WO2012014580A1 - 感光性樹脂組成物、並びに、これを用いた感光性エレメント、レジストパターン製造方法、リードフレームの製造方法、プリント配線板、及びプリント配線板の製造方法 - Google Patents
感光性樹脂組成物、並びに、これを用いた感光性エレメント、レジストパターン製造方法、リードフレームの製造方法、プリント配線板、及びプリント配線板の製造方法 Download PDFInfo
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- WO2012014580A1 WO2012014580A1 PCT/JP2011/063389 JP2011063389W WO2012014580A1 WO 2012014580 A1 WO2012014580 A1 WO 2012014580A1 JP 2011063389 W JP2011063389 W JP 2011063389W WO 2012014580 A1 WO2012014580 A1 WO 2012014580A1
- Authority
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- WIPO (PCT)
- Prior art keywords
- photosensitive resin
- mass
- meth
- resin composition
- resin layer
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 74
- 238000004519 manufacturing process Methods 0.000 title claims description 49
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- 239000011230 binding agent Substances 0.000 claims abstract description 55
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003999 initiator Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims description 80
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- 239000000758 substrate Substances 0.000 claims description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 238000007747 plating Methods 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 27
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 11
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- 238000011161 development Methods 0.000 description 24
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- 239000000047 product Substances 0.000 description 17
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
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Images
Classifications
-
- 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
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
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- 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
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- 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
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- 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
- C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
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- 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
Definitions
- the present invention relates to a photosensitive resin composition, a photosensitive element using the same, a resist pattern manufacturing method, a lead frame manufacturing method, a printed wiring board, and a printed wiring board manufacturing method.
- photosensitive resin layers In the field of printed wiring board production, as a resist material used for etching and plating, supports photosensitive resin compositions and layers containing these photosensitive resin compositions (hereinafter referred to as “photosensitive resin layers”). Photosensitive elements (laminates) that are formed on a film and have a structure in which a protective film is disposed on a photosensitive resin layer are widely used.
- a printed wiring board is manufactured by using the above photosensitive element, for example, by the following procedure. That is, first, the photosensitive resin layer of the photosensitive element is laminated on a circuit forming substrate such as a copper-clad laminate. At this time, the surface (hereinafter referred to as the “upper surface” of the photosensitive resin layer) opposite to the surface in contact with the support film of the photosensitive resin layer (hereinafter referred to as the “lower surface” of the photosensitive resin layer) The circuit forming substrate is brought into close contact with the surface on which the circuit is formed. Therefore, when the protective film is arrange
- the photosensitive resin layer is pattern-exposed through a mask film or the like.
- the support film is peeled off at any timing before or after exposure.
- the unexposed portion of the photosensitive resin layer is dissolved or dispersed and removed with a developer.
- an etching process or a plating process is performed to form a pattern, and finally the cured portion is peeled and removed.
- the etching treatment is a method of removing the cured resist after etching away the metal surface of the circuit forming substrate not covered with the cured resist formed after development.
- the plating treatment was performed by plating copper and solder on the metal surface of the circuit forming substrate that was not covered with the cured resist formed after development, and then the cured resist was removed and covered with this resist. This is a method of etching a metal surface.
- DLP Digital Light Processing
- the width between circuits is narrow, it is also important that the resist shape is excellent. If the cross-sectional shape of the resist is trapezoidal or inverted trapezoidal, or if the resist is skirted, it may cause a short circuit or disconnection in the circuit formed by the subsequent etching process or plating process. Is preferably rectangular and without skirting.
- the etching method has an effect of side etching at the time of etching. There is a limit to increasing the density (coexistence of circuit thickness and circuit width). Further, in the plating method, since it is difficult to obtain a required circuit thickness (copper thickness) when the photosensitive resin layer is made a thin film, there is a limit to increasing the density of the printed wiring board.
- JP-A-1-221735 and JP-A-2-230149 disclose that two or more photosensitive resin layers are used and a layer that is in direct contact with the phototool is a non-adhesive resin. Layering is done. However, this method takes time and effort to coat the photosensitive resin layer to make it multi-layered, and is ineffective for sensitivity reduction.
- a semi-additive construction method has attracted attention as a manufacturing method.
- printing is performed by sequentially forming an ultra-thin conductor layer by electroless plating on the substrate, forming a resist pattern, plating, stripping the resist, and quick etching (removing unnecessary ultra-thin conductor layer).
- a wiring board is formed. Advantages of this method include that a good circuit can be obtained because there is almost no influence of side etching, and that the printed wiring board can be densified.
- the photosensitive resin composition is excellent in resolution, resist stripping properties, and adhesion. If the photosensitive resin composition can provide a resist pattern with excellent resolution and adhesion, it is possible to sufficiently reduce short circuits and disconnections between circuits. In addition, if the photosensitive resin composition can form a resist with excellent peeling characteristics, the resist patterning efficiency is improved by shortening the resist peeling time, and the size of the resist peeling pieces By reducing, the resist peeling residue is reduced and the yield of circuit formation is improved.
- Japanese Patent Application Laid-Open No. 11-327137 proposes a photosensitive resin composition having excellent sensitivity, resolution, and resist stripping characteristics using a specific binder polymer, a photopolymerization initiator, and the like. ing.
- JP-A-2003-215799 and JP-A-2000-162767 a polymerization inhibitor such as catechol or hydroquinone is used in order to improve the contrast (imaging property) between the exposed part and the unexposed part.
- a photosensitive resin composition is disclosed.
- the photosensitive resin composition described in JP-A No. 11-327137 has good releasability, but is not sufficient in terms of resolution.
- the photosensitive resin compositions described in JP-A Nos. 2003-215799 and 2000-162767 are good in terms of resolution and imaging properties, the sensitivity is increased when the amount of polymerization inhibitor added is excessive. In some cases, the adhesion decreased.
- the conventional photosensitive resin composition does not sufficiently satisfy the required properties for all of sensitivity, resolution, adhesion, resist shape, and peeling characteristics after curing.
- the present invention provides a photosensitive resin composition that is excellent in all of sensitivity, resolution, adhesion, resist shape, and release characteristics after curing, and a photosensitive element, a resist pattern manufacturing method, and a lead frame manufacturing using the same. It is an object to provide a method, a printed wiring board, and a manufacturing method of the printed wiring board.
- the present invention includes the following aspects.
- the first aspect of the present invention is a binder polymer having a structural unit derived from (A) (meth) acrylic acid, and a structural unit derived from (meth) acrylic acid benzyl ester or (meth) acrylic acid benzyl ester derivative;
- a photosensitive resin composition comprising: (B) a polymerizable compound having at least one ethylenically unsaturated bond; and (C) a photopolymerization initiator containing an acylphosphine oxide compound and a hexaarylbiimidazole derivative. is there.
- the photosensitive resin composition of the said structure is excellent in all of a sensitivity, resolution, adhesiveness, a resist shape, and the peeling characteristic after hardening.
- the acylphosphine oxide compound is preferably a compound represented by the following general formula (I) or general formula (II). Thereby, the resolution is further improved, and a more excellent resist shape can be obtained.
- R 1 , R 2 and R 3 each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms.
- R 4 , R 5 and R 6 each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms.
- the hexaarylbiimidazole derivative is preferably a 2,4,5-triarylimidazole dimer. This further improves sensitivity and resolution.
- a second aspect of the present invention is a photosensitive element comprising a support and a photosensitive resin layer that is a coating film of the photosensitive resin composition formed on the support.
- a photosensitive resin layer forming step of forming a photosensitive resin layer which is a coating film of the photosensitive resin composition, on a substrate, and active in at least a part of the photosensitive resin layer.
- a fourth aspect of the present invention is a lead frame manufacturing method including a step of forming a conductor pattern by plating a substrate on which a resist pattern has been formed by the above resist pattern manufacturing method.
- a printed wiring board manufacturing method including a step of plating a substrate on which a resist pattern is formed by the resist pattern manufacturing method to form a conductor pattern. According to this manufacturing method, a high-density printed wiring board such as a high-density package substrate can be accurately and efficiently manufactured.
- a sixth aspect of the present invention is a printed wiring board manufactured by the method for manufacturing a printed wiring board.
- the photosensitive resin composition which is excellent in all of sensitivity, resolution, adhesiveness, a resist shape, and the peeling characteristic after hardening, and the photosensitive element using this, a resist pattern manufacturing method, manufacture of a lead frame A method and a printed wiring board manufacturing method can be provided.
- the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
- a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the amount of each component in the composition in the present specification when there are a plurality of substances corresponding to each component in the composition, the plurality of the components present in the composition unless otherwise specified. It means the total amount of substance.
- the photosensitive resin composition of the present invention comprises (A) a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid benzyl ester or (meth) acrylic acid benzyl ester derivative. At least one polymer, (B) at least one polymerizable compound having at least one ethylenically unsaturated bond, and (C) a photopolymerization initiator containing an acylphosphine oxide compound and a hexaarylbiimidazole derivative; , Containing.
- Such a structure exhibits excellent characteristics in all of sensitivity, resolution, adhesion, resist shape, and peeling characteristics after curing.
- the binder polymer in the present invention is particularly suitable if it has a structural unit derived from (meth) acrylic acid and a structural unit derived from benzyl (meth) acrylate or a benzyl derivative (meth) acrylate. There is no limit. In addition to the structural unit derived from the (meth) acrylic acid and the structural unit derived from a benzyl (meth) acrylate or a benzyl derivative (meth) acrylate, the binder polymer is optionally (meth) acrylic acid. Other structural units such as a structural unit derived from an alkyl ester and a structural unit derived from styrene or a styrene derivative may be further included.
- Examples of the (meth) acrylic acid benzyl ester derivative include compounds in which an alkoxy group having 1 to 6 carbon atoms, halogen, or an alkyl group having 1 to 6 carbon atoms is substituted on the aromatic ring of the benzyl group. Specific examples include ethoxybenzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, methylbenzyl (meth) acrylate, and ethylbenzyl (meth) acrylate.
- Examples of other polymerizable monomers other than (meth) acrylic acid and (meth) acrylic acid benzyl ester or (meth) acrylic acid benzyl ester derivatives include styrene; vinyltoluene, ⁇ -methylstyrene, and the like.
- Maleic acid monoester fumaric acid, cinnamic acid, ⁇ -cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. These may be used alone or in any combination of two or more.
- the (A) binder polymer preferably further includes at least one structural unit derived from a (meth) acrylic acid alkyl ester from the viewpoint of improving alkali developability and release properties.
- Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (IV).
- R 9 represents a hydrogen atom or a methyl group
- R 10 represents an alkyl group having 1 to 12 carbon atoms.
- Examples of the alkyl group having 1 to 12 carbon atoms represented by R 10 in the general formula (IV) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. Group, decyl group, undecyl group, dodecyl group and structural isomers thereof. From the viewpoint of further improving the peeling characteristics, the alkyl group preferably has 1 to 4 carbon atoms.
- Specific examples of the compound represented by the general formula (IV) include, for example, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester.
- the binder polymer preferably further contains at least one structural unit derived from styrene or a derivative thereof from the viewpoint of improving resolution and adhesion.
- each structural unit constituting the binder polymer is not particularly limited.
- the content of the structural unit derived from (meth) acrylic acid is preferably such that the acid value of the binder polymer is 100 mgKOH / g to 250 mgKOH / g, and is 120 mgKOH / g to 240 mgKOH / g.
- the content is more preferably 140 mg KOH / g to 230 mg KOH / g, still more preferably 150 mg KOH / g to 230 mg KOH / g. It can suppress that development time becomes long because the acid value of a binder polymer is 100 mgKOH / g or more.
- cured material of the photosensitive resin composition improves because an acid value is 250 mgKOH / g or less.
- the content of the structural unit derived from the (A) binder polymer (meth) acrylic acid benzyl ester or (meth) acrylic acid benzyl ester derivative is 5 mass% to 65 mass% based on the total mass of the binder polymer molecule. It is preferably 10% by mass to 55% by mass, and more preferably 20% by mass to 50% by mass.
- the resolution is further improved when the content is 5% by mass or more. Moreover, it can suppress that a peeling piece becomes large because this content rate is 65 mass% or less, and can suppress that peeling time becomes long.
- the binder polymer contains a structural unit derived from an alkyl (meth) acrylate
- the content is preferably 1% by mass to 50% by mass based on the total mass of the binder polymer molecule. % To 30% by mass is more preferable, and 3% to 20% by mass is even more preferable. It can suppress that a peeling piece becomes large because this content is 1 mass% or more, and it can suppress that peeling time becomes long. Moreover, resolution and adhesiveness improve more because this content is 50 mass% or less.
- the content is preferably 5% by mass to 65% by mass based on the total mass of the binder polymer molecule.
- the mass is more preferably from 60% by mass to 60% by mass, further preferably from 15% by mass to 55% by mass, and particularly preferably from 20% by mass to 50% by mass. Adhesiveness improves more because this content rate is 5 mass% or less. Moreover, it can suppress that a peeling piece becomes large because this content rate is 65 mass% or less, and can suppress that peeling time becomes long.
- the binder polymer preferably has a weight average molecular weight (Mw) of 10,000 to 100,000, more preferably 20,000 to 80,000, and even more preferably 25,000 to 60,000.
- Mw weight average molecular weight
- the weight average molecular weight of the binder polymer is measured by gel permeation chromatography (GPC) (converted with a calibration curve using standard polystyrene).
- the degree of dispersion (Mw / Mn) of the binder polymer is not particularly limited, but is preferably 1.0 to 3.0, and more preferably 1.5 to 2.5. When the degree of dispersion is 3.0 or less, adhesion and resolution are further improved.
- the binder polymer may have, in the molecule, a characteristic group that has photosensitivity to light having a wavelength in the range of 350 nm to 440 nm, if necessary.
- the binder polymer in the present invention contains, in the binder polymer, 5% by mass to 65% by mass of a structural unit derived from (meth) acrylic acid, a structural unit derived from benzyl (meth) acrylate or a derivative thereof, ) 1% to 50% by mass of a structural unit derived from an alkyl acrylate ester and 5% to 65% by mass of a structural unit derived from styrene or a derivative thereof, and an acid value of 100 mgKOH / g to 250 mgKOH / g, and the weight average molecular weight is preferably 10,000 to 100,000.
- it has a structural unit derived from (meth) acrylic acid, 10% to 55% by weight of a structural unit derived from benzyl (meth) acrylate, and an alkyl group having 1 to 4 carbon atoms (meta ) 2% to 30% by mass of a structural unit derived from an alkyl acrylate ester and 10% to 60% by mass of a structural unit derived from styrene or a derivative thereof, and an acid value of 120 mgKOH / g to 230 mgKOH / g, and the weight average molecular weight is 20,000 to 80,000.
- the acid value is 140 mgKOH / g to 230 mgKOH / g and a weight average molecular weight of 25,000 to 60,000.
- the binder polymer in the present invention can be produced by a usual method. Specifically, for example, radical polymerization of (meth) acrylic acid, (meth) acrylic acid benzyl ester or (meth) acrylic acid benzyl ester derivative, and other polymerizable monomers used as necessary. Can be manufactured.
- binder polymer one kind of binder polymer may be used alone, or two or more kinds of binder polymers may be used in any combination.
- a binder polymer in the case of using two or more types in combination, for example, two or more types of binder polymers comprising different copolymer components (including different monomer units as copolymer components), two or more types of different weight average molecular weights
- the binder polymer include two or more binder polymers having different degrees of dispersion.
- a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used.
- the content of the (A) binder polymer in the photosensitive resin composition of the present invention is preferably 20% by mass to 90% by mass, and preferably 30% by mass to 80% by mass in the photosensitive resin composition. More preferably, it is 40% by mass to 65% by mass.
- the moldability of a film is excellent in the content rate of a binder polymer being 20 mass% or more.
- the content of the (A) binder polymer in the photosensitive resin composition is 30 to 70 parts by mass in 100 parts by mass of the total amount of the (A) binder polymer component and (B) polymerizable compound component. Preferably, it is 35 to 65 parts by mass, more preferably 40 to 60 parts by mass. When the content is 30 parts by mass or more, the film formability is further improved. Moreover, a sensitivity and resolution improve more because it is 70 mass parts or less.
- the photosensitive resin composition of the present invention contains at least one polymerizable compound having at least one ethylenically unsaturated bond.
- the content of the polymerizable compound is preferably 3% by mass to 70% by mass in the photosensitive resin composition, more preferably 10% by mass to 60% by mass, and more preferably 25% by mass to 50% by mass. More preferably.
- sensitivity and resolution tend to be excellent.
- the polymerizable compound is not particularly limited as long as it has at least one ethylenically unsaturated bond and is a polymerizable compound.
- R 7 and R 8 each independently represent a hydrogen atom or a methyl group
- X each independently represents an alkylene group having 2 to 6 carbon atoms.
- the structural unit of — (X—O) — may be present randomly or in a block form.
- R 7 and R 8 are preferably methyl groups.
- a plurality of Xs present in one molecule are each independently an alkylene group having 2 to 6 carbon atoms (for example, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, pentylene group, and hexylene group).
- X is preferably an ethylene group, a propylene group or an isopropylene group, and more preferably an ethylene group, from the viewpoint of improving the precious metal plating resistance and the resolution of the resist pattern.
- m and n are 2 or more, two or more adjacent Xs in the molecule may be the same or different.
- the structural unit of — (X—O) — may be present randomly or in a block form.
- the content ratio (IIIa / IIIb) is preferably 1/10 to 1/1, and more preferably 1/7 to 1/3.
- bisphenol A-based (meth) acrylate compound examples include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic). Loxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) Examples include propane. Of these, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane is preferred from the viewpoint of further improving the resolution and peeling properties.
- 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane is commercially available as BPE-200 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.).
- BPE-200 product name, manufactured by Shin-Nakamura Chemical Co., Ltd.
- 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is either BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) or FA-321M (manufactured by Hitachi Chemical Co., Ltd.) The product name) is commercially available.
- the content of the bisphenol A-based (meth) acrylate compound is 30 in the total mass of the polymerizable compound component (B).
- the mass is preferably from 100% by mass to 100% by mass, and more preferably from 50% by mass to 90% by mass. The resolution of a resist improves more because the said content rate is this range.
- the polymerizable compound component (B) at least one of polyalkylene glycol di (meth) acrylates having at least one of (poly) oxyethylene chain and (poly) oxypropylene chain in the molecule. It is preferable to further include a seed, and it is more preferable to further include a polyalkylene glycol di (meth) acrylate having both a (poly) oxyethylene chain and a (poly) oxypropylene chain in the molecule. Thereby, the flexibility of the cured product (cured film) of the photosensitive resin composition is improved.
- the (poly) oxyethylene chain and the (poly) oxypropylene chain may be continuously present in blocks or randomly.
- the secondary carbon of the isopropylene group may be bonded to an oxygen atom, or the primary carbon may be bonded to an oxygen atom.
- the polyalkylene glycol di (meth) acrylate is particularly preferably a compound represented by the following general formula (V), general formula (VI) or general formula (VII). These are used individually by 1 type or in combination of 2 or more types.
- R independently represents a hydrogen atom or a methyl group
- EO represents an oxyethylene group
- PO represents an oxypropylene group
- m 1 , m 2 , m 3 and m 4 represent the number of repeating structural units composed of oxyethylene groups
- n 1 , n 2 , n 3 and n 4 represent the number of repeating structural units composed of oxypropylene groups
- the total number of repeating oxyethylene groups m 1 + m 2 , m 3 and m 4 (average value) each independently represents a number of 1 to 30, and the total number of repeating oxypropylene groups n 1 , n 2 + n 3 and n 4 (average)
- Each value is independently a number from 1 to 30.
- the total number of repeating oxyethylene groups m 1 + m 2 , m 3 and m 4 (average value) is 1. It is a number of ⁇ 30, preferably a number of 1 to 10, more preferably a number of 4 to 9, and particularly preferably a number of 5 to 8.
- the total number of repetitions is 30 or less, the resolution, adhesion, and resist shape are further improved.
- the total number of repeating oxypropylene groups n 1 , n 2 + n 3 and n 4 is a number from 1 to 30, preferably a number from 5 to 20, more preferably a number from 8 to 16. And the number is particularly preferably 10 to 14. When the total number of repetitions is 30 or less, the resolution is improved and the generation of sludge is suppressed.
- the content of the polyalkylene glycol di (meth) acrylate in the present invention is preferably 5% by mass to 50% by mass in the total mass of the polymerizable compound component (B), and 5% by mass to 15% by mass. Is more preferable.
- a flexibility improves because the said content rate is 5 mass% or more.
- resolution improves because the said content rate is 50 mass% or less.
- the photosensitive resin composition in this invention can further contain other polymerizable compounds other than the said bisphenol A type (meth) acrylate compound and polyalkylene glycol di (meth) acrylate as (B) polymeric compound.
- other polymerizable compounds include nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, (meth) acrylic acid polyol esters, (meth) acrylic acid alkyl esters, and the like.
- nonylphenoxypolyethyleneoxyacrylate examples include nonylphenoxytriethyleneoxyacrylate, nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethyleneoxyacrylate, nonylphenoxyoctaethylene Examples include oxyacrylate, nonylphenoxynonaethyleneoxyacrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate. These are used individually by 1 type or in combination of 2 or more types.
- phthalic acid compounds examples include ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth) acryloyloxyethyl-o- Phthalates, and ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate, among which ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth) acryloyloxyethyl-o-phthalate Is preferred.
- ⁇ -Chloro- ⁇ -hydroxypropyl- ⁇ ′-methacryloyloxyethyl-o-phthalate is commercially available as FA-MECH (manufactured by Hitachi Chemical Co., Ltd., product name). These are used individually by 1 type or in combination of 2 or more types.
- (meth) acrylic acid polyol ester for example, trimethylolpropane polyethoxytri (meth) acrylate, trimethylolpropane polypropoxytri (meth) acrylate, trimethylolpropane polybutoxytri (meth) acrylate, trimethylolpropane poly Ethoxy polypropoxy tri (meth) acrylate, trimethylol ethane polyethoxy tri (meth) acrylate, trimethylol ethane polypropoxy tri (meth) acrylate, trimethylol ethane polybutoxy tri (meth) acrylate, trimethylol ethane polyethoxy polypropoxy tri (Meth) acrylate, pentaerythritol polyethoxytri (meth) acrylate, pentaerythritol polypropoxytri (meta Acrylate, pentaerythritol polybutoxytri (meth) acrylate, pentaerythri
- the content ratio is a viewpoint of improving the resolution, adhesion, resist shape, and peeling property after curing in a well-balanced manner. Therefore, the content is preferably 1% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, more preferably 5% by mass to 5% by mass in the total mass of the polymerizable compound component (B). More preferably, it is 20 mass%.
- the photosensitive resin composition comprises (C-1) at least one acylphosphine oxide compound and (C-2) at least one hexaarylbiimidazole derivative. Contains initiator. By including at least two kinds of compounds as a photopolymerization initiator, sensitivity and resolution are improved, and the resist shape is also improved. Further, since the change in the line width value of the resist pattern with respect to the exposure amount becomes small, the process margin becomes wide and good.
- the content of the photopolymerization initiator is preferably 0.1% by mass to 20% by mass in the total mass of the photosensitive resin composition, and 1% by mass to 10% by mass. More preferably, it is more preferably 3% by mass to 7% by mass.
- the content of the photopolymerization initiator is 0.1% by mass or more, sufficient sensitivity and resolution tend to be obtained.
- the moldability of a film to become more favorable that it is 20 mass% or less.
- the (C-1) acylphosphine oxide compound is preferably a compound represented by the following general formula (I) or general formula (II).
- R 1 , R 2 and R 3 each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms.
- R 4 , R 5 and R 6 each independently represents an alkyl group or aryl group having 1 to 20 carbon atoms.
- R 1 , R 2 or R 3 in the general formula (I) is an alkyl group having 1 to 20 carbon atoms
- the alkyl group may be linear, branched or cyclic. Further, the alkyl group preferably has 5 to 10 carbon atoms.
- R 4 , R 5 or R 6 in the general formula (II) is an alkyl group having 1 to 20 carbon atoms
- the alkyl group may be linear, branched or cyclic. Further, the alkyl group preferably has 5 to 10 carbon atoms.
- R 1 , R 2 or R 3 in the general formula (I) is an aryl group
- the aryl group may have a substituent.
- the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
- R 4 , R 5 or R 6 in the general formula (II) is an aryl group
- the aryl group may have a substituent.
- the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
- Specific examples of the compound represented by the general formula (II) include bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide.
- the compounds represented by the general formula (I) or the general formula (II) can be used singly or in combination of two or more.
- the (C-1) acylphosphine oxide compound is preferably a compound represented by the above general formula (I) or general formula (II), and is represented by the following general formula (VIII) or general formula (IX). More preferably, it is a compound.
- R 11 , R 12 and R 13 each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 4 carbon atoms
- p1, p2 and p3 are each independently , Represents an integer of 0 to 5.
- p1, when p2 or p3 is 2 or more, there exist a plurality of R11, R 12 and R 13 may be the same as or different from each other.
- the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, and hexyl group.
- alkoxy group having 1 to 4 carbon atoms examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tert-butoxy group.
- R 11 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
- p1 is preferably an integer of 1 to 4, and more preferably 3. Moreover, it is preferable that p2 and p3 are 0.
- R 14 , R 15 and R 16 each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 4 carbon atoms
- q 1, q 2 and q 3 are each independently , Represents an integer of 0 to 5.
- q1, q2 or q3 is 2 or more
- a plurality of R 14 , R 15 and R 16 may be the same or different.
- the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, and hexyl group.
- alkoxy group having 1 to 4 carbon atoms examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tert-butoxy group.
- R 14 and R 15 are each independently preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
- q1 and q2 are preferably integers of 1 to 4, and more preferably 3. Further, q3 is preferably 0.
- the compound represented by the general formula (VIII) is preferably 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide from the viewpoint of more effectively improving sensitivity and resist shape.
- 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide is commercially available, for example, as DAROCUR-TPO (trade name, manufactured by BASF Japan).
- the compound represented by the general formula (IX) is preferably bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide from the viewpoint of more effectively improving sensitivity and resist shape.
- Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is commercially available, for example, as IRGACURE-819 (trade name, manufactured by BASF Japan).
- the compounds represented by the general formula (VIII) or the general formula (IX) can be used singly or in combination of two or more.
- the content of these (C-1) acylphosphine oxide compounds is preferably 20% by mass to 60% by mass with respect to the total amount of the (C) photopolymerization initiator, More preferably, the content is from mass% to 45 mass%.
- the (C-2) hexaarylbiimidazole derivative preferably contains at least one 2,4,5-triarylimidazole dimer from the viewpoint of improving sensitivity and adhesion.
- the 2,4,5-triarylimidazole dimer may have a symmetric structure or an asymmetric structure.
- Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis- And (m-methoxyphenyl) imidazole dimer and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer. Of these, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable.
- the content of the (C-2) hexaarylbiimidazole derivative is preferably 30% by mass to 70% by mass with respect to the total amount of the (C) photopolymerization initiator component. More preferably, it is 45 mass% to 65 mass%.
- the content ratio (C-1 / C-2) of (C-1) acylphosphine oxide compound to (C-2) hexaarylbiimidazole derivative is not particularly limited.
- the content ratio (C-1 / C-2) is preferably 0.1 to 0.9, and more preferably 0.3 to 0.9. More preferably, it is 0.5 to 0.8.
- the photosensitive resin composition may further contain other photopolymerization initiator other than the acylphosphine oxide compound and the hexaarylbiimidazole derivative.
- Other photopolymerization initiators include, for example, benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2 -Aromatic ketones such as morpholino-propanone-1, quinones such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 9-phenylacridine And acridine derivatives such as 1,7- (9,9′-acridinyl) heptane. These can be used alone or in combination of two or more.
- the content of the (C) photopolymerization initiator component in the photosensitive resin composition is 0.1 to 10 parts by mass with respect to 100 parts by mass as the total of (A) the binder polymer component and (B) the polymerizable compound component. Part by weight, more preferably from 1 part by weight to 7 parts by weight, even more preferably from 2 parts by weight to 6 parts by weight, and particularly preferably from 3 parts by weight to 5 parts by weight.
- the content of the photopolymerization initiator is 0.1 parts by mass or more, sensitivity, resolution, and adhesion are further improved. Moreover, the more excellent resist shape can be obtained because it is 10 mass parts or less.
- the photosensitive resin composition has a content of the binder polymer of 20% by mass to 90% by mass, a content of the polymerizable compound of 3% by mass to 70% by mass, and the content of the photopolymerization initiator.
- the rate is preferably 0.1% by mass to 20% by mass. More preferably, the content of the binder polymer is 30% by mass to 80% by mass, the content of the polymerizable compound is 10% by mass to 60% by mass, and the content of the photopolymerization initiator is 1% by mass. ⁇ 10% by mass.
- the content of the binder polymer is 40% by mass to 65% by mass
- the content of the polymerizable compound is 25% by mass to 50% by mass
- the content of the photopolymerization initiator is 3% by mass. -7% by mass.
- the photosensitive resin composition preferably further comprises (D) a sensitizing dye. Thereby, the curing sensitivity of the photosensitive resin composition is further improved.
- sensitizing dye examples include dialkylaminobenzophenones, pyrazolines, anthracene, coumarins, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, and triazines. , Thiophenes, naphthalimides, and triarylamines. These are used individually by 1 type or in combination of 2 or more types.
- (D) sensitizing dyes are pyrazolines, anthracenes, coumarins, and triaryls. It is preferable to include at least one selected from the group consisting of amines, and more preferable to include at least one selected from the group consisting of pyrazolines, anthracenes and triarylamines.
- the content of the (D) sensitizing dye is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the (A) binder polymer component and the (B) polymerizable compound component.
- the amount is more preferably 05 parts by mass to 5 parts by mass, and further preferably 0.1 parts by mass to 3 parts by mass.
- Sensitivity and resolution are further improved when the content of the (D) sensitizing dye is 0.01 parts by mass or more. Moreover, it is suppressed that a resist shape turns into an inverted trapezoid because it is 10 mass parts or less, and adhesiveness improves.
- the photosensitive resin composition preferably further comprises (E) an amine compound. Thereby, the sensitivity of the photosensitive resin composition is further improved.
- Examples of the (E) amine compound include bis [4- (dimethylamino) phenyl] methane, bis [4- (diethylamino) phenyl] methane, and leucocrystal violet. These are used individually by 1 type or in combination of 2 or more types.
- the photosensitive resin composition contains (E) an amine compound component
- the content is 0.01 parts by mass with respect to 100 parts by mass as a total of (A) the binder polymer component and (B) the polymerizable compound component. It is preferably from 10 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, and particularly preferably from 0.1 to 2 parts by mass. Sensitivity improves more because content of the said (E) amine compound is 0.01 mass part or more. Moreover, it is suppressed that an excessive (E) amine compound component precipitates as a foreign material after film formation because it is 10 mass parts or less.
- the said photosensitive resin composition can contain another component as needed in addition to the said component.
- Other components include, for example, a photopolymerizable compound (oxetane compound or the like) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, a dye such as malachite green, tribromophenylsulfone, photochromic color.
- the content of these other components is preferably about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of (A) the binder polymer component and (B) the polymerizable compound component.
- the photosensitive resin composition may contain at least one organic solvent.
- a commonly used organic solvent is not particularly limited and can be used. Specific examples include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, and mixed solvents thereof.
- the (A) binder polymer, (B) polymerizable compound, and (C) photopolymerization initiator are dissolved in the organic solvent to obtain a solution having a solid content of about 30% by mass to about 60% by mass (hereinafter, It can be used as a “coating liquid”.
- solid content means the remaining component remove
- the coating liquid can be used for forming a photosensitive resin layer as follows, for example.
- a photosensitive resin layer derived from the photosensitive resin composition can be formed on the support by applying the coating liquid onto the surface of a support such as a support film or a metal plate described later and drying.
- the metal plate include iron alloys such as copper, copper alloys, nickel, chromium, iron, and stainless steel, preferably copper, copper alloys, and iron alloys.
- the thickness of the photosensitive resin layer to be formed varies depending on the use, but it is preferably about 1 ⁇ m to 100 ⁇ m after drying. You may coat
- the protective film include polymer films such as polyethylene and polypropylene.
- the photosensitive resin composition can be suitably used, for example, in a resist pattern manufacturing method described later. Especially, it is suitable for the application to the manufacturing method which forms a circuit by plating processing.
- the photosensitive element 10 of the present invention is a photosensitive resin that is a coating of the support 2 and the photosensitive resin composition formed on the support, as shown in FIG. Layer 4, and other layers such as a protective film 6 provided as necessary.
- a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.
- the thickness of the support (hereinafter sometimes referred to as “support film”) is preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m, and still more preferably 5 ⁇ m to 30 ⁇ m.
- the support film can be prevented from being broken when the support film is peeled off. Moreover, it can suppress that the resolution falls by being 100 micrometers or less.
- the photosensitive element 10 may further include a protective film 6 that covers the surface (surface) opposite to the surface facing the support 2 of the photosensitive resin layer 4 as necessary.
- the protective film preferably has a lower adhesive force to the photosensitive resin layer than the adhesive force of the support film to the photosensitive resin layer, and is preferably a low fish eye film.
- fish eye means that a material constituting a protective film is melted by heat, kneaded, extruded, biaxially stretched, a film is produced by a casting method, etc., and foreign materials, undissolved materials, oxidative deterioration of the material. This means that an object or the like is taken into the film. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.
- a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester can be used.
- examples of commercially available products include polypropylene films such as Alphan MA-410 and E-200C manufactured by Oji Paper Co., Ltd., Shin-Etsu Film Co., Ltd., and PS series such as PS series such as Teijin PS-25, and the like.
- the protective film may be the same as the support.
- the thickness of the protective film is preferably 1 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m, still more preferably 5 ⁇ m to 30 ⁇ m, and particularly preferably 15 ⁇ m to 30 ⁇ m.
- the protective film can be prevented from being broken when the photosensitive resin layer and the support film are laminated on the substrate while peeling off the protective film.
- productivity improves by being 100 micrometers or less.
- the photosensitive element can be manufactured as follows, for example.
- (A) a binder polymer, (B) a polymerizable compound, and (C) a photopolymerization initiator are dissolved in an organic solvent to prepare a coating solution having a solid content of about 30% by mass to 60% by mass; It can be produced by a production method comprising applying the coating solution on a support to form a coating layer, and drying the coating layer to form a photosensitive resin layer.
- Application of the coating solution onto the support can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater.
- the drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it is preferably performed at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin layer is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.
- the thickness of the photosensitive resin layer in the photosensitive element can be appropriately selected depending on the use, but the thickness after drying is preferably 1 ⁇ m to 100 ⁇ m, more preferably 1 ⁇ m to 50 ⁇ m, and more preferably 5 ⁇ m to 40 ⁇ m. More preferably. Industrial coating becomes easy and productivity improves because the thickness of the photosensitive resin layer is 1 micrometer or more. Moreover, adhesiveness and resolution improve by being 100 micrometers or less.
- the transmittance of the photosensitive resin layer for ultraviolet rays is preferably 5% to 75%, more preferably 10% to 65%, and more preferably 15% to 55% for ultraviolet rays having a wavelength of 365 nm. Is particularly preferred. Adhesiveness improves more because this transmittance
- the transmittance can be measured with a UV spectrometer.
- An example of the UV spectrometer is a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.
- the photosensitive element may further have a known intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer, if necessary.
- a known intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer, if necessary.
- the form of the photosensitive element is not particularly limited.
- it may be in the form of a sheet, or may be in a state of being wound up in a roll shape around a core. When it winds up in roll shape, it is preferable to wind up so that a support film may become an outer side.
- the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).
- end face separator On the end face of the roll-shaped photosensitive element roll thus obtained, and it is preferable to install a moisture-proof end face separator from the standpoint of edge fusion resistance. Moreover, as a packaging method, it is preferable to wrap and package in a black sheet with low moisture permeability.
- the photosensitive element can be suitably used, for example, in a resist pattern manufacturing method described later. Especially, it is suitable for the application to the manufacturing method which forms a circuit by plating processing.
- the resist pattern manufacturing method of the present invention includes (i) a photosensitive resin layer forming step of forming a photosensitive resin layer which is a coating film of the photosensitive resin composition on a substrate, and (ii) the photosensitive resin layer An exposure step of irradiating at least a portion with actinic rays and photocuring; and (iii) removing a non-cured portion of the photosensitive resin layer from the substrate to form a cured product derived from the photosensitive resin layer.
- a developing process for forming a resist pattern includes other processes as necessary.
- the photosensitive resin layer which is a coating film of the said photosensitive resin composition is formed on a board
- substrate Usually, die pads (base material for lead frames), such as a circuit formation board
- the photosensitive resin layer on the substrate As a method of forming the photosensitive resin layer on the substrate, for example, it is performed by removing the protective film from the photosensitive element and then pressing the photosensitive resin layer of the photosensitive element on the substrate while heating. it can. Thereby, the laminated body which consists of a board
- This photosensitive resin layer forming step is preferably performed under reduced pressure from the viewpoint of adhesion and followability.
- the photosensitive resin layer and / or the substrate is preferably heated at a temperature of 70 ° C. to 130 ° C. during the pressure bonding.
- the pressure bonding is preferably performed at a pressure of about 0.1 MPa to 1.0 MPa (about 1 kgf / cm 2 to 10 kgf / cm 2 ), but these conditions are appropriately selected as necessary. If the photosensitive resin layer is heated to 70 ° C. to 130 ° C., it is not necessary to pre-heat the substrate in advance, but the substrate may be pre-heated to further improve the adhesion and followability. it can.
- (Ii) Exposure Step In the exposure step, at least part of the photosensitive resin layer formed on the substrate is irradiated with actinic rays, so that the portion irradiated with actinic rays is photocured to form a latent image. Is done.
- the support (support film) present on the photosensitive resin layer is transparent to actinic rays, it can be irradiated with actinic rays through the support film, but the support film is light-shielding.
- the photosensitive resin layer is irradiated with actinic rays after removing the support film.
- Examples of the exposure method include a method of irradiating an actinic ray in an image form through a negative or positive mask pattern called an artwork (mask exposure method).
- a method of irradiating actinic rays in an image form by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be employed.
- LDI Laser Direct Imaging
- DLP Digital Light Processing
- a known light source can be used.
- development step a resist pattern made of a cured product obtained by photocuring the photosensitive resin layer is formed on the substrate by removing an uncured portion of the photosensitive resin layer from the substrate.
- the support film exists on the photosensitive resin layer the support film is removed, and then the unexposed portions other than the exposed portions are removed (developed).
- Development methods include wet development and dry development, but wet development is widely used.
- development is performed by a known development method using a developer corresponding to the photosensitive resin composition.
- the developing method include a method using a dip method, a battle method, a spray method, brushing, slapping, scraping, rocking immersion, and the like. From the viewpoint of improving the resolution, the high pressure spray method is most suitable. You may develop by combining these 2 or more types of methods.
- the configuration of the developer is appropriately selected according to the configuration of the photosensitive resin composition.
- an alkaline aqueous solution for example, an alkaline aqueous solution, an aqueous developer, and an organic solvent developer can be used.
- An alkaline aqueous solution is safe and stable when used as a developer, and has good operability.
- Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate, and the like.
- Alkali metal phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used.
- Examples of the alkaline aqueous solution include a dilute solution of 0.1% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1% by mass to 5% by mass of potassium carbonate, and a dilute solution of 0.1% by mass to 5% by mass of sodium hydroxide.
- a dilute solution of 0.1% to 5% by weight sodium tetraborate is preferred.
- the pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the alkali developability of the photosensitive resin layer.
- a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.
- the aqueous developer is, for example, a developer composed of water or an alkaline aqueous solution and one or more organic solvents.
- the base of the alkaline aqueous solution in addition to the substances described above, for example, borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1 1,3-propanediol, 1,3-diaminopropanol-2, morpholine and the like.
- the pH of the aqueous developer is preferably as low as possible within the range where development is sufficiently performed, preferably pH 8 to 12, and more preferably pH 9 to 10.
- Examples of the organic solvent used in the aqueous developer include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. Etc. These are used alone or in combination of two or more.
- the concentration of the organic solvent in the aqueous developer is preferably 2 to 90% by mass, and the temperature can be adjusted according to the alkali developability.
- a small amount of a surfactant, an antifoaming agent or the like can be mixed in the aqueous developer.
- organic solvent developer examples include organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone and ⁇ -butyrolactone. It is preferable to add water to these organic solvents in an amount of 1 to 20% by mass in order to prevent ignition.
- organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone and ⁇ -butyrolactone. It is preferable to add water to these organic solvents in an amount of 1 to 20% by mass in order to prevent ignition.
- a resist pattern is formed by performing heating at about 60 ° C. to 250 ° C. or exposure at about 0.2 J / cm 2 to 10 J / cm 2 as necessary. May be further cured.
- the lead frame manufacturing method of the present invention includes a step of plating a substrate on which a resist pattern is formed by the resist pattern manufacturing method to form a conductor pattern, and if necessary, a resist removing step and an etching step. It is comprised including other processes, such as.
- a die pad such as an alloy substrate is used.
- the support is plated using the resist pattern formed on the support as a mask.
- the plating treatment method may be electrolytic plating treatment or electroless plating treatment, but electroless plating treatment is preferred.
- electroless plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, and hard Gold plating such as gold plating and soft gold plating can be used.
- the resist pattern on the support is removed.
- the resist pattern can be removed by, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step.
- a strong alkaline aqueous solution for example, a 1% by mass to 10% by mass sodium hydroxide aqueous solution, a 1% by mass to 10% by mass potassium hydroxide aqueous solution, or the like is used.
- a 1% by mass to 10% by mass sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is preferably used, and a 1% by mass to 5% by mass sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is more preferably used.
- Examples of the resist pattern peeling method include an immersion method and a spray method, which may be used alone or in combination.
- the lead frame After removing the resist pattern, the lead frame can be manufactured by further performing an etching process to remove an unnecessary metal layer.
- the method of etching treatment is appropriately selected according to the metal layer to be removed.
- the etching solution include a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, and a hydrogen peroxide etching solution.
- a ferric chloride solution is used because it has a good etch factor. It is preferable to use it.
- the printed wiring board manufacturing method of the present invention includes a step of forming a conductor pattern by plating a substrate on which a resist pattern is formed by the resist pattern manufacturing method, and if necessary, a resist removing step, an etching process It includes other processes such as processes.
- the plating process is performed on the conductor layer provided on the substrate using the resist pattern formed on the substrate as a mask.
- the plating method, the resist pattern removing method, and the etching process are the same as those of the lead frame manufacturing method.
- the printed wiring board produced by the method for producing a printed wiring board of the present invention may be a multilayer printed wiring board or may have a small diameter through hole.
- the printed wiring board can also be manufactured by a manufacturing method including a step of etching a substrate on which a resist pattern is formed to form a conductor pattern by the resist pattern manufacturing method.
- a manufacturing method including a step of etching a substrate on which a resist pattern is formed to form a conductor pattern by the resist pattern manufacturing method.
- an etching process is performed on a conductor layer provided on a substrate using a resist pattern formed on the substrate as a mask.
- a solution b was prepared by dissolving 1.2 g of azobisisobutyronitrile in 100 g of a mixed solution (mass ratio 3: 2) of 60 g of methyl cellosolve and 40 g of toluene.
- the solution a was added dropwise to the mixed solution in the flask over 4 hours, and then kept at 80 ° C. for 2 hours with stirring.
- the solution b was added dropwise to the solution in the flask over 10 minutes, and then the solution in the flask was kept at 80 ° C. for 3 hours while stirring. Further, the temperature of the solution in the flask was raised to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a binder polymer (A-1) solution.
- the nonvolatile content (solid content) of the binder polymer (A-1) was 47.8% by mass, the weight average molecular weight was 30,000, and the acid value was 196 mgKOH / g.
- the weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The GPC conditions are shown below.
- C Photopolymerization initiator
- C-1A 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [DAROCUR-TPO (trade name, manufactured by BASF Japan)]
- C-1B Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide [IRGACURE-819 (trade name, manufactured by BASF Japan)]
- C-2A 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole [B-CIM (trade name, manufactured by Hampton)
- the photosensitive resin composition obtained above was uniformly applied onto a polyethylene terephthalate film (product name “HTF-01” manufactured by Teijin Limited) having a thickness of 16 ⁇ m, and hot air convection at 70 ° C. and 110 ° C. It dried with the type
- a protective film (manufactured by Tamapoly Co., Ltd., product name “NF-15”) is bonded onto this photosensitive resin layer, and a polyethylene terephthalate film (support film), a photosensitive resin layer, and a protective film are laminated in order.
- the photosensitive elements P1 to P11 and P1c to P4c were obtained.
- a copper-clad laminate (substrate, manufactured by Hitachi Chemical Co., Ltd., trade name “MLC-E-679”), which is a glass epoxy material laminated on both sides with copper foil (thickness: 35 ⁇ m), is subjected to surface roughening treatment liquid “MEC”.
- MEC surface roughening treatment liquid
- Surface treatment was performed using “Hetch Bond CZ-8100” (trade name, manufactured by MEC Co., Ltd.), followed by water washing, pickling and water washing, followed by drying with an air stream.
- the surface-treated copper clad laminate was heated to 80 ° C., and the photosensitive element obtained above was laminated so that the photosensitive resin layer was in contact with the copper surface while peeling off the protective film.
- stacked in order of the copper clad laminated board, the photosensitive resin layer, and the support film was each obtained.
- the obtained laminate was used as a test piece in the following tests.
- the lamination was performed using a 120 ° C. heat roll at a pressure of 0.4 MPa and a roll speed of 1.0 m / min.
- the photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step tablet of the photocured film formed on the substrate. The photosensitivity is indicated by the number of steps of the step tablet, and the higher the number of steps of the step tablet, the higher the photosensitivity. The results are shown in Table 3.
- the space part (unexposed part) is removed neatly, and the line part (exposed part) is the smallest line width / space width value among the resist patterns formed without meandering or chipping.
- the resolution and adhesion were evaluated. A smaller value means better resolution and adhesion. The results are shown in Table 3.
- the obtained resist shape (resist pattern cross-sectional shape) was observed using a Hitachi scanning electron microscope S-500A.
- the resist shape is trapezoidal or inverted trapezoidal, or when there is a skirting or cracking of the resist, there is a tendency that a short circuit or disconnection is likely to occur in a circuit formed by the subsequent etching process or plating process. Therefore, it is desirable that the resist shape is rectangular (rectangular) and that there is no bottoming or cracking of the resist.
- the results are shown in Table 3.
- the term “crack” means that a line portion (exposed portion) of the resist pattern is cracked or cracked, or accompanying this, the line portion is chipped or broken.
- the test piece was cut into a size of 40 mm ⁇ 50 mm square, and the entire surface of the photosensitive resin layer of the laminate was exposed with an energy amount such that the number of remaining steps of the 41-step tablet was 14. After the exposure, the same development processing as in the photosensitivity measurement test was performed. Each test piece for peeling property evaluation thus obtained was immersed in a 3 mass% sodium hydroxide aqueous solution at 50 ° C. while stirring with a stirrer, and the resist surface of each test piece was visually observed. . The time from the start of stirring until the cured film was completely peeled and removed from the substrate was defined as the peeling time. Moreover, the size of the peeling piece after peeling was observed visually, and the following evaluation criteria evaluated. The shorter the peeling time and the smaller the peeling piece size, the better the peeling characteristics. The results are shown in Table 3.
- the peeled piece size was a sheet.
- M The peel piece size was 30 mm or more and less than 40 mm.
- S The peeled piece size was smaller than 30 mm square.
- the photosensitive elements prepared from the photosensitive resin compositions of Examples 1 to 11 were excellent in sensitivity, resolution, adhesion, resist shape, and release characteristics after curing. It was. Further, the line width value when the number of remaining stages of the 41-step tablet was 14 steps was close to 10 ⁇ m, and even when the exposure amount was increased to 17 steps, the change amount of the line width value was small. On the other hand, the photosensitive elements prepared from the photosensitive resin compositions of Comparative Examples 1 and 2 were inferior in any of resolution, adhesion, resist shape, resist line width accuracy, or peeling characteristics. In addition, the photosensitive elements prepared from the photosensitive resin compositions of Comparative Examples 3 to 4 had low photosensitivity and pattern formation was not possible.
- the photosensitive resin composition of the present invention is applied as a material for forming a resist pattern for producing a printed wiring board.
- the photosensitive resin composition is excellent in all of sensitivity, resolution, adhesion, resist shape, and release characteristics after curing, and therefore has a printed wiring having fine lines and high density wiring such as a high density package substrate. It is also suitably used for forming a resist pattern for manufacturing a wiring board.
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Abstract
Description
一方、めっき処理とは現像後に形成した硬化レジストによって被覆されていない回路形成用基板の金属面に銅及び半田などのめっき処理を行った後、硬化レジストを除去し、このレジストによって被覆されていた金属面をエッチングする方法である。
また、感光性樹脂組成物が、剥離特性に優れたレジストを形成可能であると、レジストの剥離時間を短縮化することによりレジストパターンの形成効率が向上し、また、レジストの剥離片の大きさを小さくすることによりレジストの剥離残りが少なくなり、回路形成の歩留まりが向上する。
本発明の第1の態様は、(A)(メタ)アクリル酸に由来する構成単位、及び(メタ)アクリル酸ベンジルエステル又は(メタ)アクリル酸ベンジルエステル誘導体に由来する構成単位を有するバインダーポリマーと、(B)少なくとも1つのエチレン性不飽和結合を有する重合性化合物と、(C)アシルホスフィンオキサイド系化合物及びヘキサアリールビイミダゾール誘導体を含む光重合開始剤と、を含有する感光性樹脂組成物である。
上記構成の感光性樹脂組成物は、感度、解像度、密着性、レジスト形状及び硬化後の剥離特性のいずれにも優れる。
この製造方法によれば、高密度パッケージ基板のような高密度化したプリント配線板を、精度良く、しかも効率的に製造することができる。
また本明細書において「~」を用いて示された数値範囲は、「~」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。
さらに本明細書において組成物中の各成分の量について言及する場合、組成物中に各成分に該当する物質が複数存在する場合には、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
本発明の感光性樹脂組成物は、(A)(メタ)アクリル酸に由来する構成単位、及び、(メタ)アクリル酸ベンジルエステル又は(メタ)アクリル酸ベンジルエステル誘導体に由来する構成単位を有するバインダーポリマーの少なくとも1種と、(B)少なくとも1つのエチレン性不飽和結合を有する重合性化合物の少なくとも1種と、(C)アシルホスフィンオキサイド系化合物及びヘキサアリールビイミダゾール誘導体を含む光重合開始剤と、を含有する。
本発明におけるバインダーポリマーは、(メタ)アクリル酸に由来する構成単位、及び(メタ)アクリル酸ベンジル又は(メタ)アクリル酸ベンジル誘導体に由来する構成単位を有するものであれば特に制限はない。また前記バインダーポリマーは、前記(メタ)アクリル酸に由来する構成単位、及び(メタ)アクリル酸ベンジル又は(メタ)アクリル酸ベンジル誘導体に由来する構成単位に加えて必要に応じて(メタ)アクリル酸アルキルエステルに由来する構成単位やスチレン又はスチレン誘導体に由来する構成単位等のその他の構成単位をさらに有して構成されてもよい。
例えば、(メタ)アクリル酸に由来する構成単位の含有率としては、バインダーポリマーの酸価が100mgKOH/g~250mgKOH/gとなる含有率であることが好ましく、120mgKOH/g~240mgKOH/gとなる含有率であることがより好ましく、140mgKOH/g~230mgKOH/gとなる含有率であることがさらに好ましく、150mgKOH/g~230mgKOH/gとなる含有率であることが特に好ましい。
バインダーポリマーの酸価が100mgKOH/g以上であることで現像時間が長くなることを抑制できる。また酸価を250mgKOH/g以下であることで、感光性樹脂組成物の硬化物の耐現像液性(密着性)が向上する。なお、溶剤現像を行う場合は、(メタ)アクリル酸等のカルボキシル基を有する重合性単量体(モノマー)を少量に調製することもまた好ましい。
この含有率が5質量%以上であることで解像度がより向上する。またこの含有率が65質量%以下であることで、剥離片が大きくなることを抑制し、剥離時間が長くなることを抑制できる。
この含有量が1質量%以上であることで剥離片が大きくなることが抑制でき、剥離時間が長くなることを抑制できる。またこの含有量が50質量%以下であることで解像度及び密着性がより向上する。
この含有率が5質量%以下であることで密着性がより向上する。またこの含有率が65質量%以下であることで、剥離片が大きくなることを抑制し、剥離時間が長くなることを抑制できる。
Mwが10000以上であると、感光性樹脂組成物の硬化物の耐現像液性(密着性)が優れる傾向があり、100000以下であると、現像時間に優れる傾向がある。
尚、バインダーポリマーの重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)により測定(標準ポリスチレンを用いた検量線により換算)される。
分散度が3.0以下であると密着性及び解像度がより向上する。
より好ましくは、(メタ)アクリル酸に由来する構成単位と、(メタ)アクリル酸ベンジルに由来する構成単位の10質量%~55質量%と、炭素数が1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来する構成単位の2質量%~30質量%と、スチレン又はその誘導体に由来する構成単位の10質量%~60質量%とを含み、酸価が120mgKOH/g~230mgKOH/gであり、重量平均分子量が20000~80000である。
さらに好ましくは、(メタ)アクリル酸に由来する構成単位と、(メタ)アクリル酸ベンジルに由来する構成単位の20質量%~50質量%と、炭素数が1~4のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来する構成単位の3質量%~20質量%と、スチレン又はその誘導体に由来する構成単位の15質量%~55質量%とを含み、酸価が140mgKOH/g~230mgKOH/gであり、重量平均分子量が25000~60000である。
2種類以上を組み合わせて使用する場合のバインダーポリマーとしては、例えば、異なる共重合成分からなる2種類以上の(異なるモノマー単位を共重合成分として含む)バインダーポリマー、異なる重量平均分子量の2種類以上のバインダーポリマー、異なる分散度の2種類以上のバインダーポリマーが挙げられる。また、特開平11-327137号公報に記載のマルチモード分子量分布を有するポリマーを使用することもできる。
バインダーポリマーの含有率が20質量%以上であると、フィルムの成形性に優れる傾向がある。また90質量%以下であると、感度及び解像度に優れる傾向がある。
この含有率が30質量部以上であることでフィルムの形成性がより向上する。また、70質量部以下であることで、感度及び解像度がより向上する。
本発明の感光性樹脂組成物は、エチレン性不飽和結合を少なくとも1つ有する重合性化合物の少なくとも1種を含有する。
前記重合性化合物の含有率は、感光性樹脂組成物中の3質量%~70質量%であることが好ましく、10質量%~60質量%であることがより好ましく、25質量%~50質量%であることがさらに好ましい。
重合性化合物の含有率が3質量%以上であると、感度及び解像度が優れる傾向がある。また70質量%以下であると、フィルムの成形性に優れる傾向がある。
また、1分子中に複数存在するXはそれぞれ独立に炭素数2~6のアルキレン基(例えば、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、ペンチレン基、及びへキシレン基)であるが、貴金属めっき耐性及びレジストパターンの解像度を良好にする観点から、Xはエチレン基、プロピレン基又はイソプロピレン基であることが好ましく、エチレン基であることがより好ましい。
m及びnが2以上の場合、分子内で隣り合った2つ以上のXはそれぞれ同一であっても異なってもよい。また、Xが2種以上のアルキレン基である場合、-(X-O)-の構造単位はランダムに存在してもよいし、ブロック的に存在してもよい。
前記感光性樹脂組成物が、上記一般式(III)で表される化合物として、m+n=3~6である化合物(IIIa)と、m+n=8~10である化合物(IIIb)とを含む場合、その含有比(IIIa/IIIb)としては1/10~1/1であることが好ましく、1/7~1/3であることがより好ましい。
前記感光性樹脂組成物において、前記ビスフェノールA系(メタ)アクリレート化合物(好ましくは、一般式(III)で表される化合物)の含有率は、(B)重合性化合物成分の総質量中に30質量%~100質量%であることが好ましく、50質量%~90質量%であることがより好ましい。前記含有率がかかる範囲であることでレジストの解像度がより向上する。
前記含有率が5質量%以上であることで可とう性が向上する。また前記含有率が50質量%以下であることで解像性が向上する。
その他の重合性化合物としては、ノニルフェノキシポリエチレンオキシアクリレート、フタル酸系化合物、(メタ)アクリル酸ポリオールエステル、(メタ)アクリル酸アルキルエステル等が挙げられる。中でも、解像度、密着性、レジスト形状及び硬化後の剥離特性をバランスよく向上させる観点から、ノニルフェノキシポリエチレンオキシアクリレート及びフタル酸系化合物から選ばれる少なくとも1種であることが好ましい。
これらは1種単独で、又は2種類以上を任意に組み合わせて使用される。
これらは1種単独で又は2種類以上を組み合わせて使用される。
これらは1種単独で又は2種以上を組み合わせて用いることができる。
前記感光性樹脂組成物は、(C-1)アシルホスフィンオキサイド系化合物の少なくとも1種、及び、(C-2)ヘキサアリールビイミダゾール誘導体の少なくとも1種を含む光重合開始剤を含む。光重合開始剤として少なくとも2種の化合物を含むことで、感度、解像度が向上し、さらにレジスト形状も良好となる。また露光量に対するレジストパターンの線幅値の変化が小さくなるため、プロセス裕度が広くなり、良好となる。
光重合開始剤の含有率が、0.1質量%以上であると、充分な感度、解像度が得られる傾向がある。また20質量%以下であるとフィルムの成形性がより良好になる傾向がある。
上記炭素数1~6のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、tert-ブチル基、ペンチル基、ヘキシル基が挙げられる。上記炭素数1~4のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、tert-ブトキシ基が挙げられる。
R11は炭素数1~4のアルキル基であることが好ましく、メチル基であることがより好ましい。p1は1~4の整数であることが好ましく、3であることがより好ましい。また、p2及びp3は0であることが好ましい。
上記炭素数1~6のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、tert-ブチル基、ペンチル基、ヘキシル基が挙げられる。上記炭素数1~4のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、tert-ブトキシ基が挙げられる。
R14及びR15はそれぞれ独立に、炭素数1~4のアルキル基であることが好ましく、メチル基であることがより好ましい。q1及びq2は1~4の整数であることが好ましく、3であることがより好ましい。また、q3は0であることが好ましい。
前記2,4,5-トリアリールイミダゾール二量体としては、例えば、2-(o-クロロフェニル)-4,5-ジフェニルイミダゾール二量体、2-(o-クロロフェニル)-4,5-ビス-(m-メトキシフェニル)イミダゾール二量体、2-(p-メトキシフェニル)-4,5-ジフェニルイミダゾール二量体が挙げられる。中でも、2-(o-クロロフェニル)-4,5-ジフェニルイミダゾール二量体であることが好ましい。
これらは1種単独でも、又は2種類以上を組み合わせて使用することができる。
前記光重合開始剤の含有量が、0.1質量部以上であることで、感度、解像度および密着性がより向上する。また、10質量部以下であることで、より優れたレジスト形状を得ることができる。
より好ましくは前記バインダーポリマーの含有率が30質量%~80質量%であり、前記重合性化合物の含有率が10質量%~60質量%であり、前記光重合開始剤の含有率が1質量%~10質量%である。
さらに好ましくは前記バインダーポリマーの含有率が40質量%~65質量%であり、前記重合性化合物の含有率が25質量%~50質量%であり、前記光重合開始剤の含有率が3質量%~7質量%である。
前記(D)増感色素の含有量が、0.01質量部以上であることで感度及び解像度がより向上する。また10質量部以下であることで、レジスト形状が逆台形になることを抑制し、密着性が向上する。
前記(E)アミン系化合物の含有量が、0.01質量部以上であることで、感度がより向上する。また10質量部以下であることで、フィルム形成後、過剰な(E)アミン系化合物成分が異物として析出することが抑制される。
これらは、1種単独で又は2種類以上を組み合わせて使用される。
またこれらその他の成分の含有量は、(A)バインダーポリマー成分及び(B)重合性化合物成分の総量100質量部に対して、それぞれ0.01質量部~20質量部程度とすることが好ましい。
例えば、前記(A)バインダーポリマーと、(B)重合性化合物と、(C)光重合開始剤とを前記有機溶剤に溶解して、固形分30質量%~60質量%程度の溶液(以下、「塗布液」という)として用いることができる。
尚、固形分とは、前記溶液(感光性樹脂組成物)から揮発性成分を除いた残りの成分を意味する。
金属板としては、銅、銅系合金、ニッケル、クロム、鉄、ステンレス等の鉄系合金、好ましくは銅、銅系合金、鉄系合金などが挙げられる。
本発明の感光性エレメント10は、図1にその一例の略断面図を示すように、支持体2と、前記支持体上に形成された前記感光性樹脂組成物の塗膜である感光性樹脂層4と、を備え、必要に応じて設けられる保護フィルム6等のその他の層を備えて構成される。
前記支持体(以下、「支持フィルム」ということがある)の厚みは、1μm~100μmであることが好ましく、5μm~50μmであることがより好ましく、5μm~30μmであることが更に好ましい。支持体の厚みが1μm以上であることで、支持フィルムを剥離する際に支持フィルムが破れることを抑制できる。また100μm以下であることで解像度が低下することを抑制することができる。
ここで、「フィッシュアイ」とは、保護フィルムを構成する材料を熱溶融し、混練、押し出し、2軸延伸、キャスティング法等によりフィルムを製造する際に、材料の異物、未溶解物、酸化劣化物等がフィルム中に取り込まれたものを意味する。すなわち、「低フィッシュアイ」とは、フィルム中の上記異物等が少ないことを意味する。
感光性樹脂層の厚みが1μm以上であることで、工業的な塗工が容易になり、生産性が向上する。また100μm以下であることで、密着性及び解像度が向上する。
この透過率が5%以上であることで、密着性がより向上する。また透過率が75%以下であることで、解像度がより向上する。尚、上記透過率は、UV分光計により測定することができる。UV分光計としては、日立製作所製228A型Wビーム分光光度計が挙げられる。
ロール状に巻き取る場合、支持フィルムが外側になるように巻き取ることが好ましい。
巻芯としては、ポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ABS樹脂(アクリロニトリル-ブタジエン-スチレン共重合体)等のプラスチックなどが挙げられる。このようにして得られたロール状の感光性エレメントロールの端面には、端面保護の見地から端面セパレータを設置することが好ましく、耐エッジフュージョンの見地から防湿端面セパレータを設置することが好ましい。また、梱包方法としては、透湿性の小さいブラックシートに包んで包装することが好ましい。
本発明のレジストパターン製造方法は、(i)基板上に前記感光性樹脂組成物の塗膜である感光性樹脂層を形成する感光性樹脂層形成工程と、(ii)前記感光性樹脂層の少なくとも一部に活性光線を照射して、光硬化させる露光工程と、(iii)前記感光性樹脂層の未硬化部分を基板上から除去して、前記感光性樹脂層に由来する硬化物からなるレジストパターンを形成する現像工程と、を備え、必要に応じてその他の工程を含んで構成される。
感光性樹脂層形成工程においては、基板上に前記感光性樹脂組成物の塗膜である感光性樹脂層が形成される。前記基板としては特に制限されないが、通常、絶縁層と絶縁層上に形成された導体層とを備えた回路形成用基板、又は合金基材等のダイパッド(リードフレーム用基材)が用いられる。
露光工程においては、基板上に形成された感光性樹脂層の少なくとも一部に活性光線を照射することで、活性光線が照射された部分が光硬化して、潜像が形成される。
この際、感光性樹脂層上に存在する支持体(支持フィルム)が活性光線に対して透過性である場合には、支持フィルムを通して活性光線を照射することができるが、支持フィルムが遮光性である場合には、支持フィルムを除去した後に感光性樹脂層に活性光線を照射する。
現像工程においては、前記感光性樹脂層の未硬化部分が基板上から除去されることで、前記感光性樹脂層が光硬化した硬化物からなるレジストパターンが基板上に形成される。
感光性樹脂層上に支持フィルムが存在している場合には、支持フィルムを除去してから、上記露光部分以外の未露光部分の除去(現像)を行う。現像方法には、ウェット現像とドライ現像とがあるが、ウェット現像が広く用いられている。
水系現像液のpHは、現像が充分に行われる範囲でできるだけ小さくすることが好ましく、pH8~12とすることが好ましく、pH9~10とすることがより好ましい。
本発明のリードフレームの製造方法は、前記レジストパターン製造方法によって、レジストパターンが形成された基板をめっき処理して導体パターンを形成する工程を含み、必要に応じて、レジスト除去工程、エッチング処理工程等のその他の工程を含んで構成される。
本発明においては、支持体上に形成されたレジストパターンをマスクとして、支持体にめっき処理が行われる。
なかでも、1質量%~10質量%水酸化ナトリウム水溶液又は水酸化カリウム水溶液を用いることが好ましく、1質量%~5質量%水酸化ナトリウム水溶液又は水酸化カリウム水溶液を用いることがより好ましい。
エッチング処理の方法は、除去すべき金属層に応じて適宜選択される。例えば、エッチング液としては、塩化第二銅溶液、塩化第二鉄溶液、アルカリエッチング溶液及び過酸化水素エッチング液が挙げられ、これらの中では、エッチファクタが良好な点から塩化第二鉄溶液を用いることが好ましい。
本発明のプリント配線板の製造方法は、前記レジストパターン製造方法によって、レジストパターンが形成された基板をめっき処理して導体パターンを形成する工程を含み、必要に応じて、レジスト除去工程、エッチング処理工程等のその他の工程を含んで構成される。
本発明においては、基板上に形成されたレジストパターンをマスクとして、基板上に設けられた導体層にめっき処理が行われる。
この製造方法では、基板上に形成されたレジストパターンをマスクとして、基板上に設けられた導体層に対してエッチング処理が行われる。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書に参照により取り込まれる。
(バインダーポリマー(A-1)の合成)
重合性単量体(モノマー)であるメタクリル酸150g、メタクリル酸ベンジル125g、メタクリル酸メチル25g及びスチレン200g(質量比30/25/5/40)と、アゾビスイソブチロニトリル9.0gとを混合して、溶液aを調製した。
ポンプ:日立 L-6000型((株)日立製作所製)
カラム:以下の計3本
Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440(以上、日立化成工業(株)製、商品名)
溶離液:テトラヒドロフラン
測定温度:40℃
流量:2.05mL/分
検出器:日立 L-3300型RI((株)日立製作所製)
バインダーポリマー(A-1)の合成において、重合性単量体(モノマー)として、下記表1に示す材料を同表に示す質量比で用いたほかは、バインダーポリマー(A-1)の溶液を得るのと同様にしてバインダーポリマー(A-2)~(A-6)の溶液をそれぞれ得た。
[感光性樹脂組成物の調製]
(A)バインダーポリマーとして上記で得られたA-1~A-6を、(B)重合性化合物として以下に示すB-1~B-4を、(C)光重合開始剤として以下に示すC-1A、C-1B、C-2を、その他の成分として以下に示す成分を、それぞれ用い、下記表2に示す配合量(配合部数)で混合することにより、実施例1~11及び比較例1~4の感光性樹脂組成物をそれぞれ調製した。なお、表2に示す(A)バインダーポリマーの配合量(配合部数)は、不揮発分の質量(固形分量)である。
B-1:2,2-ビス(4-(メタクリロキシペンタエトキシ)フェニル)プロパン[FA-321M(日立化成工業(株)製、製品名)]
B-2:2,2-ビス(4-((メタ)アクリロキシジプロポキシ)フェニル)プロパン[BPE-200(新中村化学工業(株)製、製品名)]
B-3:上記一般式(V)において、R=メチル基、m1+m2=6(平均値)、n1=12(平均値)である化合物[FA-023M(日立化成工業(株)製、製品名)]
B-4:上記一般式(VI)においてR=メチル基、m3=6(平均値)、n2+n3=12(平均値)である化合物[FA-024M(日立化成工業(株)製、製品名)]
C-1A:2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド[DAROCUR-TPO(BASFジャパン社製、商品名)]
C-1B:ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキサイド[IRGACURE-819(BASFジャパン社製、商品名)]
C-2A:2,2’-ビス(2-クロロフェニル)-4,4’,5,5’-テトラフェニルビスイミダゾール[B-CIM(Hampford社製、商品名)]
D-1:4,4’-ビス(ジエチルアミノ)ベンゾフェノン
E-1:ロイコクリスタルバイオレット[LCV(山田化学社製、商品名)]
MKG(大阪有機化学工業社製、商品名):マラカイトグリーン
上記で得られた感光性樹脂組成物を、それぞれ厚さ16μmのポリエチレンテレフタレートフィルム(帝人(株)製、製品名「HTF-01」)上に均一に塗布し、70℃及び110℃の熱風対流式乾燥器で乾燥して、乾燥後の膜厚が25μmである感光性樹脂層を形成した。
この感光性樹脂層上に保護フィルム(タマポリ(株)製、製品名「NF-15」)を貼り合わせ、ポリエチレンテレフタレートフィルム(支持フィルム)と、感光性樹脂層と、保護フィルムとが順に積層された感光性エレメントP1~P11及びP1c~P4cをそれぞれ得た。
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(基板、日立化成工業社製、商品名「MLC-E-679」)を、表面粗化処理液「メックエッチボンドCZ-8100」(メック社製、商品名)を用いて表面処理し、水洗、酸洗及び水洗後、空気流で乾燥した。表面処理された銅張積層板を80℃に加温し、保護フィルムを剥離しながら、感光性樹脂層が銅表面に接するように、上記で得られた感光性エレメントをそれぞれラミネートした。こうして、銅張積層板、感光性樹脂層、支持フィルムの順に積層された積層体をそれぞれ得た。得られた積層体は、以下に示す試験における試験片として用いた。
尚、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、1.0m/分のロール速度で行なった。
(光感度測定試験)
上記で得られた試験片の支持フィルム上に、ネガマスクとして濃度領域0.00~2.00、濃度ステップ0.05、タブレットの大きさ20mm×187mm、各ステップの大きさが3mm×12mmである41段ステップタブレットを有するフォトツールを載置し、高圧水銀灯ランプを有する露光機(オーク社製、商品名「EXM-1201」)を用いて、70mJ/cm2の照射エネルギー量となるように感光性樹脂層を露光した。
次に、支持フィルムを剥離し、30℃の1質量%炭酸ナトリウム水溶液を最少現像時間(未露光部分が除去される最少時間)の2倍の時間でスプレー現像し、未露光部分を除去して現像処理を行った。
現像処理後、基板上に形成された光硬化膜のステップタブレットの段数を測定することにより、感光性樹脂組成物の光感度を評価した。光感度は、ステップタブレットの段数で示され、このステップタブレットの段数が高いほど、光感度が高いことを示す。結果を表3に示す。
解像度及び密着性を調べるため、密着性評価用ネガとしてライン幅/スペース幅が2/2~30/30(単位:μm)の配線パターンを有するガラスクロムタイプのフォトツールを、上記で得られた試験片の支持フィルム上に密着させ、高圧水銀灯ランプを有する露光機を用いて、41段ステップタブレットの残存段数が14段となるエネルギー量で上記積層体の感光性樹脂層に対して露光を行った。露光後、上記光感度測定試験と同様の現像処理を行った。
上記解像度・密着性の評価において、得られたレジスト形状(レジストパターンの断面形状)を日立走査型電子顕微鏡S-500Aを用いて観察した。
レジスト形状が台形又は逆台形である場合や、レジストの裾引き又はクラックがある場合には、その後のエッチング処理又はめっき処理により形成された回路に短絡や断線が生じやすくなる傾向がある。従って、レジスト形状は矩形(長方形)で、且つレジストの裾引き又はクラックがないことが望ましい。結果を表3に示す。
尚、「クラック」とは、レジストパターンのライン部分(露光部分)に、ひびや亀裂が生じ、あるいはそれに伴いライン部分に欠けや断裂が生じたことを意味する。
レジストの線幅精度を評価するために解像度評価用ネガとしてライン幅/スペース幅が10/10(単位:μm)の配線パターン有するガラスクロムタイプのフォトツールを、上記で得られた試験片の支持フィルム上に密着させ、高圧水銀灯ランプを有する露光機を用いて、41段ステップタブレットの残存段数が14段及び17段となるエネルギー量で上記積層体の感光性樹脂層に対して露光を行った。露光後、上記光感度測定試験と同様の現像処理を行った。
得られたレジストパターンについて日立走査型電子顕微鏡S-500Aを用いてレジスト最上部の線幅値を測定した。ここで,線幅値は10μmに近い値ほど,線幅精度が高いことを示す。結果を表3に示す
試験片を40mm×50mm四方の大きさに切断し、41段ステップタブレットの残存段数が14段となるエネルギー量で上記積層体の感光性樹脂層に対して全面露光を行った。露光後、上記光感度測定試験と同様の現像処理を行った。
このようにして得られた剥離特性評価用の各試験片を、50℃の3質量%水酸化ナトリウム水溶液中に、撹拌子で撹拌しながら浸漬し、各試験片のレジスト表面を目視により観察した。
撹拌開始から、硬化膜が基板から完全に剥離除去されるまでの時間を剥離時間とした。
また、剥離後の剥離片のサイズを目視にて観察し、以下の評価基準で評価した。剥離時間が短く、剥離片サイズが小さいほど剥離特性が良好であることを意味する。結果を表3に示す
L:剥離片サイズがシート状だった。
M:剥離片サイズが30mm以上40mm未満角であった。
S:剥離片サイズが30mm角より小さかった。
一方、比較例1~2の感光性樹脂組成物から調製した感光性エレメントは、解像度、密着性、レジスト形状、レジストの線幅精度、又は、剥離特性のいずれかが劣っていた。
また、比較例3~4の感光性樹脂組成物から調製した感光性エレメントは光感度が低くパターン形成ができなかった。
4 感光性樹脂層
6 保護フィルム
10 感光性エレメント
Claims (8)
- (A)(メタ)アクリル酸に由来する構成単位、及び、(メタ)アクリル酸ベンジルエステル又は(メタ)アクリル酸ベンジルエステル誘導体に由来する構成単位を有するバインダーポリマーと、
(B)エチレン性不飽和結合を少なくとも1つ有する重合性化合物と、
(C)アシルホスフィンオキサイド系化合物及びヘキサアリールビイミダゾール誘導体を含む光重合開始剤と、を含有する感光性樹脂組成物。 - 前記ヘキサアリールビイミダゾール誘導体が、2,4,5-トリアリールイミダゾール二量体である請求項1又は請求項2に記載の感光性樹脂組成物。
- 支持体と、前記支持体上に形成された請求項1~請求項3のいずれか1項に記載の感光性樹脂組成物の塗膜である感光性樹脂層と、を備える感光性エレメント。
- 基板上に、請求項1~請求項3のいずれか1項に記載の感光性樹脂組成物の塗膜である感光性樹脂層を形成する感光性樹脂層形成工程と、
前記感光性樹脂層の少なくとも一部に活性光線を照射して光硬化させる露光工程と、
前記感光性樹脂層の未硬化部分を基板上から除去して、前記感光性樹脂層の硬化物からなるレジストパターンを形成する現像工程と、
を有するレジストパターン製造方法。 - 請求項5に記載のレジストパターン製造方法によりレジストパターンが形成された基板をめっき処理して導体パターンを形成する工程を含むリードフレームの製造方法。
- 請求項5に記載のレジストパターン製造方法によりレジストパターンが形成された基板をめっき処理して導体パターンを形成する工程を含むプリント配線板の製造方法。
- 請求項7に記載のプリント配線板の製造方法により製造されるプリント配線板。
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KR20080092839A (ko) * | 2007-04-12 | 2008-10-16 | 칫소가부시키가이샤 | 잉크젯용 잉크 |
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- 2011-06-10 KR KR1020127027682A patent/KR20130095631A/ko not_active Application Discontinuation
- 2011-06-10 WO PCT/JP2011/063389 patent/WO2012014580A1/ja active Application Filing
- 2011-06-10 CN CN2011800043618A patent/CN102597877A/zh active Pending
- 2011-06-10 JP JP2011533464A patent/JP4849197B1/ja not_active Expired - Fee Related
- 2011-06-10 CN CN201210352844.3A patent/CN102854750B/zh active Active
- 2011-06-28 TW TW100122602A patent/TWI507820B/zh not_active IP Right Cessation
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WO2008114635A1 (ja) * | 2007-03-20 | 2008-09-25 | Jsr Corporation | 感放射線性樹脂組成物 |
WO2010002129A2 (ko) * | 2008-07-01 | 2010-01-07 | 주식회사 엘지화학 | 복수의 광개시제를 포함한 감광성 수지 조성물, 이를 이용한 투명 박막층 및 액정 표시 장치 |
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JP2013249452A (ja) * | 2012-06-04 | 2013-12-12 | Hitachi Chemical Co Ltd | 液状硬化性樹脂組成物、画像表示用装置、及び画像表示用装置の製造方法 |
EP4151410A1 (en) * | 2021-09-17 | 2023-03-22 | Arkema France | Photosensitive composition |
WO2023041579A1 (en) * | 2021-09-17 | 2023-03-23 | Arkema France | Photosensitive composition |
Also Published As
Publication number | Publication date |
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JPWO2012014580A1 (ja) | 2013-09-12 |
CN102854750A (zh) | 2013-01-02 |
CN102854750B (zh) | 2014-08-27 |
TW201216002A (en) | 2012-04-16 |
KR20130095631A (ko) | 2013-08-28 |
CN102597877A (zh) | 2012-07-18 |
TWI507820B (zh) | 2015-11-11 |
JP4849197B1 (ja) | 2012-01-11 |
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