WO2018021497A1 - 感光性樹脂組成物、硬化物、層間絶縁膜、ｔｆｔアクティブマトリックス基板、及び画像表示装置 - Google Patents

感光性樹脂組成物、硬化物、層間絶縁膜、ｔｆｔアクティブマトリックス基板、及び画像表示装置 Download PDF

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WO2018021497A1
WO2018021497A1 PCT/JP2017/027325 JP2017027325W WO2018021497A1 WO 2018021497 A1 WO2018021497 A1 WO 2018021497A1 JP 2017027325 W JP2017027325 W JP 2017027325W WO 2018021497 A1 WO2018021497 A1 WO 2018021497A1
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group
ring
less
meth
acid
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PCT/JP2017/027325
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English (en)
French (fr)
Japanese (ja)
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石井　宏明
恵子 斎藤
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三菱ケミカル株式会社
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Priority to KR1020197002149A priority Critical patent/KR102351163B1/ko
Priority to CN201780048948.6A priority patent/CN109564385B/zh
Priority to JP2018530401A priority patent/JP6881455B2/ja
Publication of WO2018021497A1 publication Critical patent/WO2018021497A1/ja

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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
    • 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
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • 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
    • 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
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • 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
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film

Definitions

  • the present invention resides in a photosensitive resin composition, a cured product, an interlayer insulating film, a TFT active matrix substrate, and an image display device.
  • a liquid crystal display panel called a horizontal electric field method or a fringe field switching (FFS) method, which is a kind of liquid crystal display device, generates an electric field parallel to the substrate surface at least partially between a pixel electrode and a counter electrode.
  • the image is generated by driving the liquid crystal by the electric field and modulating light transmitted through the liquid crystal layer.
  • an organic insulating film having a high relative dielectric constant is formed on an interlayer insulating film sandwiched between a planar counter electrode and a linear pixel electrode.
  • the method used is known.
  • the FFS method is characterized in that a storage capacitor (Cst) is formed by a pixel electrode and an interlayer insulating film, and the charge charge is held more stably.
  • the capacitance C of the capacitor is expressed by the following equation (1).
  • C ⁇ r ⁇ 0 S / d (1)
  • C capacity
  • ⁇ r relative dielectric constant
  • ⁇ 0 vacuum dielectric constant
  • S electrode area
  • d distance between electrodes.
  • Japanese Unexamined Patent Publication No. 2009-235359 Japanese Unexamined Patent Publication No. 2011-116943 Japanese Unexamined Patent Publication No. 2013-237804 Japanese Unexamined Patent Publication No. 2009-249411
  • Patent Documents 1 to 3 use titania or barium titanate as high dielectric constant inorganic particles, and have a high relative dielectric constant.
  • the leakage current is large and the opening of the contact hole is insufficient, which is a practical problem.
  • Patent Document 4 uses a bisphenol A type epoxy acrylate resin as a binder resin, hole resolution appears in high resolution patterning, but a minute residue is generated on the glass substrate and developability is improved. It was found that it was not enough.
  • the present invention has been made in view of the above circumstances, and the present invention has a high dielectric constant even if it is a thin film, and can form a high-definition pattern by photolithography while suppressing leakage current. It aims at providing the photosensitive resin composition.
  • the present inventors have found that the above problems can be solved by using zirconium dioxide particles and using a specific epoxy (meth) acrylate resin as a binder resin. Reached. That is, the gist of the present invention is as follows.
  • a photosensitive resin composition containing (a) zirconium dioxide particles, (b) a dispersant, (c) a solvent, (d) a binder resin, (e) a polymerizable monomer, and (f) a polymerization initiator.
  • the (d) binder resin is an epoxy (meth) acrylate resin having a repeating unit structure represented by the following formula (I) and an epoxy (meth) acrylate resin having a partial structure represented by the following formula (II)
  • the photosensitive resin composition containing at least one of these.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a divalent hydrocarbon group which may have a substituent.
  • the benzene ring in formula (I) is Further, it may be further substituted with an arbitrary substituent. * Represents a bond.
  • each R 3 independently represents a hydrogen atom or a methyl group.
  • R 4 represents a divalent hydrocarbon group having an aliphatic ring group as a side chain. * Represents a bond. Represents.)
  • [2] The photosensitive resin composition according to [1], wherein the content ratio of the (d) binder resin is 5% by mass or more based on the total solid content.
  • [3] The photosensitive resin composition according to [1] or [2], wherein the content ratio of the (a) zirconium dioxide particles is 50% by mass or more based on the total solid content.
  • R 5 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
  • R 6 each independently represents an alkylene group which may have a substituent.
  • R 7 each independently represents a hydrogen atom or a methyl group, and k and l each independently represents an integer of 1 to 20.
  • [6] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [5].
  • a TFT active matrix substrate comprising the interlayer insulating film according to [7].
  • An image display device comprising the TFT active matrix substrate according to [8].
  • the present invention it is possible to provide a photosensitive resin composition capable of forming a high-definition pattern by photolithography while having a high dielectric constant even in the case of a thin film and suppressing leakage current. .
  • (meth) acrylic acid includes both acrylic acid and methacrylic acid
  • (meth) acrylate”, “(meth) acryloyl” and the like have the same meaning.
  • what added "(poly)" before the monomer name means this monomer and this polymer.
  • the “total solid content” means all components except the solvent among the constituent components of the photosensitive resin composition of the present invention.
  • “mass” is synonymous with “weight”.
  • the photosensitive resin composition of the present invention contains (a) zirconium dioxide particles, (b) a dispersant, (c) a solvent, (d) a binder resin, (e) a polymerizable monomer, and (f) a polymerization initiator. .
  • zirconium dioxide particles will be described in detail.
  • the photosensitive resin composition of the present invention contains (a) zirconium dioxide particles (hereinafter sometimes abbreviated as “zirconia particles”). (A) By containing zirconium dioxide particles, it is possible to obtain an organic insulating film having a high relative dielectric constant and a suppressed leakage current.
  • Long-period type periodic table Group 4 element compound particles, particularly long-period type periodic table Group 4 element oxide particles, which have a high relative dielectric constant, are suitable for high dielectric constant organic insulating film applications.
  • zirconium dioxide particles have a low relative dielectric constant, and it is necessary to increase the content ratio of the particles in order to obtain the desired dielectric constant of the obtained organic insulating film.
  • the zirconium dioxide particles are densely packed in the coating film, and the hygroscopicity of the coating film is reduced, so that the leakage current can be suppressed.
  • the average particle diameter of the primary particles of the zirconium dioxide particles is usually 100 nm or less, preferably 80 nm or less, more preferably 70 nm or less, and further preferably 60 nm or less. Moreover, it is 1 nm or more normally.
  • the particle diameter is less than or equal to the upper limit, there is no surface roughness and the patterning characteristics tend to be good. Moreover, if it is more than the said lower limit, there exists a tendency for a dispersibility to become favorable.
  • the average particle diameter of primary particles of zirconium dioxide particles is measured directly from the electron micrograph using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). Measure by method. Specifically, the primary particle diameter of each particle is calculated from the equivalent circle diameter. The measurement is performed on all particles within the range by imaging a range of 100 to 500 nm square. The different particle ranges are imaged several times, the particle sizes of a total of 200 to 1000 primary particles are measured, and the number average is taken to obtain the average particle size.
  • the primary particle size can be measured, for example, on zirconium dioxide particles alone, dispersions thereof, and cured films of the resin composition.
  • zirconium dioxide particles must be uniformly present in the sample.
  • the measurement is carried out after volatilizing the solvent using the dispersion immediately after dispersion.
  • a measurement is performed by preparing a cured film using a photosensitive resin composition in which particles are uniformly dispersed, cutting the film in the thickness direction, and observing the cross section.
  • the shape of the zirconium dioxide particles is not particularly limited, but is, for example, spherical, hollow, porous, rod-like, plate-like, fibrous, or indeterminate, and preferably spherical.
  • the content ratio of (a) zirconium dioxide particles is usually 50% by mass or more, preferably 55% by mass or more, more preferably 60% by mass or more, and further preferably 65% by mass in the total solid content of the photosensitive resin composition. % Or more, particularly preferably 70% by weight or more, preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 85% by weight or less, still more preferably 80% by weight or less, particularly preferably 75% by weight. % Or less.
  • a dielectric film with a high relative dielectric constant tends to be obtained when the lower limit value is exceeded, and a patterning characteristic tends to be better when the upper limit value is reached.
  • the photosensitive resin composition of the present invention contains (b) a dispersant.
  • (B) By containing a dispersing agent, the (a) zirconium dioxide particle can be stably disperse
  • the dispersant is preferably a polymer dispersant having a functional group, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary A polymeric dispersant having a functional group such as a quaternary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine, is preferred.
  • polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyls.
  • examples thereof include ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
  • dispersants examples include EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), DISPERBYK (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol). , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (manufactured by Ajinomoto Co., Inc.) and the like. These polymer dispersants may be used alone or in combination of two or more.
  • the weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less.
  • a dispersant having an amine value of 60 mgKOH / g or less and / or a dispersant having a phosphate group is preferable.
  • those having an ether bond such as polyesteramine and polyetheramine are preferred.
  • the amine value here represents an amine value in terms of effective solid content, and is a value represented by the mass of KOH equivalent to the amount of base per gram of solid content of the dispersant.
  • the dispersant having a phosphate group further has a polyether structure from the viewpoint of patterning characteristics.
  • the polyether structure is a part having a function of further improving the affinity with the developer and improving the dispersibility, and by having the polyether structure, patterning at a higher resolution tends to be possible.
  • the chemical structure of the dispersant having a phosphate group is not particularly limited. However, from the viewpoint of achieving both patterning characteristics and dispersibility, for example, the dispersant preferably has a chemical structure represented by the following general formula (X). .
  • R A represents an alkyl group which may have a substituent
  • ⁇ represents a polyether structure
  • ⁇ represents a direct bond or a polyester structure
  • N represents an integer of 1 to 3.
  • RA is an alkyl group which may have a substituent, but the carbon number thereof is not particularly limited, and is usually 1 or more, preferably 20 or less, more preferably 15 or less, and still more preferably 10 Hereinafter, it is particularly preferably 5 or less. By being in the said range, there exists a tendency for affinity with a developing solution to improve and a patterning characteristic to become favorable.
  • substituents that the alkyl group in RA may have include a sulfonyl group, a carboxyl group, a benzyl group, and a benzoyl group, but from the viewpoint of ease of synthesis, an unsubstituted group is preferable.
  • ⁇ represents a polyether structure, but from the viewpoint of affinity with a developer, a polyethylene glycol structure, a polypropyl ether structure, a polyisopropyl ether structure, and a butanyl ether structure are preferable, a polyethylene glycol structure is more preferable, and the following formula (X The structure represented by -1) is more preferable.
  • R B represents an alkylene group which may have a substituent.
  • the number of carbon atoms is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less. By being in the said range, there exists a tendency for a patterning characteristic to become favorable.
  • the substituent that the alkylene group in R B may have include a sulfonyl group, a carboxyl group, a benzyl group, and a benzoyl group, but from the viewpoint of ease of synthesis, an unsubstituted group is preferable.
  • x represents an integer of 5 to 30. x is preferably 10 or more, and preferably 25 or less.
  • affinity to a developing solution to become favorable by setting it as the said lower limit or more.
  • storage stability to become favorable by setting it as the said upper limit or less.
  • R B together contained more in one molecule may be the same or different and for example, as a butylene group and a pentylene group, or an alkylene group having a carbon number differs.
  • ⁇ represents a direct bond or a polyester structure, and a structure represented by the following formula (X-2) is more preferable.
  • R C represents an alkylene group which may have a substituent
  • y represents an integer of 0 to 10.
  • R C is an alkylene group which may have a substituent, but the carbon number thereof is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 15 or less. More preferably, it is 10 or less, More preferably, it is 8 or less. When it is at least the lower limit, the storage stability tends to be good, and when it is at most the upper limit, the patterning characteristics tend to be good.
  • the substituent that the alkylene group in R C may have include a sulfonyl group, a carboxyl group, a benzyl group, and a benzoyl group, but from the viewpoint of ease of synthesis, an unsubstituted group is preferable.
  • y is an integer of 0 to 10, but is preferably 1 or more, more preferably 2 or more, and preferably 7 or less from the viewpoint of both storage stability and patterning characteristics. More preferably, it is 5 or less. Storage stability tends to be good when the lower limit is exceeded. Moreover, there exists a tendency for a patterning characteristic to become favorable by setting it as the said upper limit or less.
  • RC contained in two or more in one molecule may be the same or different, for example, carbon number differs like a butylene group and a pentylene group. It may be an alkylene group.
  • the weight average molecular weight (Mw) of the dispersant having a phosphoric acid group is not particularly limited, but is preferably 1,000 or more, more preferably 5,000 or more, and 40,000 or less. It is preferable that it is 30,000 or less. Dispersibility tends to be good when it is at least the lower limit, and patterning characteristics tend to be good when it is less than or equal to the upper limit.
  • dispersant having a phosphoric acid group a commercially available one can be used.
  • DISPERBYK registered trademark, the same shall apply hereinafter
  • -102, 110, 111, 140, 142, 145, 180, 2001 manufactured by Big Chemie
  • DA-7301, DA-325, DA-375, DA-234, ED-152, ED-251 manufactured by Enomoto Kasei Co., Ltd.
  • TEGO registered trademark
  • Dispers 628, 655 manufactured by Evonik
  • the content of the dispersant is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and preferably 3% by mass or more in the total solid content of the photosensitive resin composition. It is 10 mass% or less, More preferably, it is 7 mass% or less, More preferably, it is 5 mass% or less.
  • the content of the dispersant having a phosphate group in the dispersant is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, and usually 100%. It is not more than mass%, particularly preferably 100 mass%. There exists a tendency for a patterning characteristic to improve by setting it as the said lower limit or more.
  • (b) dispersant it is preferable to contain 15 parts by mass or less of (b) dispersant, more preferably 10 parts by mass or less, and more preferably 8 parts by mass or less, relative to 100 parts by mass of (a) zirconium dioxide particles.
  • the photosensitive resin composition of the present invention contains (c) a solvent.
  • the solvent is not particularly limited as long as each component can be dissolved and dispersed and the handleability is good. Specifically, methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as “PGMEA”), methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, toluene, chloroform, dichloromethane, ethyl acetate, methyl lactate, ethyl lactate, 3-methoxymethyl propionate, 3-ethoxyethyl propionate, propylene glycol monomethyl ether (hereinafter abbreviated as “PGME”) Methanol, ethanol, propylene glycol monomethyl
  • glycol alkyl ether acetates and glycol monoalkyl ethers are preferable and glycol alkyl ether acetates are more preferable from the viewpoints of coatability and solubility of constituent components in the composition.
  • glycol alkyl ether acetates may be used alone or in combination with other solvents.
  • glycol monoalkyl ethers are particularly preferable.
  • propylene glycol monomethyl ether is particularly preferable from the viewpoints of solubility of components in the composition and dispersibility.
  • the solvent When the solvent is selected, if the polarity is high, dispersibility is hindered, and if the boiling point is high, the solvent does not fly even under reduced pressure drying (VCD) at the time of coating, and the patterning characteristics tend to be greatly deteriorated. Moreover, a residual solvent is generated even after baking of the coating film, which tends to cause a significant decrease in electrical characteristics.
  • VCD reduced pressure drying
  • a solvent having a boiling point in the range of 100 to 200 ° C. (under a pressure of 101.25 [hPa].
  • all the boiling points are the same) is selected.
  • the drying time can be shortened, which tends to be advantageous in terms of power consumption and production speed.
  • Glycol alkyl ether acetates are preferred from the standpoints of good balance of coating properties, surface tension, and the like in the solvent, and relatively high solubility of the constituent components in the composition.
  • one kind of solvent may be used alone, or two or more kinds of solvents may be mixed and used.
  • PGMEA may be mixed with one or more solvents selected from diethylene glycol dimethyl ether, methoxybutyl acetate, sorbest and carbitol.
  • the blending ratio of one or more solvents selected from diethylene glycol dimethyl ether, methoxybutyl acetate, sorbest and carbitol is usually 10% by mass or more, preferably 30% by mass or more with respect to PGMEA. Usually, it is 80% by mass or less, preferably 70% by mass or less. Furthermore, among the above mixed solvents, a mixed solvent of PGMEA and methoxybutyl acetate is suitable for flattening the unevenness of the substrate because it induces appropriate fluidity of the coating film in the coating and drying step.
  • the content rate of the (c) solvent in the photosensitive resin composition of this invention is not specifically limited, 50 mass% or more is preferable, 60 mass% or more is more preferable, 70 mass% or more is further more preferable, Usually 99 It is at most mass%, preferably at most 90 mass%, more preferably at most 85 mass%. By setting it within the above range, a sufficient amount of components such as (a) zirconium dioxide particles and (d) binder resin can be contained, and the coating property tends to be good.
  • the photosensitive resin composition of the present invention contains (d) a binder resin.
  • a binder resin By including a binder resin, a homogeneous film can be obtained.
  • a resin containing a carboxyl group or a hydroxyl group is preferable from the viewpoint of solubility in an alkaline developer, for example, an epoxy (meth) acrylate resin, an acrylic resin, a carboxyl group-containing epoxy Examples thereof include resins, carboxyl group-containing urethane resins, novolac resins, and polyvinylphenol resins. These can be used individually by 1 type or in mixture of multiple types.
  • the photosensitive resin composition of the present invention has an epoxy (meth) acrylate resin having a repeating unit structure represented by the following formula (I) and a partial structure represented by the following formula (II) as the (d) binder resin. It contains at least one of the epoxy (meth) acrylate resin which has.
  • the epoxy (meth) acrylate resin has high sensitivity, and therefore has good patterning characteristics, and has a hydrophobic skeleton and a mild dissolution rate, and thus has good substrate adhesion.
  • unlike acrylic resins it has a rigid skeleton, is easily cross-linked three-dimensionally, and has an array structure at the time of curing, so that it is considered to be able to suppress leakage current. .
  • those having a repeating unit structure represented by the following formula (I) and those having a partial structure represented by the following formula (II) have a bulky and rigid skeleton at the center, and therefore (meth) acryloyl It is considered that a hydrophilic portion such as a group is developed outward and the developability is improved.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a divalent hydrocarbon group which may have a substituent.
  • the benzene ring in formula (I) is Further, it may be further substituted with an arbitrary substituent. * Represents a bond.
  • each R 3 independently represents a hydrogen atom or a methyl group.
  • R 4 represents a divalent hydrocarbon group having an aliphatic ring group as a side chain. * Represents a bond. Represents.
  • the epoxy (meth) acrylate resin means the following (d1) and / or (d2) alkali-soluble resin, and those obtained by further reacting the carboxyl group of these resins with other compounds. means.
  • This epoxy (meth) acrylate resin has substantially no epoxy group in terms of chemical structure and is not limited to “(meth) acrylate”, but the epoxy resin is a raw material, and “( Since “meth) acrylate” is a representative example, it is named in accordance with conventional usage.
  • Alkali-soluble resin (d1) It was obtained by adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting a polybasic acid and / or an anhydride thereof. Alkali-soluble resin.
  • Alkali-soluble resin (d2) An ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof. The alkali-soluble resin obtained by this.
  • epoxy (meth) acrylate resin (d-1) an epoxy (meth) acrylate resin having a repeating unit structure represented by the formula (I) (hereinafter abbreviated as “epoxy (meth) acrylate resin (d-1)”) will be described in detail.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a divalent hydrocarbon group which may have a substituent.
  • the benzene ring in formula (I) is Further, it may be further substituted with an arbitrary substituent. * Represents a bond.
  • R 2 represents a divalent hydrocarbon group which may have a substituent.
  • the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups are linked to one or more divalent aromatic ring groups. Can be mentioned.
  • Examples of the divalent aliphatic group include linear, branched, and cyclic groups, and those obtained by connecting these. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion.
  • the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group.
  • a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
  • divalent branched aliphatic group examples include an iso-propylene group, a sec-butylene group, a tert-butylene group, and an iso-amylene group.
  • a tert-butylene group is preferable from the viewpoint of the rigidity of the skeleton.
  • the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less.
  • the lower limit value or more By setting it to the lower limit value or more, a strong film tends to be obtained, and the substrate adhesion and electrical characteristics tend to be good, and by setting the upper limit value or less, it is easy to suppress deterioration of the surface smoothness and sensitivity of the film. , The resolution tends to improve.
  • divalent aliphatic group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and the like, by removing two hydrogen atoms.
  • a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of the rigidity of the skeleton.
  • Examples of the substituent that the divalent aliphatic group may have include a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group. It is done. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
  • examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, and the like.
  • the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
  • Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences.
  • Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • unsubstituted is preferable from the viewpoint of development solubility and moisture absorption resistance.
  • divalent aliphatic groups and one or more divalent aromatic ring groups are linked
  • one or more of the above divalent aliphatic groups and the above divalent aromatic group are used.
  • the number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • the number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less.
  • the lower limit value or more it is easy to obtain a strong film, surface roughness is less likely to occur, and there is a tendency that the adhesion to the substrate and the electrical characteristics are good. It tends to suppress deterioration of surface smoothness and sensitivity, and tends to improve resolution.
  • group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (IA) to (IE): Is mentioned.
  • a group represented by the following formula (IA) is preferable from the viewpoint of skeleton rigidity and membrane hydrophobicity.
  • the benzene ring in formula (I) may be further substituted with an arbitrary substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics, and it is preferable that a methyl group is substituted at the ortho position from the viewpoint of electrical characteristics.
  • the repeating unit structure represented by the formula (I) is preferably a repeating unit structure represented by the following formula (I-1) from the viewpoint of simplicity of synthesis.
  • R 1 and R 2 have the same meanings as those in the formula (I).
  • R X represents a hydrogen atom or a polybasic acid residue. * Represents a bond.
  • the benzene ring in formula (I-1) may be further substituted with an optional substituent.
  • the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
  • Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid
  • One type or two or more types selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid may be mentioned.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, and more Tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic acid, and biphenyltetracarboxylic acid are preferable.
  • the repeating unit structure represented by the formula (I-1) contained in one molecule of the epoxy (meth) acrylate resin (d-1) may be one type or two or more types.
  • R X is a hydrogen atom.
  • those in which R X is a polybasic acid residue may be mixed.
  • the number of repeating unit structures represented by the formula (I) contained in one molecule of the epoxy (meth) acrylate resin (d-1) is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Moreover, 20 or less is preferable and 15 or less is more preferable.
  • the lower limit value or more it is easy to obtain a strong film, surface roughness is less likely to occur, and the electric characteristics tend to be good, and by setting the upper limit value or less, the surface smoothness and sensitivity of the film are reduced. Deterioration is easy to suppress and the resolution tends to improve.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate resin (d-1) is not particularly limited, but is preferably 1,000 or more, preferably 1,500 or more. Is more preferably 2,000 or more, particularly preferably 3,000 or more, more preferably 30,000 or less, more preferably 20,000 or less, further preferably 10,000 or less, and 8,000 or less. Even more preferred is 5,000 or less. There exists a tendency for the remaining film rate of the photosensitive resin composition to become favorable by setting it as the said lower limit or more, and there exists a tendency for resolution to become favorable by setting it as the said upper limit or less.
  • the acid value of the epoxy (meth) acrylate resin (d-1) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. It is preferably 150 mgKOH / g or less, more preferably 130 mgKOH / g or less, still more preferably 100 mgKOH / g or less, and particularly preferably 80 mgKOH / g or less. When the amount is not less than the lower limit, the development solubility is improved and the resolution tends to be good, and when the amount is not more than the upper limit, the residual film ratio of the curable resin composition tends to be good. There is.
  • epoxy (meth) acrylate resin (d-1) Specific examples of the epoxy (meth) acrylate resin (d-1) are given below.
  • epoxy (meth) acrylate resin (d-2) an epoxy (meth) acrylate resin having a partial structure represented by the formula (II) (hereinafter abbreviated as “epoxy (meth) acrylate resin (d-2)”) will be described in detail.
  • each R 3 independently represents a hydrogen atom or a methyl group.
  • R 4 represents a divalent hydrocarbon group having an aliphatic ring group as a side chain. * Represents a bond. Represents.
  • R 4 represents a divalent hydrocarbon group having an aliphatic ring group as a side chain.
  • the number of rings that the aliphatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less.
  • the lower limit value or more it is easy to obtain a strong film, surface roughness is less likely to occur, and the electric characteristics tend to be good, and by setting the upper limit value or less, the surface smoothness and sensitivity of the film are reduced. Deterioration is easy to suppress and the resolution tends to improve.
  • aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
  • an adamantane ring is preferable from the viewpoint of the remaining film ratio and resolution of the photosensitive resin composition.
  • the divalent hydrocarbon group in the divalent hydrocarbon group having an aliphatic ring group as a side chain is not particularly limited.
  • Examples of the divalent aliphatic group include linear, branched, and cyclic groups. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion.
  • the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 25 or less, more preferably 20 or less, and even more preferably 15 or less.
  • divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group.
  • a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
  • divalent branched aliphatic group examples include an iso-propylene group, a sec-butylene group, a tert-butylene group, and an iso-amylene group.
  • a tert-butylene group is preferable from the viewpoint of the rigidity of the skeleton.
  • the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • divalent aliphatic group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and the like, by removing two hydrogen atoms.
  • a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of the rigidity of the skeleton.
  • Examples of the substituent that the divalent aliphatic group may have include a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group. It is done. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
  • examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, and the like.
  • the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
  • Examples of the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences.
  • Examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
  • a benzene ring or naphthalene ring having two free valences is preferable, and a fluorene ring having a divalent free valence is more preferable.
  • Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • unsubstituted is preferable from the viewpoint of development solubility and moisture absorption resistance.
  • divalent aliphatic groups and one or more divalent aromatic ring groups are linked
  • one or more of the above divalent aliphatic groups and the above divalent aromatic group are used.
  • the number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • the number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less.
  • the lower limit value or more it is easy to obtain a strong film, surface roughness is less likely to occur, and there is a tendency that the adhesion to the substrate and the electrical characteristics are good. It tends to suppress deterioration of surface smoothness and sensitivity, and tends to improve resolution.
  • the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the above formulas (IA) to (IE), etc. Is mentioned.
  • the group represented by the formula (IA) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the film.
  • the bonding mode of the aliphatic cyclic group which is a side chain with respect to these divalent hydrocarbon groups is not particularly limited, but for example, one hydrogen atom of a divalent aliphatic group or a divalent aromatic ring group And an aspect in which an aliphatic cyclic group that is a side chain is included, including one of carbon atoms that constitute a divalent aliphatic group.
  • the partial structure represented by the formula (II) is preferably a partial structure represented by the following formula (II-1) from the viewpoint of hole resolution.
  • R 3 has the same meaning as in Formula (II) above, and R ⁇ represents a monovalent aliphatic cyclic group which may have a substituent.
  • N is 1 or more.
  • the benzene ring in formula (II-1) may be further substituted with an optional substituent.
  • * represents a bond.
  • R ⁇ represents a monovalent aliphatic ring group which may have a substituent.
  • the number of rings that the aliphatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, more preferably 3 or less.
  • the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable.
  • aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
  • an adamantane ring is preferable from the viewpoint of strong film characteristics and electrical characteristics.
  • Examples of the substituent that the aliphatic cyclic group may have include a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group.
  • unsubstituted is preferable from the viewpoint of ease of synthesis.
  • N represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less.
  • R ⁇ is an adamantyl group from the viewpoint of a firm film curing degree and electrical characteristics.
  • the benzene ring in formula (II-1) may be further substituted with an arbitrary substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.
  • partial structure represented by the formula (II) is preferably a partial structure represented by the following formula (II-2) from the viewpoint of skeleton rigidity and membrane hydrophobization.
  • R 3 has the same meaning as in Formula (II).
  • R ⁇ represents a divalent aliphatic ring group which may have a substituent.
  • Formula (II-) The benzene ring in 2) may be further substituted with an arbitrary substituent.
  • R ⁇ represents a divalent aliphatic ring group which may have a substituent.
  • the number of rings that the aliphatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less.
  • the lower limit value or more it is easy to obtain a strong film, surface roughness is less likely to occur, and the electric characteristics tend to be good, and by setting the upper limit value or less, the surface smoothness and sensitivity of the film are reduced. Deterioration is easy to suppress and the resolution tends to improve.
  • carbon number of an aliphatic cyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 35 or less are more preferable, and 30 or less are more preferable.
  • aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
  • an adamantane ring is preferable from the viewpoint of storage stability.
  • Examples of the substituent that the aliphatic cyclic group may have include a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group.
  • unsubstituted is preferable from the viewpoint of easy synthesis.
  • R beta is a divalent adamantane ring group.
  • the benzene ring in formula (II-2) may be further substituted with an arbitrary substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.
  • the partial structure represented by the formula (II) is preferably a partial structure represented by the following formula (II-3) from the viewpoint of the remaining film ratio and patterning characteristics.
  • R 3 and R 4 have the same meanings as those in Formula (II).
  • R Z represents a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
  • the polybasic acid residue may be shared with R Z in other molecules represented by the formula (II-3) by removing another OH group from the polybasic acid or its anhydride. That is, a plurality of formulas (II-3) may be linked via R Z.
  • Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, end methylenetetrahydrophthalic acid
  • One type or two or more types selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid may be mentioned.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, and more Tetrahydrophthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid are preferable.
  • the partial structure represented by the formula (II-3) contained in one molecule of the epoxy (meth) acrylate resin (d-2) may be one type or two or more types.
  • R Z is a hydrogen atom.
  • those in which R Z is a polybasic acid residue may be mixed.
  • the number of partial structures represented by the formula (II) contained in one molecule of the epoxy (meth) acrylate resin (d-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Moreover, 20 or less is preferable, 15 or less is more preferable, and 10 or less is further more preferable.
  • the lower limit value or more it is easy to obtain a strong film, surface roughness is less likely to occur, and the electric characteristics tend to be good, and by setting the upper limit value or less, the surface smoothness and sensitivity of the film are reduced. Deterioration is easy to suppress and the resolution tends to improve.
  • the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth) acrylate resin (d-2) is not particularly limited, but is preferably 1,000 or more, preferably 1,500 or more. Is more preferable, 2,000 or more is more preferable, 30,000 or less is preferable, 20,000 or less is more preferable, 10,000 or less is further preferable, and 5,000 or less is particularly preferable. When it is at least the lower limit value, the patterning characteristics tend to be good, and when it is at most the upper limit value, a strong film is likely to be obtained and surface roughness tends not to occur.
  • the acid value of the epoxy (meth) acrylate resin (d-2) is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, more preferably 60 mgKOH / g or more. More preferably, 80 mgKOH / g or more is particularly preferable, 200 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, and 120 gKOH / g or less is more preferable.
  • By setting the lower limit value or more it is easy to obtain a strong film, and the electric characteristics tend to be improved.
  • By setting the upper limit value or less the development solubility is improved, and the resolution tends to be good. There is.
  • Epoxy (meth) acrylate resins (d-1) and (d-2) are obtained by adding (i) an ⁇ , ⁇ -unsaturated monoester to an epoxy resin having a structure corresponding to the formula (I) and the formula (II).
  • An ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxylic acid or a carboxyl group is added, and a polybasic acid and / or an anhydride thereof is reacted; or (ii) an ⁇ , ⁇ -unsaturated monocarboxylic acid or It can be obtained by adding an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group and further reacting with a polyhydric alcohol and a polybasic acid and / or an anhydride thereof.
  • Examples of the epoxy resin used as a raw material include phenol novolac type epoxy resins (for example, “EPPN-201” manufactured by Nippon Kayaku Co., Ltd., “EP-152”, “EP-154” manufactured by Mitsubishi Chemical Corporation), (o , M, p-) Cresol novolac type epoxy resin (for example, “EOCN-102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), phenol resin by reaction of dicyclopentadiene and phenol Glycidylated epoxy resins (for example, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (D1) to (D3), and the like can be suitably used.
  • phenol novolac type epoxy resins for example, “EPPN-201” manufactured by Nippon Kayaku Co., Ltd., “EP-152”, “EP-154” manufactured by Mitsubishi Chemical Corporation
  • a is an average value and represents a number from 0 to 10.
  • R 11 represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, and a biphenyl group.
  • a plurality of R 11 present in one molecule may be the same or different.
  • R 21 represents any one of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, and a biphenyl group.
  • a plurality of R 21 present in one molecule may be the same or different.
  • X represents a linking group represented by the following general formula (D3-1) or (D3-2). However, one or more adamantane structures are included in the molecular structure.
  • c represents an integer of 2 or 3.
  • R 31 to R 34 and R 35 to R 37 are each independently an adamantyl group, a hydrogen atom, or a substituent, which may have a substituent.
  • epoxy resins represented by general formulas (D1) to (D3) it is preferable to use epoxy resins represented by general formulas (D1) to (D3).
  • Examples of the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meta ) Monocarboxylic acids such as ⁇ -position haloalkyl, alkoxyl, halogen, nitro, and cyano substituents of acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- ( (Meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (Met
  • (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.
  • an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group can be used as a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group.
  • a known method can be used as a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group.
  • an epoxy resin at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. it can.
  • esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.
  • the epoxy resin, ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst may be used alone or in combination of two types. You may use the above together.
  • the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of the epoxy resin. More preferably, it is in the range of 0.7 to 1.1 equivalents.
  • the amount of unsaturated group introduced is sufficient, and the subsequent polybasic acid and The reaction with / or its anhydride also tends to be sufficient.
  • Polybasic acids and / or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methyl hexahydrophthal
  • examples thereof include one or more selected from acids, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • maleic acid succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or anhydrides thereof.
  • Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.
  • a known method can be used for addition reaction of polybasic acid and / or anhydride thereof, and ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid having a carboxyl group to epoxy resin.
  • the target product can be obtained by continuing the reaction under the same conditions as in the ester addition reaction.
  • the addition amount of the polybasic acid and / or its anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, and further 20 The degree is preferably in the range of ⁇ 140 mgKOH / g. When the acid value of the carboxyl group-containing epoxy (meth) acrylate resin is within the above range, alkali developability and curing performance tend to be good.
  • transduced polyfunctional alcohol such as a trimethylol propane, a pentaerythritol, a dipentaerythritol, and introduce
  • the carboxyl group-containing epoxy (meth) acrylate resin is usually a polybasic acid and a reaction product of an epoxy resin and an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group. Or after mixing the anhydride, or a reaction product of an epoxy resin with an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group, Or it is obtained by heating after mixing the anhydride and polyfunctional alcohol. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyfunctional alcohol is not particularly limited.
  • Any hydroxyl group present in the mixture of the reaction product of the epoxy resin with the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group and the polyfunctional alcohol by heating.
  • the binder resin (d) contained in the photosensitive resin composition of the present invention includes an epoxy (meth) acrylate resin having a repeating unit structure represented by the formula (I) and a partial structure represented by the formula (II). It contains at least one of the epoxy (meth) acrylate resins having a binder, but may contain other binder resins (hereinafter abbreviated as “other binder resins”). Examples of other binder resins include acrylic resins, carboxyl group-containing epoxy resins, carboxy group-containing urethane resins, novolac resins, polyvinylphenol resins, and the like, and these may be used alone. You may mix and use multiple types.
  • the content ratio of (d) binder resin in the photosensitive resin composition of the present invention is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass in the total solid content. % Or more, usually 50% by mass or less, preferably 45% by mass or less, more preferably 35% by mass or less, and particularly preferably 25% by mass or less.
  • amount is not less than the above lower limit value, a strong film can be easily obtained, surface roughness is unlikely to occur, and the adhesion to the substrate tends to be good. There is a tendency that the penetration of the liquid is kept low and deterioration of the surface smoothness and sensitivity of the film is easily suppressed.
  • the content ratio of the epoxy (meth) acrylate resin in the binder resin is not particularly limited, but is preferably 5% by mass or more, more preferably 30% by mass or more, and 50% by mass or more. Is more preferably 100% by mass or less, and particularly preferably 100% by mass. By setting it as the said lower limit or more, there exists a tendency for a patterning characteristic and board
  • an epoxy (meth) acrylate resin having a repeating unit structure represented by the formula (I) and an epoxy (meth) acrylate resin having a partial structure represented by the following formula (II) in the binder resin The content ratio of at least one of is not particularly limited, but is preferably 5% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, and usually 100% by mass. Or less, particularly preferably 100% by mass. Water resistance improves by setting it as the said lower limit or more, and there exists a tendency for a coating-film surface to become uniform.
  • the photosensitive resin composition of the present invention contains (e) a polymerizable monomer.
  • (E) By containing a polymerizable monomer, a highly curable film can be obtained.
  • a compound having an ethylenically unsaturated group (hereinafter sometimes abbreviated as “ethylenically unsaturated compound”) is preferably exemplified.
  • An ethylenically unsaturated compound means a compound having at least one ethylenically unsaturated bond in the molecule.
  • the photosensitive resin composition in this invention contains the compound which has 2 or more of ethylenically unsaturated groups.
  • Examples of the compound having one ethylenically unsaturated bond include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid, and alkyl esters thereof, (meth) Examples include acrylonitrile, (meth) acrylamide, and styrene.
  • Examples of compounds having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, (meth) acryloyloxy group-containing phosphates, and hydroxy (meth) acrylate compounds. And urethane (meth) acrylates of polyisocyanate compounds and epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds.
  • esters of Unsaturated Carboxylic Acid and Polyhydroxy Compound Esters of Unsaturated Carboxylic Acid and Polyhydroxy Compound (hereinafter may be abbreviated as “ester (meth) acrylates”). Specifically, the following compounds can be exemplified.
  • Reaction product of unsaturated carboxylic acid and sugar alcohol examples include ethylene glycol, polyethylene glycol (addition number 2-14), propylene glycol, polypropylene glycol (addition number 2-14), trimethylene glycol, Examples include tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol and the like.
  • Reaction product of unsaturated carboxylic acid and alkylene oxide adduct of sugar alcohol examples of sugar alcohol are the same as described above.
  • Examples of the alkylene oxide adduct include an ethylene oxide adduct or a propylene oxide adduct.
  • Reaction product of unsaturated carboxylic acid and alcoholamine examples of alcoholamines include diethanolamine and triethanolamine.
  • esters of the unsaturated carboxylic acid and the polyhydroxy compound the unsaturated carboxylic acid and an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or addition of ethylene oxide thereof.
  • an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or addition of ethylene oxide thereof.
  • a reaction product with the product include bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], and the like.
  • examples of the ester of the unsaturated carboxylic acid and the polyhydroxy compound include a reaction product of the unsaturated carboxylic acid and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate.
  • a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate.
  • Specific examples include tris (2-hydroxyethyl) isocyanurate di (meth) acrylate and tri (meth) acrylate.
  • examples of the ester of the unsaturated carboxylic acid and the polyhydroxy compound include a reaction product of the unsaturated carboxylic acid, the polyvalent carboxylic acid, and the polyhydroxy compound.
  • a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol a condensate of (meth) acrylic acid, maleic acid and diethylene glycol, (meth) acrylic acid, terephthalic acid and pentaerythritol
  • (E-2) Urethane (meth) acrylates of hydroxy (meth) acrylate compound and polyisocyanate compound
  • the hydroxy (meth) acrylate compound include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylol.
  • examples include hydroxy (meth) acrylate compounds such as ethanetri (meth) acrylate.
  • polyisocyanate compound for example, Aliphatic polyisocyanates such as hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane; Cycloaliphatic polyisocyanates such as cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, bicycloheptane triisocyanate; Aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate, tris (isocyanatephenyl) thiophosphate; Heterocyclic polyisocyanates such as isocyanurates; Allophanate-modified polyisocyanurate produced by the method described in JP-A-2001-260261; And polyisocyanate compounds such as
  • urethane (meth) acrylates of a hydroxy (meth) acrylate compound and a polyisocyanate compound urethane (meth) acrylates containing the above allophanate-modified polyisocyanurate are preferable.
  • Urethane (meth) acrylates containing allophanate-modified polyisocyanurate have low viscosity, excellent solubility in solvents, and are effective in improving adhesion to the substrate and film strength by photocuring and / or thermal curing. This is preferable in terms of points.
  • urethane (meth) acrylates in this invention A commercially available thing can be used as said urethane (meth) acrylates in this invention.
  • trade names “U-4HA”, “UA-306A”, “UA-MC340H”, “UA-MC340H”, “U6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd., allophanate skeleton manufactured by Bayer Japan Examples thereof include “AGROR 4060” which is a compound having the same.
  • the urethane (meth) acrylates in the present invention include 4 or more (preferably 6 or more, more preferably 8 or more) urethane bonds [—NH—CO—O— in one molecule.
  • a compound having 4 or more (preferably 6 or more, more preferably 8 or more) (meth) acryloyloxy groups Such a compound can be obtained, for example, by reacting the following compound (i) with the following compound (ii).
  • (I) a compound having 4 or more urethane bonds in one molecule, for example, Compound (i) obtained by reacting a compound having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerol with a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate -1); Or To compounds having two or more hydroxyl groups in one molecule such as ethylene glycol, “Duranate 24A-100”, “Duranate 22A-75PX”, “Duranate 21S-75E”, “Duranate 21S-75E”, and “Duranate 18H— 3 or more per molecule such as biuret type such as “70B”, adduct type such as “Duranate P-301-75E”, “Duranate E-402-90T”, “Duranate E-405-80T”, etc. Compound (i-2) obtained
  • a commercially available product can be used, and examples thereof include “Duranate ME20-100” manufactured by Asahi Kasei Chemicals Corporation.
  • (Ii) Compounds having four or more (meth) acryloyloxy groups in one molecule, for example, pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipenta Examples thereof include compounds having one or more hydroxyl groups and two or more, preferably three or more (meth) acryloyloxy groups in one molecule, such as erythritol penta (meth) acrylate and dipentaerythritol hexaacrylate.
  • the molecular weight of the compound (i) is preferably 500 to 200,000, particularly preferably 1,000 to 150,000.
  • the molecular weight of the urethane (meth) acrylates is preferably 600 to 150,000.
  • Such urethane (meth) acrylates include, for example, the above compound (i) and the above compound (ii) in an organic solvent such as toluene and ethyl acetate at 10 to 150 ° C. for 5 minutes to It can be produced by a method of reacting for about 3 hours. In this case, it is preferable that the molar ratio of the former isocyanate group and the latter hydroxyl group is 1/10 to 10/1, and a catalyst such as n-butyltin dilaurate is used if necessary.
  • the polyepoxy compound include: (Poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly ) Aliphatic polyepoxy compounds such as hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether;
  • Aromatic polyepoxy compounds such as phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds; And polyepoxy compounds such as heterocyclic polyepoxy compounds such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, and triglycidyl tris (2-hydroxyethyl) isocyanurate;
  • epoxy (meth) acrylates which are a reaction product of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound, such a polyepoxy compound and (meth) acrylic acid or the above hydroxy ( Examples include a reaction product with a (meth) acrylate compound.
  • ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, and allyl esters such as diallyl phthalate. And vinyl group-containing compounds such as divinyl phthalate, and thioether bond-containing compounds whose crosslinking rate is improved by sulfurizing ether bonds of ether-containing ethylenically unsaturated compounds with phosphorus pentasulfide to convert them into thioether bonds. It is done.
  • the ethylenically unsaturated compound preferably includes a compound having two or more ethylenically unsaturated groups in the molecule from the viewpoints of polymerizability and crosslinkability.
  • ester (meth) acrylates, (meth) acryloyloxy group-containing phosphates, or urethane (meth) acrylates are preferable, and ester (meth) acrylates are more preferable.
  • ester (meth) acrylates aromatic polyhydroxy compounds such as bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], or Particularly preferred are those reactants with ethylene oxide adducts.
  • a compound that does not contain an aromatic ring, or that contains no phenyl group or a phenyl group having a substituent at the p (para) position is a heat treatment of the interlayer insulating film. This is preferable because discoloration (red coloring) due to is suppressed.
  • ethylenically unsaturated compounds include aliphatic polyfunctional (meth) acrylates and polyhydric alcohol (meth) acrylate compounds having a bisphenol A or fluorene skeleton.
  • Acrylates are preferably used, and in particular, a (meth) acrylate compound represented by the following formula (III) is preferably used.
  • R 5 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
  • R 6 each independently represents an alkylene group which may have a substituent.
  • R 7 each independently represents a hydrogen atom or a methyl group, and k and l each independently represents an integer of 1 to 20.
  • R 5 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings that the aliphatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, more preferably 3 or less. When the amount is not less than the lower limit value, a strong coating film tends to be obtained and the remaining film ratio tends to be good, and when the value is not more than the upper limit value, development solubility tends to be improved and patterning characteristics tend to be good. .
  • the number of carbon atoms of the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 30 or less, more preferably 25 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable.
  • aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
  • an adamantane ring is preferable from the viewpoint of strong film quality and patterning characteristics.
  • the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 6 or less, preferably 4 or less.
  • the aromatic ring group examples include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and preferably 30 or less, preferably 25 or less. More preferably, it is more preferably 20 or less, and particularly preferably 15 or less.
  • aromatic ring in the aromatic ring group examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
  • a benzene ring is preferable from the viewpoint of development solubility.
  • the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited.
  • Examples of the divalent aliphatic group include linear, branched, cyclic, and combinations thereof. Among these, a linear one is preferable from the viewpoint of development solubility, and a cyclic one is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion.
  • the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • divalent linear aliphatic group examples include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, and an n-heptylene group.
  • a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
  • divalent branched aliphatic group examples include an iso-propylene group, a sec-butylene group, a tert-butylene group, and an iso-amylene group.
  • a tert-butylene group is preferable from the viewpoint of the rigidity of the skeleton.
  • the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • divalent cyclic aliphatic group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and the like, by removing two hydrogen atoms.
  • a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of the rigidity of the skeleton.
  • Examples of the substituent that the divalent aliphatic group may have include a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group. It is done. Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
  • examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, 40 or less, more preferably 35 or less, and even more preferably 30 or less.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences, Examples include a triphenylene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, and the like.
  • the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
  • the divalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free valences.
  • Examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
  • a benzene ring or naphthalene ring having two free valences is preferable, and a benzene ring having a divalent free valence is more preferable.
  • Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • unsubstituted is preferable from the viewpoint of development solubility and moisture absorption resistance.
  • divalent aliphatic groups and one or more divalent aromatic ring groups are linked
  • one or more of the above divalent aliphatic groups and the above divalent aromatic group are used.
  • the number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • the number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, more preferably 3 or less.
  • the lower limit value or more it is easy to obtain a strong film, surface roughness is less likely to occur, and there is a tendency that the adhesion to the substrate and the electrical characteristics are good. It tends to suppress deterioration of surface smoothness and sensitivity, and tends to improve resolution.
  • the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the above formulas (IA) to (IE), etc. Is mentioned.
  • the group represented by the formula (IA) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the film.
  • the bonding mode of the cyclic hydrocarbon group which is a side chain with respect to these divalent hydrocarbon groups is not particularly limited.
  • one hydrogen atom of a divalent aliphatic group or a divalent aromatic ring group
  • a mode in which a cyclic hydrocarbon group that is a side chain is formed including one of carbon atoms that constitute a divalent aliphatic group.
  • each R 6 independently represents an alkylene group which may have a substituent.
  • the alkylene group include linear, branched, cyclic, and combinations thereof. Among these, linear is preferable from the viewpoint of solubility during development.
  • the number of carbon atoms is usually 1 or more, preferably 2 or more, more preferably 6 or more, further preferably 10 or more, preferably 30 or less, more preferably 25 or less, and still more preferably 20 or less.
  • alkylene group examples include ethylene group, n-propylene group, iso-propylene group, sec-butylene group, tert-butylene group, cyclohexylene group and the like.
  • an ethylene group is preferable from the viewpoint of development solubility.
  • Examples of the substituent that the alkylene group may have include a hydroxyl group, a methoxy group, an ethoxy group, a sulfone group, a sulfonyl group, a carboxyl group, and a benzyl group.
  • unsubstituted is preferable from the viewpoint of exposure sensitivity
  • a hydroxyl group is preferable from the viewpoint of development solubility.
  • k and l each independently represents an integer of 1 to 20. Preferably it is 2 or more, More preferably, it is 3 or more, Preferably it is 15 or less, More preferably, it is 13 or less.
  • a (meth) acrylate compound represented by the following formula (III-1) is preferred from the viewpoint of high resolution.
  • R 6 , R 7 , k and l have the same meanings as in the formula (III).
  • R ⁇ is a monovalent cyclic hydrocarbon group which may have a substituent.
  • M is an integer greater than or equal to 1.
  • the benzene ring in formula (III-1) may be further substituted with an arbitrary substituent.
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings that the aliphatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, more preferably 3 or less.
  • the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 30 or less, more preferably 25 or less, still more preferably 20 or less, and particularly preferably 15 or less. preferable.
  • aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
  • an adamantane ring is preferable from the viewpoint of suppressing the penetration of the developer into the exposed portion and suppressing the surface smoothness and sensitivity of the film.
  • the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 6 or less, preferably 5 or less.
  • the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 6 or less, preferably 5 or less.
  • the aromatic ring group examples include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is usually 6 or more, preferably 8 or more, more preferably 10 or more, 40 or less, more preferably 35 or less, and even more preferably 30 or less.
  • aromatic ring in the aromatic ring group examples include benzene ring, naphthalene ring, biphenyl, triphenylene ring, phenanthrene ring, fluorene ring and the like.
  • a fluorene ring is preferable from the viewpoint of ensuring the penetration characteristics and resolution of the developer.
  • Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples thereof include alkyl groups having 1 to 5 carbon atoms such as amyl group and iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; Among these, unsubstituted is preferable from the viewpoint of ease of synthesis.
  • M represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less.
  • R ⁇ is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group, from the viewpoint of moisture absorption resistance of the coating film and alkali solubility of the unexposed area.
  • the benzene ring in formula (III-1) may be further substituted with an arbitrary substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.
  • the (meth) acrylate compound represented by the formula (III) is represented by the following formula (III-2) from the viewpoint of moisture absorption resistance of the coating film and alkali solubility in the unexposed area.
  • a (meth) acrylate compound is preferred.
  • R 6 , R 7 , k and l have the same meanings as in the formula (III).
  • R ⁇ is a divalent cyclic hydrocarbon group which may have a substituent.
  • the benzene ring in formula (III-2) may be further substituted with an arbitrary substituent.
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings that the aliphatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less.
  • carbon number of an aliphatic cyclic group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 30 or less are preferable, 25 or less are more preferable, and 20 or less are more preferable.
  • the film hydrophobicity tends to be improved and the adhesion to the substrate tends to be improved.
  • the upper limit value or less patterning characteristics are improved by increasing development solubility at the time of unexposed. Tend.
  • aliphatic ring in the aliphatic ring group examples include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
  • an adamantane ring is preferable from the viewpoint of substrate adhesion.
  • the number of rings of the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 6 or less, preferably 4 or less.
  • the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, more preferably 30 or less, more preferably 25 or less, and further preferably 20 or less.
  • 15 or less is particularly preferable.
  • a coating film becomes hydrophobic and there exists a tendency for board
  • aromatic ring in the aromatic ring group examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like.
  • a fluorene ring is preferable from the viewpoint of substrate adhesion due to the hydrophobization of the coating film.
  • Examples of the substituent that the cyclic hydrocarbon group may have include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples thereof include alkyl groups having 1 to 5 carbon atoms such as amyl group and iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; Among these, unsubstituted is preferable from the viewpoint of development solubility and exposure sensitivity.
  • R ⁇ is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group.
  • R ⁇ is preferably a divalent aromatic ring group, more preferably a divalent fluorene ring group, from the viewpoint of low hygroscopicity and patterning characteristics of the coating film.
  • the benzene ring in formula (III-2) may be further substituted with an arbitrary substituent.
  • substituents include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited, either one or two or more. Among these, unsubstituted is preferable from the viewpoint of patterning characteristics.
  • the content of the polymerizable monomer (e) is usually 1% by mass or more, preferably 3% by mass or more, and usually 20% by mass or less, based on the total solid content. It is preferably 18% by mass or less, more preferably 15% by mass or less, further preferably 12% by mass or less, and particularly preferably 10% by mass or less.
  • film membrane sclerosis
  • the content ratio of the (meth) acrylate compound represented by the formula (III) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, further based on the total solid content.
  • it is 2 mass% or more, Preferably it is 15 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 8 mass% or less.
  • the electrical characteristics and hole resolution tend to be improved, and when it is at most the upper limit, film roughness on the coating film surface tends to be suppressed.
  • the photosensitive resin composition of the present invention contains (f) a polymerization initiator.
  • a polymerization initiator any known one can be used, and examples thereof include compounds capable of generating radicals that polymerize ethylenically unsaturated groups from ultraviolet rays to visible rays. Specific examples of the polymerization initiator that can be used in the present invention are listed below.
  • Benzoin alkyl ethers such as benzoin methyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.
  • Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone.
  • V A benzanthrone derivative.
  • benzophenone derivatives such as benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone.
  • Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone.
  • (Ix) Derivatives of benzoic acid esters such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.
  • (X) Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine.
  • acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
  • acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
  • acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.
  • Xv 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] -1- (O-acety
  • oxime ester compounds are preferable, (xv) and (xvi) are more preferable, and compound Y having the following structure is particularly preferable.
  • polymerization initiators are used alone or in combination.
  • combinations include, for example, Japanese Patent Publication No. 53-12802, Japanese Patent Laid-Open No. 1-227903, Japanese Laid-Open Patent Publication No. 2-48664, Japanese Laid-Open Patent Publication No. 4-164902, or Japanese Special Examples thereof include combinations of polymerization initiators described in Kaihei 6-75373.
  • the content of the polymerization initiator in the photosensitive resin composition of the present invention is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, based on the total solid content. More preferably 2% by mass or more, particularly preferably 3% by mass or more, and usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, Especially preferably, it is 7 mass% or less. If the amount is not less than the lower limit value, the curability tends to be sufficient and a decrease in film strength tends to be suppressed. If the amount is not more than the upper limit value, the degree of thermal shrinkage decreases, and cracks and cracks after heat curing are suppressed. There is a tendency to be able to.
  • the photosensitive resin composition in the present invention is a nonionic, anionic, cationic, amphoteric surfactant for the purpose of improving the coating property of the composition as a coating liquid and the developability of the photosensitive resin composition layer.
  • it may contain a fluorine-based or silicone-based surfactant.
  • nonionic surfactant examples include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, Glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxy And ethylene sorbite fatty acid esters.
  • examples of these commercially available products include polyoxyethylene surfactants such as “Emulgen 104P” and “Emulgen A60” manufactured by Kao Corporation.
  • anionic surfactant examples include alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, and higher alcohol sulfates.
  • an anionic surfactant a commercially available product can be used.
  • “Emar 10” manufactured by Kao Co., Ltd. is used for alkyl sulfates
  • “Perex NB-L” manufactured by Kao Co., Ltd. is used for alkyl naphthalene sulfonates.
  • “Homogenol L-18”, “Homogenol L-100” manufactured by Kao Corporation and the like are mentioned.
  • the cationic surfactant quaternary ammonium salts, imidazoline derivatives, amine salts, etc.
  • betaine type compounds imidazolium salts, imidazolines, amino acids Etc.
  • quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred.
  • Examples of commercially available products include “Acetamine (registered trademark) 24” manufactured by Kao Co., Ltd. for alkylamine salts, and “Cotamine (registered trademark, the same applies hereinafter) 24P”, “Cotamine 86W” manufactured by Kao Corporation for quaternary ammonium salts. Or the like.
  • a compound having a fluoroalkyl group or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable.
  • silicone-based surfactant examples include “Toray Silicone DC3PA”, “Same SH7PA”, “Same DC11PA”, “Shi21 PA”, “Shi28PA”, “Shi29PA”, “Shoe29PA” manufactured by Toray Dow Corning Co., Ltd. "SH30PA”, “SH8400”, “FZ2122”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF-4442” manufactured by Momentive Performance Materials And commercially available products such as “KP341” manufactured by Silicone, “BYK323”, “BYK330” manufactured by BYK Chemie.
  • a fluorine-based surfactant and a silicone-based surfactant are preferable from the viewpoint of coating film thickness uniformity.
  • the surfactant may be a combination of two or more types: silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant / special polymer surfactant Examples include combinations of agents. Among these, silicone surfactant / fluorine surfactant is preferable.
  • silicone surfactant / fluorine surfactant combination for example, “TSF4460” manufactured by Momentive Performance Materials / “DFX-18” manufactured by Neos, “BYK-300” manufactured by BYK Chemie, or “BYK” -330 "/" S-393 "manufactured by Seimi Chemical Co., Ltd.," KP340 “manufactured by Shin-Etsu Silicone Co., Ltd.,” F-478 “or” F-475 “manufactured by Dainippon Ink Co., Ltd.,” SH7PA “manufactured by Toray Dow Corning Co., Ltd./Daikin “DS-401” manufactured by Toray Dow Corning “FZ2122” manufactured by Toray Dow Corning “FC4432” manufactured by 3M, “L-77” manufactured by Nippon Unicar Co., Ltd., “FC4430” manufactured by 3M, and the like.
  • TSF4460 manufactured by Momentive Performance Materials / “DFX-18” manufactured by Neos,
  • the content of the surfactant in the photosensitive resin composition is preferably 10% by mass or less in the total solid content, 0.01 More preferably, it is ⁇ 5% by mass.
  • the photosensitive resin composition of the present invention may further contain additives such as a thermal crosslinking agent, an adhesion aid, a curing agent, and an ultraviolet absorber.
  • additives such as a thermal crosslinking agent, an adhesion aid, a curing agent, and an ultraviolet absorber. Examples of these components include International Publication No. 2007/139005. The thing of description is mentioned.
  • an inorganic particle dispersion contains (a) zirconium dioxide particles, (b) a dispersant, (c) a solvent, and optionally contains a dispersion resin.
  • the dispersing method is not particularly limited, and examples thereof include a method using a paint shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer and the like.
  • the order of mixing the components is not particularly limited as long as the effects of the present invention are not impaired.
  • C After adding a solvent, (a) zirconium dioxide particles, (b) a dispersing agent, and optionally a dispersing resin. Or vice versa.
  • the dispersion resin those described as the above-mentioned (d) binder resin can be used.
  • D used when preparing the photosensitive resin composition (d) A part of the binder resin can also be used as a dispersion resin, and is different from that used when preparing the photosensitive resin composition (d) the binder resin Can also be used.
  • zirconium dioxide particles are dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.05 to 5 mm are preferably used.
  • the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C.
  • the above-mentioned inorganic particle dispersion is made from the essential component (c) solvent, (d) binder resin, (e) polymerizable monomer, and (f) polymerization initiator, and in some cases, an optional component, a surfactant.
  • the photosensitive resin composition is obtained by mixing with other components to obtain a uniform solution. Mixing is preferably performed at room temperature, and is usually performed under ultraviolet light blocking so that the polymerization reaction does not start.
  • a cured product can be obtained by applying and curing the photosensitive resin composition of the present invention.
  • the photosensitive resin composition of the present invention can be suitably used as a material for forming an interlayer insulating film. Below, the formation method of the interlayer insulation film using the photosensitive resin composition of this invention is demonstrated.
  • a coating apparatus such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, or a spray is applied to the photosensitive resin composition of the present invention described above on a substrate on which a TFT array is formed.
  • a coating thickness of the photosensitive resin composition is usually 0.1 to 5 ⁇ m.
  • Drying Step A volatile component is removed (dried) from the coating film to form a dry coating film.
  • drying vacuum drying, hot plate, IR oven, convection oven or the like can be used.
  • Preferred drying conditions are a temperature of 40 to 150 ° C. and a drying time of 10 seconds to 60 minutes.
  • Exposure / Development Step a photomask is placed on the dry coating film of the photosensitive resin composition layer, and image exposure is performed through the photomask. After exposure, an unexposed uncured portion is removed by development to form a pixel.
  • post-exposure baking may be performed after exposure for the purpose of improving sensitivity before development.
  • a hot plate, an IR oven, a convection oven, or the like can be used.
  • Post-exposure bake conditions are usually in the range of 40 to 150 ° C. and drying time of 10 seconds to 60 minutes.
  • a contact hole for connecting the active element and the pixel electrode is formed in the interlayer insulating film.
  • the contact hole can be obtained by patterning exposure of the coating film and development. High-definition displays are required to have smaller contact holes. For example, a square hole having a side of 3 to 10 ⁇ m may be required.
  • Examples of the light source used in the exposure process of the dried coating film include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, and the like, an argon ion laser, a YAG laser.
  • laser light sources such as excimer laser and nitrogen laser. When only light of a specific wavelength is used, an optical filter can be used.
  • the solvent used for the development process is not particularly limited as long as it is a solvent capable of dissolving the coating film of the uncured part, but it is not a solvent from the viewpoint of environmental pollution, harm to human body, fire risk, etc. It is preferable to use an alkaline developer.
  • alkali developer include inorganic alkali compounds such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethylamine, An aqueous solution containing an organic alkali compound such as ethanolamine or tetramethylammonium hydroxide can be mentioned.
  • the alkaline developer may contain a surfactant, a water-soluble solvent, a wetting agent, a low molecular compound having a hydroxyl group or a carboxylic acid group, etc., if necessary.
  • a surfactant used in the developer include an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, and a tetraalkylammonium group.
  • anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group
  • a nonionic surfactant having a polyalkyleneoxy group
  • tetraalkylammonium group a tetraalkylammonium group.
  • cationic surfactants cationic surfactants.
  • the development processing method is not particularly limited, but it is usually carried out by immersion development, paddle development, spray development, brush development, ultrasonic development or the like at a development temperature of 10 to 50 ° C., preferably 15 to 45 ° C.
  • ultraviolet light or visible light is used as the light source.
  • a laser light source such as an argon ion laser, a YAG laser, an excimer laser, and a nitrogen laser.
  • a hot plate, IR oven, convection oven or the like can be used for hard baking.
  • the hard baking conditions are usually in the range of 100 to 250 ° C. and drying time of 30 seconds to 90 minutes.
  • a liquid crystal display device usually includes a TFT (Thin Film Transistor) active matrix substrate.
  • the above-mentioned cured product is formed as an interlayer insulating film on the substrate on which the TFT element array is formed, an ITO film is formed thereon, and then an ITO wiring is formed using a photolithography method. It is produced by this.
  • the liquid crystal display device can be completed by bonding the TFT active matrix substrate to the counter substrate to form a liquid crystal cell, injecting liquid crystal into the formed liquid crystal cell, and further connecting the counter electrode.
  • a color filter substrate having an alignment film is suitably used.
  • a resin film such as polyimide is suitable.
  • a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm.
  • the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted. Note that an interlayer insulating film similar to the above may be formed on the alignment film.
  • the bonding gap between the TFT active matrix substrate and the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 ⁇ m or more and 8 ⁇ m or less.
  • a sealing material such as an epoxy resin.
  • a material that can be cured by UV irradiation and / or heating is usually used, and the periphery of the liquid crystal cell is sealed.
  • the pressure is reduced in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and the pressure is returned to atmospheric pressure, thereby injecting liquid crystal into the liquid crystal cell. be able to.
  • the degree of decompression in the liquid crystal cell is usually 1 ⁇ 10 ⁇ 2 Pa or more, preferably 1 ⁇ 10 ⁇ 3 Pa or more, and usually 1 ⁇ 10 ⁇ 7 Pa or less, preferably 1 ⁇ 10 ⁇ 6 Pa or less. Range.
  • the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and is usually 100 ° C. or lower, preferably 90 ° C. or lower.
  • the heating and holding condition during decompression is usually in the range of 10 minutes to 60 minutes.
  • the liquid crystal cell is immersed in the liquid crystal.
  • the liquid crystal cell into which the liquid crystal is injected cures the UV curable resin and seals the liquid crystal injection port. In this way, a liquid crystal display device (panel) can be completed.
  • thermotropic liquid crystal nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.
  • a ′ Other high dielectric constant inorganic particles 1: T-BTO-020RF (BaTiO 3 manufactured by Toda Kogyo Co., Ltd.) Primary particle size: 10-30 nm 2: TTO-51N (Ishihara Sangyo TiO 2 ) Primary particle size: 10-30 nm
  • TMP trimethylolpropane
  • BPDA biphenyltetracarboxylic dianhydride
  • THPA tetrahydrophthalic anhydride
  • the epoxy compound was synthesized in the same manner as in Synthesis Example 1 except that the epoxy compound was replaced with the epoxy compound having the above structure.
  • the acid value was 60 mgKOH / g, and the weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 6,500. Binder resin (3) was obtained.
  • Synthesis Example 4 Synthesis of bisphenol A-type epoxy (meth) acrylate resin Synthesis was performed in the same manner as in Synthesis Example 1 except that the epoxy compound was replaced with bisphenol A-type epoxy resin (RE-310S manufactured by Nippon Kayaku) in Synthesis Example 1. Thus, a binder resin (4) having an acid value of 60 mg KOH / g and a weight average molecular weight (Mw) of 8,600 in terms of polystyrene measured by GPC was obtained.
  • Synthesis Example 5 Synthesis of bisphenol F-type epoxy (meth) acrylate resin Same as Synthesis Example 1 except that the epoxy compound in Synthesis Example 1 was replaced with a bisphenol F-type epoxy resin (RE-303S-L manufactured by Nippon Kayaku). And a binder resin (5) having an acid value of 60 mgKOH / g and a weight average molecular weight (Mw) of 10,500 in terms of polystyrene measured by GPC was obtained.
  • a binder resin (5) having an acid value of 60 mgKOH / g and a weight average molecular weight (Mw) of 10,500 in terms of polystyrene measured by GPC was obtained.
  • Synthesis Example 6 Synthesis of Acrylic Resin 150 parts by mass of propylene glycol monomethyl ether acetate was stirred while being purged with nitrogen, and the temperature was raised to 120 ° C.
  • 4.0 parts by mass of methyl methacrylate, 37.4 parts by mass of methacrylic acid and 73.2 parts by mass of cyclohexyl methacrylate The mixed solution was added dropwise over 3 hours, and the mixture was further stirred at 90 ° C. for 2 hours to obtain a binder resin (6).
  • the weight average molecular weight (Mw) in terms of polystyrene measured by GPC of the obtained binder resin (6) was 5,800, and the acid value was 60 mgKOH / g.
  • a high dielectric constant inorganic particle, a dispersant, a dispersion resin, and a solvent were prepared with the following composition, and a high dielectric constant inorganic particle dispersion was prepared by the following method.
  • the solid contents of the high dielectric constant inorganic particles, the dispersant, and the dispersion resin were prepared as follows.
  • the amount of the following solvent is a total amount including the amount of the solvent contained in the dispersant and the dispersion resin.
  • High-permittivity inorganic particles UEP 100 parts by mass Dispersant: DISPERBYK-111 (by Big Chemie) 5 parts by mass / solid content conversion Dispersion resin: adamantyl group-containing alkali-soluble resin (the binder resin (1)) 10 parts by mass Parts / solid content / solvent: 350 parts by mass of propylene glycol monomethyl ether acetate (PGMEA)
  • a dispersion treatment was performed for 6 hours in the range of 25 to 45 ° C. using a paint shaker.
  • beads zirconia beads having a diameter of 0.3 mm were used, and 10 g of a dispersion and 20 g of beads were added. After the completion of dispersion, the beads and the dispersion were separated by a filter to prepare a high dielectric constant inorganic particle dispersion 1 having a solid content of 25% by mass.
  • high dielectric constant inorganic particle dispersions 2 and 3 were prepared in the same manner as above except that the high dielectric constant inorganic particles were changed from UEP to T-BTO-020RF and TTO-51N.
  • An ITO electrode was entirely sputtered with a film thickness of 70 nm on a glass substrate to obtain a conductive substrate.
  • the photosensitive resin composition was applied onto the conductive substrate using a spin coater, and dried on a hot plate at 100 ° C. for 90 seconds. Thereafter, the entire exposure was performed with an exposure apparatus MA-1100 (manufactured by Dainippon Kaken Co., Ltd.) with an exposure amount of 120 mJ / cm 2 (intensity at a wavelength of 365 nm).
  • a terminal was brought into contact with the ITO electrode on the substrate of the electrical measurement sample and one aluminum electrode on the dielectric film, and a voltage from 1 V to 50 V was applied at intervals of 2 V, and the current at that time was measured.
  • a current value when 15 V was applied was used.
  • An ultra high resistance meter R8340A manufactured by ADVANTEST was used for this measurement.
  • the photosensitive resin composition was applied onto a glass substrate on which an ITO electrode was sputtered with a spin coater, and dried on a hot plate at 100 ° C. for 90 seconds. Thereafter, patterning exposure was performed using an exposure apparatus MA-1100 (manufactured by Dainippon Kaken Co., Ltd.) using a 15/15 ⁇ m and 50/50 ⁇ m line and space (L / S) mask. At this time, the gap between the mask and the substrate was 5 ⁇ m, and the exposure amount was 20 to 100 mJ / cm 2 (intensity at a wavelength of 365 nm).
  • each component shown in Table 1 was mixed in the glass bottle by the compounding quantity shown in Table 1, and each photosensitive resin composition was prepared.
  • the value in Table 1 represents the mass part of solid content, and the solvent (PGMEA) was used so that the total solid content of each photosensitive resin composition might be 20 mass%.
  • the high dielectric constant inorganic particle dispersions the above-described high dielectric constant inorganic particle dispersions 1 to 3 were used.
  • the dispersion resin was prepared by replacing the binder resin (1) with the binder resin. Dielectric constant inorganic particle dispersion was used.
  • the compounding quantity of binder resin in Table 1 represents the total amount including the compounding quantity of a dispersion resin.
  • Example 1 although the zirconium dioxide particles were contained at a very high ratio in the total solid content of the photosensitive resin composition, the leakage current when 15 V was applied was 10 ⁇ 9 (A / cm 2 ). The order is low and the developability is also good. On the other hand, Comparative Examples 1 and 2 contained barium titanate particles and titania particles in a high ratio, so that the leakage current increased and the developability was poor.
  • the zirconium dioxide particles have a small number of surface functional groups, it is considered that the hygroscopicity of the coating film is suppressed and the leakage current is low. Further, since the zirconium dioxide particles have high dispersibility and are easily adsorbed with a dispersant or a resin, they are coated with a highly soluble dispersant or resin, and are considered to have good developability. On the other hand, since barium titanate particles and titania particles have low dispersibility and poor compatibility with highly soluble resins, film roughness occurs during development, and the leakage current is considered to be high. In addition, it is considered that barium titanate particles and titania particles have a high polarity on the particle surface and a strong adhesion at the interface with the glass substrate, so that they cannot be sufficiently dissolved during development, and undissolved parts are generated.
  • the fluorene ring-containing epoxy (meth) acrylate resin is bulky and strong in hydrophobicity, the developability is considered to be poor.
  • the bisphenol A-type epoxy-containing (meth) acrylate resin and the bisphenol F-type epoxy-containing (meth) acrylate resin have a rotatable skeleton, the sensitivity is improved compared to a resin having a non-rotatable skeleton. It is considered that the developability is poor under conditions where unevenness occurs and the hydrophilic portion is likely to aggregate, particularly in the presence of a low-polar solvent.
  • Example 1 uses hexafunctional (meth) acrylate as the polymerizable monomer
  • Examples 4 and 5 use bifunctional (meth) acrylate as the polymerizable monomer.
  • the sensitivity was somewhat reduced, the strong and hydrophobic skeleton formed a strong film against alkali development, resulting in improved electrical characteristics.

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