization initiator examples include 9-phenylacrine, 9- (p-methylphenyl) acrydin, 9- (m-methylphenyl) acrydin, 9- (p-chlorophenyl) acrydin, and 9- (m-).
- Chlorophenyl) acrydin 9-aminoacrine, 9-dimethylaminoacrine, 9-diethylaminoacrine, 9-pentylaminoacrine, 1,2-bis (9-acridinyl) ethane, 1,4-bis (9-acridinyl) butane, 1,6-bis (9-acridinyl) hexane, 1,8-bis (9-acridinyl) octane, 1,10-bis (9-acridinyl) decane, 1,12-bis (9-acridinyl) dodecane, 1, Bis (9) such as 14-bis (9-acridinyl) tetradecane, 1,16-bis (9-acridinyl) hexadecane, 1,18-bis (9-acridinyl) octadecane, 1,20-bis (9-acridinyl) icosane, etc.
- phenylglycine-based photopolymerization initiator examples include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
- hexaarylbiimidazole-based photopolymerization initiator examples include 2- (o-chlorophenyl) -4,5-diphenylbimidazole, 2,2', 5-tris- (o-chlorophenyl) -4- (3,).
- the content of the component (C) is 0.1 to 10 parts by mass, 1 to 5 parts by mass, or 2 to 4.5 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). It may be.
- the content of the component (C) is 0.1 parts by mass or more, the light sensitivity, resolution and adhesion tend to be improved, and when the content is 10 parts by mass or less, the resist pattern forming property tends to be better.
- the photosensitive resin composition according to the present embodiment may further contain (D) a photosensitizer (hereinafter, also referred to as "(D) component").
- a photosensitizer hereinafter, also referred to as "(D) component”
- the absorption wavelength of the active light beam used for exposure can be effectively used.
- the component (D) one type can be used alone or two or more types can be used in combination.
- Examples of the component (D) include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds, stillben compounds, and triazine. Examples thereof include compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoacridin compounds.
- the component (D) may contain a pyrazoline compound or an anthracene compound from the viewpoint of further improving the resolution.
- Examples of the pyrazoline compound include 1- (4-methoxyphenyl) -3-styryl-5-phenyl-pyrazolin, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazolin, and the like.
- anthracene compound examples include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene. ..
- the content of the component (D) is 0.01 to 5 parts by mass and 0.01 to 1 with respect to 100 parts by mass of the total amount of the components (A) and (B) from the viewpoint of improving the light sensitivity and the resolution. It may be parts by mass or 0.01 to 0.2 parts by mass.
- the photosensitive resin composition according to the present embodiment includes dyes, photocolorants, thermal color inhibitors, plasticizers, pigments, fillers, defoaming agents, flame retardants, adhesion imparting agents, and leveling, if necessary.
- Additives such as agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal cross-linking agents, and polymerization inhibitors may be further contained. These additives may be used alone or in combination of two or more.
- dyes include malachite green, Victoria pure blue, brilliant green, and methyl violet.
- photocoloring agent include tribromophenyl sulfone, leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, and o-chloroaniline.
- plasticizer include p-toluenesulfonamide.
- the photosensitive resin composition is dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof, if necessary. Therefore, it can be prepared as a solution having a solid content of about 30 to 60% by mass.
- a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof, if necessary. Therefore, it can be prepared as a solution having a solid content of about 30 to 60% by mass.
- the thickness of the photosensitive layer 20 may be 1 to 200 ⁇ m, 5 to 100 ⁇ m, 10 to 50 ⁇ m, or 10 to 30 ⁇ m.
- the photosensitive element according to the present embodiment may include a protective film (not shown) on the side of the photosensitive layer 20 opposite to the support film 10.
- a protective film it is preferable to use a film in which the adhesive force between the photosensitive layer 20 and the protective film is smaller than the adhesive force between the photosensitive layer 20 and the support film 10.
- a polyolefin film such as polyethylene or polypropylene can be used.
- the protective film may be a polyethylene film.
- the thickness of the protective film may be 5 to 100 ⁇ m, 5 to 70 ⁇ m, 10 to 60 ⁇ m, 10 to 50 ⁇ m, 15 to 40 ⁇ m, or 15 to 30 ⁇ m.
- the photosensitive element of the present embodiment may include an intermediate layer (not shown) between the support film and the photosensitive layer.
- the adhesive force between the support film and the intermediate layer may be smaller than the adhesive force between the intermediate layer and the photosensitive layer.
- the intermediate layer may have water solubility or solubility in a developing solution.
- the intermediate layer is a layer formed by using a resin composition for forming an intermediate layer, which will be described later.
- the resin composition for forming the intermediate layer may contain a water-soluble resin.
- the inclusion of the water-soluble resin tends to improve the solubility of the formed intermediate layer. In addition, the stability tends to be improved because the layer separation between the formed intermediate layer and the photosensitive layer can be easily maintained for a long period of time.
- the water-soluble resin include polyvinyl alcohol and polyvinylpyrrolidone.
- the resin composition for forming an intermediate layer may contain polyvinyl alcohol from the viewpoint of having a low oxygen permeability coefficient and being able to further suppress the inactivation of radicals generated by the active light rays used for exposure. Polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate.
- the degree of saponification of the polyvinyl alcohol used in the present embodiment may be 50 mol% or more, 70 mol% or more, or 80 mol% or more.
- the "saponification degree" in the present specification refers to a value measured in accordance with JIS K 6726 (1994) (polyvinyl alcohol test method) specified in Japanese Industrial Standards. Further, the upper limit of the saponification degree may be 100 mol%.
- the average degree of polymerization of polyvinyl alcohol may be 300 to 3500, 300 to 2500, or 300 to 1000.
- the average degree of polymerization of polyvinylpyrrolidone may be 10,000 to 100,000 or 10,000 to 50,000.
- As the polyvinyl alcohol two or more kinds of polyvinyl alcohols having different saponification degree, viscosity, degree of polymerization, modified species and the like may be used in combination.
- the resin composition for forming the intermediate layer may contain a resin having solubility in a developing solution.
- the resin having solubility in the developing solution may contain, for example, the component (A) used in the photosensitive resin composition, or may contain the component (B).
- the resin composition for forming an intermediate layer may contain at least one solvent, if necessary, in order to improve the handleability of the resin composition and adjust the viscosity and storage stability.
- the solvent include water, organic solvents and the like.
- the organic solvent include methanol, acetone, toluene, a mixed solvent thereof and the like. Methanol may be contained from the viewpoint of improving the efficiency of drying when forming the intermediate layer.
- the content of methanol is 1 to 100 parts by mass with respect to 100 parts by mass of water from the viewpoint of solubility in the water-soluble resin. It may be 10 to 80 parts by mass, or 20 to 60 parts by mass.
- the content of the water-soluble resin may be 1 to 50 parts by mass or 10 to 30 parts by mass with respect to 100 parts by mass of water.
- the resin composition for forming the intermediate layer may contain known additives such as a surfactant, a plasticizer, and a leveling agent.
- the leveling agent include silicone-based leveling agents.
- examples of commercially available silicone-based leveling agents include Polyflow KL-401 (manufactured by Kyoeisha Chemical Co., Ltd.).
- the content of the leveling agent is 0.01 to 2.0 parts by mass or 0 with respect to 100 parts by mass of the resin composition for forming the intermediate layer from the viewpoint of ease of forming the intermediate layer. It may be 0.05 to 1.0 parts by mass.
- the surfactant may include a silicone-based surfactant or a fluorine-based surfactant from the viewpoint of improving the peelability from the support film. These surfactants can be used alone or in combination of two or more.
- the content of the surfactant is 0.01 to 1.0 parts by mass with respect to 100 parts by mass of the resin composition for forming the intermediate layer from the viewpoint of ease of forming the intermediate layer. , 0.05 to 0.5 parts by mass, or 0.1 to 0.3 parts by mass.
- a polyhydric alcohol compound can be contained from the viewpoint of improving the ease of forming the intermediate layer.
- the plasticizer include glycerins such as glycerin, diglycerin and triglycerin; (poly) alkylene such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol and polypropylene glycol. Glycos; and trimethylol propane. These plasticizers can be used alone or in combination of two or more.
- the thickness of the intermediate layer is not particularly limited, but may be 12 ⁇ m or less, 10 ⁇ m or less, or 8 ⁇ m or less from the viewpoint of developability.
- the thickness of the intermediate layer may be 1.0 ⁇ m or more, 1.5 ⁇ m or more, or 2 ⁇ m or more from the viewpoint of ease of forming the intermediate layer and resolvability.
- the method for forming the resist pattern according to the present embodiment includes a laminating step of laminating the photosensitive layer 20 of the photosensitive element 1 on the substrate in the order of the photosensitive layer and the supporting film, and a predetermined portion of the photosensitive layer 20 through which the active light is emitted through the supporting film 10. It is provided with an exposure step of irradiating the photosensitive layer 20 to form a photocurable portion and a developing step of removing a region other than the photocurable portion of the photosensitive layer 20.
- the photosensitive layer of the photosensitive element and the supporting film are laminated on the substrate in this order.
- the laminating step as a method of laminating the photosensitive layer 20 on the substrate, for example, when a protective film is present on the photosensitive layer 20, after removing the protective film, the photosensitive layer 20 is placed at 70 to 130 ° C. Examples thereof include a method of laminating by crimping the substrate with a pressure of about 0.1 to 1 MPa while heating to a certain degree. In the laminating step, laminating is also possible under reduced pressure.
- the surface of the substrate on which the photosensitive layer 20 is laminated is usually a metal surface, but is not particularly limited. Further, in order to further improve the stackability, the substrate may be preheat-treated.
- the exposure method includes a method of irradiating an active ray in an image shape through a negative or positive mask pattern called artwork (mask exposure method), a method of irradiating an active light beam in an image shape by a projection exposure method, and an LDI (Laser Direct). Examples thereof include a method of irradiating an active light beam in an image shape by a direct drawing exposure method such as an Imaging) exposure method and a DLP (Digital Light Processing) exposure method.
- artwork mask exposure method
- LDI Laser Direct
- Examples thereof include a method of irradiating an active light beam in an image shape by a direct drawing exposure method such as an Imaging) exposure method and a DLP (Digital Light Processing) exposure method.
- a known light source can be used, for example, a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, a gas laser such as an argon laser, a solid-state laser such as a YAG laser, a semiconductor laser, or the like. Those that effectively emit ultraviolet rays and visible light are used.
- PEB Post exposure break
- the temperature at which PEB is performed may be 50 to 100 ° C.
- a hot plate, a box dryer, a heating roll, or the like may be used as the heater.
- a resist pattern is formed on the substrate by removing at least a part of the photosensitive layer other than the photocurable portion from the substrate.
- the region other than the photocurable portion in the photosensitive layer is removed.
- the unexposed portion (unlightened portion) of the photosensitive layer 20 is removed by wet development with a developing solution such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, or dry development to develop a resist pattern. Can be manufactured.
- the alkaline aqueous solution examples include a 0.1 to 5% by mass sodium carbonate solution, a 0.1 to 5% by mass potassium carbonate solution, and a 0.1 to 5% by mass sodium hydroxide solution.
- the pH of the alkaline aqueous solution is preferably in the range of 9-11.
- the temperature of the alkaline aqueous solution is adjusted according to the developability of the photosensitive layer 20.
- the alkaline aqueous solution may contain a surface active agent, an antifoaming agent, an organic solvent and the like.
- Examples of the developing method include a dip method, a spray method, brushing and slapping.
- the resist pattern may be further cured by heating at about 60 to 250 ° C. or exposing at about 0.2 to 10 J / cm 2, if necessary.
- the method for manufacturing a printed wiring board according to the present embodiment includes a step of forming a conductor pattern by etching or plating a substrate having a resist pattern formed by the method for forming a resist pattern.
- the etching or plating of the substrate can be performed by etching or plating the surface of the substrate by a known method using the resist pattern as a mask.
- etching solution used for etching for example, a cupric chloride solution, a ferric chloride solution, and an alkaline etching solution can be used.
- the plating include copper plating, solder plating, nickel plating, and gold plating.
- the resist pattern can be peeled off with, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used for development.
- a stronger alkaline aqueous solution for example, a 1 to 10% by mass sodium hydroxide aqueous solution and a 1 to 10% by mass potassium hydroxide aqueous solution are used.
- the peeling method include a dipping method and a spraying method.
- the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small-diameter through hole.
- a photosensitive resin composition was prepared by mixing each component in the blending amount (part by mass) shown in Table 1. The details of each component shown in Table 1 are as follows.
- (Binder polymer) A-1 Ethylene glycol monomethyl ether / toluene of a copolymer of methacrylic acid / methyl methacrylate / styrene / benzyl methacrylate (mass ratio: 27/5/45/23, Mw: 45000, acid value: 107 mgKOH / g) Solution (solid content: 40% by mass)
- (Photopolymerizable compound) FA-321M: EO-modified bisphenol A dimethacrylate (Hitachi Kasei Co., Ltd., number of EO groups: 10 (average value))
- FA-024M Polyalkylene glycol dimethacrylate (Hitachi Kasei Co., Ltd., number of EO groups: 12 (average value), number of PO groups: 4 (average value))
- BPE-200 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (Shin Nakamura Chemical Industry Co., Ltd.) (
- Support films S1 to S7 As the support film for the photosensitive element, support films S1 to S7 (thickness: 16 ⁇ m) having the layer structure shown in Table 2 were prepared.
- S1 Biaxially oriented polyester film with a three-layer structure (Toray Industries, Inc., trade name "QS64", thickness of first layer and second layer: 1 ⁇ m or less)
- S2 Biaxially oriented polyester film with a three-layer structure (Toray Industries, Inc., trade name "QS66”, thickness of first layer and second layer: 1 ⁇ m or less)
- S3 Biaxially oriented polyester film with a two-layer structure (manufactured by Mitsubishi Chemical Corporation, trade name "R-705", thickness of the second layer: 1 ⁇ m or less)
- S4 Biaxially oriented polyester film with a three-layer structure (Toray Industries, Inc., trade name "FB40", thickness of first layer and second layer: 1 ⁇ m or less)
- S5 Biaxially oriented polyester film with a three-
- the support film cut into 10 cm ⁇ 10 cm was placed in an environment of a temperature of 23 ° C. and a humidity of 60 ⁇ 10%.
- the electrode was placed on the support film, and the surface resistivity after being left at 100 V for 1 minute was measured using a digital ultra-high resistance / micro ammeter (ADCMT Co., Ltd., trade name "8340A").
- the surface of the support film was observed using a scanning electron microscope "SU-1500" (manufactured by Hitachi, Ltd.), and the average particle size of the lubricant was measured.
- Photosensitive element The solution of the photosensitive resin composition was uniformly applied onto the first layer of the support film using a comma coater. Subsequently, it was dried in a hot air convection dryer at 100 ° C. for 2 minutes to form a photosensitive layer having a thickness of 15 ⁇ m. Next, a PE film (manufactured by Tamapoli Co., Ltd., trade name "NF-15A", thickness: 28 ⁇ m) was laminated on the photosensitive layer as a protective film to prepare a photosensitive element.
- NF-15A thickness: 28 ⁇ m
- a projection exposure machine UX-7 series, manufactured by Ushio, Inc.
- the photosensitive layer of the laminated body was exposed with an irradiation energy amount such that the number of remaining steps after development of the 41-step step tablet was 9. ..
- the support film was peeled off, and a 1% by mass sodium carbonate aqueous solution was spray-developed at 30 ° C. for twice the minimum development time, and the unexposed portion was removed for development.
- Photosensitive element 10 ... Support film, 10a ... First surface, 10b ... Second surface, 12, 22 ... First layer, 14, 24 ... Second layer, 16 ... Base layer, 20 ... Photosensitive layer.
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Abstract
Description
本実施形態の感光性エレメントは、支持フィルムと、該支持フィルムの第1の面上に形成された感光層とを備える。図1は、感光性エレメントの一実施形態を示す模式断面図である。本実施形態に係る感光性エレメント1は、図1に示すように支持フィルム10と、感光層20とを備える。
支持フィルム10の第1の面10a上に感光層20が設けられている。支持フィルム10は、第1の面10aとは反対側に第2の面10bを有している。支持フィルムにおける第1の面10aの表面抵抗率は、第2の面10bの表面抵抗率よりも大きい。
感光層20は、感光性樹脂組成物から形成された層である。感光層20を形成するために用いられる感光性樹脂組成物としては、特に限定されない。感光性樹脂組成物は、(A)バインダーポリマー、(B)光重合性化合物及び(C)光重合開始剤を含有してもよい。
本実施形態に係る感光性エレメントは、感光層20の支持フィルム10とは反対側に保護フィルム(図示せず。)を備えてもよい。保護フィルムとしては、感光層20と支持フィルム10との間の接着力よりも、感光層20と保護フィルムとの間の接着力が小さくなるようなフィルムを用いることが好ましい。保護フィルムとしては、ポリエチレン、ポリプロピレン等のポリオレフィンフィルムを用いることができる。保護フィルムはポリエチレンフィルムであってもよい。
本実施形態の感光性エレメントは、支持フィルムと感光層との間に中間層(図示せず。)を備えてもよい。支持フィルムと中間層との接着力は、中間層と感光層との接着力より小さくてもよい。中間層は、水溶性を有していてもよく、現像液に対する溶解性を有していてもよい。中間層は、後述する中間層形成用樹脂組成物を用いて形成される層である。
本実施形態に係るレジストパターンの形成方法は、感光性エレメント1の感光層20を感光層、支持フィルムの順に基板上に積層する積層工程と、支持フィルム10を通して活性光線を感光層20の所定部分に照射して光硬化部を形成する露光工程と、感光層20における光硬化部以外の領域を除去する現像工程と、を備える。
本実施形態に係るプリント配線板の製造方法は、上記レジストパターンの形成方法により形成されたレジストパターンを有する基板を、エッチング処理又はめっき処理して導体パターンを形成する工程を備える。ここで、基板のエッチング又はめっきは、レジストパターンをマスクとして用いて、基板の表面を公知の方法によりエッチング又はめっきすることによって行うことができる。
表1に示す配合量(質量部)の各成分を混合することにより、感光性樹脂組成物を調製した。表1に示す各成分の詳細は、以下のとおりである。
A-1:メタクリル酸/メタクリル酸メチル/スチレン/メタクリル酸ベンジルの共重合体(質量比:27/5/45/23、Mw:45000、酸価:107mgKOH/g)のエチレングリコールモノメチルエーテル/トルエン溶液(固形分:40質量%)
(光重合性化合物)
FA-321M:EO変性ビスフェノールAジメタクリレート(日立化成株式会社、EO基の数:10(平均値))
FA-024M:ポリアルキレングリコールジメタクリレート(日立化成株式会社、EO基の数:12(平均値)、PO基の数:4(平均値))
BPE-200:2,2-ビス(4-(メタクリロキシジエトキシ)フェニル)プロパン(新中村化学工業株式会社)
(光重合開始剤)
B-CIM:2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニルビイミダゾール(保土谷化学工業株式会社)
(増感剤)
EAB:4,4’-ビス(ジエチルアミノ)ベンゾフェノン(保土谷化学工業株式会社製)
感光性エレメントの支持フィルムとして、表2に示す層構造を有する支持フィルムS1~S7(厚さ:16μm)を用意した。
S1:3層構造の二軸配向ポリエステルフィルム(東レ株式会社、商品名「QS64」、第1の層及び第2の層の厚さ:1μm以下)
S2:3層構造の二軸配向ポリエステルフィルム(東レ株式会社、商品名「QS66」、第1の層及び第2の層の厚さ:1μm以下)
S3:2層構造の二軸配向ポリエステルフィルム(三菱ケミカル株式会社製、商品名「R-705」、第2の層の厚さ:1μm以下)
S4:3層構造の二軸配向ポリエステルフィルム(東レ株式会社、商品名「FB40」、第1の層及び第2の層の厚さ:1μm以下)
S5:3層構造の二軸配向ポリエステルフィルム(東レ株式会社、商品名「QS61」、第1の層及び第2の層の厚さ:1μm以下)
S6:3層構造の二軸配向ポリエステルフィルム(東レ株式会社、商品名「QS63」、第1の層及び第2の層の厚さ:1μm以下)
10cm×10cmにカットした支持フィルムを、温度23℃、湿度60±10%の環境下においた。支持フィルム上に電極を置き、デジタル超高抵抗/微少電流計(株式会社エーディーシーADCMT社、商品名「8340A」)を用いて、100Vで1分間放置した後の表面抵抗率を測定した。
走査型電子顕微鏡「SU-1500」(株式会社日立製作所製)を用いて、支持フィルムの表面を観察し、滑剤の平均粒径を測定した。
共焦点レーザ顕微鏡「OPTELICS HYBRID」(レーザーテック株式会社)を用いて、支持フィルムの表面を観察し、150μm×150μm角に存在する滑剤の個数を測定した。
感光性樹脂組成物の溶液を、支持フィルムの第1の層上にコンマコーターを用いて均一に塗布した。続いて、100℃の熱風対流式乾燥機で2分間乾燥して、厚さ15μmの感光層を形成した。次いで、感光層の上に、保護フィルムとしてPEフィルム(タマポリ株式会社製、商品名「NF-15A」、厚さ:28μm)をラミネートして、感光性エレメントを作製した。
銅箔(厚さ:35μm)を両面に積層したガラスエポキシ材である銅張積層板(日立化成株式会社製、商品名「MLC-E-679」)の銅表面を、酸洗、水洗後、空気流で乾燥した。得られた銅張積層板を80℃に加温し、保護フィルムを剥離しながら、感光層が銅表面に接するように感光性エレメントをラミネートした。こうして、銅張積層板、感光層、支持フィルムの順に積層された積層体を得た。ラミネートは、120℃のヒートロールを用いて、0.4MPaの圧着圧力、1.5m/分のロール速度で行なった。
Claims (8)
- 支持フィルムと、該支持フィルムの第1の面上に形成された感光層と、を備える感光性エレメントであって、
前記支持フィルムにおける前記第1の面の表面抵抗率が1×1013~1×1017Ωであり、前記第1の面と反対側の第2の面の表面抵抗率が1×108~1×1012Ωである、感光性エレメント。 - 前記支持フィルムが、前記第1の面側に滑剤を含む第1の層を有し、前記第2の面側に耐電防止剤及び滑剤を含む第2の層を有する、請求項1に記載の感光性エレメント。
- 前記滑剤の平均粒径が、1μm以下である、請求項2に記載の感光性エレメント。
- 前記第1の層に含まれる滑剤の平均粒径が、前記第2の層に含まれる滑剤の平均粒径よりも小さい、請求項2又は3に記載の感光性エレメント。
- 前記支持フィルムが、前記第1の層と前記第2の層との間に基材層を更に有し、前記基材層が滑剤及び帯電防止剤を含まない層である、請求項2~4のいずれか一項に記載の感光性エレメント。
- 前記支持フィルムが、3層構造の二軸配向ポリエステルフィルムである、請求項5に記載の感光性エレメント。
- 請求項1~6のいずれか一項に記載の感光性エレメントを、感光層、支持フィルムの順に基板上に積層する積層工程と、
前記支持フィルムを通して前記感光層の所定部分に活性光線を照射して、光硬化部を形成させる露光工程と、
前記感光層における前記光硬化部以外の領域を除去する現像工程と、
を含む、レジストパターンの形成方法。 - 請求項7に記載のレジストパターンの形成方法により形成されたレジストパターンを有する基板を、エッチング処理又はめっき処理して導体パターンを形成する工程を備える、プリント配線板の製造方法。
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