WO2014010473A1 - 感光性樹脂組成物、感光性ドライフィルム、パターン形成方法、プリント配線板およびその製造方法 - Google Patents
感光性樹脂組成物、感光性ドライフィルム、パターン形成方法、プリント配線板およびその製造方法 Download PDFInfo
- Publication number
- WO2014010473A1 WO2014010473A1 PCT/JP2013/068165 JP2013068165W WO2014010473A1 WO 2014010473 A1 WO2014010473 A1 WO 2014010473A1 JP 2013068165 W JP2013068165 W JP 2013068165W WO 2014010473 A1 WO2014010473 A1 WO 2014010473A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- monomer
- photosensitive resin
- vinyl
- compound
- Prior art date
Links
- CEHDSLDFUCVNKA-UHFFFAOYSA-N Cc(cc1Cc(cc2)ccc2O)cc(Cc(cc2)ccc2O)c1O Chemical compound Cc(cc1Cc(cc2)ccc2O)cc(Cc(cc2)ccc2O)c1O CEHDSLDFUCVNKA-UHFFFAOYSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N Oc(cc1)ccc1C(c(ccc(O)c1O)c1O)=O Chemical compound Oc(cc1)ccc1C(c(ccc(O)c1O)c1O)=O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- NBTCXIZQSZQNKJ-UHFFFAOYSA-N Oc1ccc(Cc(ccc(O)c2O)c2O)cc1 Chemical compound Oc1ccc(Cc(ccc(O)c2O)c2O)cc1 NBTCXIZQSZQNKJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
- C08F212/24—Phenols or alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
-
- 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
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
-
- 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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
-
- 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
-
- 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
- G03F7/322—Aqueous alkaline compositions
-
- 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
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- 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
- G03F7/40—Treatment after imagewise removal, e.g. baking
- G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
-
- 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
-
- 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
- H05K3/061—Etching masks
- H05K3/064—Photoresists
-
- 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
- H05K3/181—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 by electroless plating
- H05K3/182—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 by electroless plating characterised by the patterning method
- H05K3/184—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 by electroless plating characterised by the patterning method using masks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
Definitions
- a process using a photosensitive resin composition is generally used.
- a step of forming a resist film made of the photosensitive resin composition on the surface of the substrate, and a step of forming a latent image by irradiating the resist film with light through a mask An electronic circuit is formed through a process of forming a resist pattern by developing a resist film on which a latent image is formed with a developing solution, and a process of chemically etching or plating a portion without the resist. .
- chip-on-film with bare chip mounted directly on flexible substrate; multilayer printed wiring board by build-up method; miniaturization of electronic circuit in lead-out wiring used for touch panel sensor circuit, tablet terminal, etc. Is being considered.
- negative dry film resists are often used, but there are many technical problems in response to recent miniaturization requirements.
- a positive photosensitive resin composition is a material suitable for miniaturization, and is expected as a material that can meet future miniaturization requirements. However, it lacks flexibility and forms a circuit on a flexible substrate or a dry film. There are a lot of problems in making it.
- the following are known as conventional positive photosensitive resin compositions.
- a vinyl polymer (I) obtained by polymerizing a monomer mixture containing a vinyl monomer having a phenolic hydroxyl group, and a monomer mixture containing a carboxyl group-containing vinyl monomer
- a photosensitive resin composition containing a vinyl polymer (II) obtained by polymerizing a quinonediazide compound and an aromatic polyhydroxy compound Patent Document 1).
- a positive photosensitive composition comprising an o-quinonediazide compound, an alkali-soluble resin, and a specific bisphenolcarboxylic acid derivative (Patent Document 2).
- the vinyl polymer (I) is rigid and lacks flexibility, and the solubility in the developer is insufficient.
- the suppression of cracks in the resist film and the resolution are not sufficient.
- the photosensitive resin composition (1) is formed into a dry film, the dry film is wound, so that the above problem becomes significant.
- the alkali-soluble resin is rigid and lacks flexibility, and the solubility in the developer is insufficient. Therefore, the photosensitive resin composition of (2) is used as a resist film. When used as, it is not sufficient to suppress both crack suppression and resolution of the resist film.
- Patent Document 2 does not have a description regarding dry film formation.
- An object of the present invention is to provide a resist film that is less susceptible to cracks and has excellent resolution in a circuit formation process in COF; multilayer printed wiring board by a build-up method; lead wiring used in touch panel sensor circuits, tablet terminals, and the like
- R 1 is a hydrogen atom or a methyl group
- R 2 is a hydrocarbon group having 1 to 4 carbon atoms
- R 3 is a hydrogen atom or a methyl group
- k is 1 An integer of ⁇ 90.
- X is a hydrocarbon group having 1 to 6 carbon atoms, l and m are each an integer of 1 to 3, n is 1 or 2, and p and q are each 0 or 1.
- ⁇ 2> The photosensitive resin composition according to ⁇ 1>, wherein the monomer (b) is 2-methoxyethyl acrylate.
- ⁇ 3> The photosensitive resin composition according to ⁇ 1> or ⁇ 2>, wherein the proportion of the monomer (b) in the monomer mixture ( ⁇ ) is 5 to 30 mol%.
- ⁇ 4> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the photosensitive substance (III) is a quinonediazide compound.
- ⁇ 8> A copolymer obtained by polymerizing the monomer mixture ( ⁇ ) containing the monomer (a) and the monomer (c).
- a resist film made of the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 8> is formed on the surface of a support film.
- One aspect of the pattern forming method of the present invention includes a step of forming a resist film made of the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 8> on the surface of a substrate, and exposing the resist film. Forming a latent image, and developing the resist film on which the latent image is formed with an alkaline developer to form a resist pattern.
- One aspect of the printed wiring board of the present invention is produced using the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 8>.
- One aspect of the method for producing a printed wiring board of the present invention is a method using the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 8>.
- the photosensitive resin composition of the present invention in a circuit formation process in COF; multilayer printed wiring board by a build-up method; lead-out wiring used for touch panel sensor circuits, tablet terminals, etc., cracks are unlikely to occur and resolution.
- a resist film having excellent properties can be formed.
- cracks are less likely to occur in a circuit formation process in COF; multilayer printed wiring board by a build-up method; lead-out wiring used in touch panel sensor circuits, tablet terminals, etc. It is possible to form an excellent resist film.
- the pattern forming method of the present invention in a circuit forming process in COF; multilayer printed wiring board by build-up method; lead-out wiring used in touch panel sensor circuits, tablet terminals, etc., high-precision fine patterns with few defects are formed. Can be formed.
- the printed wiring board of the present invention can be applied to COF; multilayer printed wiring board by a build-up method; lead wiring used for touch panel sensor circuits, tablet terminals, and the like. According to the method for producing a printed wiring board of the present invention, it is possible to realize miniaturization of electronic circuits in COF; multilayer printed wiring board by a build-up method; lead wiring used in touch panel sensor circuits, tablet terminals, and the like.
- (Meth) acrylic acid means acrylic acid or methacrylic acid.
- (Meth) acryloyl means acryloyl or methacryloyl.
- “Monomer” means a compound having a polymerizable carbon-carbon double bond.
- (Co) polymer means a homopolymer or a copolymer.
- the photosensitive resin composition of the present invention contains a vinyl-based (co) polymer (I), a vinyl-based copolymer (II), a photosensitive material (III), and a compound (IV). Contains the ingredients.
- the vinyl (co) polymer (I) comprises a monomer mixture ( ⁇ ) containing a vinyl monomer (a) having a phenolic hydroxyl group (hereinafter also simply referred to as monomer (a)).
- a monomer mixture ( ⁇ ) which is a polymer obtained by polymerization and further contains a carboxyl group-containing vinyl monomer (c) (hereinafter also simply referred to as monomer (c)) as necessary.
- the monomer (a) is a monomer having one or more aromatic rings, wherein one or more hydrogen atoms of the aromatic rings are substituted with hydroxyl groups.
- the monomer (a) is represented by the monomer (a1) represented by the following formula (6), the monomer (a2) represented by the following formula (7), or the following formula (8).
- Monomer (a3) is preferred.
- R 11 to R 15 are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 24 carbon atoms, an aryl group having 1 to 24 carbon atoms, or an aralkyl group having 1 to 24 carbon atoms, and R 11 to R 15 At least one of them is a hydroxyl group.
- R 11 to R 15 excluding the hydroxyl group are preferably a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, and more preferably a hydrogen atom from the viewpoint of availability of the monomer (a).
- Z is an oxygen atom or NH.
- the monomer (a1) from the viewpoint of availability, the monomer (a1-1) represented by the following formula (6-1) or the single monomer represented by the following formula (6-2)
- the body (a1-2) is preferred.
- the monomer (a2) is preferably a monomer (a2-1) represented by the following formula (7-1) from the viewpoint of availability.
- the monomer (a3) is preferably a monomer (a3-1) represented by the following formula (8-1) from the viewpoint of availability.
- the proportion of the monomer (a) in the monomer mixture ( ⁇ ) is preferably 5 to 100 mol%, more preferably 10 to 95 mol%, out of 100 mol% of the total charge amount of monomers, More preferably, it is ⁇ 90 mol%, particularly preferably 30-80 mol%.
- the proportion of the monomer (a) is 5 mol% or more, the resolution of the resist film is sufficiently high, and the reduction of the unexposed portion of the resist film is sufficiently suppressed. 90 mol% or less is preferable in terms of improving the resolution.
- the monomer (c) is used as necessary for improving the resolution.
- (meth) acrylic acid, itaconic acid, itaconic acid monoester, fumaric acid, fumaric acid monoester, maleic acid, maleic acid monoester, 2- (meth) acryloyloxyethylphthalic acid examples include 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
- the proportion of the monomer (c) in the monomer mixture ( ⁇ ) is preferably 0 to 30 mol%, more preferably 5 to 30 mol%, out of 100 mol% of the total amount of monomers charged. More preferably, it is ⁇ 30 mol%.
- the proportion of the monomer (c) is 5 mol% or more, the resolution of the resist film is sufficiently high.
- the proportion of the monomer (c) is 30 mol% or less, the film loss in the unexposed portion of the resist film is sufficiently suppressed, and cracks in the resist film are sufficiently suppressed.
- the monomer mixture ( ⁇ ) may further contain another vinyl monomer copolymerizable with the monomer (a) and the monomer (c) as necessary.
- vinyl monomers include acrylate monomers such as ethyl acrylate, methacrylic acid esters such as methyl methacrylate, and styrene monomers such as styrene.
- the proportion of the other vinyl monomers in the monomer mixture ( ⁇ ) is the balance excluding the monomer (a) and the monomer (c) out of the total monomer charge of 100 mol%. is there.
- the mass average molecular weight of the vinyl (co) polymer (I) is not particularly limited, preferably 5,000 to 80,000, more preferably 6,000 to 30,000, and 7,000 to 15 Is most preferred. If the mass average molecular weight is 80,000 or less, sufficient resolution can be obtained. If the mass average molecular weight is 5,000 or more, the durability of the resist film can be maintained.
- the mass average molecular weight of the vinyl (co) polymer (I) is a polystyrene-reduced mass average molecular weight measured by gel permeation chromatography (GPC).
- the vinyl copolymer (II) includes a vinyl monomer (b) represented by the following formula (1) (hereinafter also simply referred to as a monomer (b)) and a monomer (c).
- R 1 is a hydrogen atom or a methyl group
- R 2 is a hydrocarbon group having 1 to 4 carbon atoms
- R 3 is a hydrogen atom or a methyl group
- k is an integer of 1 to 90. .
- Monomer (b) includes 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methoxymethyl acrylate, methoxymethyl methacrylate, polyethylene glycol methacrylate (polyethylene glycol repeating unit) (K in formula (1) is 1 to 90), polypropylene glycol methacrylate (polypropylene glycol repeat unit (k in formula (1) is 1 to 90)), polyethylene glycol acrylate (polyethylene glycol repeat unit (formula K) in (1) is 1 to 90), polypropylene glycol acrylate (polypropylene glycol repeating unit (k in formula (1) is 1 to 90)), methoxypolyethylene glycol methacrylate (polyethylene glycol) Call repeating unit (formula (k in 1)) is 1 to 90), it can be cited 1 to 90), etc.
- the proportion of the monomer (b) in the monomer mixture ( ⁇ ) is preferably from 5 to 30 mol%, more preferably from 7 to 20 mol%, out of 100 mol% of the total charged amount of monomers, More preferred is ⁇ 15 mol%.
- the proportion of the monomer (b) is 5 mol% or more, the resist film can be provided with sufficient flexibility.
- the proportion of the monomer (b) is 30 mol% or less, the amount of film loss during development can be suppressed.
- the proportion of the monomer (c) in the monomer mixture ( ⁇ ) is preferably from 3 to 30 mol%, more preferably from 5 to 30 mol%, out of 100 mol% of the total charged amount of monomers. More preferably, it is ⁇ 30 mol%.
- the proportion of the monomer (c) is 5 mol% or more, the resolution of the resist film is sufficiently high.
- the proportion of the monomer (c) is 30 mol% or less, the film loss in the unexposed portion of the resist film is sufficiently suppressed, and cracks in the resist film are sufficiently suppressed.
- the monomer mixture ( ⁇ ) may further contain another vinyl monomer copolymerizable with the monomer (b) and the monomer (c) as necessary.
- monomer (a) is not included.
- vinyl monomers include acrylic acid esters such as ethyl acrylate and 2-ethylhexyl acrylate, methacrylic acid esters such as methyl methacrylate, and styrene monomers such as styrene.
- the proportion of the other vinyl monomer in the monomer mixture ( ⁇ ) is the remainder excluding the monomer (b) and the monomer (c) out of 100 mol% of the total charge of the monomers. is there.
- the weight average molecular weight of the vinyl copolymer (II) is 15,000 to 120,000, preferably 20,000 to 100,000, and more preferably 40,000 to 80,000. When the mass average molecular weight is 15,000 or more, the etching resistance and plating resistance of the resist film are sufficiently high. When the mass average molecular weight is 120,000 or less, the compatibility with other components when the resist solution is used and the developability are good.
- the mass average molecular weight of the vinyl copolymer (II) is a polystyrene equivalent mass average molecular weight measured by GPC.
- the vinyl (co) polymer (I) and the vinyl copolymer (II) can be produced by a known polymerization method such as a solution polymerization method, a suspension polymerization method or an emulsion polymerization method.
- a solution polymerization method or a suspension polymerization method is preferable from the viewpoint of less contamination of impurities such as an emulsifier.
- the vinyl (co) polymer (I) and the vinyl copolymer (II) can be prepared by azobisisobutyronitrile (in the presence of an organic solvent heated to about 60 to 120 ° C. in a polymerization vessel.
- a monomer mixture in which a radical polymerization initiator such as AIBN) is mixed and dissolved is dropped over several hours, and the monomer mixture is polymerized by a known radical polymerization method such as a solution polymerization method in which polymerization proceeds.
- a known radical polymerization method such as a solution polymerization method in which polymerization proceeds.
- Each monomer may be mixed and supplied to the polymerization vessel to be polymerized, or each monomer may be supplied alone to the polymerization vessel, or any two of the mixtures and the other may be supplied separately. Also good.
- the content (mass of the vinyl (co) polymer (I) and the vinyl copolymer (II) in the total 100 mass% of the vinyl (co) polymer (I) and the vinyl copolymer (II).
- the ratio is preferably 20/80 to 95/5, more preferably 50/50 to 90/10. If the vinyl (co) polymer (I) is 20% by mass or more and the vinyl copolymer (II) is 80% by mass or less, the sensitivity and resolution of the resist film are not impaired, and the film in the unexposed area Reduction is sufficiently suppressed. If the vinyl (co) polymer (I) is 95% by mass or less and the vinyl copolymer (II) is 5% by mass or more, cracks in the resist film are sufficiently suppressed.
- Photosensitive material (III) examples include known 1,2-quinonediazide-4-sulfonic acid ester compounds, 1,2-quinonediazide-5-sulfonic acid ester compounds, 1,2-quinonediazide-6-sulfonic acid ester compounds, Examples include 1,2-quinonediazide-7-sulfonic acid ester compounds, 1,2-quinonediazide-8-sulfonic acid ester compounds, bisazide compounds, diazodisulfone compounds, triphenylsulfonium compounds, and iodonium compounds.
- 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenone 1,2-naphthoquinone diazide sulfonic acid esters of tetrahydroxybenzophenone, 1,2-naphthoquinone diazide sulfonic acid esters of pentahydroxybenzophenone
- Examples include 1,2-naphthoquinone diazide sulfonic acid esters of hexahydroxybenzophenone, 1,2-naphthoquinone diazide sulfonic acid esters of (polyhydroxy) alkane, and the like.
- the photosensitive substance (III) is preferably a quinonediazide compound, and from the viewpoint of sensitivity and resolution of the resist film, an aromatic polyhydroxy compound having 1 to 3 aromatic rings and 1,2-naphthoquinonediazide-5
- An ester with at least one compound selected from the group consisting of -sulfonic acid and 1,2-naphthoquinonediazide-4-sulfonic acid is preferable, and a compound represented by the following formula (3), represented by the following formula (4)
- at least one compound selected from the group consisting of 1,2-naphthoquinonediazide-5-sulfonic acid and 1,2-naphthoquinonediazide-4-sulfonic acid Are particularly preferred.
- the content of the photosensitive substance (III) is preferably 5 to 70 parts by mass with respect to 100 parts by mass in total of the vinyl (co) polymer (I) and the vinyl copolymer (II). Mass parts are more preferred, and 5 to 15 parts by mass are even more preferred. If the content ratio of the photosensitive substance (III) is 5 parts by mass or more, cracks in the resist film can be sufficiently suppressed. When the content ratio of the photosensitive substance (III) is 70 parts by mass or less, the resolution of the resist film is sufficiently high.
- Compound (IV) is a compound represented by the following formula (2), and is a component that improves the alkali dissolution rate of the resist film and, as a result, improves the resolution of the resist film.
- X is a non-cyclic hydrocarbon group having 1 to 6 carbon atoms, and an alkanetriyl group having 1 to 3 carbon atoms is preferable from the viewpoint of resolution of the resist film.
- Each of l and m is an integer of 1 to 3, and is preferably 1 or 2 from the viewpoint of resolution of the resist film.
- n is 1 or 2, and 1 is preferable from the viewpoint of the resolution of the resist film.
- p and q are each 0 or 1, and 0 is preferable from the viewpoint of the resolution of the resist film.
- the compound (IV) is particularly preferably a compound represented by the following formula (2-1) or a compound represented by the following formula (2-2) from the viewpoint of resolution of the resist film.
- the content ratio of the compound (IV) is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass in total of the vinyl (co) polymer (I) and the vinyl copolymer (II). Mass parts are more preferred, and 2 to 6 parts by mass are even more preferred. If the content rate of compound (IV) is 0.5 mass part or more, the alkali dissolution rate of a resist film will become high enough. If the content rate of compound (IV) is 10 mass parts or less, the film loss of the unexposed part of a resist film is fully suppressed.
- alkali-soluble resins other than vinyl-based (co) polymer (I) and vinyl-based copolymer (II), leveling agents, storage stabilizers, plasticizers, light-absorbing agents, crosslinking agents, adhesion aids.
- alkali-soluble resin examples include poly (meth) acrylic acid, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester, and the like.
- the content of other components is preferably 0 to 30% by mass in 100% by mass of the solid content of the photosensitive resin composition.
- Examples of ethylene glycol monoalkyl ether acetates include ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate.
- Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether and propylene glycol monoethyl ether.
- Examples of ethylene glycol monoalkyl ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.
- Examples of diethylene glycol alkyl ethers include diethylene glycol dimethyl ether and diethylene glycol monomethyl ether.
- Examples of the esters include ethyl acetate and ethyl lactate.
- Examples of alcohols include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexanol, 1-octanol and the like.
- Examples of aliphatic hydrocarbon solvents having 5 to 11 carbon atoms include pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2-dibutylbutane, 2,3-dibutylbutane, n-heptane, n- Examples include octane, isooctane, 2,2,3-trimethylpentane, n-nonane, 2,2,5-trimethylhexane, n-decane, and n-dodecane.
- Examples of other compounds include 1,4-dioxane, ethylene carbonate, and ⁇ -butyrolactone.
- Examples of the exposure method include an ultraviolet exposure method and a visible light exposure method.
- a method for selectively performing the exposure a method using a photomask and a scanning exposure method using laser light can be given.
- an exposure method when using a photomask either a contact exposure method or an off-contact exposure method can be used.
- the resist film is exposed through the support film to form a latent image, and then the support film is peeled off.
- the photosensitive resin composition of the present invention is useful as a resist in a circuit formation process in COF; multilayer printed wiring board by a build-up method; lead wiring used for touch panel sensor circuits, tablet terminals, and the like.
- the printed wiring board of the present invention is manufactured using the photosensitive resin composition of the present invention. Specifically, conductor wiring is formed on a base material (insulating plate, sheet, etc.). Electronic components are mounted on these so as to have a function as a target electronic circuit.
- the method for producing a printed wiring board of the present invention is a method using the photosensitive resin composition of the present invention. Specifically, it is a method of forming a wiring by etching or plating a circuit forming substrate on which a resist pattern is formed by the pattern forming method of the present invention, and further mounting electronic components as necessary.
- the mass average molecular weight (Mw) of the vinyl polymer was measured using GPC manufactured by Tosoh Corporation. For the measurement, three columns of Shodex GPC K-805L (trade name) manufactured by Showa Denko Co., Ltd. were used as a separation column, tetrahydrofuran (flow rate: 1.0 mL / min) was used as a solvent, and a differential was used as a detector. A refractometer was used, and polystyrene was used as a standard polymer. The measurement was performed at 40 ° C. and an injection amount of 0.1 mL.
- the resist film was exposed with an ultra-high pressure mercury lamp so as to form a 10 ⁇ m line and space pattern, developed with a 1% by mass aqueous sodium carbonate solution (pH about 11.6) for 2 minutes, and then the pattern shape was examined with an electron microscope. And evaluated according to the following criteria.
- X Many residues remain in the exposed area.
- a polymerization initiator manufactured by Otsuka Chemical Co., Ltd., 2,2′-azobis-2-methylbutyronitrile
- 2-Methoxyethyl acrylate 11.5 mol% 16.8 mol% methacrylic acid, 2.7 mol% methyl methacrylate, 17 mol% of styrene, 43.1 mol% ethyl acrylate, 2-ethylhexyl acrylate 8.9 mol% 0.6 parts by mass of a polymerization initiator (2,2′-azobis-2-methylbutyronitrile, manufactured by Otsuka Chemical Co., Ltd.) with respect to a total of 100 parts by mass of the monomers.
- a polymerization initiator (2,2′-azobis-2-methylbutyronitrile, manufactured by Otsuka Chemical Co., Ltd.
- monomer (a1-1) is a monomer represented by the above formula (6-1) (manufactured by Osaka Organic Chemical Industry); monomer (a2-1) is represented by the above formula The monomer represented by (7-1) (parahydroxystyrene); 2-MTA is 2-methoxyethyl acrylate; MAA is methacrylic acid; MMA is methyl methacrylate; Styrene; EA is ethyl acrylate; 2-EHA is 2-ethylhexyl acrylate.
- Example 1 70 parts by mass of a vinyl copolymer (I-1) solution, 30 parts by mass of a vinyl copolymer (II-1) solution, and a compound represented by the above formula (3) (1 mol) as a photosensitive substance (III) ) And 1,2-naphthoquinonediazide-5-sulfonic acid (3 mol), 10 parts by mass of the compound, 2 parts by mass of the compound represented by the formula (2-1) as the specific compound (IV), and 200 parts by mass of MEK Were mixed to obtain a resist solution.
- the resist solution was applied on the surface of a PET film having a thickness of 16 ⁇ m so that the thickness after drying was 5 ⁇ m, dried to form a dry film, and the dry film was evaluated.
- the results are shown in Table 3.
- Table 2 shows the types and blending amounts of vinyl (co) polymer (I), types and blending amounts of vinyl copolymer (II), photosensitive materials (III), and specific compounds (IV).
- a dry film was obtained in the same manner as in Example 1 except that the dry film was changed as shown in FIG. The results are shown in Table 3.
- the photosensitive resin composition of the present invention is useful as a resist in a circuit formation process in chip-on-film (COF); multilayer printed wiring board by a build-up method; Therefore, it is extremely effective in industry.
- COF chip-on-film
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
本願は、2012年07月10日に日本に出願された特願2012-154959に基づき優先権を主張し、その内容をここに援用する。
感光性樹脂組成物を用いた回路形成プロセスでは、基材表面に感光性樹脂組成物からなるレジスト膜を形成する工程と、レジスト膜にマスクを介して光を照射して潜像を形成する工程と、潜像が形成されたレジスト膜を現像液で現像処理してレジストパターンを形成する工程と、レジストのない部分を化学的にエッチングやメッキする工程を経ることによって、電子回路が形成される。
従来のポジ型感光性樹脂組成物としては、下記のものが知られている。
(1)フェノール性の水酸基を有するビニル系単量体を含む単量体混合物を重合して得られたビニル系重合体(I)と、カルボキシル基含有ビニル系単量体を含む単量体混合物を重合して得られたビニル系重合体(II)と、キノンジアジド化合物と、芳香族ポリヒドロキシ化合物とを含む、感光性樹脂組成物(特許文献1)。
(2)o-キノンジアジド化合物、アルカリ可溶性樹脂および特定のビスフェノールカルボン酸誘導体を含有することを特徴とするポジ型感光性組成物(特許文献2)。
(2)のポジ型感光性組成物においては、アルカリ可溶性樹脂が剛直で柔軟性に欠け、また現像液への溶解性が不十分であるため、(2)の感光性樹脂組成物をレジスト膜として用いた場合、レジスト膜のクラックの抑制と解像性の両立が十分ではない。また、特許文献2には、ドライフィルム化に関する記載もない。
<3>前記単量体混合物(β)における単量体(b)の割合が、5~30モル%である、<1>または<2>の感光性樹脂組成物。
<4>前記感光性物質(III)が、キノンジアジド化合物である、<1>~<3>のいずれかの感光性樹脂組成物。
<5>前記キノンジアジド化合物が、芳香族環を1~3個有する芳香族ポリヒドロキシ化合物と、1,2-ナフトキノンジアジド-5-スルホン酸および/または1,2-ナフトキノンジアジド-4-スルホン酸とのエステルである、<4>の感光性樹脂組成物。
<6>前記キノンジアジド化合物が、下記式(3)で表される化合物、下記式(4)で表される化合物または下記式(5)で表される化合物と、1,2-ナフトキノンジアジド-5-スルホン酸および/または1,2-ナフトキノンジアジド-4-スルホン酸とのエステルである、<5>の感光性樹脂組成物。
<9>本発明の感光性ドライフィルムの一態様は、<1>~<8>のいずれかの感光性樹脂組成物からなるレジスト膜が支持フィルムの表面に形成されたものである。
<11>本発明のプリント配線板の一態様は、<1>~<8>のいずれかの感光性樹脂組成物を用いて製造したものである。
<12>本発明のプリント配線板の製造方法の一態様は、<1>~<8>のいずれかの感光性樹脂組成物を用いる方法である。
本発明の感光性ドライフィルムによれば、COF;ビルドアップ工法による多層プリント配線板;タッチパネルセンサ回路、タブレット端末等に用いられる引出配線等における回路形成プロセスにおいて、クラックが発生しにくく、解像性に優れたレジスト膜を形成できる。
本発明のパターン形成方法によれば、COF;ビルドアップ工法による多層プリント配線板;タッチパネルセンサ回路、タブレット端末等に用いられる引出配線等における回路形成プロセスにおいて、欠陥の少ない高精度の微細なパターンを形成できる。
本発明のプリント配線板は、COF;ビルドアップ工法による多層プリント配線板;タッチパネルセンサ回路、タブレット端末等に用いられる引出配線等に適用できる。
本発明のプリント配線板の製造方法によれば、COF;ビルドアップ工法による多層プリント配線板;タッチパネルセンサ回路、タブレット端末等に用いられる引出配線等における電子回路の微細化を実現できる。
「(メタ)アクリル酸」とは、アクリル酸またはメタクリル酸を意味する。
「(メタ)アクリロイル」とは、アクリロイルまたはメタクリロイルを意味する。
「単量体」とは、重合性の炭素-炭素二重結合を有する化合物を意味する。
「(共)重合体」とは、単独重合体または共重合体を意味する。
本発明の感光性樹脂組成物は、ビニル系(共)重合体(I)、ビニル系共重合体(II)、感光性物質(III)および化合物(IV)を含み、さらに必要に応じて他の成分を含む。
ビニル系(共)重合体(I)は、フェノール性の水酸基を有するビニル系単量体(a)(以下、単に単量体(a)とも記す。)を含む単量体混合物(α)を重合して得られた重合体であり、必要に応じてさらにカルボキシル基含有ビニル系単量体(c)(以下、単に単量体(c)とも記す。)を含む単量体混合物(α)を重合して得られた重合体である。
単量体(a)としては、下記式(6)で表される単量体(a1)、下記式(7)で表される単量体(a2)、または下記式(8)で表される単量体(a3)が好ましい。
Zは、酸素原子またはNHである。
また、単量体(a2)としては、入手しやすさの点から、下記式(7-1)で表される単量体(a2-1)が好ましい。
また、単量体(a3)としては、入手しやすさの点から、下記式(8-1)で表される単量体(a3-1)が好ましい。
単量体(c)としては、(メタ)アクリル酸、イタコン酸、イタコン酸モノエステル、フマル酸、フマル酸モノエステル、マレイン酸、マレイン酸モノエステル、2-(メタ)アクリロイルオキシエチルフタル酸、2-(メタ)アクリロイルオキシエチルヘキサヒドロフタル酸等が挙げられる。
単量体混合物(α)における他のビニル系単量体の割合は、単量体の合計の仕込み量100モル%のうち、単量体(a)および単量体(c)を除く残部である。
ビニル系(共)重合体(I)の質量平均分子量は、ゲルパーミエイションクロマトグラフィ(GPC)によって測定されるポリスチレン換算の質量平均分子量である。
ビニル系共重合体(II)は、下記式(1)で表されるビニル系単量体(b)(以下、単に単量体(b)とも記す。)および単量体(c)を含む単量体混合物(β)を重合して得られた、質量平均分子量が15,000~120,000の重合体である。
単量体(c)としては、上述のビニル系(共)重合体(I)において例示したものと同様なものが挙げられる。
単量体混合物(β)における他のビニル系単量体の割合は、単量体の合計の仕込み量100モル%のうち、単量体(b)および単量体(c)を除く残部である。
ビニル系共重合体(II)の質量平均分子量は、GPCによって測定されるポリスチレン換算の質量平均分子量である。
ビニル系(共)重合体(I)およびビニル系共重合体(II)は、溶液重合法、懸濁重合法、乳化重合法等の公知の重合法で製造できる。重合法としては、乳化剤等の不純物の混入が少ない点から、溶液重合法または懸濁重合法が好ましい。
ビニル系(共)重合体(I)とビニル系共重合体(II)の合計100質量%中、ビニル系(共)重合体(I)とビニル系共重合体(II)の含有割合(質量比)は、20/80~95/5が好ましく、50/50~90/10がより好ましい。ビニル系(共)重合体(I)が20質量%以上、ビニル系共重合体(II)が80質量%以下であれば、レジスト膜の感度、解像性を損なわず、未露光部の膜減りが十分に抑えられる。ビニル系(共)重合体(I)が95質量%以下、ビニル系共重合体(II)が5質量%以上であれば、レジスト膜のクラックが十分に抑えられる。
感光性物質(III)としては、公知の1,2-キノンジアジド-4-スルホン酸エステル化合物、1,2-キノンジアジド-5-スルホン酸エステル化合物、1,2-キノンジアジド-6-スルホン酸エステル化合物、1,2-キノンジアジド-7-スルホン酸エステル化合物、1,2-キノンジアジド-8-スルホン酸エステル化合物、ビスアジド化合物、ジアゾジスルホン系化合物、トリフェニルスルホニウム系化合物、ヨードニウム系化合物等が挙げられる。具体的には、トリヒドロキシベンゾフェノンの1,2-ナフトキノンジアジドスルホン酸エステル類、テトラヒドロキシベンゾフェノンの1,2-ナフトキノンジアジドスルホン酸エステル類、ペンタヒドロキシベンゾフェノンの1,2-ナフトキノンジアジドスルホン酸エステル類、ヘキサヒドロキシベンゾフェノンの1,2-ナフトキノンジアジドスルホン酸エステル類、(ポリヒドロキシ)アルカンの1,2-ナフトキノンジアジドスルホン酸エステル類等が挙げられる。
化合物(IV)は、下記式(2)で表わされる化合物であり、レジスト膜のアルカリ溶解速度を向上させ、その結果、レジスト膜の解像性を向上させる成分である。
lおよびmは、それぞれ1~3の整数であり、レジスト膜の解像性の点から、1または2が好ましい。
nは、1または2であり、レジスト膜の解像性の点から、1が好ましい。
pおよびqは、それぞれ0または1であり、レジスト膜の解像性の点から、0が好ましい。
下記式(2-a)(式中、l、pは上記と同じ意味を有する。)で示される化合物およびオキシ塩化リンを、アミド類(例えばN,N-ジメチルホルムアミド等)中で反応(ビルスマイヤー反応)させる。ついで、得られた反応混合物にシアン化ナトリウムを反応させた後、この反応混合物を酸またはアルカリの存在下で加水分解して下記式(2-b)(式中、l、n、p、Xは上記と同じ意味を有する。)で示される化合物を得る。ついで、この化合物と下記式(2-c)(式中、m、qは上記と同じ意味を有する。)で示される化合物とを、酸性触媒(例えば塩酸等)の存在下で縮合させる。その結果、化合物(IV)が得られる。
他の成分としては、ビニル系(共)重合体(I)およびビニル系共重合体(II)以外のアルカリ可溶性樹脂、レベリング剤、保存安定剤、可塑剤、吸光剤、架橋剤、接着助剤等が挙げられる。
アルカリ可溶性樹脂としては、ポリ(メタ)アクリル酸、(メタ)アクリル酸と(メタ)アクリル酸エステルとの共重合体等が挙げられる。
他の成分の含有割合は、感光性樹脂組成物の固形分100質量%中、0~30質量%が好ましい。
本発明の感光性樹脂組成物は、通常、ドライフィルム化して用いる。
ドライフィルムは、例えば、支持フィルムの表面に後述のレジスト液を塗布し、乾燥させてレジスト膜を形成することによって製造される。
レジスト膜の厚さは、ドライフィルムとしての実用性を考慮すると、3μm以上が好ましい。
本発明の感光性樹脂組成物は、溶媒に溶解したレジスト液の状態で用いてもよい。レジスト液は、例えば、ビニル系(共)重合体(I)、ビニル系共重合体(II)、感光性物質(III)、化合物(IV)、および溶媒を混合する方法;懸濁重合法または溶液重合法で得られたビニル系(共)重合体(I)、およびビニル系共重合体(II)を含む溶液に、感光性物質(III)、化合物(IV)を添加する方法等によって調製される。
ケトン類としては、アセトン、メチルエチルケトン(以下、MEKと記す。)、メチルイソブチルケトン、2-ペンタノン、2-ヘキサノン等の直鎖状もしくは分岐状ケトン;シクロペンタノン、シクロヘキサノン等の環状ケトン等が挙げられる。
プロピレングリコールモノアルキルアセテート類としては、プロピレングリコールモノメチルエーテルアセテート(以下、PGMEAと記す。)、プロピレングリコールモノエチルエーテルアセテート等が挙げられる。
エチレングリコールモノアルキルエーテルアセテート類としては、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート等が挙げられる。
プロピレングリコールモノアルキルエーテル類としては、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等が挙げられる。
エチレングリコールモノアルキルエーテル類としては、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等が挙げられる。
ジエチレングリコールアルキルエーテル類としては、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノメチルエーテル等が挙げられる。
エステル類としては、酢酸エチル、乳酸エチル等が挙げられる。
アルコール類としては、メチルアルコール、エチルアルコール、n-プロピルアルコール、イソプロピルアルコール、n-ブチルアルコール、シクロヘキサノール、1-オクタノール等が挙げられる。
炭素数5~11の脂肪族炭化水素系溶媒としては、ペンタン、2-メチルブタン、n-ヘキサン、2-メチルペンタン、2,2-ジブチルブタン、2,3-ジブチルブタン、n-ヘプタン、n-オクタン、イソオクタン、2,2,3-トリメチルペンタン、n-ノナン、2,2,5-トリメチルヘキサン、n-デカン、n-ドデカン等が挙げられる。
その他の化合物としては、1,4-ジオキサン、炭酸エチレン、γ-ブチロラクトン等が挙げられる。
溶媒としては、安全性の点、汎用的に用いられている点から、アセトン、メチルアルコール、エチルアルコール、イソプロピルアルコール、MEK、PGMEA、乳酸エチル、シクロヘキサノン、γ-ブチロラクトン等が好ましい。
以上説明した本発明の感光性樹脂組成物は、特定のビニル系(共)重合体(I)および特定のビニル系共重合体(II)を含んでいるため、クラックが発生しにくいレジスト膜を形成できる。また、感光性物質(III)および特定の化合物(IV)を含んでいるため、レジスト膜の解像性がさらに良好となる。
一方、特許文献1の感光性樹脂組成物は、ビニル系重合体が特定の単量体(b)からなる構成単位を含まないため、ビニル系重合体が剛直で柔軟性に欠け、また現像液への溶解性が不十分であり、これを含むレジスト膜のクラックの抑制と解像性の両立が十分ではない。
本発明のパターン形成方法は、下記の工程を有する方法である。
(A)感光性樹脂組成物からなるレジスト膜を基材表面に形成する工程。
(B)レジスト膜を露光して潜像を形成する工程。
(C)潜像が形成されたレジスト膜を、アルカリ性の現像液で現像処理してレジストパターンを形成する工程。
(D)レジストのない部分に加工を施し、所望のパターンを基材表面に形成する工程。
上述のレジスト液を用いる場合、パターンを形成する基材の表面に、レジスト液をスピナー、コーター等により塗布、乾燥し、基材表面にレジスト膜を形成する。
上述のドライフィルムを用いる場合、パターンを形成する基材とレジスト膜とが接するように、基材の表面にドライフィルムをラミネートする。
露光方法としては、紫外線露光法、可視光露光法等が挙げられる。
露光を選択的に行う方法としては、フォトマスクを用いる方法、レーザー光を用いた走査露光法が挙げられる。フォトマスクを用いる場合の露光方法としては、コンタクト露光法、オフコンタクト露光法のいずれも使用可能である。
上述のドライフィルムを用いた場合、支持フィルム越しにレジスト膜を露光して潜像を形成した後、支持フィルムを剥離する。
現像液としては、アルカリ類の水溶液が挙げられる。
アルカリ類としては、無機アルカリ類(水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水等)、第一アミン類(エチルアミン、n-プロピルアミン等)、第二アミン類(ジエチルアミン、ジ-n-ブチルアミン等)、第三アミン類(トリエチルアミン、メチルジエチルアミン等)、アルコールアミン類(ジメチルエタノールアミン、トリエタノールアミン等)、第四級アンモニウム塩(テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリンヒドロキシド等)、環状アミン類(ピロール、ピペリジン等)等が挙げられる。
現像液としては、通常のプリント配線板における回路形成プロセスと同じ工程を利用できることから、1質量%炭酸ナトリウム水溶液が特に好ましい。
加工方法としては、公知のエッチング、メッキ等が挙げられる。
本発明の感光性樹脂組成物は、COF;ビルドアップ工法による多層プリント配線板;タッチパネルセンサ回路、タブレット端末等に用いられる引出配線等における回路形成プロセスにおけるレジストとして有用である。
本発明のプリント配線板は、本発明の感光性樹脂組成物を用いて製造したものである。具体的には、基材(絶縁板、シート等)上に導体の配線を形成したものである。これらに電子部品を実装し、目標とする電子回路としての機能を持たせる。
本発明のプリント配線板の製造方法は、本発明の感光性樹脂組成物を用いる方法である。具体的には、本発明のパターン形成方法によってレジストパターンが形成された回路形成用基材をエッチングまたはメッキして配線を形成し、必要に応じてさらに電子部品を実装する方法である。
実施例における評価方法は、下記の通りである。
東ソー社製のGPCを用いて、ビニル系重合体の質量平均分子量(Mw)を測定した。
前記測定は、分離カラムとして昭和電工社製、Shodex GPC K-805L(商品名)を3本直列にしたものを用い、溶媒としてテトラヒドロフラン(流量:1.0mL/分)を用い、検出器として示差屈折計を用い、標準ポリマーとしてポリスチレンを用い、測定温度40℃、注入量0.1mLの条件で行った。
JIS K 5600-5-1:塗料一般試験方法、耐屈曲性(円筒形マンドレル法)を参考にして、ドライフィルムを、直径2mmの円筒の外周に沿って折り曲げ、クラックの発生を目視にて観察し、下記の基準で評価した。
○:クラックが発生しない。
×:クラックが確認された。
レジスト膜を、10μmのラインアンドスペースパターンを形成するように超高圧水銀灯で露光し、1質量%炭酸ナトリウム水溶液(pH約11.6)にて2分間現像を行った後、パターン形状を電子顕微鏡にて観察し、下記の基準で評価した。
◎:露光部が完全に溶解している。
○:パターンのエッジ部分に若干の残渣が残る。
△:露光部に若干の残渣が残る。
×:露光部に残渣が多く残る。
窒素導入口、攪拌機、コンデンサー、滴下漏斗、および温度計を備えたフラスコに、窒素雰囲気下で、MEK40質量部を入れた。フラスコ内を攪拌しながら内温を80℃に上げた。
その後、下記の化合物を混合した滴下溶液を、滴下漏斗を用いて6時間かけてフラスコ内に滴下し、さらに80℃の温度で1時間保持した。
前記式(7-1)で表される単量体(a2-1)(パラヒドロキシスチレン)40モル%、
メタクリル酸20モル%、
メタクリル酸メチル15モル%、
スチレン10モル%、
アクリル酸エチル15モル%、
前記単量体の合計100質量部に対して7質量部の重合開始剤(大塚化学社製、2,2’-アゾビス-2-メチルブチロニトリル)、および
MEK100質量部。
単量体の仕込み量を表1に示す量に変更した以外は、製造例1と同様の操作でビニル系共重合体(I-2)溶液およびビニル系共重合体(I-3)溶液を得た。
窒素導入口、攪拌機、コンデンサー、滴下漏斗、および温度計を備えたフラスコに、窒素雰囲気下で、MEK50質量部を入れた。フラスコ内を攪拌しながら内温を85℃に上げた。
その後、下記の化合物を混合した滴下溶液を、滴下漏斗を用いて4時間かけてフラスコ内に滴下し、さらに85℃の温度で1時間保持した。
アクリル酸2-メトキシエチル11.5モル%
メタクリル酸16.8モル%、
メタクリル酸メチル2.7モル%、
スチレン17モル%、
アクリル酸エチル43.1モル%、
アクリル酸2-エチルヘキシル8.9モル%
前記単量体の合計100質量部に対して0.6質量部の重合開始剤(大塚化学社製、2,2’-アゾビス-2-メチルブチロニトリル)。
フラスコに入れるMEKを45質量部に変更し、重合開始剤の仕込み量を単量体の合計100質量部に対して0.2質量部に変更し、温度を室温まで下げた後に添加するMEKを70質量部に変更した以外は、製造例4と同様の操作でビニル系共重合体(II-2)溶液を得た。
重合開始剤の仕込み量を単量体の合計100質量部に対して3質量部に変更した以外は、製造例4と同様の操作でビニル系共重合体(II-3)溶液を得た。
単量体の仕込み量を表1に示す量に変更した以外は、製造例4と同様の操作でビニル系共重合体(II-4)溶液を得た。
式(2-1)で表される化合物の合成:
4-ヒドロキシマンデル酸16.8質量部、フェノール37.6質量部および10%塩酸170質量部を混合した混合物を60~65℃で2時間反応させた。反応終了後、前記混合物に、イオン交換水300質量部およびアセトン300質量部を混合した混合物を加えて60℃で分液した。得られた有機層をイオン交換水で洗浄した。洗浄後の有機層を減圧条件で濃縮し、得られた濃縮残分に、アセトン5質量部およびトルエン80質量部を混合した混合液を添加して、再結晶化し、前記式(2-1)で表される特定の化合物(IV)を得た。1H-NMRおよびIRから目的の化合物が得られたことを確認した。
フェノール94質量部、レブリン酸58質量部、水45質量部および濃硫酸180質量部を混合した混合物を20℃で20時間反応させた。反応終了後、前記混合物に、イオン交換水300質量部および酢酸エチル300質量部を混合した混合物を加えて分液した。得られた有機層に重炭酸ナトリウム水溶液を加え、有機層を抽出した。得られた重炭酸塩抽出物を酸性にして、エーテルで抽出し、真空脱揮して前記式(2-2)で示される特定の化合物(IV)を得た。1H-NMRおよびIRから目的の化合物が得られたことを確認した。
ビニル系共重合体(I-1)溶液70質量部、ビニル系共重合体(II-1)溶液30質量部、感光性物質(III)として前記式(3)で表される化合物(1モル)と1,2-ナフトキノンジアジド-5-スルホン酸(3モル)とのエステル10質量部、特定の化合物(IV)として前記式(2-1)で表される化合物2質量部およびMEK200質量部を混合し、レジスト液を得た。
ビニル系(共)重合体(I)の種類および配合量、ビニル系共重合体(II)の種類および配合量、感光性物質(III)の種類、特定の化合物(IV)の種類を表2に示すように変更した以外は、実施例1と同様にしてドライフィルムを得て、前記ドライフィルムの評価を行った。結果を表3に示す。
Claims (12)
- フェノール性の水酸基を有するビニル系単量体(a)を含む単量体混合物(α)を重合して得られたビニル系(共)重合体(I)、
下記式(1)で表されるビニル系単量体(b)およびカルボキシル基含有ビニル系単量体(c)を含む単量体混合物(β)を重合して得られた、質量平均分子量が15,000~120,000であるビニル系共重合体(II)(ただし、前記ビニル系(共)重合体(I)を除く。)、
感光性物質(III)、並びに
下記式(2)で表される化合物(IV)
を含む、感光性樹脂組成物。
- 前記単量体(b)が、アクリル酸2-メトキシエチルである、請求項1に記載の感光性樹脂組成物。
- 前記単量体混合物(β)における単量体(b)の割合が、5~30モル%である、請求項1に記載の感光性樹脂組成物。
- 前記感光性物質(III)が、キノンジアジド化合物である、請求項1に記載の感光性樹脂組成物。
- 前記キノンジアジド化合物が、芳香族環を1~3個有する芳香族ポリヒドロキシ化合物と、1,2-ナフトキノンジアジド-5-スルホン酸および/または1,2-ナフキノンジアジド-4-スルホン酸とのエステルである、請求項4に記載の感光性樹脂組成物。
- 前記ビニル系(共)重合体(I)が、前記単量体(a)および前記単量体(c)を含む単量体混合物(α)を重合して得られた共重合体である、請求項1に記載の感光性樹脂組成物。
- 請求項1~8のいずれか一項に記載の感光性樹脂組成物からなるレジスト膜が支持フィルムの表面に形成された、感光性ドライフィルム。
- 請求項1~8のいずれか一項に記載の感光性樹脂組成物からなるレジスト膜を基材の表面に形成する工程、前記レジスト膜を露光して潜像を形成する工程、および潜像が形成された前記レジスト膜を、アルカリ性現像液で現像処理してレジストパターンを形成する工程を有する、パターン形成方法。
- 請求項1~8のいずれか一項に記載の感光性樹脂組成物を用いて製造したプリント配線板。
- 請求項1~8のいずれか一項に記載の感光性樹脂組成物を用いたプリント配線板の製造方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201380036547.0A CN104541203B (zh) | 2012-07-10 | 2013-07-02 | 感光性树脂组合物、感光性干膜、图案形成方法、印刷布线板及其制造方法 |
US14/413,557 US9625812B2 (en) | 2012-07-10 | 2013-07-02 | Photosensitive resin composition, photosensitive dry film, pattern formation method, printed circuit board, and method for producing same |
JP2013531999A JP5710769B2 (ja) | 2012-07-10 | 2013-07-02 | 感光性樹脂組成物、感光性ドライフィルム、パターン形成方法、プリント配線板およびその製造方法 |
KR1020157000424A KR101595709B1 (ko) | 2012-07-10 | 2013-07-02 | 감광성 수지 조성물, 감광성 드라이 필름, 패턴 형성 방법, 프린트 배선판 및 그의 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012-154959 | 2012-07-10 | ||
JP2012154959 | 2012-07-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014010473A1 true WO2014010473A1 (ja) | 2014-01-16 |
Family
ID=49915934
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/068165 WO2014010473A1 (ja) | 2012-07-10 | 2013-07-02 | 感光性樹脂組成物、感光性ドライフィルム、パターン形成方法、プリント配線板およびその製造方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9625812B2 (ja) |
JP (1) | JP5710769B2 (ja) |
KR (1) | KR101595709B1 (ja) |
CN (1) | CN104541203B (ja) |
TW (1) | TWI574107B (ja) |
WO (1) | WO2014010473A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016188922A (ja) * | 2015-03-30 | 2016-11-04 | 日立化成株式会社 | 感光性樹脂組成物、感光性エレメント、レジストパターン付き基材の製造方法、プリント配線板の製造方法及びタッチパネルの製造方法 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107278039A (zh) * | 2016-04-08 | 2017-10-20 | 东莞市斯坦得电子材料有限公司 | 一种用于印制线路板的有机碱干膜退除工艺 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01280748A (ja) * | 1988-05-06 | 1989-11-10 | Fuji Yakuhin Kogyo Kk | ポジ型感光性組成物 |
JPH07133449A (ja) * | 1993-05-28 | 1995-05-23 | Kansai Paint Co Ltd | ポジ型感光性アニオン電着レジスト組成物及びこの組成物を用いたパターンの形成方法 |
JP2004117882A (ja) * | 2002-09-26 | 2004-04-15 | Fuji Photo Film Co Ltd | ポジ型感光性平版印刷版 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3424369B2 (ja) | 1995-02-07 | 2003-07-07 | 住友化学工業株式会社 | ポジ型レジスト組成物 |
JP3710717B2 (ja) * | 2001-03-06 | 2005-10-26 | 東京応化工業株式会社 | 厚膜用ポジ型ホトレジスト組成物、ホトレジスト膜およびこれを用いたバンプ形成方法 |
JP4384570B2 (ja) | 2003-12-01 | 2009-12-16 | 東京応化工業株式会社 | 厚膜用ホトレジスト組成物及びレジストパターンの形成方法 |
JP2006154434A (ja) | 2004-11-30 | 2006-06-15 | Jsr Corp | 感光性樹脂組成物、感光性樹脂膜およびこれらを用いたバンプ形成方法 |
TW200739265A (en) * | 2005-12-06 | 2007-10-16 | Tokyo Ohka Kogyo Co Ltd | Positive photoresist composition and method of forming photoresist pattern using the same |
EP2284611B1 (en) * | 2008-06-02 | 2013-11-20 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive element, resist pattern manufacturing method, and printed circuit board manufacturing method |
JP5592064B2 (ja) | 2008-07-07 | 2014-09-17 | 東京応化工業株式会社 | ポジ型レジスト組成物 |
KR100913058B1 (ko) | 2008-08-25 | 2009-08-20 | 금호석유화학 주식회사 | 포지티브형 감광성 수지 조성물, 패턴 형성 방법 및 반도체소자 |
US8808960B2 (en) * | 2009-03-11 | 2014-08-19 | Sumitomo Chemical Company, Limited | Compound and chemically amplified positive resist composition |
JP5685180B2 (ja) * | 2009-12-28 | 2015-03-18 | 株式会社 マイクロプロセス | 感光性樹脂組成物、感光性ドライフィルムおよびパターン形成方法 |
KR101831130B1 (ko) | 2009-12-28 | 2018-02-26 | 가부시키가이샤 마이쿠로 푸로세스 | 감광성 수지 조성물, 감광성 드라이 필름 및 패턴 형성 방법 |
JP5695928B2 (ja) | 2010-04-14 | 2015-04-08 | 東京応化工業株式会社 | 櫛型電極の製造方法 |
JP5498874B2 (ja) | 2010-06-28 | 2014-05-21 | 東京応化工業株式会社 | ポジ型感光性樹脂組成物 |
-
2013
- 2013-07-02 JP JP2013531999A patent/JP5710769B2/ja active Active
- 2013-07-02 WO PCT/JP2013/068165 patent/WO2014010473A1/ja active Application Filing
- 2013-07-02 CN CN201380036547.0A patent/CN104541203B/zh active Active
- 2013-07-02 KR KR1020157000424A patent/KR101595709B1/ko active IP Right Grant
- 2013-07-02 US US14/413,557 patent/US9625812B2/en active Active
- 2013-07-08 TW TW102124431A patent/TWI574107B/zh active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01280748A (ja) * | 1988-05-06 | 1989-11-10 | Fuji Yakuhin Kogyo Kk | ポジ型感光性組成物 |
JPH07133449A (ja) * | 1993-05-28 | 1995-05-23 | Kansai Paint Co Ltd | ポジ型感光性アニオン電着レジスト組成物及びこの組成物を用いたパターンの形成方法 |
JP2004117882A (ja) * | 2002-09-26 | 2004-04-15 | Fuji Photo Film Co Ltd | ポジ型感光性平版印刷版 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016188922A (ja) * | 2015-03-30 | 2016-11-04 | 日立化成株式会社 | 感光性樹脂組成物、感光性エレメント、レジストパターン付き基材の製造方法、プリント配線板の製造方法及びタッチパネルの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20150009614A (ko) | 2015-01-26 |
KR101595709B1 (ko) | 2016-02-24 |
TW201407278A (zh) | 2014-02-16 |
US20150168832A1 (en) | 2015-06-18 |
TWI574107B (zh) | 2017-03-11 |
JPWO2014010473A1 (ja) | 2016-06-23 |
CN104541203A (zh) | 2015-04-22 |
US9625812B2 (en) | 2017-04-18 |
CN104541203B (zh) | 2021-06-08 |
JP5710769B2 (ja) | 2015-04-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2017107211A (ja) | レジスト組成物 | |
CN106019831B (zh) | 抗蚀剂组合物及抗蚀图案的制造方法 | |
JP4481789B2 (ja) | エポキシ硬化剤 | |
JP5753074B2 (ja) | 感光性樹脂組成物、感光性ドライフィルムおよびパターン形成方法 | |
US20110117332A1 (en) | Acrylate resin, photoresist composition comprising the same, and photoresist pattern | |
JP5691657B2 (ja) | 感光性樹脂組成物およびその用途 | |
TWI710855B (zh) | 感光性樹脂組合物及由其製造的光固化圖案 | |
JP5710769B2 (ja) | 感光性樹脂組成物、感光性ドライフィルム、パターン形成方法、プリント配線板およびその製造方法 | |
JP4455499B2 (ja) | 感光性樹脂組成物 | |
KR20100088525A (ko) | 포지티브형 레지스트 조성물 및 이것을 이용한 레지스트 패턴의 형성 방법 | |
JP5685180B2 (ja) | 感光性樹脂組成物、感光性ドライフィルムおよびパターン形成方法 | |
JP5884551B2 (ja) | 感光性樹脂組成物およびその用途 | |
CN107219724B (zh) | 化学增幅型正型感光性有机绝缘膜树脂组合物及绝缘膜 | |
KR20110048479A (ko) | 아크릴레이트 수지, 이를 포함하는 포토레지스트 조성물, 및 포토레지스트 패턴 | |
JP5637024B2 (ja) | 感光性樹脂組成物およびその用途 | |
JP2015179121A (ja) | 感光性樹脂組成物およびその用途 | |
JP2015161942A (ja) | ポジ型感光性樹脂組成物およびその用途 | |
JP2009280683A (ja) | モノマー、ポリマー及び感光性樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2013531999 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13817612 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20157000424 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14413557 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13817612 Country of ref document: EP Kind code of ref document: A1 |