WO2014136922A1 - Composition de résine photosensible, article durci, leur procédé de fabrication, procédé de fabrication d'un motif de résine, film durci, dispositif d'affichage à cristaux liquides, dispositif d'affichage électroluminescent organique et dispositif d'affichage de panneau tactile - Google Patents

Composition de résine photosensible, article durci, leur procédé de fabrication, procédé de fabrication d'un motif de résine, film durci, dispositif d'affichage à cristaux liquides, dispositif d'affichage électroluminescent organique et dispositif d'affichage de panneau tactile Download PDF

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WO2014136922A1
WO2014136922A1 PCT/JP2014/055909 JP2014055909W WO2014136922A1 WO 2014136922 A1 WO2014136922 A1 WO 2014136922A1 JP 2014055909 W JP2014055909 W JP 2014055909W WO 2014136922 A1 WO2014136922 A1 WO 2014136922A1
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group
resin composition
component
photosensitive resin
acid
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PCT/JP2014/055909
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English (en)
Japanese (ja)
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史絵 山下
中村　秀之
藤本　進二
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富士フイルム株式会社
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Priority to JP2015504408A priority Critical patent/JPWO2014136922A1/ja
Publication of WO2014136922A1 publication Critical patent/WO2014136922A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/0412—Digitisers structurally integrated in a display
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/02—Materials and properties organic material
    • G02F2202/022—Materials and properties organic material polymeric
    • G02F2202/023—Materials and properties organic material polymeric curable
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/122—Pixel-defining structures or layers, e.g. banks

Definitions

  • the present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Further, a cured product obtained by curing the photosensitive resin composition and a production method thereof, a resin pattern production method using the photosensitive resin composition, a cured film obtained by curing the photosensitive resin composition, and The present invention relates to various image display devices using the cured film. More specifically, a photosensitive resin composition suitable for forming a flattening film, a protective film, and an interlayer insulating film of electronic components such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state image sensor, and the use thereof The present invention relates to a method for producing a cured film.
  • An object of the present invention is to provide a photosensitive resin composition from which a cured product having a high refractive index and excellent transparency can be obtained. Furthermore, the present invention provides a cured product obtained by curing the photosensitive resin composition, a method for producing the cured product, a method for producing a resin pattern using the photosensitive resin composition, and a cured product obtained by curing the photosensitive resin composition.
  • An object is to provide a film, and a liquid crystal display device, an organic EL display device, and a touch panel display device using the cured film.
  • a1-1) a polymer having a constitutional unit having a group in which an acid group is protected by an acid-decomposable group
  • (a1-2) a polymer having a constitutional unit having a crosslinkable group
  • Component F The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a thermal crosslinking agent, ⁇ 8>
  • Component L The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 7>, further including a heterocyclic compound having two or more nitrogen atoms, ⁇ 9>
  • component L is a compound represented by the following formula (1-1) or formula (1-2):
  • R 6 to R 8 each independently represents a hydrogen atom or a monovalent organic group
  • L 2 and L 3 each independently represents a 5-membered ring.
  • it represents a divalent linking group that forms a 6-membered ring
  • R 6 and L 2 may combine to form a ring
  • R 7 or R 8 and L 3 combine to form a ring. You may do it.
  • a method for producing a cured product comprising at least steps (a) to (c) in this order, (A) Application step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 9> on a substrate (b) Solvent removal step of removing the solvent from the applied resin composition (c) ) Heat treatment step of heat-treating the resin composition from which the solvent has been removed ⁇ 11>
  • a resin pattern manufacturing method comprising at least steps (1) to (5) in this order, (1) Application step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 9> on a substrate (2) Solvent removal step of removing the solvent from the applied resin composition (3) ) An exposure step in which the resin composition from which the solvent has been removed is exposed to a pattern with actinic rays.
  • a heat treatment is performed on the developed resin composition.
  • Heat treatment step ⁇ 12> The cured product obtained by the method for producing a cured product according to ⁇ 10> or the resin pattern production method according to ⁇ 11>, ⁇ 13> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 9>, ⁇ 14>
  • the cured film according to ⁇ 13> which is an interlayer insulating film, ⁇ 15>
  • a touch panel display device having the cured film according to ⁇ 13> or ⁇ 14>.
  • a photosensitive resin composition capable of obtaining a cured product having a high refractive index and excellent transparency can be provided. Furthermore, according to the present invention, a cured product obtained by curing the photosensitive resin composition and a method for producing the cured product, a method for producing a resin pattern using the photosensitive resin composition, and a method for curing the photosensitive resin composition. And a liquid crystal display device, an organic EL display device, and a touch panel display device using the cured film can be provided.
  • 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
  • the schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.
  • 1 shows a conceptual diagram of a configuration of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • It is sectional drawing which shows the structure of an electrostatic capacitance type input device.
  • the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “mass%” and “part by mass” are synonymous with “% by weight” and “part by weight”, respectively.
  • a combination of preferable embodiments in the following description is more preferable.
  • the photosensitive resin composition of the present invention (hereinafter also simply referred to as “resin composition”) has (Component A) inorganic particles, (Component B) dispersant, (Component C) solvent, and (Component D) acid groups.
  • Component A inorganic particles
  • Component B dispersant
  • Component C solvent
  • Component D acid groups
  • a polymer containing a structural unit having a group protected by an acid-decomposable group and
  • Component E a metal oxide particle containing a photoacid generator, wherein Component A contains titanium as an element, and volume
  • the average particle diameter (D 50 ) is from 0.1 nm to 20 nm.
  • the photosensitive resin composition of the present invention can be suitably used as a positive resist composition.
  • the photosensitive resin composition of the present invention is preferably a resin composition having a property of being cured by heat.
  • the photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition, and is a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition). Is more preferable.
  • the photosensitive resin composition of the present invention preferably contains no 1,2-quinonediazide compound as a photoacid generator sensitive to actinic rays. A 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is always 1 or less.
  • (Component E) photoacid generator used in the present invention is such that the acid generated in response to actinic light acts as a catalyst for the deprotection of the protected acid group in Component A. Therefore, the acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10, which is a result of so-called chemical amplification. As a result, high sensitivity can be obtained.
  • the photosensitive resin composition of the present invention is a resin composition for optical members such as microlenses, optical waveguides, antireflection films, LED sealing materials, and LED chip coating materials, or wiring used for touch panels.
  • a resin composition for reducing the visibility of an electrode is preferable.
  • the composition for reducing the visibility of the wiring electrode used for the touch panel is a composition for a member that reduces the visibility of the wiring electrode used for the touch panel, that is, makes the wiring electrode difficult to see. Examples thereof include an interlayer insulating film between ITO (indium tin oxide) electrodes, and the photosensitive resin composition of the present invention can be suitably used for the application.
  • a chemically amplified positive photosensitive resin composition is exposed to an action with a photoacid generator to remove a leaving group of a polymer contained therein and dissolve in a developing solution, and an unexposed portion becomes a pattern. It is formed.
  • a resin composition containing inorganic particles, a dispersant, and a polymer containing a leaving group and a crosslinking group is used as a positive photosensitive resin composition
  • the dispersibility of the inorganic particles is very important and the dispersion is not successful.
  • the average particle size is not reduced, too large, aggregated particles are produced, coarse particles remain without being pulverized, and finally when the photosensitive resin composition is applied, there is a problem of poor transparency is there.
  • the compatibility between the dispersion liquid and the binder in the photosensitive resin composition is also important.
  • zirconium oxide and titanium oxide have been used as inorganic particles added to a photosensitive resin composition for obtaining a highly refractive cured product.
  • a highly refractive material using zirconium oxide as inorganic particles has a small particle diameter and a small haze, but its refractive index is smaller than that when titanium oxide is used at the same concentration. Therefore, when trying to increase the refractive index, it is necessary to increase the concentration of zirconium oxide. However, if zirconium oxide is contained at a high concentration, the patterning property is lowered and it is difficult to obtain a good pattern.
  • titanium-based particles titanium oxide particles
  • haze increases.
  • the present inventors have improved the dispersibility of inorganic particles by using a photosensitive resin composition containing component A to component E, and have a small average particle size and no coarse particles. It was found that a photosensitive resin composition capable of forming a cured product having good compatibility with the composition, excellent transparency (small haze), and high refraction can be obtained.
  • the composition of the present invention will be described in detail.
  • the above particles are more preferable, particles having a refractive index of 1.70 or more are further preferable, and particles having a refractive index of 1.90 or more are particularly preferable. Further, particles having a refractive index of 5.00 or less are preferable.
  • the refractive index of light having a wavelength of 400 to 750 nm being 1.50 or more means that the average refractive index of light having a wavelength in the above range is 1.50 or more. It is not necessary that the refractive index of all light having a wavelength is 1.50 or more.
  • the average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.
  • the component A is preferably a composite metal oxide particle (hereinafter also simply referred to as a composite oxide) containing titanium as an element and at least one other metal element.
  • the complex oxide is also called a complex oxide, and is an oxide containing two or more kinds of metal ions, in which the presence of an oxo acid ion is not recognized in the structure.
  • the metal of the metal oxide particles in the present invention includes semimetals such as B, Si, Ge, As, Sb, and Te.
  • the metal oxides for example ZnO, GeO 2, TiO 2, ZrO 2, HfO 2, SiO 2, Sn 2 O 3, Mn 2 O 3, Ga 2 O 3, Mo 2 O 3, In 2 O 3 Sb 2 O 3 , Ta 2 O 5 , V 2 O 5 , Y 2 O 3 , Nb 2 O 5 and the like.
  • the photocatalytic action is suppressed by the coating and the light resistance is improved, but it is difficult to maintain the high refractive index peculiar to titanium oxide.
  • composite oxide particles of titanium oxide and other metal elements which is a preferred embodiment of component A (other metal elements are included in the crystal structure of titanium oxide, but the original crystal structure is maintained and solid
  • the composite oxide particles mixed in the state) can greatly improve the light resistance, and since the composite oxide particles are in solid solution, the high refractive index peculiar to titanium oxide is maintained. Further, when dispersed in a resin or the like, aggregation is suppressed and the nanoparticle state is maintained, whereby a high refractive index can be imparted to the cured film while maintaining transparency and light resistance of the material. Therefore, for example, in an optical material in which component A is dispersed in a curable resin, a high refractive index, light resistance, and transparency can be simultaneously imparted.
  • the component A is a composite metal oxide containing titanium and at least one element selected from the group consisting of cerium, zinc, silicon, iron, zirconium, tungsten, antimony, tin, aluminum, and strontium. Preferably there is.
  • it is a composite oxide containing titanium and at least one atom selected from the group consisting of cerium, zinc, iron, zirconium, tin, antimony, tungsten, cerium, hafnium, zirconium, hafnium, barium, More preferably, it is a composite metal oxide particle containing at least one element selected from the group consisting of silicon and zirconium, and at least one selected from the group consisting of titanium, zirconium, silicon, and tin. More preferably, it is a metal oxide particle containing two elements. In addition to titanium, a plurality of metal elements may be contained.
  • the proportion of the titanium element in the metal element of the composite oxide particle is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. Moreover, it is preferable that an upper limit is 85 mass% or less, it is more preferable that it is 80 mass% or less, and it is still more preferable that it is 75 mass% or less.
  • the ratio of the titanium element in the metal element of the composite oxide particle can be determined using a fluorescent X-ray analysis (XRF) apparatus.
  • the composite metal oxide examples include a composite oxide of titanium and zirconium, a composite oxide of titanium, zirconia and hafnium, a composite oxide of titanium and barium, a composite oxide of titanium and silicon, and a composite of titanium, zirconium and silicon.
  • examples thereof include oxides, composite oxides of titanium and tin, and composite oxides of titanium, zirconia, and tin.
  • the X-ray diffraction spectrum of the composite metal oxide has a rutile structure.
  • the surface of the metal oxide particles may be coated with a material having low photocatalytic activity, or may be combined with doping with a metal that recombines electrons and holes.
  • a metal oxide for example, TiO 2 , ZrO 2 , and SnO 2 are preferable, and TiO 2 is more preferable in terms of a high refractive index.
  • the refractive index can be further improved by forming a rutile structure with a composite oxide with tin.
  • such a rutile composite oxide of tin and titanium is used as a core and the surface of the core is coated with ZrO 2 , Al 2 O 3 , SiO 2 or the like.
  • these particles may be metal oxide fine particles whose surface is modified with a silane coupling agent, a titanate coupling agent or the like for various purposes such as reduction of photocatalytic activity and reduction of water absorption.
  • the transparency and other optical properties of the nanoparticle-resin composite material are not impaired.
  • the particle size is large or the dispersibility is poor, the transparency is lowered.
  • the composite oxide particles obtained by the combustion method are nanoparticles, and since the state of the nanoparticles can be maintained even in the composite material, high transparency can be obtained even when applied to the composite material.
  • desired metal oxide particles can be obtained by using a metal salt or metal alkoxide as a raw material and hydrolyzing in a reaction system containing water.
  • the metal salt include a desired metal chloride, bromide, iodide, nitrate, sulfate, organic acid salt and the like.
  • the organic acid salt include acetate, propionate naphthenate, octylate, stearate, oleate, and the like.
  • the metal alkoxide include methoxide, ethoxide, propoxide, butoxide of a desired metal.
  • metal oxide particles examples include, for example, Japanese Journal of Applied Physics, Vol. 37, 4603-4608 (1998), or Langmuir, Vol. 16, No. 1, pages 241-246 (2000). Can be used.
  • metal oxide particles are synthesized by a sol formation method, for example, as in the synthesis of titanium oxide particles using titanium tetrachloride as a raw material, this is done via a precursor such as hydroxide, and then by acid or alkali.
  • a procedure for dehydrating condensation or peptization to form a hydrosol is also possible.
  • the precursor is isolated and purified by any method such as filtration or centrifugation.
  • the metal oxide particles may be produced in an organic solvent or an organic solvent in which a thermoplastic resin is dissolved.
  • the solvent used in these methods is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone, and anisole. One of these may be used alone, or a plurality of these may be mixed and used.
  • the metal oxide particles containing titanium element and other elements may be synthesized according to a known method, or a commercially available product may be used.
  • synthesis methods JP 2009-067613 A, JP 2009-078946 A, JP 2010-042369 A, JP 2010-052985 A, JP 2010-058031 A, JP 2012-031353 A, and the like. No. publication etc. are referred.
  • the product made by Optlake series JGC Catalysts and Chemicals Co., Ltd.
  • Optlake 6320 and Optlake 502 is exemplified.
  • the volume average particle diameter (D 50 ) of component A is 0.1 nm to 20 nm, more preferably 0.1 nm to 18 nm, and still more preferably 0.1 to 15 nm.
  • the volume average particle diameter of the particles is measured on a volume basis by a laser diffraction / scattering particle size distribution analyzer MT-3000II manufactured by Nikkiso Co., Ltd.
  • the volume average particle diameter (D 50 ) is a point where, when there is a set of powders, the cumulative curve is 50% when the total curve of the set of powders is taken as 100%. means the particle size, as well as 10% diameter particle size of points cumulative curve becomes 10% (D 10), that the particle diameter and the 90% size of points cumulative curve becomes 90% (D 90). That is, the volume average particle diameter (D 50 ) is the particle diameter when the cumulative mass% is 50 mass% when the mass of powder aggregate is 100 mass% and the mass is accumulated from small particles. That means. Further, the D 90, cumulative mass% when integrating the mass of small particles refers to the particle diameter when the 90 mass%.
  • the 90% diameter (D 90 ) of component A is preferably 0.2 to 40 nm, more preferably 0.5 to 30 nm, and even more preferably 1 to 25 nm.
  • component A may be used individually by 1 type, and can also use 2 or more types together.
  • the content of component A in the resin composition of the present invention may be appropriately determined in consideration of the refractive index, light transmittance, etc. required for the optical member obtained from the resin composition. It is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 40 to 70% by mass, and more preferably 55 to 65% by mass with respect to the total solid content of the composition. More preferably.
  • the photosensitive resin composition of the present invention contains (Component B) a dispersant.
  • a dispersing agent By containing a dispersing agent, the dispersibility in the resin composition of the component A can be improved more.
  • a known dispersant can be used.
  • a known pigment dispersant can be appropriately selected and used.
  • the (Component B) dispersant is at least a compound other than Component D described later.
  • a polymer dispersant can be preferably used.
  • the polymer dispersant is a dispersant having a molecular weight (weight average molecular weight) of 1,000 or more.
  • the molecular weight (weight average molecular weight) of the polymer dispersant is preferably 500,000 or less.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl
  • Nonionic surfactants such as ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester
  • anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), DE Polymer dispersants such as Sparse Aid 6, Disperse Aid 8,
  • a dispersing agent may be used individually by 1 type, or may be used together 2 or more types.
  • the content of the dispersant in the photosensitive resin composition of the present invention is preferably in the range of 5 to 70% by mass and more preferably in the range of 10 to 50% by mass with respect to the total solid content of the photosensitive resin composition.
  • the photosensitive resin composition of the present invention contains (Component C) a solvent.
  • the photosensitive resin composition of the present invention is preferably prepared as a solution obtained by dissolving the essential components of the present invention and further optional components described later in (Component C) solvent.
  • solvent used in the photosensitive resin composition of the present invention known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl.
  • Ethers propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like.
  • Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A, and the paragraphs 0167 to 0168 of JP2012-194290A. The solvents described are also included, the contents of which are incorporated herein.
  • Component C is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
  • Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
  • Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
  • the content of the (component C) solvent in the photosensitive resin composition of the present invention is preferably 10 to 95% by mass, and preferably 50 to 95% by mass with respect to the total mass of the photosensitive resin composition. More preferably, it is 60 to 90% by mass.
  • Component D Polymer containing a structural unit having an acid group protected with an acid-decomposable group
  • the photosensitive resin composition of the present invention is composed of (Component D) a group in which an acid group is protected with an acid-decomposable group.
  • Component D is preferably a polymer component including a polymer that satisfies at least one of the following (1) and (2).
  • composition of the present invention may further contain a polymer other than these.
  • the component D in the present invention means, in addition to the above (1) and / or (2), including other polymers added as necessary, unless otherwise specified.
  • the photosensitive resin composition of this invention contains the component which satisfy
  • the photosensitive resin composition of the present invention preferably contains a component satisfying the above (2) as the component D. Even when the component satisfying the above (1) is contained, (a1) a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group and / or (a2) cross-linking A polymer having a structural unit having a functional group may be contained.
  • Component D is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof.
  • a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
  • the “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”.
  • (meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.
  • Component D includes (a1) a polymer having at least a structural unit having a group in which an acid group is protected with an acid-decomposable group.
  • component D contains a polymer having the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
  • group in which the acid group is protected with an acid-decomposable group those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
  • Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
  • Examples of the acid-decomposable group include groups that are relatively easily decomposed by an acid (for example, an ester structure of a group represented by the formula (a1-10) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group).
  • An acetal functional group) or a group that is relatively difficult to decompose by an acid for example, a tertiary alkyl ester group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group
  • a tertiary alkyl ester group such as a tert-butyl ester group
  • a tertiary alkyl carbonate group such as a tert-butyl carbonate group
  • a structural unit having a group in which an acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group in which a carboxyl group is protected with an acid-decomposable group (“protection protected with an acid-decomposable group” Or a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected by an acid-decomposable group (having a protected phenolic hydroxyl group protected by an acid-decomposable group). It is also preferably referred to as a “structural unit”.
  • the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a protected carboxyl in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
  • a structural unit having a group is not particularly limited, and a known structural unit can be used.
  • a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid
  • a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
  • the structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.
  • ⁇ (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>
  • the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those listed below. . That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyl.
  • Examples include loxyethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl phthalic acid.
  • Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
  • the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
  • the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.
  • the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ⁇ -carboxypolycaprolactone monoacrylate and ⁇ -carboxypolycaprolactone monomethacrylate.
  • unsaturated carboxylic acid acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
  • the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, anhydride of unsaturated polyvalent carboxylic acid, etc. It is preferable to use acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
  • the structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds. May be.
  • a structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride is obtained by reacting a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride.
  • a unit derived from the obtained monomer is preferred.
  • the acid anhydride known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc.
  • phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
  • the reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.
  • the above-mentioned acid-decomposable groups can be used.
  • these acid-decomposable groups it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal. It is preferable from the viewpoint of the storage stability of the composition.
  • the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following formula (a1-10) from the viewpoint of sensitivity.
  • the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula (a1-10)
  • the entire protected carboxyl group is — (C ⁇ O) —O—CR 101 R
  • the structure is 102 (OR 103 ).
  • R 101 and R 102 each independently represent a hydrogen atom, an alkyl group or an aryl group, provided that, .R 103 except in the case of the R 101 and R 102 are both hydrogen atoms Represents an alkyl group or an aryl group, and R 101 or R 102 and R 103 may be linked to form a cyclic ether.
  • R 101 and R 102 each independently represents a hydrogen atom, an alkyl group or an aryl group
  • R 103 represents an alkyl group or an aryl group
  • the alkyl group is linear or branched Either a chain or a ring may be used.
  • both R 101 and R 102 do not represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.
  • R 101 , R 102 and R 103 represent an alkyl group
  • the alkyl group may be linear, branched or cyclic.
  • the linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
  • the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms.
  • Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
  • the alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group.
  • R 101 , R 102 and R 103 When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms.
  • Specific examples include a phenyl group, an ⁇ -methylphenyl group, a naphthyl group, and the like, and examples of the entire alkyl group substituted with an aryl group, that is, an aralkyl group include a benzyl group, an ⁇ -methylbenzyl group, a phenethyl group, A naphthylmethyl group etc. can be illustrated.
  • the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group.
  • the alkyl group is a cycloalkyl group
  • the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is a linear chain. Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent. These substituents may be further substituted with the above substituents.
  • R 101 , R 102 and R 103 represent an aryl group
  • the aryl group preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.
  • the aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
  • R 101 , R 102 and R 103 can be bonded together to form a ring together with the carbon atom to which they are bonded.
  • Examples of the ring structure when R 101 and R 102 , R 101 and R 103 or R 102 and R 103 are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
  • any one of R 101 and R 102 is preferably a hydrogen atom or a methyl group.
  • radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the above formula (a1-10) a commercially available one may be used, or one synthesized by a known method Can also be used. For example, it can be synthesized by the synthesis method described in paragraphs 0037 to 0040 of JP2011-212494A.
  • a first preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the following formula.
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is an alkyl group. Or R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. .
  • R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R 1 and R 2 are aryl groups, a phenyl group is preferred. R 1 and R 2 are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. X represents a single bond or an arylene group, and a single bond is preferable.
  • a second preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the following formula.
  • R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • L 1 represents a carbonyl group or a phenylenecarbonyl group
  • R 122 to R 128 each independently represents a hydrogen atom or 1 to 4 represents an alkyl group.
  • R 121 is preferably a hydrogen atom or a methyl group.
  • L 1 is preferably a carbonyl group.
  • R 122 to R 128 are preferably hydrogen atoms.
  • R represents a hydrogen atom or a methyl group.
  • the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a protected phenolic group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below.
  • ⁇ (a1-2-1) Structural unit having phenolic hydroxyl group Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene-based structural unit and a structural unit in a novolac-based resin. Among these, a structural unit derived from hydroxystyrene or ⁇ -methylhydroxystyrene is sensitive. From the viewpoint of In addition, as a structural unit having a phenolic hydroxyl group, a structural unit represented by the following formula (a1-20) is also preferable from the viewpoint of sensitivity.
  • R 220 represents a hydrogen atom or a methyl group
  • R 221 represents a single bond or a divalent linking group
  • R 222 represents a halogen atom or a linear or branched group having 1 to 5 carbon atoms.
  • R 220 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
  • R 221 represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved.
  • Examples of the divalent linking group for R 221 include an alkylene group.
  • R 221 is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 3 carbon atoms. Is more preferable.
  • R 221 is an alkylene group
  • R 221 is an alkylene group
  • R 221 is preferably a single bond, a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, or a 2-hydroxy-1,3-propylene group.
  • the said bivalent coupling group may have a substituent and a halogen atom, a hydroxyl group, an alkoxy group etc.
  • R 222 each independently represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.
  • a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
  • B represents 0 or an integer of 1 to 4;
  • the acid-decomposable group that can be used in the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group includes a structure having a protected carboxyl group protected by the acid-decomposable group Similar to the acid-decomposable group that can be used for the unit (a1-1), known ones can be used and are not particularly limited.
  • a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability.
  • the phenolic hydroxyl group is more preferably a protected phenolic hydroxyl group protected in the form of an acetal represented by the above formula (a1-10) from the viewpoint of sensitivity.
  • the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the above formula (a1-10)
  • the entire protected phenolic hydroxyl group is —Ar—O—CR 101 R 102.
  • the structure is (OR 103 ).
  • Ar represents an arylene group.
  • Examples of the radical polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include, for example, paragraph 0042 of JP2011-215590A And the like.
  • a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
  • acetal protecting group for the phenolic hydroxyl group examples include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group.
  • 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually by 1 type or in combination of 2 or more types.
  • the radical polymerizable monomer used for forming the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group a commercially available one may be used, or a known method may be used. What was synthesize
  • combined by can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.
  • the structural unit (a1) is 20 to 100 mol% in the polymer having the structural unit (a1). Preferably, 30 to 90 mol% is more preferable.
  • the polymer having the structural unit (a1) has the following structural unit (a2)
  • the single structural unit (a1) has a sensitivity in the polymer having the structural unit (a1) and the structural unit (a2). From the viewpoint, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
  • the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, 20 to 50 mol% is preferable.
  • the “structural unit” is synonymous with the “monomer unit”.
  • the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
  • the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, when it is desired to develop quickly, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
  • Component D contains a polymer having a structural unit (a2) having a crosslinkable group.
  • the crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment.
  • Preferred embodiments of the structural unit having a crosslinkable group are represented by an epoxy group, an oxetanyl group, and —NH—CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).
  • the component D includes a structural unit including at least one of an epoxy group and an oxetanyl group.
  • Component D preferably contains a polymer having a structural unit (structural unit (a2-1)) having an epoxy group and / or an oxetanyl group.
  • a 3-membered cyclic ether group is also called an epoxy group, and a 4-membered cyclic ether group is also called an oxetanyl group.
  • the structural unit (a2-1) having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, one or more epoxy groups and one It may have an oxetanyl group, two or more epoxy groups, or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, It is more preferable to have one or two epoxy groups and / or oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.
  • radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, and glycidyl ⁇ -n-propyl acrylate.
  • radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Acid esters, and the like, the contents of which are incorporated herein.
  • radical polymerizable monomer used for forming the structural unit (a2-1) having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. It is preferable that it is a monomer to contain.
  • These structural units can be used individually by 1 type or in combination of 2 or more types.
  • R represents a hydrogen atom or a methyl group.
  • (a2-2) Structural unit having an ethylenically unsaturated group is a structural unit (a2-2) having an ethylenically unsaturated group (hereinafter also referred to as “structural unit (a2-2)”).
  • the structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms.
  • a structural unit having a side chain is more preferred.
  • the copolymer used in the present invention is a structural unit (a2-3) having a group represented by —NH—CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Is also preferable.
  • a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained.
  • R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
  • the structural unit (a2) is more preferably a structural unit having a group represented by the following formula (a2-30).
  • R 31 represents a hydrogen atom or a methyl group
  • R 32 represents an alkyl group having 1 to 20 carbon atoms.
  • R 32 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
  • Specific examples of R 32 include methyl group, ethyl group, n-butyl group, i-butyl group, cyclohexyl group, and n-hexyl group. Of these, i-butyl group, n-butyl group and methyl group are preferable.
  • the structural unit (a2) is 5 to 90 mol% in the polymer having the structural unit (a2). 20 to 80 mol% is more preferable.
  • the polymer having the structural unit (a2) has the structural unit (a1), the content of the single structural unit (a2) in the polymer having the structural unit (a1) and the structural unit (a2) From the viewpoint of chemical resistance, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
  • the structural unit (a2) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol% in all the structural units of the component D, regardless of any embodiment.
  • the cured film obtained from the photosensitive resin composition has good transparency and chemical resistance.
  • a monomer used as another structural unit (a3) For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to.
  • the monomer which becomes another structural unit (a3) can be used individually by 1 type or in combination of 2 or more types.
  • the structural unit (a3) is styrene, methyl styrene, hydroxy styrene, ⁇ -methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxy Benzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth)
  • Examples of structural units are 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (
  • a structural unit derived from a monomer having a styrene or an aliphatic cyclic skeleton is preferable from the viewpoint of electrical characteristics.
  • styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.
  • the other structural unit (a3) a structural unit derived from (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.
  • the content of the structural unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less.
  • 0 mol% may be sufficient, it is preferable to set it as 1 mol% or more, for example, and it is more preferable to set it as 5 mol% or more.
  • various properties of the cured film obtained from the photosensitive resin composition are improved.
  • the polymer contained in Component D preferably has a structural unit having an acid group as the other structural unit (a3).
  • the acid group in the present invention means a proton dissociable group having a pKa of less than 10.5.
  • the acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
  • Examples of the acid group used in the present invention include a carboxylic acid group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonamide group, a sulfonylimide group, and acid anhydride groups of these acid groups, And the group etc. which neutralized these acid groups and made it into salt structure are illustrated, and a carboxylic acid group and / or a phenolic hydroxyl group are preferable.
  • An alkali metal salt, alkaline-earth metal salt, and organic ammonium salt can illustrate preferably.
  • the structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof.
  • a structural unit derived from styrene a structural unit derived from a vinyl compound
  • a structural unit derived from (meth) acrylic acid and / or an ester thereof .
  • compounds described in paragraphs 0021 to 0023 and paragraphs 0029 to 0044 of JP2012-88459A can be used, the contents of which are incorporated herein.
  • structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferred.
  • a polymer having another structural unit (a3) substantially not including the structural unit (a1) and the structural unit (a2) is included. You may go out.
  • a resin having a carboxyl group in the side chain is preferable.
  • methacrylic acid copolymer acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc.
  • side chain examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.
  • benzyl (meth) acrylate / (meth) acrylic acid copolymer 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid
  • Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein. These polymers may contain only 1 type and may contain 2 or more types.
  • SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), JONCRYL 690, JONCRYL 678, JONCRYL 67, JONCRYL 586 (above, manufactured by BASF), etc. are used. You can also.
  • the structural unit containing an acid group is preferably from 1 to 80 mol%, more preferably from 1 to 50 mol%, still more preferably from 5 to 40 mol%, particularly preferably from 5 to 30 mol%, based on the structural units of all polymer components. 5 to 20 mol% is particularly preferable.
  • the molecular weight of the polymer in Component D is a weight average molecular weight in terms of polystyrene, and is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value.
  • the ratio (dispersity, Mw / Mn) between the number average molecular weight Mn and the weight average molecular weight Mw is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
  • the weight average molecular weight and the number average molecular weight are preferably measured by gel permeation chromatography.
  • HLC-8020GPC manufactured by Tosoh Corporation
  • TSKgel Super HZ MH TSK gel Super HZ4000
  • TSKgel SuperHZ200 manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm
  • THF tetrahydrofuran
  • the content of component D in the photosensitive resin composition of the present invention is preferably 20 to 99.9% by mass, and preferably 50 to 98% by mass, based on the total solid content of the photosensitive resin composition. More preferred is 70 to 95% by mass. When the content is within this range, the pattern formability during development is good, and a cured product having a higher refractive index can be obtained.
  • the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
  • the photosensitive resin composition of the present invention contains (Component E) a photoacid generator.
  • the photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • the photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less. Most preferred is a photoacid generator that generates an acid. Further, a photoacid generator that generates an acid having a pKa of ⁇ 15 or more is preferable.
  • photoacid generator examples include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation and sensitivity.
  • photoacid generators can be used singly or in combination of two or more.
  • trichloromethyl-s-triazines diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP2011-212494A. It can be illustrated.
  • oxime sulfonate compound that is, a compound having an oxime sulfonate structure
  • a compound containing an oxime sulfonate structure represented by the following formula (B1) can be preferably exemplified, and the contents thereof are incorporated herein.
  • R 21 represents an alkyl group or an aryl group, and a wavy line represents a bonding site with another group.
  • aryl group for R 21 an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable.
  • the aryl group of R 21 may be substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.
  • R 1 represents an alkyl group or an aryl group
  • R 2 represents an alkyl group, an aryl group, or a heteroaryl group
  • R 3 to R 6 are each a hydrogen atom, Represents an alkyl group, an aryl group, or a halogen atom, provided that R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form an alicyclic ring or an aromatic ring, Represents -O- or -S-.
  • R 1 represents an alkyl group or an aryl group.
  • the alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
  • the alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable, and when the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.
  • substituents examples include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.
  • R 1 is preferably an alkyl group from the viewpoint of transparency, and R 1 has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity.
  • An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. .
  • an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.
  • Examples of the aryl group include a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
  • Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
  • the alkyl group, aryl group, and heteroaryl group represented by R 2 may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which R ⁇ 1 > may have.
  • R 2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group.
  • As the substituent for the phenyl group a methyl group is preferred.
  • R 3 to R 6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom).
  • the alkyl group represented by R 3 to R 6 has the same meaning as the alkyl group represented by R 2 , and the preferred range is also the same.
  • the aryl group represented by R 3 to R 6 has the same meaning as the aryl group represented by R 1 , and the preferred range is also the same.
  • R 3 to R 6 may combine to form a ring, and the ring forms an alicyclic ring or an aromatic ring And a benzene ring is more preferable.
  • R 3 to R 6 are a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are bonded.
  • X represents -O- or -S-.
  • Ts represents a tosyl group (p-toluenesulfonyl group)
  • Me represents a methyl group
  • Bu represents an n-butyl group
  • Ph represents a phenyl group.
  • the photoacid generator is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of Component D in the photosensitive resin composition. It is more preferable to use 5 to 10 parts by mass.
  • the component E may be used individually by 1 type, and may use 2 or more types together.
  • the photosensitive resin composition of the present invention may contain other components.
  • Other components include (Component F) thermal crosslinking agent, (Component G) antioxidant, (Component H) sensitizer, (Component I) adhesion improver, (Component J) basic compound, (Component K)
  • a surfactant can be preferably added.
  • the photosensitive resin composition of the present invention includes an ultraviolet absorber, a metal deactivator, an acid multiplier, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, a thickener, and Known additives such as organic or inorganic suspending agents can be added.
  • the descriptions in paragraphs 0201 to 0224 of JP2012-8859A can be referred to, and the contents thereof are incorporated in the present specification. Each will be described below.
  • the photosensitive resin composition of the present invention preferably contains (Component F) a thermal crosslinker, if necessary.
  • a thermal crosslinking agent By adding a thermal crosslinking agent, the cured film obtained from the photosensitive resin composition of the present invention can be made a stronger film.
  • the thermal cross-linking agent is not limited as long as it causes a cross-linking reaction by heat (except for component D).
  • a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing thermal crosslinking agent, a compound having at least one ethylenically unsaturated double bond, or a blocked isocyanate compound, etc. Can be added.
  • the addition amount of the thermal crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition, preferably 0.1 to The amount is more preferably 30 parts by mass, and further preferably 0.5 to 20 parts by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained.
  • a plurality of thermal crosslinking agents can be used in combination, and in that case, the content is calculated by adding all the thermal crosslinking agents.
  • ⁇ Compound having two or more epoxy groups or oxetanyl groups in the molecule Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.
  • the total number of epoxy groups and oxetanyl groups of a compound having two or more epoxy groups or oxetanyl groups in the molecule is preferably 2 or more and 1,000 or less, and more preferably 2 or more and 10 or less.
  • JER152, JER157S70, JER157S65, JER806, JER828, JER1007 manufactured by Mitsubishi Chemical Holdings Co., Ltd.
  • ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S aboveve, manufactured by ADEKA Corporation
  • NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN- 502 aboveve, manufactured by ADEKA Corporation
  • bisphenol A type epoxy resins bisphenol F type epoxy resins, phenol novolac type epoxy resins and aliphatic epoxy resins are more preferable, and bisphenol A type epoxy resins are particularly preferable.
  • Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX manufactured by Toagosei Co., Ltd.
  • the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.
  • thermal crosslinking agents include alkoxymethyl group-containing thermal crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223, and compounds having at least one ethylenically unsaturated double bond. It can be preferably used.
  • alkoxymethyl group-containing thermal crosslinking agent alkoxymethylated glycoluril is preferable.
  • a blocked isocyanate compound can also be preferably employed as the thermal crosslinking agent.
  • the blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability. More preferred is a compound having 10 to 10 blocked isocyanate groups.
  • the blocked isocyanate group in this invention is a group which can produce
  • the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
  • the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
  • the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and may be aliphatic, alicyclic or aromatic. Polyisocyanate may be used.
  • a compound and a prepolymer type skeleton compound derived from these compounds can be preferably used.
  • tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
  • Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
  • Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to.
  • a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
  • Examples of the oxime compound include aldoxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime.
  • Examples of the lactam compound include ⁇ -caprolactam and ⁇ -butyrolactam.
  • Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
  • Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
  • amine compound a primary amine and a secondary amine are mentioned, Any of an aromatic amine, an aliphatic amine, and an alicyclic amine may be sufficient, An aniline, diphenylamine, ethyleneimine, polyethyleneimine etc. can be illustrated.
  • Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
  • pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
  • the mercaptan compound include alkyl mercaptans and aryl mercaptans.
  • the blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available.
  • Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL
  • the photosensitive resin composition of the present invention preferably contains (Component G) an antioxidant.
  • an antioxidant a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat resistant transparency is excellent.
  • antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives.
  • phenol-based antioxidants amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. preferable. These may be used individually by 1 type and may mix 2 or more types. Specific examples include the compounds described in JP-A-2005-29515, paragraphs 0026 to 0031, the contents of which are incorporated herein. Preferred commercial products include ADK STAB AO-60, ADK STAB AO-80, IRGANOX 1726, IRGANOX 1035, and IRGANOX 1098.
  • the content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation can be improved.
  • various ultraviolet absorbers described in “New Development of Polymer Additives” (Nikkan Kogyo Shimbun Co., Ltd.), metal deactivators, and the like are used in the present invention. You may add to a resin composition.
  • Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene
  • xanthenes Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • xanthones eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone
  • cyanines eg, thiacarbocyanine, oxacarbocyanine
  • merocyanines For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, to
  • polynuclear aromatics polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.
  • polynuclear aromatics anthracene derivatives are most preferred.
  • the addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator of the photosensitive resin composition.
  • the amount is more preferably part by mass, and further preferably 50 to 200 parts by mass.
  • a sensitizer may be used individually by 1 type and can also use 2 or more types together.
  • the photosensitive resin composition of the present invention may contain (Component I) an adhesion improving agent.
  • the (Component I) adhesion improver that can be used in the photosensitive resin composition of the present invention is an inorganic substance that serves as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, or aluminum. It is a compound that improves the adhesion between the insulating film and the insulating film. Specific examples include silane coupling agents and thiol compounds.
  • the silane coupling agent as an adhesion improving agent used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
  • Preferred examples of the silane coupling agent include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, ⁇ - Methacryloxypropyltrialkoxysilane, ⁇ -methacryloxypropylalkyldialkoxysilane, ⁇ -chloropropyltrialkoxysilane, ⁇ -mercaptopropyltrialkoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned.
  • ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, and ⁇ -glycidoxypropyltrialkoxysilane is more preferable.
  • the content of the (Component I) adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of Component D.
  • the photosensitive resin composition of the present invention may contain (Component J) a basic compound.
  • the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraphs 0204 to 0207 of JP2011-221494A.
  • aliphatic amine examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like.
  • examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
  • aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
  • the basic compounds that can be used in the present invention may be used singly or in combination of two or more.
  • the content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, 0.005 More preferred is 1 part by mass.
  • the photosensitive resin composition of the present invention may contain (Component K) a surfactant.
  • a surfactant any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
  • examples of the surfactant used in the composition of the present invention include those described in paragraphs 0201 to 0205 in JP2012-88459A and those described in paragraphs 0185 to 0188 in JP2011-215580A. And these descriptions are incorporated herein.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
  • the following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No.
  • the surfactant includes a structural unit A and a structural unit B represented by the following formula (J-1), and the weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
  • Preferred examples include copolymers having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.
  • R 401 and R 403 each independently represent a hydrogen atom or a methyl group
  • R 402 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 404 represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is 10 mass% to 80 mass%.
  • a numerical value is represented, q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 to 18 and s represents an integer of 1 to 10)
  • L is preferably a branched alkylene group represented by the following formula (J-2).
  • R 405 in formula (J-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • the addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, and 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, the amount is 0.01 to 3 parts by mass.
  • Component L is not particularly limited except that it has two or more nitrogen atoms, but is preferably a heterocyclic compound having two or more nitrogen atoms as a ring member of the heterocyclic ring, and nitrogen at the 1,3-position.
  • a compound having a heterocyclic structure having at least an atom is more preferable, and a compound having a 5-membered or 6-membered heterocyclic structure having at least a nitrogen atom at the 1,3-positions is more preferable. If it is the said aspect, the hardened
  • the “heterocyclic structure having at least a nitrogen atom at positions 1 and 3” may be a structure in which nitrogen atoms are bonded to both sides of a carbon atom in the heterocyclic ring. It does not have to be in the third or third place.
  • the ring member of the heterocyclic ring in component L is preferably composed of at least a carbon atom and a nitrogen atom, and may further contain an oxygen atom or a sulfur atom as a ring member, but consists of a carbon atom and a nitrogen atom. Is particularly preferred.
  • the number of nitrogen atoms contained in the component L is 2 or more, preferably 2 to 10, more preferably 2 to 6, and still more preferably 2 to 4.
  • Component L preferably has 2 to 4 nitrogen atoms, more preferably 2 or 3 as ring members of the heterocyclic ring, and more preferably 2 members. Further preferred.
  • the heterocyclic ring in component L may be a saturated heterocyclic ring, an unsaturated heterocyclic ring, or an aromatic heterocyclic ring.
  • the heterocyclic ring in component L may be further condensed with another ring.
  • said other ring not only a heterocyclic ring but an aliphatic ring or an aromatic ring may be sufficient.
  • heterocyclic structure of component L include imidazole structure, benzimidazole structure, 1,2,4-triazole structure, 4,5-dihydro-1,2,4-triazole structure, tetrazole structure, 2-imidazoline.
  • Preferred examples thereof include a ring structure selected from the group consisting of a structure, 4-imidazoline structure (2,3-dihydroimidazole structure), imidazolidine structure, pyrimidine structure, quinoxaline structure, purine structure, pteridine structure, and peridimine structure, Imidazole structure, benzimidazole structure, 1,2,4-triazole structure, 4,5-dihydro-1,2,4-triazole structure, tetrazole structure, 2-imidazoline structure, 4-imidazoline structure, imidazolidine structure, and A ring structure selected from the group consisting of pyrimidine structures Mentioned
  • benzimidazole structure or imidazolidine structure are exemplified particularly preferred. If it is the said aspect, the hardened
  • Component L preferably has a mercapto group (—SH) or a thioxo group ( ⁇ S). If it is the said aspect, the hardened
  • Component L is preferably a compound represented by the following formula (1).
  • R 1 and R 2 each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and R 1 and R 2 may be bonded to form a divalent organic group.
  • R 3 and R 4 each independently represents a hydrogen atom or a monovalent organic group
  • L 1 represents a divalent linking group forming a 5-membered ring or a 6-membered ring
  • R 3 or R 4 L 1 may be bonded to form a ring
  • the dotted bond represents that when the nitrogen-containing double bond described by the dotted line is present, R 2 and R 4 are not present, (If the nitrogen-containing double bond indicated by the dotted line is not present, it represents that R 2 and R 4 are present.)
  • Examples of the monovalent organic group in R 1 to R 4 include an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), and alkynyl.
  • aryl group heterocyclic group (also referred to as heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, Carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group , Aryloxycarbonylamino group Sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, alkyldithio group, aryldithio group, heterocyclic dithio group, sulfamoyl group,
  • a mercapto group is particularly preferable as the monovalent organic group for R 1 and R 2 .
  • the carbon number of the monovalent organic group in R 1 and R 2 is preferably 0 to 20, more preferably 0 to 8, and particularly preferably 0.
  • the divalent organic group formed by combining R 1 and R 2 include an oxo group, a thioxo group, and an alkylidene group. Of these, a thioxo group is particularly preferable.
  • R 1 and R 2 are each independently preferably a hydrogen atom or a mercapto group, and when R 1 and R 2 are combined to form a divalent organic group, they are thioxo groups. Is particularly preferred.
  • the monovalent organic group in R 3 and R 4 is preferably an alkyl group or an aryl group, and more preferably a morpholinomethyl group or a phenyl group.
  • the alkyl group or aryl group may be substituted with a substituent.
  • the carbon number of the monovalent organic group in R 3 and R 4 is preferably 0 to 20, more preferably 1 to 10, and still more preferably 4 to 8.
  • R 3 and R 4 are each independently preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, a morpholinomethyl group or a phenyl group, and a hydrogen atom or a phenyl group. Further preferred.
  • L 1 represents a divalent linking group that forms a 5-membered ring or a 6-membered ring, and forms a heterocyclic ring together with the carbon atom and the two nitrogen atoms in the formula (1).
  • the divalent linking group is not particularly limited as long as it is a group that forms a 5-membered heterocyclic ring or a 6-membered heterocyclic ring together with the carbon atom and the two nitrogen atoms in the formula (1).
  • a group formed from a carbon atom and / or a nitrogen atom is preferable, and a group forming a specific example of the heterocyclic structure described above is more preferable.
  • a group that forms a benzimidazole structure that is, a 1,2-phenylene group, a group that forms an imidazolidine structure, that is, a 1,2-ethylene group, a 1,1-dimethyl-1,2-ethylene group, or And more preferably an ethene-1,2-diyl group, and a 1,2-ethylene group, a 1,1-dimethyl-1,2-ethylene group, or an ethene-1,2-diyl group.
  • a group that forms a benzimidazole structure that is, a 1,2-phenylene group
  • a group that forms an imidazolidine structure that is, a 1,2-ethylene group, a 1,1-dimethyl-1,2-ethylene group, or And more preferably an ethene-1,2-diyl group, and a 1,2-ethylene group, a 1,1-dimethyl-1,2-ethylene group, or an ethene-1,2-diyl group.
  • component L is more preferably a compound represented by the following formula (1-1) or formula (1-2).
  • R 6 to R 8 each independently represents a hydrogen atom or a monovalent organic group
  • L 2 and L 3 each independently represents a 5-membered ring.
  • it represents a divalent linking group that forms a 6-membered ring
  • R 6 and L 2 may combine to form a ring
  • R 7 or R 8 and L 3 combine to form a ring. You may do it.
  • R 6 to R 8 in formula (1-1) or formula (1-2) have the same meanings as R 3 and R 4 in formula (1), and the preferred embodiments are also the same.
  • L 2 and L 3 in formula (1-1) or formula (1-2) have the same meaning as L 1 in formula (1), and the preferred embodiments are also the same.
  • Preferred specific examples (h-1 to h-14) of component L are shown below. However, the present invention is not limited to these.
  • h-3 to h-14 are preferable, h-3, h-5, h-6, h-9, h-12, h-13 or h-14 are more preferable, and h-5, h-14 -9, h-12, h-13 or h-14 is more preferred, and h-9, h-12, h-13 or h-14 is particularly preferred.
  • component L may be used individually by 1 type, and can also use 2 or more types together.
  • the content of component L in the photosensitive resin composition of the present invention is preferably 0.1 to 20% by mass, preferably 0.5 to 15%, based on the total solid content of the photosensitive resin composition of the present invention. More preferably, it is more preferably 0.5 to 10% by mass. When it is in the above range, a cured product having excellent dispersibility of the metal oxide particles and smaller haze can be obtained.
  • an acid proliferating agent can be used for the purpose of improving sensitivity.
  • the acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
  • Specific examples of such an acid proliferating agent include the acid proliferating agents described in paragraphs 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.
  • the content of the acid proliferating agent in the photosensitive resin composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator. From the viewpoint of dissolution contrast between the exposed part and the unexposed part. And more preferably 20 to 500 parts by mass.
  • the photosensitive resin composition of the present invention can contain a development accelerator.
  • a development accelerator any compound having a development acceleration effect can be used, and the development accelerator may be a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group.
  • a compound having a carboxyl group or a phenolic hydroxyl group is more preferable, and a compound having a phenolic hydroxyl group is most preferable.
  • the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
  • a development accelerator may be used individually by 1 type, and can also use 2 or more types together.
  • the addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition, from the viewpoint of sensitivity and residual film ratio. More preferably, it is 1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass.
  • the molecular weight of the development accelerator is preferably from 100 to 2,000, more preferably from 150 to 1,500, still more preferably from 150 to 1,000.
  • thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, and the nitrogen-containing compounds and thermal acid generators described in International Publication No. 2011-136004 may be used. The contents of which are incorporated herein by reference.
  • a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio.
  • the composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore size of 0.2 ⁇ m.
  • the method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
  • the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. It is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning before applying the photosensitive resin resin composition to the substrate, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesion of the photosensitive resin composition to the substrate is improved.
  • the method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
  • the substrate examples include inorganic substrates, resins, resin composite materials, ITO, Cu substrates, polyethylene terephthalate, and plastic substrates such as cellulose triacetate (TAC).
  • the inorganic substrate examples include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
  • the resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester resin, cyclic polyolefin, Is it a synthetic resin such as aromatic ether resin, maleimide-olefin resin, cellulose, episulfide resin, etc.
  • the coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
  • the coating film thickness is not particularly limited, and can be applied with a film thickness according to the application, but it is preferably used in the range of 0.5 to 10 ⁇ m.
  • the solvent removal step (2) the solvent is removed from the applied film by reducing pressure (vacuum) and / or heating to form a dry coating film on the substrate.
  • the heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are within the above ranges, the pattern adhesion is good and the residue can be reduced.
  • the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern.
  • the photoacid generator is decomposed to generate an acid.
  • the acid-decomposable group contained in the coating film component is hydrolyzed to produce an acid group, for example, a carboxyl group or a phenolic hydroxyl group.
  • an exposure light source using actinic light a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc.
  • g-line (436 nm), i-line (365 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used.
  • irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
  • PEB Post Exposure Bake
  • the temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
  • the acid-decomposable group in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to produce an acid group, for example, a carboxyl group or a phenolic hydroxyl group.
  • a positive image can be formed by development without performing PEB.
  • a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer.
  • a positive image is formed by removing an exposed area containing a resin composition having an acid group that easily dissolves in an alkaline developer, such as a carboxyl group or a phenolic hydroxyl group.
  • the developer used in the development step preferably contains a basic compound.
  • Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used.
  • An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
  • Preferred examples of the developer include a 0.4% by mass aqueous solution, a 0.5% by mass aqueous solution, a 0.7% by mass aqueous solution, or a 2.38% by mass aqueous solution of tetraethylammonium hydroxide.
  • the pH of the developer is preferably 10.0 to 14.0.
  • the development time is preferably 30 to 500 seconds, and the development method may be either a liquid piling method or a dipping method. After development, washing with running water can be performed for 30 to 300 seconds to form a desired pattern.
  • a rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like.
  • a known method can be used as the rinsing method. For example, a shower rinse, a dip rinse, etc. can be mentioned.
  • the obtained positive image is heated to thermally decompose the acid-decomposable group to generate an acid group, for example, a carboxyl group or a phenolic hydroxyl group,
  • a cured film can be formed by crosslinking with a thermal crosslinking agent or the like.
  • This heating is performed using a heating device such as a hot plate or oven at a predetermined temperature, for example, 180 ° C. to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to process.
  • heat treatment is preferably performed at 80 to 140 ° C. for 5 to 120 minutes.
  • the heat treatment step can be performed after baking at a relatively low temperature (addition of a middle bake step).
  • middle baking it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Further, middle baking and post baking can be heated in three or more stages.
  • the taper angle of the pattern can be adjusted by devising such middle baking and post baking.
  • These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
  • post-exposure the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film.
  • the preferred exposure amount in the case of including a post-exposure step preferably 100 ⁇ 3,000mJ / cm 2, particularly preferably 100 ⁇ 500mJ / cm 2.
  • the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.
  • dry etching processing such as ashing, plasma etching, ozone etching, or the like can be performed as the etching processing.
  • the cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
  • the cured film of the present invention can be suitably used as an interlayer insulating film.
  • the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
  • an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
  • the cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention.
  • the shape does not have to be a film, and may be any shape.
  • the production method of the cured product of the present invention is not particularly limited, but preferably includes at least the following steps (a) to (c) in this order.
  • Step (c) is the same step as the heat treatment step except that the heat treatment target is a resin composition from which the solvent obtained in step (b) has been removed. Preferred embodiments such as time and heating means are also preferred.
  • the cured product or cured film of the present invention is for reducing the visibility of wiring members used for optical members such as microlenses, optical waveguides, antireflection films, LED sealing materials and LED chip coating materials, or touch panels. It can be suitably used as a cured product.
  • the cured product or cured film of the present invention is, for example, a flattening film or interlayer insulating film in a liquid crystal display device or an organic EL device as described later, a protective film for a color filter, and a thickness of a liquid crystal layer in a liquid crystal display device.
  • the liquid crystal display device of the present invention comprises the cured film of the present invention.
  • the liquid crystal display device of the present invention is not particularly limited except that it has a planarizing film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal display devices having various structures. Can be mentioned.
  • specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • the liquid crystal driving methods that the liquid crystal display device of the present invention can take are TN (Twisted Nematic) method, VA (Virtical Alignment) method, IPS (In-Place-Switching) method, FFS (Fringe Field Switching) method, OCB (OCB). Optically Compensated Bend) method.
  • the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device.
  • the organic insulating film (115) described in JP-A-2005-284291 It can be used as the organic insulating film (212) described in Japanese Unexamined Patent Publication No. 2005-346054.
  • the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method.
  • the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in Japanese Patent Application Laid-Open Nos. 2003-149647 and 2011-257734.
  • the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses.
  • a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
  • FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10.
  • the color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
  • the elements of the TFT 16 corresponding to are arranged.
  • Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
  • an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
  • the light source of the backlight is not particularly limited, and a known light source can be used.
  • the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interphase insulating film (48) described in JP2011-145686A or the interphase insulating film (520) described in JP2009-258758A. Can do.
  • the organic EL display device of the present invention comprises the cured film of the present invention.
  • the organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic materials having various structures.
  • An EL display device and a liquid crystal display device can be given.
  • specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • FIG. 2 is a conceptual diagram of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • a bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3.
  • the wiring 2 is used to connect the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
  • a planarizing layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
  • a bottom emission type organic EL element is formed on the planarizing film 4 on the planarizing film 4. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • the first electrode 5 corresponds to the anode of the organic EL element.
  • An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do. Further, although not shown in FIG.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate.
  • An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it.
  • An EL display device is obtained.
  • a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part.
  • MEMS devices include, for example, SAW (surface acoustic wave) filters, BAW (bulk acoustic wave) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, biochips, sealants. And the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.
  • the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. Partition wall (12) and planarization film (102) shown in FIG. 4 (a) of JP-A-9793, and bank layer (221) and third interlayer insulating film (FIG. 10 of JP 2010-27591A). 216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and the configuration described in FIG. 3 of JP-A-2010-182638. It can also be used to form a planarization film (12), a pixel isolation insulating film (14), and the like.
  • the touch panel display device of the present invention includes a capacitive input device having the cured film of the present invention. Moreover, the capacitance-type input device of the present invention has the cured film of the present invention.
  • the capacitance-type input device of the present invention has at least the following elements (1) to (5) on the front plate and the non-contact side of the front plate, and the above (4) is the cured product of the present invention. Preferably there is.
  • (1) Mask layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) The first transparent electrode pattern and the electric
  • a plurality of second transparent electrode patterns comprising a plurality of pad portions which are insulated and extend in a direction intersecting the first direction.
  • a transparent protective layer is further provided so as to cover all or part of the elements (1) to (5).
  • the transparent protective layer is preferably And more preferably the cured film.
  • FIG. 3 is a cross-sectional view showing the configuration of the capacitive input device.
  • the capacitive input device 30 includes a front plate 31, a mask layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, and a conductive element 36. And a transparent protective layer 37.
  • the front plate 31 is composed of a light-transmitting substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. Moreover, in FIG. 3, the side in which each element of the front plate 31 is provided is called a non-contact surface. In the capacitive input device 30 of the present invention, input is performed by bringing a finger or the like into contact with the contact surface (the surface opposite to the non-contact surface) of the front plate 31.
  • the front plate may be referred to as a “base material”.
  • a mask layer 32 is provided on the non-contact surface of the front plate 31.
  • the mask layer 32 is a frame-like pattern around the display area formed on the non-contact side of the touch panel front plate, and is formed so as not to show the lead wiring and the like.
  • a mask layer 32 is provided so as to cover a part of the front plate 31 (a region other than the input surface in FIG. 4).
  • the front plate 31 can be provided with an opening 38 in a part thereof as shown in FIG. A mechanical switch by pressing can be installed in the opening 38.
  • a plurality of first transparent electrode patterns 33 formed with a plurality of pad portions extending in the first direction via the connection portions, A plurality of second transparent electrode patterns 34 each including a plurality of pad portions that are electrically insulated from one transparent electrode pattern 33 and extend in a direction crossing the first direction; An insulating layer 35 that electrically insulates the electrode pattern 33 and the second transparent electrode pattern 34 is formed.
  • the first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 to be described later are translucent conductive materials such as ITO (Indium Tin Oxide) and IZO (Indium Zinc Oxide). It can be made of a conductive metal oxide film.
  • metal films examples include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO 2 .
  • the film thickness of each element can be set to 10 to 200 nm.
  • the first transparent electrode pattern 33, the second transparent electrode pattern 34, and the conductive element 36 described later use a photosensitive transfer material having a curable resin composition using the conductive fibers. Can also be manufactured.
  • paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to.
  • At least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 extends over both the non-contact surface of the front plate 31 and the region opposite to the front plate 31 of the mask layer 32. Can be installed.
  • FIG. 3 a diagram is shown in which the second transparent electrode pattern is installed across both areas of the non-contact surface of the front plate 31 and the surface opposite to the front plate 31 of the mask layer 32. Yes.
  • FIG. 5 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern in the present invention.
  • the first transparent electrode pattern 33 is formed such that a pad portion 33a extends in a first direction via a connection portion 33b.
  • the second transparent electrode pattern 34 is electrically insulated by the first transparent electrode pattern 33 and the insulating layer 35 and extends in a direction intersecting the first direction (second direction in FIG. 5). It is constituted by a plurality of pad portions that are formed.
  • the pad portion 33a and the connection portion 33b may be manufactured as one body, or only the connection portion 33b is manufactured, and the pad portion 33a and the second portion 33b are formed.
  • the transparent electrode pattern 34 may be integrally formed (patterned).
  • the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), as shown in FIG. 5, a part of the connection part 33b and a part of the pad part 33a are connected, and an insulating layer is formed. Each layer is formed so that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by 35.
  • a conductive element 36 is provided on the surface of the mask layer 32 opposite to the front plate 31.
  • the conductive element 36 is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34, and is different from the first transparent electrode pattern 33 and the second transparent electrode pattern 34. Is another element.
  • FIG. 3 a view in which the conductive element 36 is connected to the second transparent electrode pattern 34 is shown.
  • the transparent protective layer 37 is installed so that all of each component may be covered.
  • the transparent protective layer 37 may be configured to cover only a part of each component.
  • the insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.
  • the capacitance-type input device obtained by the manufacturing method of the present invention and the touch panel display device including the capacitance-type input device as a constituent element are “latest touch panel technology” (issued July 6, 2009 (stock) ) Techno Times), supervised by Yuji Mitani, “Technology and Development of Touch Panels”, CMC Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. Can be applied.
  • MATHF tetrahydrofuran-2-yl methacrylate (synthetic product)
  • MAEVE 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MACHOE 1- (cyclohexyloxy) ethyl methacrylate (synthetic product)
  • MATHP Tetrahydro-2H-pyran-2-yl methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • GMA Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • OXE-30 Methacrylic acid (3-ethyloxetane-3-yl) methyl (Osaka Organic Chemical Industry Co., Ltd.)
  • NBMA n-butoxymethylacrylamide (Mitsubishi Rayon Co., Ltd.)
  • MAA Methacrylic acid (manuv) (manufactured by Wako
  • MACHOE was synthesized in the same manner as MATH, except that 2-dihydrofuran was changed to the corresponding compound.
  • the ratio of the total amount of MEDG and other components was 60:40. That is, a polymer solution having a solid content concentration of 40% was prepared.
  • the type of monomer used, the polymerization initiator, etc. were changed as shown in the following table, and other polymers were synthesized. In the table, “-” means that the component is not contained.
  • the numerical values without particular units are in mol%.
  • the numerical value of a polymerization initiator is mol% when a monomer component is 100 mol%.
  • the solid content concentration can be calculated by the following equation. Solid content concentration: monomer mass / (monomer mass + solvent mass) ⁇ 100 (unit: mass%) When V-601 was used as an initiator, the reaction temperature was 90 ° C., and when V-65 was used, the reaction temperature was 70 ° C.
  • Dispersion A Dispersion F to Dispersion H> -Dispersion A: Optlake 6320Z (manufactured by JGC Catalysts & Chemicals, solid content 20% by mass) -Dispersion F: SZR-K (manufactured by Sakai Chemical Industry Co., Ltd., solid content: 33% by mass) -Dispersion G: Nano-use (manufactured by Nissan Chemical Industries, Ltd., solid content 30% by mass) -Dispersion H: Nanotec (Ci Kasei Co., Ltd., solid content 30% by mass)
  • ⁇ Preparation of dispersion D> Under acidic conditions of pH 0.5, a 5 mass% aqueous nanoparticle dispersion of TiO 2 particles containing 10 mol% SnO 2 and 17 mol% ZrO 2 was produced. This dispersion contains about 5% by volume of ethanol and about 7% by volume of isopropanol. Further, the by-product salt and the remaining raw material in the dispersion were removed by electrodialysis until the electric conductivity was 100 ⁇ S / cm or less. Next, solvent replacement from the water (first dispersion medium) which is the main dispersion medium of the above dispersion liquid to an organic solvent was performed by the method shown below.
  • Butyl acetate was selected as the second dispersion medium, p-propylbenzoic acid as the dispersant, and 1-propanol as the third dispersion medium to be interposed.
  • 10 g of p-propylbenzoic acid was dissolved in 3,000 ml of 1-propanol, and 1,000 ml of the above dispersion was slowly added with stirring.
  • This liquid was distilled under reduced pressure (first time) under the conditions of 55 ° C. and 100 hPa to 80 hPa until the liquid volume reached about 1,000 ml.
  • 1,000 ml of 1-propanol was added while stirring, and then distillation under reduced pressure (second time) was performed until the volume became 1,000 ml under the conditions of 55 ° C.
  • a composite metal oxide particle dispersion B was prepared in the same manner as the dispersion D except that SnO 2 and ZrO 2 were changed to SiO 2 in the preparation of the dispersion D.
  • a composite metal oxide particle dispersion C was prepared in the same manner as the dispersion D except that SnO 2 and ZrO 2 were changed to SnO 2 in the preparation of the dispersion D.
  • PGMEA solution of the following compound (basic compound, manufactured by Toyo Kasei Kogyo Co., Ltd., CMTU): 2.57 parts-30% PGMEA solution of polymer D1 : 26.33 parts ⁇
  • Photoacid generator B-1 (the following compound): 0.51 parts ⁇ JER157S65 (thermal crosslinking agent, epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 200 to 220 g / eq): 1 79 parts 3-glycidoxypropyltrimethoxysilane (adhesion improver, KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.45 parts Irganox 1726 (antioxidant, manufactured by BASF): 0 .3 parts-2.0% PGMEA solution of perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC Corporation): 1.1 parts-Dispersion
  • Ts represents a p-toluenesulfonyl group.
  • Crude B-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-2A.
  • B-2A (1.7 g) and p-xylene (6 mL) were mixed, 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and 140 ° C. for 2 hours. Heated. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated.
  • the whole amount of the intermediate crude B-2C was mixed with acetone (10 mL), and triethylamine (Wako Pure Chemical Industries, Ltd.) (1.2 g) and p-toluenesulfonyl chloride (Tokyo Chemical Industry Co., Ltd.) were cooled with ice. ) (1.4 g) was added, and the mixture was warmed to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture to separate it, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-2. Crude B-2 was reslurried with cold methanol, filtered and dried to obtain B-2 (1.2 g).
  • the photosensitive resin composition was apply
  • the solvent was removed on a hot plate at 80 ° C. for 120 seconds to form a coating film having a thickness of 2.4 ⁇ m.
  • exposure was performed at an exposure amount of 200 mj / cm 2 (measured by i-line) with an ultra-high pressure mercury lamp exposure machine through a 1: 1 line and space mask.
  • the film is developed with a 10% aqueous solution of CDK-1 (KOH-based developer) manufactured by Fuji Film Electronics Materials Co., Ltd. at 24 ° C. for 50 seconds, rinsed with pure water for 10 seconds, and then watered with an air gun. Were removed and observed with an electron microscope.
  • the evaluation criteria are as follows. 1: No residue 2: Residue 3: No pattern formation
  • a haze value refers to the value represented by the ratio (%) of the diffuse transmitted light with respect to all the light transmitted light. The smaller the haze value, the higher the transparency.
  • the evaluation criteria are as follows. 1: Haze value is less than 0.5 2: Haze value is 0.5 or more and less than 1.0 3: Haze value is 1.0 or more
  • the obtained photosensitive resin composition was applied onto a silicon wafer substrate using a spinner, and dried at 80 ° C. for 120 seconds to form a film having a thickness of 0.5 ⁇ m.
  • This substrate was exposed to 200 mJ / cm 2 (measured with i-line) using an ultrahigh pressure mercury lamp, and then heated in an oven at 220 ° C. for 45 minutes.
  • the refractive index of the cured film at 589 nm was measured using an ellipsometer VUV-VASE (manufactured by JA Woollam Japan Co., Ltd.). A higher refractive index is preferable, and 1.70 or more is more preferable.
  • Example 24 In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3312003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 24 was obtained. That is, the photosensitive resin composition of Example 1 was spin-coated on a substrate, pre-baked (90 ° C./120 seconds) on a hot plate, and then i-line (365 nm) was 45 mJ / mm from the mask using a high-pressure mercury lamp.
  • liquid crystal display device When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 25 An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
  • a bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3. .
  • the wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
  • the flattening film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded.
  • the planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiating 45 mJ / cm 2 (illuminance 20 mW / cm 2 ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C./30 minutes.
  • the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.
  • a bottom emission type organic EL element was formed on the obtained flattening film 4.
  • a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed.
  • pattern processing was performed by wet etching using an ITO etchant.
  • the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials).
  • the first electrode 5 thus obtained corresponds to the anode of the organic EL element.
  • an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed.
  • the photosensitive resin composition of Example 1 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus.
  • a second electrode made of Al was formed on the entire surface above the substrate.
  • substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
  • Example 26 A touch panel display device was prepared by using the high refractive index curable resin material of the present invention by the method described below.
  • ⁇ Formation of first transparent electrode pattern> [Formation of transparent electrode layer]
  • a 40 nm thick ITO thin film is formed by DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent electrode layer is formed.
  • a front plate was obtained.
  • the surface resistance of the ITO thin film was 80 ⁇ / ⁇ .
  • etching resist was applied onto ITO and dried to form an etching resist layer.
  • Development was performed, and a post-bake treatment at 130 ° C. for 30 minutes was further performed to obtain a front plate on which a transparent electrode layer and a photocurable resin layer pattern for etching were formed.
  • the front plate on which the transparent electrode layer and the photocurable resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and etched resist.
  • ITO etchant hydroochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.
  • the exposed transparent electrode layer not covered with the layer was dissolved and removed to obtain a front plate with a transparent electrode layer pattern with an etching resist layer pattern.
  • the front plate with the transparent electrode layer pattern with the etching resist layer pattern is immersed in a dedicated resist stripping solution, the photocurable resin layer for etching is removed, and the mask layer and the first transparent electrode pattern A front plate formed was obtained.
  • the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 ⁇ m, 90 ° C., 120 seconds) to form a photosensitive resin composition layer.
  • the distance between the exposure mask (quartz exposure mask having the insulating layer pattern) surface and the photosensitive resin composition layer was set to 30 ⁇ m, and pattern exposure was performed at an exposure amount of 50 mJ / cm 2 (i-line).
  • the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds by immersion and further rinsed with ultrapure water for 10 seconds.
  • a post-bake treatment at 220 ° C. for 45 minutes was performed to obtain a front plate on which a mask layer, a first transparent electrode pattern, and an insulating layer pattern were formed.
  • the first transparent electrode pattern In the same manner as in the formation of the first transparent electrode pattern, a commercially available etching resist is used, the first transparent electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 1, and the transparent electrode A front plate on which a layer and an etching resist pattern were formed was obtained (post-bake treatment; 130 ° C. for 30 minutes). Further, by etching and removing the etching resist layer in the same manner as the formation of the first transparent electrode pattern, the mask layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1 were used. A front plate on which the formed insulating layer pattern and second transparent electrode pattern were formed was obtained.
  • a front plate on which a pattern, a second transparent electrode pattern, and an etching resist pattern were formed was obtained (post-bake treatment; 130 ° C. for 30 minutes). Further, in the same manner as in the formation of the first transparent electrode pattern, etching (30 ° C. for 50 seconds) is performed, and the etching resist layer is removed (45 ° C. for 200 seconds), whereby the mask layer and the first transparent electrode pattern are removed.
  • an insulating layer pattern formed using the photosensitive resin composition of Example 1, a second transparent electrode pattern, and a front plate on which conductive elements different from the first and second transparent electrode patterns were formed were obtained. .
  • the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 ⁇ m) on the front plate formed up to the conductive element different from the first and second transparent electrode patterns. , 90 ° C. for 120 seconds) to obtain a photosensitive resin composition film.
  • the front exposure is performed with an exposure amount of 50 mJ / cm 2 (i-line) without using an exposure mask, development, post-exposure (1,000 mJ / cm 2 ), and post-bake treatment are performed to obtain a mask layer and a first transparent
  • the electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 1, the second transparent electrode pattern, and all the conductive elements different from the first and second transparent electrode patterns are covered.
  • stacked the insulating layer (transparent protective layer) formed using the photosensitive resin composition of Example 1 was obtained.
  • a liquid crystal display device manufactured by the method described in Japanese Patent Application Laid-Open No. 2009-47936 is bonded to the previously manufactured front plate, and an image display device including a capacitive input device as a constituent element is manufactured by a known method. did.
  • TFT thin film transistor
  • 2 wiring
  • 3 insulating film
  • 4 planarization film
  • 5 first electrode
  • 6 glass substrate
  • 7 contact hole
  • 8 insulating film
  • 10 liquid crystal display device
  • 12 Backlight unit
  • 14 15: Glass substrate
  • 16 TFT
  • 17 Cured film
  • 18 Contact hole
  • 19 ITO transparent electrode
  • 20 Liquid crystal
  • 22 Color filter 30: Capacitive input device, 31: Front plate, 32: Mask layer, 33: First transparent electrode pattern, 33a: Pad portion, 33b: Connection portion, 34: Second transparent electrode pattern, 35: Insulating layer, 36: Conductive element, 37 : Transparent protective layer, 38: Opening

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  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Human Computer Interaction (AREA)
  • Materials For Photolithography (AREA)
  • Liquid Crystal (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention a pour but de proposer une composition de résine photosensible qui permet d'obtenir un article durci ayant une transparence supérieure et un indice élevé de réfraction. La composition de résine photosensible est caractérisée en ce qu'elle contient (composant A) des particules inorganiques, (composant B) un agent dispersant, (composant C) un solvant, (composant D) un polymère contenant une unité constituante ayant un groupe tel qu'un groupe acide est protégé par un groupe labile acide, et (composant E) un générateur de photoacide, où le composant A est des particules d'oxyde métallique contenant du titane comme élément et ayant une dimension moyenne de particule en volume (D50) de 0,1-20 nm, bornes incluses. Egalement, le composant A est de préférence des particules d'oxyde métallique complexes contenant du titane comme élément et au moins un autre élément métallique.
PCT/JP2014/055909 2013-03-08 2014-03-07 Composition de résine photosensible, article durci, leur procédé de fabrication, procédé de fabrication d'un motif de résine, film durci, dispositif d'affichage à cristaux liquides, dispositif d'affichage électroluminescent organique et dispositif d'affichage de panneau tactile WO2014136922A1 (fr)

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KR20160126906A (ko) * 2015-04-24 2016-11-02 제이에스알 가부시끼가이샤 감방사선성 수지 조성물, 적외선 차폐막, 그의 형성 방법, 및 고체 촬상 소자, 조도 센서
CN107229185A (zh) * 2016-03-25 2017-10-03 东京应化工业株式会社 能量敏感性组合物、固化物及固化物的制造方法
WO2017175545A1 (fr) * 2016-04-06 2017-10-12 富士フイルム株式会社 Composition, film, film durci, capteur optique et procédé de production de film
WO2017204090A1 (fr) * 2016-05-26 2017-11-30 Jsr株式会社 Composition sensible aux rayonnements et procédé de formation de motif
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JP2016151641A (ja) * 2015-02-17 2016-08-22 富士フイルム株式会社 感光性組成物、硬化物の製造方法、硬化物、硬化膜、タッチパネル及び表示装置
WO2016158406A1 (fr) * 2015-03-27 2016-10-06 東レ株式会社 Composition de résine photosensible pour des transistors à couches minces, film durci, transistor à couches minces, dispositif d'affichage à cristaux liquides, dispositif d'affichage électroluminescent organique, procédé de production d'un film durci, procédé de fabrication d'un transistor à couches minces, et procédé de fabrication d'un dispositif d'affichage à cristaux liquides ou d'un dispositif d'affichage électroluminescent organique
KR102245394B1 (ko) 2015-03-27 2021-04-28 도레이 카부시키가이샤 박막 트랜지스터용 감광성 수지 조성물, 경화막, 박막 트랜지스터, 액정 표시 장치 또는 유기 전계 발광 표시 장치, 경화막의 제조 방법, 박막 트랜지스터의 제조 방법 및 액정 표시 장치 또는 유기 전계 발광 표시 장치의 제조 방법
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KR20170131382A (ko) * 2015-03-27 2017-11-29 도레이 카부시키가이샤 박막 트랜지스터용 감광성 수지 조성물, 경화막, 박막 트랜지스터, 액정 표시 장치 또는 유기 전계 발광 표시 장치, 경화막의 제조 방법, 박막 트랜지스터의 제조 방법 및 액정 표시 장치 또는 유기 전계 발광 표시 장치의 제조 방법
CN107431020B (zh) * 2015-03-27 2020-07-24 东丽株式会社 薄膜晶体管用感光性树脂组合物、固化膜、薄膜晶体管
CN107431020A (zh) * 2015-03-27 2017-12-01 东丽株式会社 薄膜晶体管用感光性树脂组合物、固化膜、薄膜晶体管、液晶显示装置或有机场致发光显示装置、固化膜的制造方法、薄膜晶体管的制造方法以及液晶显示装置或有机场致发光显示装置的制造方法
JPWO2016158406A1 (ja) * 2015-03-27 2018-01-18 東レ株式会社 薄膜トランジスタ用感光性樹脂組成物、硬化膜、薄膜トランジスタ、液晶表示装置または有機電界発光表示装置、硬化膜の製造方法、薄膜トランジスタの製造方法および液晶表示装置または有機電界発光表示装置の製造方法
KR102599303B1 (ko) * 2015-04-24 2023-11-06 제이에스알 가부시끼가이샤 감방사선성 수지 조성물, 적외선 차폐막, 그의 형성 방법, 및 고체 촬상 소자, 조도 센서
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CN107229185A (zh) * 2016-03-25 2017-10-03 东京应化工业株式会社 能量敏感性组合物、固化物及固化物的制造方法
CN107229185B (zh) * 2016-03-25 2022-04-15 东京应化工业株式会社 能量敏感性组合物、固化物及固化物的制造方法
WO2017175545A1 (fr) * 2016-04-06 2017-10-12 富士フイルム株式会社 Composition, film, film durci, capteur optique et procédé de production de film
JPWO2017175545A1 (ja) * 2016-04-06 2019-02-14 富士フイルム株式会社 組成物、膜、硬化膜、光学センサおよび膜の製造方法
JPWO2017204090A1 (ja) * 2016-05-26 2019-03-22 Jsr株式会社 感放射線性組成物及びパターン形成方法
WO2017204090A1 (fr) * 2016-05-26 2017-11-30 Jsr株式会社 Composition sensible aux rayonnements et procédé de formation de motif
US11194252B2 (en) 2016-09-21 2021-12-07 Nissan Chemical Corporation Cured film-forming composition

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