WO2014065351A1 - Photosensitive resin composition, cured product and method for producing same, method for producing resin pattern, cured film, organic el display device, liquid crystal display device, and touch panel display device - Google Patents

Photosensitive resin composition, cured product and method for producing same, method for producing resin pattern, cured film, organic el display device, liquid crystal display device, and touch panel display device Download PDF

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Publication number
WO2014065351A1
WO2014065351A1 PCT/JP2013/078766 JP2013078766W WO2014065351A1 WO 2014065351 A1 WO2014065351 A1 WO 2014065351A1 JP 2013078766 W JP2013078766 W JP 2013078766W WO 2014065351 A1 WO2014065351 A1 WO 2014065351A1
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group
resin composition
photosensitive resin
acid
component
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PCT/JP2013/078766
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French (fr)
Japanese (ja)
Inventor
史絵 山下
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富士フイルム株式会社
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Priority to JP2014543337A priority Critical patent/JPWO2014065351A1/en
Publication of WO2014065351A1 publication Critical patent/WO2014065351A1/en

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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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—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
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/133345—Insulating layers

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 production method of a resin pattern production method using the photosensitive resin composition, a cured film obtained by curing the photosensitive composition, In addition, 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 or an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, a touch panel display device, an integrated circuit element, and a solid-state imaging element. And a method for producing a cured film using the same.
  • the solid content concentration may rapidly increase and aggregates may be generated. Due to these agglomerates, the discharge flow rate is non-uniform, resulting in streaky irregularities. Furthermore, this agglomerate adheres to the tip of the coater nozzle or slit blade edge, and when the resist is discharged again, it peels off from the tip of the nozzle and moves onto the substrate. These agglomerates are not easily removed in the subsequent process and remain on the substrate until the end. Such agglomerates become defects and cause quality defects. If this defect phenomenon occurs frequently, the yield of the product decreases.
  • An object of the present invention is to provide a photosensitive resin composition that is excellent in applicability when applied by a liquid-saving coating method such as slit coating and spray coating, and has a high refractive index.
  • ⁇ 2> The photosensitive resin composition according to the above ⁇ 1>, wherein component C comprises propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and / or diethylene glycol ethyl methyl ether, ⁇ 3>
  • component C comprises propylene glycol monomethyl ether acetate as a solvent having a boiling point of less than 160 ° C. and ethyl 3-ethoxypropionate and / or diethylene glycol ethyl methyl ether as a solvent having a boiling point of 160 ° C.
  • photosensitive resin composition ⁇ 4> The photosensitive resin composition according to any one of the above ⁇ 1> to ⁇ 3>, wherein the content of component C is 70% by mass or more and 95% by mass or less, ⁇ 5> The photosensitive resin composition according to any one of the above ⁇ 1> to ⁇ 4>, wherein the viscosity is 15 mPa ⁇ s or less, ⁇ 6> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the component A is metal oxide particles, ⁇ 7> The photosensitive resin composition according to any one of the above ⁇ 1> to ⁇ 6>, wherein the component A is titanium oxide particles or zirconium oxide particles, ⁇ 8> The photosensitive composition according to any one of ⁇ 1> to ⁇ 7>, wherein the structural unit having a group in which the acid group is protected with an acid-decomposable group is a structural unit represented by the following formula: Functional resin composition,
  • R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • L 1 represents a carbonyl group or a phenylene group
  • R 122 to R 128 each independently represents a hydrogen atom or 1 to 4 carbon atoms. Represents an alkyl group of
  • the developed resin composition is heat-treated.
  • Heat treatment step ⁇ 13> A cured product obtained by the method for producing a cured product according to ⁇ 11> or the resin pattern production method according to ⁇ 12>, ⁇ 14> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10> above, ⁇ 15>
  • the cured film according to ⁇ 14> which is an interlayer insulating film
  • ⁇ 16> A liquid crystal display device having the cured film according to ⁇ 14> or ⁇ 15> above, ⁇ 17>
  • An organic EL display device having the cured film according to ⁇ 14> or ⁇ 15> above, ⁇ 18> A touch panel display device having the cured film according to ⁇ 14> or ⁇ 15>.
  • a photosensitive resin composition that is excellent in applicability when applied by a liquid-saving coating method such as slit coating and spray coating and has a high refractive index.
  • 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.
  • component A inorganic particles or the like is also simply referred to as “component A” or the like, and “(a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group” and the like described later. Is also simply referred to as “structural unit (a1)”.
  • the description which does not describe substitution and non-substitution includes what does not have a substituent and what has 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 “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous. In the present invention, a combination of two or more preferred embodiments is more preferred.
  • 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 C contains a solvent having a boiling point of 160 ° C. or higher, and the boiling point of 160 ° C. or higher.
  • the content of the solvent is 3% by mass or more and 40% by mass or less based on the total amount of the solvent in the photosensitive resin composition.
  • 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 liquid-saving coating photosensitive resin composition, and more preferably a slit coating or spray coating photosensitive resin composition.
  • 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 carboxy 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 an acid generated in response to actinic rays acts as a catalyst for deprotection of protected acid groups in Component D. Therefore, the acid generated by the action of one photon contributes to a number of 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 is used as a positive photosensitive resin composition, the dispersibility of the inorganic particles is very important, and if the dispersion is not good, the average There is a problem that the particle size is not reduced, too large, aggregated particles are generated, coarse particles remain without being pulverized, and finally the transparency is inferior when the photosensitive resin composition is applied.
  • the compatibility between the dispersion liquid and the binder in the photosensitive resin composition is also important.
  • the present inventors have made a photosensitive resin composition containing component A to component E, so that there are few coating stripes and unevenness when applied by a liquid-saving coating method such as slit coating and spray coating. It has been found that a photosensitive resin composition having excellent coating properties, clogging of nozzles and generation of agglomerates at the tips of nozzles and slit blade tips, excellent coating properties over time, and a high refractive index can be obtained.
  • the photosensitive resin composition of the present invention will be described in detail.
  • the viscosity at 25 ° C. of the photosensitive resin composition of the present invention is preferably 50 mPa ⁇ s or less, and more preferably 40 mPa ⁇ s or less, from the viewpoint of improving coating suitability. Moreover, it is preferable that the said viscosity is 1 mPa * s or more.
  • the viscosity at 25 ° C. of the photosensitive resin composition in the present invention is a value measured using an E-type viscometer at 25 ° C. In spray coating, from the viewpoint that nozzle clogging during spray coating does not occur, the viscosity at 25 ° C.
  • the photosensitive resin composition of the present invention during spray coating is preferably 15 mPa ⁇ s or less, and preferably 1 to 15 mPa ⁇ s. S is more preferable, and 2 to 10 mPa ⁇ s is still more preferable.
  • Component A Inorganic Particles
  • the resin composition of the present invention contains inorganic particles for the purpose of adjusting the refractive index and light transmittance.
  • Component A preferably has a refractive index higher than that of the resin composition made of a material excluding the particles. Specifically, the refractive index in light having a wavelength of 400 to 750 nm is 1.50.
  • the above particles are more preferable, particles having a refractive index of 1.70 or more are more preferable, and particles having a refractive index of 1.90 or more are particularly preferable.
  • a refractive index is 5.00 or less.
  • 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 inorganic particles having such a high refractive index metal oxide particles are preferable. Since the metal oxide particles have high transparency and light transmittance, a photosensitive resin composition having a high refractive index and excellent transparency can be easily obtained.
  • the metal of the metal oxide particles in the present invention includes semimetals such as B, Si, Ge, As, Sb, and Te.
  • the light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb.
  • Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable. Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferable, titanium oxide, titanium composite oxide and zirconium oxide are more preferable, titanium oxide and zirconium oxide are particularly preferable, and titanium oxide is most preferable. Titanium oxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.
  • the average primary particle size of component A is preferably 1 to 200 nm, particularly preferably 3 to 80 nm.
  • the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.
  • the 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 and light transmittance required for an optical member obtained from the resin composition.
  • the content is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the total solid content of the composition.
  • the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
  • the inorganic particles can also be used as a dispersion prepared by mixing and dispersing using a mixing device such as a ball mill or a rod mill in the component (B), which will be described later, and a solvent.
  • a mixing device such as a ball mill or a rod mill in the component (B), which will be described later
  • a solvent examples of the solvent used in the preparation of the dispersion include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, in addition to the (Component C) solvent described below.
  • -Alcohols such as pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, cyclohexanol, etc. Can be mentioned.
  • solvent can be used individually by 1 type or in mixture of 2 or more types.
  • the photosensitive resin composition of the present invention contains (Component B) a dispersant.
  • a dispersant 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.
  • 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 polymer dispersant preferably has a weight average molecular weight of 1,000 or more and 1,000,000 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 (component C) solvent contains a solvent having a boiling point of 160 ° C. or higher, and the content of the solvent having a boiling point of 160 ° C. or higher is the total solvent amount in the photosensitive resin composition. On the other hand, it is 3 mass% or more and 40 mass% or less. By including a solvent having a boiling point of 160 ° C.
  • the “boiling point” in the present invention is the normal boiling point, that is, the boiling point at 1 atmosphere.
  • the (Component C) solvent is preferably a solvent having a boiling point of 250 ° C. or lower.
  • the photosensitive resin composition of the present invention is preferably prepared as a solution obtained by dissolving and / or dispersing the essential components of the present invention and optional components described below in the (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 JP2011-22214A.
  • a solvent can be used individually by 1 type or in mixture of 2 or more types. It is preferable to use a mixture of two or more solvents that can be used in the present invention.
  • 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 solvent having a boiling point of 160 ° C or higher is preferably a solvent having a boiling point of 160 ° C or higher and 250 ° C or lower, more preferably a solvent having a boiling point of 160 ° C or higher and 190 ° C or lower, and a solvent having a boiling point of 165 ° C or higher.
  • a solvent of 180 ° C. or lower is more preferable, ethyl 3-ethoxypropionate and / or diethylene glycol methyl ethyl ether is particularly preferable, and ethyl 3-ethoxypropionate or diethylene glycol methyl ethyl ether is most preferable.
  • the content of the solvent having a boiling point of 160 ° C. or higher in the photosensitive resin composition of the present invention is 3% by mass or more and 40% by mass or less, and 3% by mass or more and 35% by mass with respect to the total amount of the solvent in the photosensitive resin composition. % Or less, and more preferably 3% by mass or more and 30% by mass or less. It is excellent in the applicability
  • the photosensitive resin composition of the present invention is preferably 1% by mass or more and 35% by mass or less with respect to the total mass in the photosensitive resin composition.
  • the content is more preferably no less than 30% by mass and no greater than 30% by mass, and more preferably no less than 2% by mass and no greater than 25% by mass. It is excellent in the applicability
  • the component C is preferably used in combination with a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C.
  • 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.).
  • propylene glycol monoalkyl ether acetates are preferable, and propylene glycol monomethyl ether acetate is particularly preferable.
  • the content mass ratio of the solvent having a boiling point of 130 ° C. or more and less than 160 ° C. and the solvent having a boiling point of 160 ° C. or more is a solvent having a boiling point of 130 ° C. or more and less than 160 ° C.
  • the ratio is preferably 50:50 to 97: 3, more preferably 55:45 to 97: 3, and still more preferably 60:40 to 97: 3. It is excellent in the applicability
  • the content mass ratio of the solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C. and the solvent having a boiling point of 160 ° C. or higher is 130 ° C. or higher and 160 ° C. in the photosensitive resin composition of the present invention.
  • Less than solvent: Solvent with boiling point of 160 ° C. or higher 70: 30 to 97: 3 is particularly preferable. It is excellent in the applicability
  • solvent having a boiling point of 160 ° C. or higher is 130 ° C. or higher and lower than 160 ° C.
  • the component C is preferably a solvent selected from the group consisting of ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether, and includes ethyl 3-ethoxypropionate and propylene glycol monomethyl Two mixtures with ether acetate, or two mixtures of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate, or 3 of ethyl 3-ethoxypropionate, diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate Particular preference is given to a mixture of seeds.
  • the content of the (component C) solvent in the photosensitive resin composition of the present invention is preferably 65% by mass or more and 95% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and 75% by mass. % To 95% by mass is more preferable.
  • the content of (Component C) solvent is in the above range, the flatness at the time of application, particularly at the time of application by the liquid-saving coating method is good.
  • (Component D) Polymer having a constitutional unit having a group in which an acid group is protected with an acid-decomposable group The photosensitive resin composition of the present invention is a group in which (Component D) an acid group is protected with an acid-decomposable group
  • the polymer which has a structural unit which has is contained is also referred to as “(a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group”.
  • the photosensitive resin composition of the present invention may further contain a polymer other than a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group.
  • the photosensitive resin composition of the present invention preferably contains a polymer component including a polymer that satisfies at least one of the following (1) and (2). (1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group (2) (a1) an acid group having an acid-decomposable group And (a2) a polymer having a structural unit having a crosslinkable group
  • the photosensitive resin composition of the present invention further contains a polymer other than these. May be.
  • the component D in the present invention means the above (1) and / or (2) unless otherwise specified. It is preferable that the photosensitive resin composition of this invention contains the component which satisfy
  • an acrylic resin having a structural unit having a group in which an acid group is protected with an acid-decomposable group and / or (a2) cross-linking An acrylic resin having a structural unit having a functional group may be contained.
  • it contains a component satisfying the above (2) it has (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group.
  • 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.
  • the acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal group such as an ester structure of a group represented by the formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group).
  • a functional group or a group that is relatively difficult to decompose by an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).
  • the acid-decomposable group a group in which a carboxyl group or a phenolic hydroxyl group is protected in the form of an acetal or a group protected by a tertiary alkyl group is preferably exemplified.
  • 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”
  • 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.
  • Basic properties of the photosensitive resin composition in particular, sensitivity and pattern shape, contact hole formation, photosensitive resin 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 represents a hydrogen atom or an alkyl group, except that R 101 and R 102 are both hydrogen atoms, and R 103 represents an alkyl group.
  • R 101 or R 102 and R 103 may be linked to form a cyclic ether.
  • R 101 to R 103 each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic.
  • 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.
  • the 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 phenylene group
  • R 122 to R 128 each independently represents a hydrogen atom or 1 to 4 carbon atoms. Represents an alkyl group of
  • 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.
  • the divalent linking group of R 221 may be exemplified alkylene groups, specific examples R 221 is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among these, R 221 is preferably a single bond, a methylene group, or an ethylene group.
  • the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.
  • A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production.
  • the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
  • 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.
  • R represents a hydrogen atom or a methyl group.
  • the structural unit (a1) is 20 to 100 mol% in the polymer having the structural unit (a1). It is preferably 30 to 90 mol%.
  • the single structural unit (a1) is sensitive to the polymer having the structural unit (a1) and the structural unit (a2). From this 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.
  • 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.
  • the 3-membered cyclic ether group is also called an epoxy group, and the 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. Examples include acid esters.
  • 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.
  • glycidyl methacrylate 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-ethyl-3-oxetanylmethyl acrylate, and 3-ethyl-3-oxetanyl.
  • Methyl methacrylate 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, and a structural unit having a side chain represented by the following formula (a2-2-1) is still more preferred.
  • R 301 represents a divalent linking group having 1 to 13 carbon atoms
  • R 302 represents a hydrogen atom or a methyl group
  • the wavy line part represents a structural unit having a crosslinkable group ( It represents a site linked to the main chain of a2).
  • R 301 is a divalent linking group having 1 to 13 carbon atoms, and includes an alkenyl group, a cycloalkenyl group, an arylene group, or a combination thereof, and includes an ester bond, an ether bond, an amide bond, a urethane bond, and the like. Bonds may be included.
  • the divalent linking group may have a substituent such as a hydroxy group or a carboxyl group at an arbitrary position. Specific examples of R 301 include the following divalent linking groups.
  • an aliphatic side chain including the divalent linking group represented by R 301 is preferable.
  • 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 a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an 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). Is preferable, and 20 to 80 mol% is more preferable.
  • the polymer having the structural unit (a2) has the structural unit (a1)
  • the single structural unit (a2) has chemical resistance in the polymer having the structural unit (a1) and the structural unit (a2). From this viewpoint, 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.
  • the component D may have another structural unit (a3) in addition to the structural units (a1) and / or (a2). These structural units may be contained in the polymer component (1) and / or (2).
  • the polymer component has another structural unit (a3) substantially free from the structural unit (a1) and the structural unit (a2). It may be.
  • the blending amount of the polymer component is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in all polymer components.
  • 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.
  • any polymer includes a structural unit containing at least an acid group as the other structural unit (a3).
  • -Fifth embodiment- In addition to the polymer component (1) or (2), an embodiment having a polymer having another structural unit (a3) substantially not having the structural unit (a1) and the structural unit (a2). .
  • -Sixth embodiment- A mode comprising a combination of two or more of the first to fifth embodiments.
  • the structural unit (a3) specifically includes styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid.
  • compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.
  • 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 pKa is preferably ⁇ 15 or more.
  • the acid group is usually incorporated into the polymer as a structural unit having an acid group using a monomer capable of forming an acid group. By including such a structural unit having 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 having an acid group used in the present invention is more preferably a structural unit derived from a styrene compound, a structural unit derived from a vinyl compound, (meth) acrylic acid and / or an ester thereof. preferable.
  • 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.
  • 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. 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 molecular weight of the polymer in Component D is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000 in terms of polystyrene-converted weight average molecular weight. 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.
  • radicals used to form at least the structural unit (a1) and the structural unit (a3) can be synthesized by polymerizing a radical polymerizable monomer mixture containing a polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
  • 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 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.
  • the pKa is preferably ⁇ 15 or more.
  • 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.
  • Preferred examples of the oxime sulfonate compound that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following formula (E1).
  • R 21 represents an alkyl group or an aryl group, the wavy line portion represents a bonding site to another group.
  • the alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the alkyl group represented by R 21 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like). It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
  • 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.
  • the above compound containing an oxime sulfonate structure represented by the above formula (E1) is also preferably an oxime sulfonate compound represented by the following formula (E2).
  • R 42 represents an alkyl group or an aryl group
  • X represents an alkyl group, an alkoxy group, or a halogen atom
  • m4 represents an integer of 0 to 3
  • m4 is 2 or 3. In some cases, multiple Xs may be the same or different.
  • the alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • the halogen atom as X is preferably a chlorine atom or a fluorine atom.
  • m4 is preferably 0 or 1. In the above formula (E2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl A compound having a -2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.
  • the compound containing an oxime sulfonate structure represented by the above formula (E1) is also preferably an oxime sulfonate compound represented by the following formula (E3).
  • R 43 has the same meaning as R 42 in the formula (E2).
  • X 1 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and n4 represents an integer of 0 to 5.
  • R 43 in the above formula (E3) is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferred, and an n-octyl group is particularly preferred.
  • X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
  • n4 is preferably an integer of 0 to 2, particularly preferably 0 or 1.
  • Specific examples of the compound represented by the above formula (E3) include ⁇ - (methylsulfonyloxyimino) benzyl cyanide, ⁇ - (ethylsulfonyloxyimino) benzyl cyanide, ⁇ - (n-propylsulfonyloxyimino) Benzyl cyanide, ⁇ - (n-butylsulfonyloxyimino) benzyl cyanide, ⁇ - (4-toluenesulfonyloxyimino) benzyl cyanide, ⁇ -[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, ⁇ -[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, ⁇ -[(n-propylsulfonyloxyimino) -4-methoxyphenyl]
  • oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used alone or in combination of two or more.
  • Compounds (i) to (viii) can be obtained as commercial products. It can also be used in combination with other types of (component E) photoacid generators.
  • the compound containing an oxime sulfonate structure represented by the above formula (E1) is also preferably a compound represented by the following formula (OS-1).
  • R 101 represents a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, aryl group, or hetero Represents an aryl group.
  • R102 represents an alkyl group or an aryl group.
  • X 101 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups. Or an aryl group.
  • R 121 to R 124 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or Represents an aryl group.
  • Two of R 121 to R 124 may be bonded to each other to form a ring.
  • R 121 to R 124 are each independently preferably a hydrogen atom, a halogen atom or an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferable. Can be mentioned. Among these, an embodiment in which R 121 to R 124 are all hydrogen atoms is preferable from the viewpoint of sensitivity. Any of the aforementioned functional groups may further have a substituent.
  • the compound represented by the above formula (OS-1) is more preferably a compound represented by the following formula (OS-2).
  • R 101 , R 102 and R 121 to R 124 have the same meanings as those in the formula (OS-1), and preferred examples thereof are also the same.
  • the formulas (OS-1) and the formula (OS-2) in R 101 is a cyano group, or, more preferably embodiment an aryl group is represented by the above formula (OS-2), R 101
  • the embodiment in which is a cyano group, a phenyl group or a naphthyl group is most preferred.
  • the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
  • the compound having an oxime sulfonate structure represented by the above formula (E1) is represented by the following formula (OS-3), the following formula (OS-4) or the following formula (OS-5). It is preferably an oxime sulfonate compound.
  • R 22 , R 25 and R 28 each independently represents an alkyl group, an aryl group or a heteroaryl group
  • R 23 , R 26 and R 29 are Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom
  • R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxy group.
  • X 1 to X 3 each independently represents an oxygen atom or a sulfur atom
  • n 1 to n 3 each independently represents 1 or 2
  • m 1 to m 3 each independently represents 0 Represents an integer of ⁇ 6)
  • the alkyl group, aryl group or heteroaryl group in R 22 , R 25 and R 28 may have a substituent.
  • the alkyl group in R 22 , R 25 and R 28 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.
  • the aryl group in R 22 , R 25 and R 28 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent. .
  • the heteroaryl group in R 22 , R 25 and R 28 is a heteroaryl group having a total of 4 to 30 carbon atoms which may have a substituent. Is preferred.
  • at least one of the heteroaryl groups in R 22 , R 25 and R 28 may be a heteroaromatic ring, such as a heteroaromatic ring and a benzene ring. And may be condensed.
  • R 23 , R 26 and R 29 are preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
  • one or two of R 23 , R 26 and R 29 present in the compound may be an alkyl group, an aryl group or a halogen atom. More preferably, one is an alkyl group, an aryl group or a halogen atom, more preferably one is an alkyl group and the rest is a hydrogen atom.
  • the alkyl group for R 23 , R 26 and R 29 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.
  • the aryl group for R 23 , R 26 and R 29 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
  • X 1 to X 3 each independently represents O or S, and is preferably O.
  • the ring containing X 1 to X 3 as a ring member is a 5-membered ring or a 6-membered ring.
  • n 1 to n 3 each independently represents 1 or 2, and when X 1 to X 3 are O, n 1 to n 3 are each independently In addition, it is preferably 1, and when X 1 to X 3 are S, n 1 to n 3 are each independently preferably 2.
  • R 24 , R 27 and R 30 each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group.
  • R 24 , R 27 and R 30 are preferably each independently an alkyl group or alkyloxy group.
  • the alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R 24 , R 27 and R 30 may have a substituent.
  • the alkyl group in R 24 , R 27 and R 30 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.
  • the alkyloxy group in R 24 , R 27 and R 30 is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. It is preferable.
  • m 1 to m 3 each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0.
  • substitution of (OS-3) to (OS-5) described in paragraphs 0092 to 0109 of JP2011-221494A The preferred range of groups is likewise preferred.
  • the compound containing an oxime sulfonate structure represented by the above formula (E1) is particularly preferably an oxime sulfonate compound represented by any of the following formulas (OS-6) to (OS-11).
  • R 301 to R 306 represent an alkyl group, an aryl group, or a heteroaryl group
  • R 307 represents a hydrogen atom or a bromine atom
  • R 308 to R 310 , R 313 , R 316 and R 318 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group.
  • R 311 and R 314 each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group
  • R 312 , R 315 , R 317 and R 319 each independently represent a hydrogen atom or a methyl group.
  • oxime sulfonate compounds represented by the above formulas (OS-3) to (OS-5) include the compounds described in paragraphs 0114 to 0120 of JP2011-221494A. The invention is not limited to these.
  • 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 can also use 2 or more types together.
  • thermo crosslinking agent it is preferable that the photosensitive resin composition of the present invention contains a thermal crosslinking agent, if necessary. 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 crosslinking agent is not limited as long as it causes a crosslinking reaction by heat (excluding component D). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing 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.
  • 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 crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A, and compounds having at least one ethylenically unsaturated double bond. It can be preferably used.
  • alkoxymethyl group-containing 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.
  • 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 is aliphatic, alicyclic or aromatic.
  • Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • 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, benzophenone oxime, and acetoxime.
  • 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.
  • Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
  • Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
  • Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
  • Examples of 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 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, phenol 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. These may be used individually by 1 type and may mix 2 or more types. Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO.
  • ADK STAB AO-51 ADK STAB AO-60
  • ADK STAB AO-70 ADK STAB AO-80
  • ADK STAB AO-330 ADK STAB AO-412S
  • ADK STAB AO-503 ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 13510, ADK STAB 3010, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS-90 -91 (above, manufactured by ADEKA Corporation), Irga
  • 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.
  • additives other than antioxidants 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.
  • the photosensitive resin composition of the present invention in addition to the above components, as necessary, (Component H) sensitizer, (Component I) adhesion improver, (Component J) basic compound, (Component K) A surfactant can be preferably added. Furthermore, the photosensitive resin composition of the present invention includes the ultraviolet absorber, metal deactivator, acid multiplier, development accelerator, plasticizer, thermal radical generator, thermal acid generator, thickener, and Known additives such as organic or inorganic suspending agents can be added.
  • the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (Component E) a photoacid generator.
  • the sensitizer absorbs actinic rays or radiation and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur.
  • a photo-acid generator raise
  • Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
  • 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
  • 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 an adhesion improving agent.
  • the adhesion improver that can be used in the photosensitive resin composition of the present invention is an inorganic material serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum, and an insulating film. It is a compound that improves the adhesion. Specific examples include silane coupling agents and thiol compounds. Among these, a silane coupling agent is preferable.
  • 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 adhesion improving agent 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 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 a surfactant.
  • a surfactant any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
  • 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. .
  • fluorine surfactants and silicone surfactants include JP-A Nos. 62-36663, 61-226746, 61-226745, and 62-170950.
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • F-Top manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.
  • MegaFuck manufactured by DIC Corporation
  • Fluorard manufactured by Sumitomo 3M Co., Ltd.
  • Asahi Guard manufactured by Asahi Glass Co., Ltd.
  • Surflon manufactured by AGC Seimi Chemical Co., Ltd.
  • PolyFox manufactured by OMNOVA
  • SH-8400 Toray Dow Corning Co., Ltd.
  • a fluorine-based surfactant or a silicone-based surfactant is preferable, a fluorine-based surfactant is more preferable, a fluorine-based nonionic surfactant is further preferable, and a perfluoro group-containing nonionic surfactant is particularly preferable.
  • the surfactant includes a structural unit A and a structural unit B represented by the following formula (K-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 mass% or more and 90 mass% or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.
  • L is preferably a branched alkylene group represented by the following formula (K-2).
  • R 405 in formula (K-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.
  • the photosensitive resin composition of the present invention may contain an acid proliferating agent 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. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here.
  • the strength of the acid is preferably 3 or less, particularly preferably 2 or less, as the acid dissociation constant, pKa.
  • the pKa is preferably ⁇ 15 or more.
  • Specific examples of the acid proliferating agent include paragraphs 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39, line 12 of JP-A-9-512498. Examples of the compounds described on page 47, line 2 are listed.
  • Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids. Specific examples include the following compounds.
  • the content of the acid proliferating agent in the photosensitive 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 and unexposed parts. It is preferably 20 to 500 parts by mass.
  • the photosensitive resin composition of the present invention may contain a development accelerator.
  • a development accelerator any compound having a development acceleration effect can be used, but a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group is preferable. A compound having a carboxyl group or a phenolic hydroxyl group is more preferred, and a compound having a phenolic hydroxyl group is most preferred.
  • the development accelerator the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
  • 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.
  • 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 composition, from the viewpoint of sensitivity and residual film ratio. 1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
  • the resin composition of the present invention may contain a plasticizer.
  • the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
  • the plasticizer content in the resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component D content. .
  • the 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. it can.
  • 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, methods such as a slit coating method, a spray coating method, a roll coating method, a spin coating method, a casting coating method, and a slit and spin method 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 photosensitive resin composition of the present invention in order to sufficiently exhibit the excellent effect of the photosensitive resin composition of the present invention, it is preferable to apply the photosensitive resin composition of the present invention on a substrate by a liquid-saving coater method, It is more preferable to apply the photosensitive resin composition of the present invention on a substrate by a slit coat method or a spray coat method.
  • Liquid-saving coaters such as slit coat and spray coat greatly reduce the amount of coating solution used, reduce the influence of mist that adheres when using the spin coat method, and suppress foreign matter generation. This is also preferable from a comprehensive viewpoint.
  • the coating conditions by the slit coating method may be appropriately selected depending on the composition of the curable resin composition, the type of coating film to be manufactured, and the like.
  • the lip width at the nozzle tip is preferably 50 to 500 ⁇ m, and the distance between the nozzle tip and the substrate surface is preferably 30 to 300 ⁇ m.
  • the running speed of the lip and the discharge amount of the liquid curable resin composition from the lip may be adjusted.
  • a spray coater used for the spray coat method What is necessary is just to apply a well-known spray coating method and injection apparatus. Specific examples include an ultrasonic spray coating apparatus, a two-fluid spray coating apparatus, and a one-fluid spray coating apparatus.
  • the solvent removal step (2) the solvent is removed from the applied film by vacuum or reduced 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 generate 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, and a crosslinkable group
  • a cured film can be formed by crosslinking with a 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.
  • liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtical Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (OCB). Optical Compensated Bend) method.
  • the cured film of the present invention can also be used in a COA (Color Filter on Allay) 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)
  • OXE-30 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
  • GMA Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MAA Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MMA Methyl methacrylate (Wako Pure Chemical Industries, Ltd.) St: Styrene (Wako Pure Chemical Industries, Ltd.)
  • DCPM Dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
  • V-601 Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
  • PGMEA Propylene glycol monomethyl
  • dispersion D1 A dispersion having the following composition was prepared, mixed with 17,000 parts of zirconia beads (0.3 mm ⁇ ), and dispersed for 12 hours using a paint shaker. Zirconia beads (0.3 mm ⁇ ) were filtered off to obtain dispersion D1.
  • ⁇ Titanium dioxide made by Ishihara Sangyo Co., Ltd., trade name: TTO-51 (C), average primary particle size: 10 to 30 nm
  • Dispersant (DISPERBYK-111: manufactured by Big Chemie Japan Co., Ltd.) 30% PGMEA solution): 2,200 parts / solvent PGMEA: 2,825 parts / solvent EEP: 600 parts
  • Dispersions D2 to D6 were obtained in the same manner as the dispersion D1, except that TTO-51 (C) and DISPERBYK-111 were changed to those shown in Table 1, respectively.
  • TTO-51 (C) and DISPERBYK-111 were changed to those shown in Table 1, respectively.
  • the solvent to be used it changed into EEP and MEDG suitably so that it might match with the solvent composition of the photosensitive resin composition.
  • -Titanium oxide (TiO 2 ) particle pigment (2 types)- TTO-55 (C): Titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd., average primary particle size: 30-50 nm
  • Dispersant 3 types
  • DISPERBYK-111 Dispersant, manufactured by Big Chemie Japan Co., Ltd.
  • DISPERBYK-2001 Dispersant, manufactured by Big Chemie Japan Co., Ltd.
  • Solsperse 41000 Dispersant, manufactured by Lubrizol
  • radical polymerization initiator V-601 (dimethyl 2,2′-azobis (2-methylpropionate)), manufactured by Wako Pure Chemical Industries, Ltd., 12.0 parts) and PGMEA ( 80 parts) was added dropwise over 3.5 hours.
  • the PGMEA solution of polymer P1 was obtained by reacting at 70 ° C. for 2 hours. Further, PGMEA was added to adjust the solid content concentration to 40% by mass.
  • the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained polymer P1 was 15,000. The acid value was 45 mg KOH / g.
  • PGMEA solutions of polymers P2 and P3 were obtained by the same method as polymer P1, except that the monomer composition was changed to the following. Further, PGMEA was added to adjust the solid content concentration to 40% by mass. In addition, about the solvent to be used, it changed into EEP and MEDG suitably so that it might match with the solvent composition of the photosensitive resin composition.
  • Example 1 Preparation of photosensitive resin composition> After mixing and mixing with the following composition to make a uniform solution, the mixture was filtered using a polyethylene filter having a pore size of 0.2 ⁇ m to prepare a photosensitive resin composition of Example 1. Various evaluations described later were performed using the obtained photosensitive resin composition. The evaluation results are shown in Table 3 described later.
  • PGMEA solution of the following compound (Toyo Kasei Kogyo Co., Ltd., CMTU): 25.7 parts-30% PGMEA solution of polymer P1: 263.3 parts-Photoacid generator E-1 (below Compound): 5.1 parts JER157S65 (epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 200 to 220 g / eq): 17.9 parts 3-glycidoxypropyltrimethoxysilane (KBM-403, Shin-Etsu) Chemical Industry Co., Ltd.): 4.5 parts Irganox 1726 (Antioxidant, manufactured by BASF): 3.0 parts Perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC Corporation) ) 2.0% PGMEA solution: 11.0 parts-Dispersion D1: 478.4 parts-Solvent (Solvent type, solvent ratio, amount used and content in Table 3 below give a composition having the desired viscosity) Adjust as appropriate
  • the obtained photosensitive resin composition was applied on a silicon wafer substrate 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.
  • the obtained substrate was observed with the naked eye in the bright room while tilting, and the visibility was evaluated as compared with the case where the photosensitive resin composition was not provided on the ITO pattern.
  • the evaluation criteria are as follows, and it is better that the ITO pattern is less visible. 1 or 2 is a practical range. 1: The ITO line is not visible or almost invisible. 2: The ITO line is slightly visible. 3: The ITO line is clearly visible.
  • Example 2 to 19 and Comparative Examples 1 to 6 In Examples 2 to 19 and Comparative Examples 1 to 6, the dispersion, the polymer, the solvent, and / or the photosensitivity were the same as in Example 1 except that the coating methods were changed to those shown in Table 3, respectively. Resin compositions were prepared and evaluated. The evaluation results are shown in Table 3. Comparative Examples 2 and 3 were prepared by changing all the solvents in the dispersion D1 to EEP or MEDG.
  • solvent content A having a boiling point of 160 ° C. or higher in Table 3 above represents the content of a solvent having a boiling point of 160 ° C. or higher relative to the total amount of solvent in the photosensitive resin composition.
  • Content B represents the content of a solvent having a boiling point of 160 ° C or higher with respect to the total mass of the photosensitive resin composition.
  • Example 20 In the active matrix type liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 20 was obtained. That is, the photosensitive resin composition of Example 3 was slit-coated on a substrate, pre-baked (90 ° C./120 seconds) on a hot plate, and then i-line (365 nm) was 45 mJ / mm using a high-pressure mercury lamp from above the mask.
  • 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 21 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 planarization film 4 is formed on the insulating film 3 by slit coating the photosensitive resin composition of Example 12 on the 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 12 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 22 A touch panel display device was prepared using the high refractive index photosensitive resin composition of the present invention by the method described below.
  • ⁇ Formation of first transparent electrode pattern> [Formation of transparent electrode layer]
  • a formed 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.
  • the distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the etching resist layer is set to 100 ⁇ m, pattern exposure is performed at an exposure amount of 50 mJ / cm 2 (i-line), and then a dedicated developer And a post-bake treatment at 130 ° C. for 30 minutes 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 an 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 using a commercially available etching resist, the first transparent electrode pattern, an insulating layer pattern formed using the photosensitive resin composition of Example 1, a transparent electrode layer, A front plate on which an etching resist pattern was formed was obtained (post-baking treatment; 130 ° C. for 30 minutes). Further, etching was performed in the same manner as the formation of the first transparent electrode pattern, and the etching resist layer was removed to form the mask layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. A front plate on which an insulating layer pattern and a second transparent electrode pattern were formed was 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 flattening film
  • 5 first electrode
  • 6 glass substrate
  • 7 contact hole
  • 8 insulating film
  • 10 liquid crystal display device
  • 12 Backlight unit
  • 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
  • 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

Abstract

The purpose of the present invention is to provide a photosensitive resin composition which has high refractive index, while exhibiting excellent coatability in cases where the photosensitive resin composition is coated by a liquid-saving coating method such as a slit coating method or a spray coating method. A photosensitive resin composition of the present invention is characterized by containing: (component A) inorganic particles; (component B) a dispersant; (component C) a solvent; (component D) a polymer which contains a constituent unit that has a group wherein an acid group is protected by an acid-decomposable group; and (component E) a photoacid generator. This photosensitive resin composition is also characterized in that the component (C) contains a solvent having a boiling point of 160°C or more and the content of the solvent having a boiling point of 160°C or more is from 3% by mass to 40% by mass (inclusive) relative to the total solvent content in the photosensitive resin composition.

Description

感光性樹脂組成物、硬化物及びその製造方法、樹脂パターン製造方法、硬化膜、有機ＥＬ表示装置、液晶表示装置、並びに、タッチパネル表示装置Photosensitive resin composition, cured product and method for producing the same, resin pattern production method, cured film, organic EL display device, liquid crystal display device, and touch panel display device
　本発明は、感光性樹脂組成物（以下、単に、「本発明の組成物」ということがある。）に関する。また、上記感光性樹脂組成物を硬化してなる硬化物及びその製造方法、上記感光性樹脂組成物を用いた樹脂パターン製造方法の製造方法、上記感光性組成物を硬化してなる硬化膜、並びに、上記硬化膜を用いた各種画像表示装置に関する。
　更に詳しくは、液晶表示装置、有機ＥＬ表示装置、タッチパネル表示装置、集積回路素子、固体撮像素子などの電子部品の平坦化膜、保護膜や層間絶縁膜の形成に好適な、感光性樹脂組成物及びそれを用いた硬化膜の製造方法に関する。 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 production method of a resin pattern production method using the photosensitive resin composition, a cured film obtained by curing the photosensitive composition, In addition, 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 or an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, a touch panel display device, an integrated circuit element, and a solid-state imaging element. And a method for producing a cured film using the same.
　固体撮像素子や液晶表示装置の発達により、有機素材（樹脂）によりマイクロレンズ、光導波路、反射防止膜などの光学部材を作製することが広く行われるようになっている。
　これら光学部材は、高屈折率にするために、酸化チタンなどの粒子を添加することが検討されている（下記特許文献１参照）。
　また、従来の感光性樹脂組成物としては、特許文献２～４に記載のネガ型感光性樹脂組成物が知られている。 With the development of solid-state imaging devices and liquid crystal display devices, it has become widely practiced to produce optical members such as microlenses, optical waveguides, and antireflection films using organic materials (resins).
In order to make these optical members have a high refractive index, it has been studied to add particles such as titanium oxide (see Patent Document 1 below).
Further, as conventional photosensitive resin compositions, negative photosensitive resin compositions described in Patent Documents 2 to 4 are known.
特開２００６－９８９８５号公報JP 2006-98985 A 特開２０１１－１２７０９６号公報JP 2011-127096 A 特開２００９－１７９６７８号公報JP 2009-179678 A 特開２００８－１８５６８３号公報JP 2008-185683 A
　スリットコーター、スプレーコーターなどの省液コーターを用いた塗布方法を採用した場合、スピンコート方式であれば塗布ムラがなく均一に塗布可能なレジストであっても、スリットコート塗布に使用すると、吐出流量の不均一や、スリットの刃先の形状の不均一に起因して、幅方向の塗布が不均一になり、筋状の膜状ムラを生じるという問題があった。また、薄膜でスリットコート塗布する際は、更に液切れという問題も生じる。
　また、塗布枚数を重ねることにより、コーターノズルやスリット刃先の先端は、湿潤、乾燥を繰り返す。粒子を分散させたレジストがコーターノズルやスリット刃先の先端で乾燥すると、固形分濃度が急激に増加し、凝集塊が発生する場合がある。これらの凝集塊により、吐出流量の不均一が生じ、筋状のムラとなる。更に、この凝集塊がコーターノズルやスリット刃先に先端に付着し、再度レジストを吐出した際にノズルの先端から剥離して基板上に移動する。これら凝集塊は、その後の工程では容易に除去されず、最後まで基板上に残留する。このような凝集塊は、欠陥となり、品質不良の原因となる。この不良現象が頻発すると製品の歩留りが低下する。 When a coating method using a liquid-saving coater such as a slit coater or spray coater is adopted, even if the resist can be applied uniformly without coating unevenness if it is a spin coat method, the discharge flow rate when used for slit coat coating Due to the non-uniformity and the non-uniformity of the shape of the blade edge of the slit, there is a problem that the application in the width direction becomes non-uniform, resulting in streaky film-like unevenness. Further, when the slit coat is applied with a thin film, the problem of running out of liquid also occurs.
Further, by repeating the coating number, the tip of the coater nozzle and the slit blade edge repeats wet and dry. When the resist in which the particles are dispersed is dried at the tip of the coater nozzle or the slit blade edge, the solid content concentration may rapidly increase and aggregates may be generated. Due to these agglomerates, the discharge flow rate is non-uniform, resulting in streaky irregularities. Furthermore, this agglomerate adheres to the tip of the coater nozzle or slit blade edge, and when the resist is discharged again, it peels off from the tip of the nozzle and moves onto the substrate. These agglomerates are not easily removed in the subsequent process and remain on the substrate until the end. Such agglomerates become defects and cause quality defects. If this defect phenomenon occurs frequently, the yield of the product decreases.
　本発明は、スリットコート及びスプレーコート等の省液コート法で塗布した際における塗布性に優れ、高屈折率である感光性樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a photosensitive resin composition that is excellent in applicability when applied by a liquid-saving coating method such as slit coating and spray coating, and has a high refractive index.
　本発明の上記課題は、以下の＜１＞、＜１１＞～＜１４＞又は＜１６＞～＜１８＞に記載の手段により解決された。好ましい実施態様である＜２＞～＜１０＞及び＜１５＞とともに以下に記載する。
　＜１＞（成分Ａ）無機粒子、（成分Ｂ）分散剤、（成分Ｃ）溶剤、（成分Ｄ）酸基が酸分解性基で保護された基を有する構成単位を含む重合体、及び、（成分Ｅ）光酸発生剤を含有し、成分Ｃが、沸点１６０℃以上の溶剤を含み、上記沸点１６０℃以上の溶剤の含有量が、感光性樹脂組成物中の全溶剤量に対し、３質量％以上４０質量％以下であることを特徴とする感光性樹脂組成物、
　＜２＞成分Ｃが、プロピレングリコールモノメチルエーテルアセテート、３－エトキシプロピオン酸エチル、及び／又は、ジエチレングリコールエチルメチルエーテルを含む、上記＜１＞に記載の感光性樹脂組成物、
　＜３＞成分Ｃが、沸点１６０℃未満の溶剤としてプロピレングリコールモノメチルエーテルアセテートと、沸点１６０℃以上の溶剤として３－エトキシプロピオン酸エチル及び／又はジエチレングリコールエチルメチルエーテルとを含む、上記＜１＞又は＜２＞に記載の感光性樹脂組成物、
　＜４＞成分Ｃの含有量が、７０質量％以上９５質量％以下である、上記＜１＞～＜３＞のいずれか１つに記載の感光性樹脂組成物、
　＜５＞粘度が、１５ｍＰａ・ｓ以下である、上記＜１＞～＜４＞のいずれか１つに記載の感光性樹脂組成物、
　＜６＞成分Ａが、金属酸化物粒子である、上記＜１＞～＜５＞のいずれか１つに記載の感光性樹脂組成物、
　＜７＞成分Ａが、酸化チタン粒子又は酸化ジルコニウム粒子である、上記＜１＞～＜６＞のいずれか１つに記載の感光性樹脂組成物、
　＜８＞上記酸基が酸分解性基で保護された基を有する構成単位が、下記式で表される構成単位である、上記＜１＞～＜７＞のいずれか１つに記載の感光性樹脂組成物、 The above-described problems of the present invention have been solved by means described in the following <1>, <11> to <14>, or <16> to <18>. It is described below together with <2> to <10> and <15> which are preferred embodiments.
<1> (Component A) inorganic particles, (Component B) dispersant, (Component C) solvent, (Component D) a polymer containing a structural unit having a group in which an acid group is protected with an acid-decomposable group, and (Component E) containing a photoacid generator, Component C contains a solvent having a boiling point of 160 ° C. or higher, and the content of the solvent having a boiling point of 160 ° C. or higher is based on the total amount of solvent in the photosensitive resin composition. 3 to 40% by weight of a photosensitive resin composition,
<2> The photosensitive resin composition according to the above <1>, wherein component C comprises propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and / or diethylene glycol ethyl methyl ether,
<3> The above <1>, wherein component C comprises propylene glycol monomethyl ether acetate as a solvent having a boiling point of less than 160 ° C. and ethyl 3-ethoxypropionate and / or diethylene glycol ethyl methyl ether as a solvent having a boiling point of 160 ° C. or higher <2> photosensitive resin composition,
<4> The photosensitive resin composition according to any one of the above <1> to <3>, wherein the content of component C is 70% by mass or more and 95% by mass or less,
<5> The photosensitive resin composition according to any one of the above <1> to <4>, wherein the viscosity is 15 mPa · s or less,
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the component A is metal oxide particles,
<7> The photosensitive resin composition according to any one of the above <1> to <6>, wherein the component A is titanium oxide particles or zirconium oxide particles,
<8> The photosensitive composition according to any one of <1> to <7>, wherein the structural unit having a group in which the acid group is protected with an acid-decomposable group is a structural unit represented by the following formula: Functional resin composition,
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ121は水素原子又は炭素数１～４のアルキル基を表し、Ｌ1はカルボニル基又はフェニレン基を表し、Ｒ122～Ｒ128はそれぞれ独立に、水素原子又は炭素数１～４のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000002
 Wherein R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 1 represents a carbonyl group or a phenylene group, and R 122 to R 128 each independently represents a hydrogen atom or 1 to 4 carbon atoms. Represents an alkyl group of
　＜９＞（成分Ｆ）熱架橋剤を更に含む、上記＜１＞～＜８＞のいずれか１つに記載の感光性樹脂組成物、
　＜１０＞（成分Ｇ）酸化防止剤を更に含む、上記＜１＞～＜９＞のいずれか１つに記載の感光性樹脂組成物、
　＜１１＞少なくとも工程（ａ）～（ｃ）をこの順に含むことを特徴とする硬化物の製造方法、
　（ａ）上記＜１＞～＜１０＞のいずれか１つに記載の感光性樹脂組成物を基板上に塗布する塗布工程
　（ｂ）塗布された樹脂組成物から溶剤を除去する溶剤除去工程
　（ｃ）溶剤が除去された樹脂組成物を熱処理する熱処理工程
　＜１２＞少なくとも工程（１）～（５）をこの順に含むことを特徴とする樹脂パターン製造方法、
　（１）上記＜１＞～＜１０＞のいずれか１つに記載の感光性樹脂組成物を基板上に塗布する塗布工程
　（２）塗布された樹脂組成物から溶剤を除去する溶剤除去工程
　（３）溶剤が除去された樹脂組成物を活性光線によりパターン状に露光する露光工程
　（４）露光された樹脂組成物を水性現像液により現像する現像工程
　（５）現像された樹脂組成物を熱処理する熱処理工程
　＜１３＞上記＜１１＞に記載の硬化物の製造方法、又は、上記＜１２＞に記載の樹脂パターン製造方法により得られた硬化物、
　＜１４＞上記＜１＞～＜１０＞のいずれか１つに記載の感光性樹脂組成物を硬化してなる硬化膜、
　＜１５＞層間絶縁膜である、上記＜１４＞に記載の硬化膜、
　＜１６＞上記＜１４＞又は＜１５＞に記載の硬化膜を有する液晶表示装置、
　＜１７＞上記＜１４＞又は＜１５＞に記載の硬化膜を有する有機ＥＬ表示装置、
　＜１８＞上記＜１４＞又は＜１５＞に記載の硬化膜を有するタッチパネル表示装置。 <9> (Component F) The photosensitive resin composition according to any one of <1> to <8>, further including a thermal crosslinking agent,
<10> (Component G) The photosensitive resin composition according to any one of <1> to <9>, further including an antioxidant,
<11> 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 the above <1> to <10> on a substrate (b) Solvent removal step of removing the solvent from the applied resin composition ( c) a heat treatment step of heat-treating the resin composition from which the solvent has been removed <12> 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 the above <1> to <10> onto 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 in a pattern with actinic rays. (4) A development step in which the exposed resin composition is developed with an aqueous developer. (5) The developed resin composition is heat-treated. Heat treatment step <13> A cured product obtained by the method for producing a cured product according to <11> or the resin pattern production method according to <12>,
<14> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <10> above,
<15> The cured film according to <14>, which is an interlayer insulating film,
<16> A liquid crystal display device having the cured film according to <14> or <15> above,
<17> An organic EL display device having the cured film according to <14> or <15> above,
<18> A touch panel display device having the cured film according to <14> or <15>.
　本発明によれば、スリットコート及びスプレーコート等の省液コート法で塗布した際における塗布性に優れ、高屈折率である感光性樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a photosensitive resin composition that is excellent in applicability when applied by a liquid-saving coating method such as slit coating and spray coating and has a high refractive index.
液晶表示装置の一例の構成概念図を示す。液晶表示装置におけるアクティブマトリックス基板の模式的断面図を示し、層間絶縁膜である硬化膜１７を有している。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. 有機ＥＬ表示装置の一例の構成概念図を示す。ボトムエミッション型の有機ＥＬ表示装置における基板の模式的断面図を示し、平坦化膜４を有している。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. 静電容量型入力装置の構成を示す断面図である。It is sectional drawing which shows the structure of an electrostatic capacitance type input device. 前面板の一例を示す説明図である。It is explanatory drawing which shows an example of a front plate. 第一の透明電極パターン及び第二の透明電極パターンの一例を示す説明図である。It is explanatory drawing which shows an example of a 1st transparent electrode pattern and a 2nd transparent electrode pattern.
　以下において、本発明の内容について詳細に説明する。以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
　なお、本発明において、数値範囲を表す「下限～上限」の記載は、「下限以上、上限以下」を表し、「上限～下限」の記載は、「上限以下、下限以上」を表す。すなわち、上限及び下限を含む数値範囲を表す。
　また、本発明において、「（成分Ａ）無機粒子」等を、単に「成分Ａ」等ともいい、後述する「（ａ１）酸基が酸分解性基で保護された基を有する構成単位」等を、単に「構成単位（ａ１）」等ともいう。
　更に、本明細書における基（原子団）の表記において、置換及び無置換を記していない表記は置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　また、本発明において、「質量％」と「重量％」とは同義であり、「質量部」と「重量部」とは同義である。
　また、本発明において、２以上の好ましい態様の組み合わせはより好ましい。 Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present invention, the description of “lower limit to upper limit” representing a numerical range represents “lower limit or higher and lower limit or lower”, and the description of “upper limit to lower limit” represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit.
In the present invention, “(component A) inorganic particles” or the like is also simply referred to as “component A” or the like, and “(a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group” and the like described later. Is also simply referred to as “structural unit (a1)”.
Furthermore, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, 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).
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present invention, a combination of two or more preferred embodiments is more preferred.
（感光性樹脂組成物）
　本発明の感光性樹脂組成物（以下、単に「樹脂組成物」ともいう。）は、（成分Ａ）無機粒子、（成分Ｂ）分散剤、（成分Ｃ）溶剤、（成分Ｄ）酸基が酸分解性基で保護された基を有する構成単位を含む重合体、及び、（成分Ｅ）光酸発生剤を含有し、成分Ｃが、沸点１６０℃以上の溶剤を含み、上記沸点１６０℃以上の溶剤の含有量が、感光性樹脂組成物中の全溶剤量に対し、３質量％以上４０質量％以下であることを特徴とする。 (Photosensitive resin composition)
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. A polymer containing a structural unit having a group protected by an acid-decomposable group, and (Component E) a photoacid generator, Component C contains a solvent having a boiling point of 160 ° C. or higher, and the boiling point of 160 ° C. or higher. The content of the solvent is 3% by mass or more and 40% by mass or less based on the total amount of the solvent in the photosensitive resin composition.
　本発明の感光性樹脂組成物は、ポジ型レジスト組成物として好適に用いることができる。
　本発明の感光性樹脂組成物は、熱で硬化する性質を有する樹脂組成物であることが好ましい。
　また、本発明の感光性樹脂組成物は、省液コート用感光性樹脂組成物であることが好ましく、スリットコート又はスプレーコート用感光性樹脂組成物であることがより好ましい。
　また、本発明の感光性樹脂組成物は、ポジ型感光性樹脂組成物であることが好ましく、化学増幅型のポジ型感光性樹脂組成物（化学増幅ポジ型感光性樹脂組成物）であることがより好ましい。
　本発明の感光性樹脂組成物は、活性光線に感応する光酸発生剤として１，２－キノンジアジド化合物を含まない方が好ましい。１，２－キノンジアジド化合物は、逐次型光化学反応によりカルボキシ基を生成するが、その量子収率は必ず１以下である。
　これに対して、本発明で使用する（成分Ｅ）光酸発生剤は、活性光線に感応して生成される酸が、成分Ｄ中の保護された酸基の脱保護に対して触媒として作用するので、１個の光量子の作用で生成した酸が、多数の脱保護反応に寄与し、量子収率は１を超え、例えば、１０の数乗のような大きい値となり、いわゆる化学増幅の結果として、高感度が得られる。 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.
In addition, the photosensitive resin composition of the present invention is preferably a liquid-saving coating photosensitive resin composition, and more preferably a slit coating or spray coating photosensitive resin composition.
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 carboxy group by a sequential photochemical reaction, but its quantum yield is always 1 or less.
On the other hand, (Component E) photoacid generator used in the present invention is such that an acid generated in response to actinic rays acts as a catalyst for deprotection of protected acid groups in Component D. Therefore, the acid generated by the action of one photon contributes to a number of 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.
　更に、本発明の感光性樹脂組成物は、マイクロレンズ、光導波路、反射防止膜、ＬＥＤ用封止材及びＬＥＤ用チップコート材等の光学部材用樹脂組成物、又は、タッチパネルに使用される配線電極の視認性低減用樹脂組成物であることが好ましい。なお、タッチパネルに使用される配線電極の視認性低減用組成物とは、タッチパネルに使用される配線電極の視認性を低減する、すなわち、配線電極を見えにくくする部材用組成物であり、例えば、ＩＴＯ（酸化インジウムスズ）電極間の層間絶縁膜などが挙げられ、本発明の感光性樹脂組成物は、当該用途に好適に使用することができる。 Furthermore, 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. In addition, 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.
　一般的に化学増幅ポジ型感光性樹脂組成物は、露光すると光酸発生剤との作用により、含有されるポリマーが有する脱離基が外れて、現像液に溶解し、未露光部がパターンとして形成される。
　無機粒子、分散剤及び脱離基を含むポリマーを含有する樹脂組成物をポジ型感光性樹脂組成物として使用する場合、無機粒子の分散性が非常に重要で、分散が上手くいかないと、平均粒子径が小さくならず、大きすぎたり、凝集粒子が生じたり、粗大粒子が、粉砕されず残り、最終的に感光性樹脂組成物を塗布したときに透明性に劣ってしまう問題がある。一方、分散液と感光性樹脂組成物中のバインダーとの相溶性も重要で、組み合わせが悪いと液ににごりを生じてしまう。
　本発明者は詳細な検討の結果、成分Ａ～成分Ｅを含有する感光性樹脂組成物とすることにより、スリットコート及びスプレーコート等の省液コート法で塗布した際における塗布スジやムラが少なく塗布性に優れ、ノズルの目詰まり及びノズルやスリット刃先の先端での凝集塊の発生が少なく経時での塗布性に優れ、高屈折率である感光性樹脂組成物が得られることを見いだした。
　以下、本発明の感光性樹脂組成物について詳細に説明する。 In general, 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.
When a resin composition containing inorganic particles, a dispersant and a polymer containing a leaving group is used as a positive photosensitive resin composition, the dispersibility of the inorganic particles is very important, and if the dispersion is not good, the average There is a problem that the particle size is not reduced, too large, aggregated particles are generated, coarse particles remain without being pulverized, and finally the transparency is inferior when the photosensitive resin composition is applied. On the other hand, the compatibility between the dispersion liquid and the binder in the photosensitive resin composition is also important.
As a result of detailed studies, the present inventors have made a photosensitive resin composition containing component A to component E, so that there are few coating stripes and unevenness when applied by a liquid-saving coating method such as slit coating and spray coating. It has been found that a photosensitive resin composition having excellent coating properties, clogging of nozzles and generation of agglomerates at the tips of nozzles and slit blade tips, excellent coating properties over time, and a high refractive index can be obtained.
Hereinafter, the photosensitive resin composition of the present invention will be described in detail.
　本発明の感光性樹脂組成物の２５℃における粘度は、塗布適性向上の観点から、５０ｍＰａ・ｓ以下であることが好ましく、４０ｍＰａ・ｓ以下であることがより好ましい。また、上記粘度が、１ｍＰａ・ｓ以上であることが好ましい。なお、本発明における感光性樹脂組成物の２５℃における粘度は、２５℃においてＥ型粘度計を使用して測定した値である。
　また、スプレー塗布では、スプレー塗布時のノズル詰まりがないという観点から、スプレー塗布時における本発明の感光性樹脂組成物の２５℃における粘度は、１５ｍＰａ・ｓ以下であることが好ましく、１～１５ｍＰａ・ｓであることがより好ましく、２～１０ｍＰａ・ｓであることが更に好ましい。 The viscosity at 25 ° C. of the photosensitive resin composition of the present invention is preferably 50 mPa · s or less, and more preferably 40 mPa · s or less, from the viewpoint of improving coating suitability. Moreover, it is preferable that the said viscosity is 1 mPa * s or more. The viscosity at 25 ° C. of the photosensitive resin composition in the present invention is a value measured using an E-type viscometer at 25 ° C.
In spray coating, from the viewpoint that nozzle clogging during spray coating does not occur, the viscosity at 25 ° C. of the photosensitive resin composition of the present invention during spray coating is preferably 15 mPa · s or less, and preferably 1 to 15 mPa · s. S is more preferable, and 2 to 10 mPa · s is still more preferable.
（成分Ａ）無機粒子
　本発明の樹脂組成物は、屈折率や光透過性を調節することを目的として、無機粒子を含有する。
　成分Ａは、当該粒子を除いた材料からなる樹脂組成物の屈折率より屈折率が高いものであることが好ましく、具体的には、４００～７５０ｎｍの波長を有する光における屈折率が１．５０以上の粒子がより好ましく、屈折率が１．７０以上の粒子が更に好ましく、屈折率が１．９０以上の粒子が特に好ましい。また、屈折率が５．００以下であることが好ましい。
　ここで、４００～７５０ｎｍの波長を有する光における屈折率が１．５０以上であるとは、上記範囲の波長を有する光における平均屈折率が１．５０以上であることを意味し、上記範囲の波長を有する全ての光における屈折率が１．５０以上であることを要しない。また、平均屈折率は、上記範囲の波長を有する各光に対する屈折率の測定値の総和を、測定点の数で割った値である。 (Component A) Inorganic Particles The resin composition of the present invention contains inorganic particles for the purpose of adjusting the refractive index and light transmittance.
Component A preferably has a refractive index higher than that of the resin composition made of a material excluding the particles. Specifically, the refractive index in light having a wavelength of 400 to 750 nm is 1.50. The above particles are more preferable, particles having a refractive index of 1.70 or more are more preferable, and particles having a refractive index of 1.90 or more are particularly preferable. Moreover, it is preferable that a refractive index is 5.00 or less.
Here, 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.
　このような高い屈折率を有する無機粒子としては、金属酸化物粒子が好ましい。金属酸化物粒子は、透明性が高く、光透過性を有するため、高屈折率で、透明性に優れた感光性樹脂組成物が容易に得られる。
　なお、本発明における金属酸化物粒子の金属には、Ｂ、Ｓｉ、Ｇｅ、Ａｓ、Ｓｂ、Ｔｅ等の半金属も含まれるものとする。
　光透過性で屈折率の高い金属酸化物粒子としては、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｇｄ、Ｔｂ、Ｄｙ、Ｙｂ、Ｌｕ、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｍｏ、Ｗ、Ｚｎ、Ｂ、Ａｌ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｓｂ、Ｂｉ、Ｔｅ等の原子を含む酸化物粒子が好ましく、酸化チタン、チタン複合酸化物、酸化亜鉛、酸化ジルコニウム、インジウム／スズ酸化物、アンチモン／スズ酸化物がより好ましく、酸化チタン、チタン複合酸化物、酸化ジルコニウムが更に好ましく、酸化チタン、酸化ジルコニウムが特に好ましく、酸化チタンが最も好ましい。酸化チタンとしては、特に屈折率の高いルチル型が好ましい。これら金属酸化物粒子は、分散安定性付与のために表面を有機材料で処理することもできる。 As the inorganic particles having such a high refractive index, metal oxide particles are preferable. Since the metal oxide particles have high transparency and light transmittance, a photosensitive resin composition having a high refractive index and excellent transparency can be easily obtained.
Note that the metal of the metal oxide particles in the present invention includes semimetals such as B, Si, Ge, As, Sb, and Te.
The light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb. Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable. Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferable, titanium oxide, titanium composite oxide and zirconium oxide are more preferable, titanium oxide and zirconium oxide are particularly preferable, and titanium oxide is most preferable. Titanium oxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.
　樹脂組成物の透明性の観点から、成分Ａの平均一次粒子径は、１～２００ｎｍが好ましく、３～８０ｎｍが特に好ましい。ここで粒子の平均一次粒子径は、電子顕微鏡により任意の粒子２００個の粒子径を測定し、その算術平均をいう。また、粒子の形状が球形でない場合には、最も長い辺を径とする。 From the viewpoint of the transparency of the resin composition, the average primary particle size of component A is preferably 1 to 200 nm, particularly preferably 3 to 80 nm. Here, the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.
　また、成分Ａは、１種単独で使用してもよいし、２種以上を併用することもできる。
　本発明の樹脂組成物における成分Ａの含有量は、樹脂組成物により得られる光学部材に要求される屈折率や、光透過性等を考慮して、適宜決定すればよいが、本発明の樹脂組成物の全固形分に対して、５～８０質量％とすることが好ましく、１０～７０質量％とすることがより好ましい。なお、感光性樹脂組成物の固形分量とは、溶剤などの揮発性成分を除いた量を表す。 Moreover, the 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 and light transmittance required for an optical member obtained from the resin composition. The content is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the total solid content of the composition. In addition, the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.
　本発明において、無機粒子は、後述する（成分Ｂ）分散剤及び溶媒中でボールミル、ロッドミル等の混合装置を用いて混合・分散することにより調製された分散液として使用に供することもできる。
　上記分散液の調製に使用される溶媒としては、例えば、後述する（成分Ｃ）溶剤のほか、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、２－メチル－２－プロパノール、１－ペンタノール、２－ペンタノール、３－ペンタノール、３－メチル－１－ブタノール、２－メチル－２－ブタノール、ネオペンタノール、シクロペンタノール、１－ヘキサノール、シクロヘキサノール等のアルコール類等を挙げることができる。
　これらの溶媒は、１種単独又は２種以上を混合して使用することができる。 In the present invention, the inorganic particles can also be used as a dispersion prepared by mixing and dispersing using a mixing device such as a ball mill or a rod mill in the component (B), which will be described later, and a solvent.
Examples of the solvent used in the preparation of the dispersion include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, in addition to the (Component C) solvent described below. -Alcohols such as pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, neopentanol, cyclopentanol, 1-hexanol, cyclohexanol, etc. Can be mentioned.
These solvent can be used individually by 1 type or in mixture of 2 or more types.
（成分Ｂ）分散剤
　本発明の感光性樹脂組成物は、（成分Ｂ）分散剤を含有する。分散剤を含有することにより、成分Ａの樹脂組成物中での分散性をより向上させることができる。
　分散剤としては、公知の分散剤を用いることができ、例えば、公知の顔料分散剤を適宜選択して用いることができる。
　また、分散剤としては、高分子分散剤を好ましく用いることができる。なお、高分子分散剤とは、分子量（重量平均分子量）が１，０００以上の分散剤である。また、高分子分散剤は、重量平均分子量が、１，０００以上１，０００，０００以下であることが好ましい。 (Component B) Dispersant The photosensitive resin composition of the present invention contains (Component B) a dispersant. By containing a dispersing agent, the dispersibility in the resin composition of the component A can be improved more.
As the dispersant, a known dispersant can be used. For example, a known pigment dispersant can be appropriately selected and used.
As the dispersant, 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 polymer dispersant preferably has a weight average molecular weight of 1,000 or more and 1,000,000 or less.
　分散剤としては、多くの種類の化合物を使用可能であり、具体的には、例えば、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、（メタ）アクリル酸系（共）重合体ポリフローＮｏ．７５、Ｎｏ．９０、Ｎｏ．９５（共栄社化学（株）製）、Ｗ００１（裕商（株）製）等のカチオン系界面活性剤；ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル等のノニオン系界面活性剤；Ｗ００４、Ｗ００５、Ｗ０１７（裕商（株）製）等のアニオン系界面活性剤；ＥＦＫＡ－４６、ＥＦＫＡ－４７、ＥＦＫＡ－４７ＥＡ、ＥＦＫＡポリマー１００、ＥＦＫＡポリマー４００、ＥＦＫＡポリマー４０１、ＥＦＫＡポリマー４５０（いずれもチバ・スペシャルティ・ケミカルズ社製）、ディスパースエイド６、ディスパースエイド８、ディスパースエイド１５、ディスパースエイド９１００（いずれもサンノプコ（株）製）等の高分子分散剤；ソルスパース３０００、５０００、９０００、１２０００、１３２４０、１３９４０、１７０００、２４０００、２６０００、２８０００などの各種ソルスパース分散剤（アストラゼネカ（株）製）；アデカプルロニックＬ３１，Ｆ３８，Ｌ４２，Ｌ４４，Ｌ６１，Ｌ６４，Ｆ６８，Ｌ７２，Ｐ９５，Ｆ７７，Ｐ８４，Ｆ８７、Ｐ９４，Ｌ１０１，Ｐ１０３，Ｆ１０８、Ｌ１２１、Ｐ－１２３（ＡＤＥＫＡ（株）製）及びイソネットＳ－２０（三洋化成工業（株）製）、ＤＩＳＰＥＲＢＹＫ　１０１，１０３，１０６，１０８，１０９，１１１，１１２，１１６，１３０，１４０，１４２，１６２，１６３，１６４，１６６，１６７，１７０，１７１，１７４，１７６，１８０，１８２，２０００，２００１，２０５０，２１５０（ビックケミー社製）が挙げられる。その他、アクリル系共重合体など、分子末端又は側鎖に極性基を有するオリゴマー又はポリマーが挙げられる。 As the dispersant, many types of compounds can be used. Specifically, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. . 75, no. 90, no. 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, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000 , 26000, 28000, and the like (manufactured by AstraZeneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103 , F108, L121, P-123 (manufactured by ADEKA) and ISONET S-20 (manufactured by Sanyo Chemical Industries), DISPERBYK 101, 103, 106, 108, 109, 111, 112, 116, 130, 140 , 14 , It includes the 162,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (manufactured by BYK-Chemie GmbH). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.
　分散剤は、１種単独で使用しても、２種以上併用してもよい。
　本発明の感光性樹脂組成物における分散剤の含有量は、感光性樹脂組成物の全固形分に対して、５～７０質量％の範囲が好ましく、１０～５０質量％の範囲がより好ましい。 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.
（成分Ｃ）溶剤
　本発明の感光性樹脂組成物は、（成分Ｃ）溶剤を含有する。
　また、本発明の感光性樹脂組成物において、（成分Ｃ）溶剤は、沸点１６０℃以上の溶剤を含み、上記沸点１６０℃以上の溶剤の含有量が、感光性樹脂組成物中の全溶剤量に対し、３質量％以上４０質量％以下である。沸点が１６０℃以上の溶剤を上記含有量で含むことにより、溶剤の乾燥が抑制され、スリットコート及びスプレーコート等の省液コート法で塗布した際における塗布スジやムラが少なく塗布性に優れ、ノズルの目詰まり及びノズルやスリット刃先の先端での凝集塊の発生が少なく経時での塗布性に優れる。なお、本発明における「沸点」とは、標準沸点、すなわち、１気圧における沸点である。
　また、（成分Ｃ）溶剤は、沸点２５０℃以下の溶剤であることが好ましい。
　本発明の感光性樹脂組成物は、本発明の必須成分と、更に後述の任意の成分を（成分Ｃ）溶剤に溶解及び／又は分散した液として調製されることが好ましい。
　本発明の感光性樹脂組成物に使用される溶剤としては、公知の溶剤を用いることができ、エチレングリコールモノアルキルエーテル類、エチレングリコールジアルキルエーテル類、エチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールジアルキルエーテル類、プロピレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジアルキルエーテル類、ジエチレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノアルキルエーテル類、ジプロピレングリコールジアルキルエーテル類、ジプロピレングリコールモノアルキルエーテルアセテート類、エステル類、ケトン類、アミド類、ラクトン類等が例示できる。また、本発明の感光性樹脂組成物に使用される溶剤の具体例としては特開２０１１－２２１４９４号公報の段落０１７４～０１７８に記載の溶剤も挙げられる。 (Component C) Solvent The photosensitive resin composition of the present invention contains (Component C) a solvent.
In the photosensitive resin composition of the present invention, the (component C) solvent contains a solvent having a boiling point of 160 ° C. or higher, and the content of the solvent having a boiling point of 160 ° C. or higher is the total solvent amount in the photosensitive resin composition. On the other hand, it is 3 mass% or more and 40 mass% or less. By including a solvent having a boiling point of 160 ° C. or higher in the above content, drying of the solvent is suppressed, and there are few coating stripes and unevenness when applied by a liquid-saving coating method such as slit coating and spray coating, The clogging of the nozzle and the generation of agglomerates at the tip of the nozzle and the slit blade edge are small, and the coating property with time is excellent. The “boiling point” in the present invention is the normal boiling point, that is, the boiling point at 1 atmosphere.
Further, the (Component C) solvent is preferably a solvent having a boiling point of 250 ° C. or lower.
The photosensitive resin composition of the present invention is preferably prepared as a solution obtained by dissolving and / or dispersing the essential components of the present invention and optional components described below in the (Component C) solvent.
As the 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 JP2011-22214A.
　また、これらの溶剤に更に必要に応じて、ベンジルエチルエーテル、ジヘキシルエーテル、エチレングリコールモノフェニルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、イソホロン、カプロン酸、カプリル酸、１－オクタノール、１－ノナール、ベンジルアルコール、アニソール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、炭酸エチレン、炭酸プロピレン等の溶剤を添加することもできる。
　（成分Ｃ）溶剤は、１種単独で又は２種以上を混合して使用することができる。本発明に用いることができる溶剤は、２種以上を混合して使用することが好ましい。 In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added.
(Component C) A solvent can be used individually by 1 type or in mixture of 2 or more types. It is preferable to use a mixture of two or more solvents that can be used in the present invention.
　沸点１６０℃以上の溶剤としては、３－エトキシプロピオン酸エチル（沸点１７０℃）、ジエチレングリコールメチルエチルエーテル（沸点１７６℃）、プロピレングリコールモノメチルエーテルプロピオネート（沸点１６０℃）、ジプロピレングリコールメチルエーテルアセテート（沸点２１３℃）、３－メトキシブチルエーテルアセテート（沸点１７１℃）、ジエチレングリコールジエチエルエーテル（沸点１８９℃）、ジエチレングリコールジメチルエーテル（沸点１６２℃）、プロピレングリコールジアセテート（沸点１９０℃）、ジエチレングリコールモノエチルエーテルアセテート（沸点２２０℃）、ジプロピレングリコールジメチルエーテル（沸点１７５℃）、１，３－ブチレングリコールジアセテート（沸点２３２℃）が例示できる。沸点が１６０℃以上の溶剤は、１種単独で又は２種以上を混合して使用することができる。
　これらの中でも、沸点１６０℃以上の溶剤としては、沸点１６０℃以上２５０℃以下の溶剤であることが好ましく、沸点１６０℃以上１９０℃以下の溶剤であることがより好ましく、沸点１６５℃以上の溶剤１８０℃以下の溶剤であることが更に好ましく、３－エトキシプロピオン酸エチル及び／又はジエチレングリコールメチルエチルエーテルであることが特に好ましく、３－エトキシプロピオン酸エチル又はジエチレングリコールメチルエチルエーテルであることが最も好ましい。上記態様であると、スリットコート及びスプレーコート等の省液コート法で塗布した際における塗布スジやムラが少なく塗布性により優れ、ノズルの目詰まり及びノズルやスリット刃先の先端での凝集塊の発生が少なく経時での塗布性により優れる。 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. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be. A solvent having a boiling point of 160 ° C. or higher can be used singly or in combination of two or more.
Among these, the solvent having a boiling point of 160 ° C or higher is preferably a solvent having a boiling point of 160 ° C or higher and 250 ° C or lower, more preferably a solvent having a boiling point of 160 ° C or higher and 190 ° C or lower, and a solvent having a boiling point of 165 ° C or higher. A solvent of 180 ° C. or lower is more preferable, ethyl 3-ethoxypropionate and / or diethylene glycol methyl ethyl ether is particularly preferable, and ethyl 3-ethoxypropionate or diethylene glycol methyl ethyl ether is most preferable. In the above mode, there are few coating streaks and unevenness when applied by a liquid-saving coating method such as slit coating and spray coating, and the coating property is excellent, and clogging of the nozzle and generation of agglomerates at the tip of the nozzle or slit blade tip There are few, and it is excellent by the applicability | paintability with time.
　本発明の感光性樹脂組成物における沸点１６０℃以上の溶剤の含有量は、感光性樹脂組成物中の全溶剤量に対し、３質量％以上４０質量％以下であり、３質量％以上３５質量％以下であることが好ましく、３質量％以上３０質量％以下であることがより好ましい。上記範囲であると、スリットコート及びスプレーコート等の省液コート法で塗布した際における塗布性により優れる。
　また、本発明の感光性樹脂組成物中の沸点１６０℃以上の溶剤の含有量は、感光性樹脂組成物中の全質量に対し、１質量％以上３５質量％以下であることが好ましく、２質量％以上３０質量％以下であることがより好ましく、２質量％以上２５質量％以下であることがより好ましい。上記範囲であると、スリットコート及びスプレーコート等の省液コート法で塗布した際における塗布性により優れる。 The content of the solvent having a boiling point of 160 ° C. or higher in the photosensitive resin composition of the present invention is 3% by mass or more and 40% by mass or less, and 3% by mass or more and 35% by mass with respect to the total amount of the solvent in the photosensitive resin composition. % Or less, and more preferably 3% by mass or more and 30% by mass or less. It is excellent in the applicability | paintability at the time of apply | coating by liquid-saving coating methods, such as a slit coat and a spray coat, as it is the said range.
The content of the solvent having a boiling point of 160 ° C. or higher in the photosensitive resin composition of the present invention is preferably 1% by mass or more and 35% by mass or less with respect to the total mass in the photosensitive resin composition. The content is more preferably no less than 30% by mass and no greater than 30% by mass, and more preferably no less than 2% by mass and no greater than 25% by mass. It is excellent in the applicability | paintability at the time of apply | coating by liquid-saving coating methods, such as a slit coat and a spray coat, as it is the said range.
　また、成分Ｃとしては、沸点１６０℃以上の溶剤に加え、沸点１３０℃以上１６０℃未満の溶剤を併用することが好ましい。
　沸点１３０℃以上１６０℃未満の溶剤としては、プロピレングリコールモノメチルエーテルアセテート（沸点１４６℃）、プロピレングリコールモノエチルエーテルアセテート（沸点１５８℃）、プロピレングリコールメチル－ｎ－ブチルエーテル（沸点１５５℃）、プロピレングリコールメチル－ｎ－プロピルエーテル（沸点１３１℃）が例示できる。
　これらの中でも、沸点１３０℃以上１６０℃未満の溶剤としては、プロピレングリコールモノアルキルエーテルアセテート類が好ましく、プロピレングリコールモノメチルエーテルアセテートが特に好ましい。 In addition to the solvent having a boiling point of 160 ° C. or higher, the component C is preferably used in combination with a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C.
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.).
Among these, as a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., propylene glycol monoalkyl ether acetates are preferable, and propylene glycol monomethyl ether acetate is particularly preferable.
　本発明の感光性樹脂組成物において、沸点１３０℃以上１６０℃未満の溶剤と沸点１６０℃以上の溶剤との含有質量比が、沸点１３０℃以上１６０℃未満の溶剤：沸点１６０℃以上の溶剤＝５０：５０～９７：３であることが好ましく、５５：４５～９７：３であることがより好ましく、６０：４０～９７：３であることが更に好ましい。上記範囲であると、スリットコート及びスプレーコート等の省液コート法で塗布した際における塗布性により優れる。
　また、スリットコート法により塗布する場合は、本発明の感光性樹脂組成物において、沸点１３０℃以上１６０℃未満の溶剤と沸点１６０℃以上の溶剤との含有質量比が、沸点１３０℃以上１６０℃未満の溶剤：沸点１６０℃以上の溶剤＝７０：３０～９７：３であることが特に好ましい。上記範囲であると、スリットコート法で塗布した際における塗布性により優れる。
　スプレーコート法により塗布する場合は、本発明の感光性樹脂組成物において、沸点１３０℃以上１６０℃未満の溶剤と沸点１６０℃以上の溶剤との含有質量比が、沸点１３０℃以上１６０℃未満の溶剤：沸点１６０℃以上の溶剤＝６０：４０～９５：５であることが特に好ましい。上記範囲であると、スプレーコート法で塗布した際における塗布性により優れる。 In the photosensitive resin composition of the present invention, the content mass ratio of the solvent having a boiling point of 130 ° C. or more and less than 160 ° C. and the solvent having a boiling point of 160 ° C. or more is a solvent having a boiling point of 130 ° C. or more and less than 160 ° C. The ratio is preferably 50:50 to 97: 3, more preferably 55:45 to 97: 3, and still more preferably 60:40 to 97: 3. It is excellent in the applicability | paintability at the time of apply | coating by liquid-saving coating methods, such as a slit coat and a spray coat, as it is the said range.
In the case of coating by the slit coating method, the content mass ratio of the solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C. and the solvent having a boiling point of 160 ° C. or higher is 130 ° C. or higher and 160 ° C. in the photosensitive resin composition of the present invention. Less than solvent: Solvent with boiling point of 160 ° C. or higher = 70: 30 to 97: 3 is particularly preferable. It is excellent in the applicability | paintability at the time of apply | coating with the slit coat method as it is the said range.
When applied by spray coating, in the photosensitive resin composition of the present invention, the mass ratio of the solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C. and the solvent having a boiling point of 160 ° C. or higher is 130 ° C. or higher and lower than 160 ° C. Solvent: Solvent having a boiling point of 160 ° C. or higher = 60: 40 to 95: 5 is particularly preferable. It is excellent in the applicability | paintability at the time of apply | coating by the spray coat method as it is the said range.
　これらの中でも、成分Ｃとしては、３－エトキシプロピオン酸エチル、プロピレングリコールモノメチルエーテルアセテート及びジエチレングリコールエチルメチルエーテルよりなる群から選ばれた溶剤であることが好ましく、３－エトキシプロピオン酸エチルとプロピレングリコールモノメチルエーテルアセテートとの２種の混合物、又は、ジエチレングリコールエチルメチルエーテルとプロピレングリコールモノメチルエーテルアセテートとの２種の混合物、又は、３－エトキシプロピオン酸エチルとジエチレングリコールエチルメチルエーテルとプロピレングリコールモノメチルエーテルアセテートとの３種の混合物であることが特に好ましい。上記態様であると、スリットコート及びスプレーコート等の省液コート法で塗布した際における塗布スジやムラが少なく塗布性により優れ、ノズルの目詰まり及びノズルやスリット刃先の先端での凝集塊の発生が少なく経時での塗布性により優れる。 Among these, the component C is preferably a solvent selected from the group consisting of ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether, and includes ethyl 3-ethoxypropionate and propylene glycol monomethyl Two mixtures with ether acetate, or two mixtures of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate, or 3 of ethyl 3-ethoxypropionate, diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate Particular preference is given to a mixture of seeds. In the above mode, there are few coating streaks and unevenness when applied by a liquid-saving coating method such as slit coating and spray coating, and the coating property is excellent, and clogging of the nozzle and generation of agglomerates at the tip of the nozzle or slit blade tip There are few and it is excellent by the applicability | paintability with time.
　本発明の感光性樹脂組成物における（成分Ｃ）溶剤の含有量は、６５質量％以上９５質量％以下であることが好ましく、７０質量％以上９５質量％以下であることがより好ましく、７５質量％以上９５質量％以下であることが更に好ましい。（成分Ｃ）溶剤の含有量が上記範囲であると、塗布時、特に省液コート法による塗布時の平坦性が良好である。 The content of the (component C) solvent in the photosensitive resin composition of the present invention is preferably 65% by mass or more and 95% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and 75% by mass. % To 95% by mass is more preferable. When the content of (Component C) solvent is in the above range, the flatness at the time of application, particularly at the time of application by the liquid-saving coating method is good.
（成分Ｄ）酸基が酸分解性基で保護された基を有する構成単位を有する重合体
　本発明の感光性樹脂組成物は、（成分Ｄ）酸基が酸分解性基で保護された基を有する構成単位を有する重合体を含有する。
　なお、本発明において、「酸基が酸分解性基で保護された基を有する構成単位」を「（ａ１）酸基が酸分解性基で保護された基を有する構成単位」ともいう。 (Component D) Polymer having a constitutional unit having a group in which an acid group is protected with an acid-decomposable group The photosensitive resin composition of the present invention is a group in which (Component D) an acid group is protected with an acid-decomposable group The polymer which has a structural unit which has is contained.
In the present invention, the “structural unit having a group in which an acid group is protected by an acid-decomposable group” is also referred to as “(a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group”.
　本発明の感光性樹脂組成物は、更に、酸基が酸分解性基で保護された基を有する構成単位を有する重合体以外の重合体を含んでいてもよい。
　本発明の感光性樹脂組成物は、下記（１）及び（２）の少なくとも一方を満たす重合体を含む重合体成分を含有することが好ましい。
　（１）（ａ１）酸基が酸分解性基で保護された基を有する構成単位及び（ａ２）架橋性基を有する構成単位を有する重合体
　（２）（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体、及び、（ａ２）架橋性基を有する構成単位を有する重合体
　本発明の感光性樹脂組成物は、更に、これら以外の重合体を含んでいてもよい。本発明における成分Ｄは、特に述べない限り、上記（１）及び／又は（２）を意味するものとする。
　本発明の感光性樹脂組成物は、硬化後における透明性（ヘイズ）及び未露光部の残膜率の観点からは、成分Ｄとして、上記（１）を満たす成分を含むことが好ましい。
　一方、分子設計の自由度の観点からは、本発明の感光性樹脂組成物は、成分Ｄとして、上記（２）を満たす成分を含むことが好ましい。
　なお、上記（１）を満たす成分を含有する場合であっても、更に、（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有するアクリル樹脂及び／又は（ａ２）架橋性基を有する構成単位を有するアクリル樹脂を含有していてもよい。
　また、上記（２）を満たす成分を含有する場合であっても、（ａ１）酸基が酸分解性基で保護された基を有する構成単位及び（ａ２）架橋性基を有する構成単位を有するポリマーに該当するものを少なくとも含有する場合は、上記（１）を満たす成分を含有する場合に該当するものとする。 The photosensitive resin composition of the present invention may further contain a polymer other than a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group.
The photosensitive resin composition of the present invention preferably contains a polymer component including a polymer that satisfies at least one of the following (1) and (2).
(1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group (2) (a1) an acid group having an acid-decomposable group And (a2) a polymer having a structural unit having a crosslinkable group The photosensitive resin composition of the present invention further contains a polymer other than these. May be. The component D in the present invention means the above (1) and / or (2) unless otherwise specified.
It is preferable that the photosensitive resin composition of this invention contains the component which satisfy | fills said (1) as a component D from a viewpoint of the transparency (haze) after hardening, and the remaining film rate of an unexposed part.
On the other hand, from the viewpoint of the degree of freedom in molecular design, the photosensitive resin composition of the present invention preferably contains a component satisfying the above (2) as the component D.
In addition, even when it contains a component satisfying the above (1), (a1) an acrylic resin having a structural unit having a group in which an acid group is protected with an acid-decomposable group and / or (a2) cross-linking An acrylic resin having a structural unit having a functional group may be contained.
Moreover, even when it contains a component satisfying the above (2), it has (a1) a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group. When it contains at least what corresponds to a polymer, it corresponds when it contains the component which satisfy | fills said (1).
　成分Ｄは、付加重合型の樹脂であることが好ましく、（メタ）アクリル酸及び／又はそのエステルに由来する構成単位を含む重合体であることがより好ましい。なお、（メタ）アクリル酸及び／又はそのエステルに由来する構成単位以外の構成単位、例えば、スチレンに由来する構成単位や、ビニル化合物に由来する構成単位等を有していてもよい。
　なお、「（メタ）アクリル酸及び／又はそのエステルに由来する構成単位」を「アクリル系構成単位」ともいう。また、「（メタ）アクリル酸」は、「メタクリル酸及び／又はアクリル酸」を意味するものとする。 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. In addition, 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”. Further, “(meth) acrylic acid” means “methacrylic acid and / or acrylic acid”.
＜構成単位（ａ１）＞
　成分Ｄは、（ａ１）酸基が酸分解性基で保護された基を有する構成単位を少なくとも有する重合体を含む。成分Ｄが構成単位（ａ１）を有する重合体を含むことにより、極めて高感度な感光性樹脂組成物とすることができる。
　本発明における「酸基が酸分解性基で保護された基」は、酸基及び酸分解性基として公知のものを使用でき、特に限定されない。具体的な酸基としては、カルボキシル基、及び、フェノール性水酸基が好ましく挙げられる。また、酸分解性基としては、酸により比較的分解し易い基（例えば、後述する式（Ａ１）で表される基のエステル構造、テトラヒドロピラニルエステル基、又は、テトラヒドロフラニルエステル基等のアセタール系官能基）や酸により比較的分解し難い基（例えば、ｔｅｒｔ－ブチルエステル基等の第三級アルキル基、ｔｅｒｔ－ブチルカーボネート基等の第三級アルキルカーボネート基）を用いることができる。
　酸分解性基としては、カルボキシル基若しくはフェノール性水酸基がアセタールの形で保護された基又は第三級アルキル基により保護された基が好ましく挙げられる。 <Structural unit (a1)>
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. When component D contains a polymer having the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, 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. The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal group such as an ester structure of a group represented by the formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group). A functional group) or a group that is relatively difficult to decompose by an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group).
As the acid-decomposable group, a group in which a carboxyl group or a phenolic hydroxyl group is protected in the form of an acetal or a group protected by a tertiary alkyl group is preferably exemplified.
　（ａ１）酸基が酸分解性基で保護された基を有する構成単位は、カルボキシル基が酸分解性基で保護された保護カルボキシル基を有する構成単位（「酸分解性基で保護された保護カルボキシル基を有する構成単位」ともいう。）、又は、フェノール性水酸基が酸分解性基で保護された保護フェノール性水酸基を有する構成単位（「酸分解性基で保護された保護フェノール性水酸基を有する構成単位」ともいう。）であることが好ましい。
　以下、酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）と、酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）について、順にそれぞれ説明する。 (A1) 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” A structural unit having a protected phenolic hydroxyl group in which a phenolic hydroxyl group is protected with an acid-decomposable group (having a protected phenolic hydroxyl group protected with an acid-decomposable group). It is also preferably referred to as a “structural unit”.
Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order. To do.
＜＜（ａ１－１）酸分解性基で保護された保護カルボキシル基を有する構成単位＞＞
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）は、カルボキシル基を有する構成単位のカルボキシル基が、以下で詳細に説明する酸分解性基によって保護された保護カルボキシル基を有する構成単位である。
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）に用いることができる上記カルボキシル基を有する構成単位としては、特に制限はなく公知の構成単位を用いることができる。例えば、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和トリカルボン酸などの、分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）や、エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位（ａ１－１－２）が挙げられる。
　以下、上記カルボキシル基を有する構成単位として用いられる（ａ１－１－１）分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位と、（ａ１－１－２）エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位について、それぞれ順に説明する。 << (a1-1) Structural unit having a protected carboxyl group protected with an acid-decomposable group >>
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.
The structural unit having a carboxyl group that can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is not particularly limited, and a known structural unit can be used. For example, 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, And a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
Hereinafter, (a1-1-1) used as a structural unit having a carboxyl group, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) ethylene The structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.
＜＜＜（ａ１－１－１）分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位＞＞＞
　上記分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）として本発明で用いられる不飽和カルボン酸としては以下に挙げるようなものが用いられる。すなわち、不飽和モノカルボン酸としては、例えば、アクリル酸、メタクリル酸、クロトン酸、α－クロロアクリル酸、けい皮酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチルフタル酸などが挙げられる。また、不飽和ジカルボン酸としては、例えば、マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸などが挙げられる。また、カルボキシル基を有する構成単位を得るために用いられる不飽和多価カルボン酸は、その酸無水物であってもよい。具体的には、無水マレイン酸、無水イタコン酸、無水シトラコン酸などが挙げられる。また、不飽和多価カルボン酸は、多価カルボン酸のモノ（２－メタクリロイロキシアルキル）エステルであってもよく、例えば、コハク酸モノ（２－アクリロイロキシエチル）、コハク酸モノ（２－メタクリロイロキシエチル）、フタル酸モノ（２－アクリロイロキシエチル）、フタル酸モノ（２－メタクリロイロキシエチル）などが挙げられる。更に、不飽和多価カルボン酸は、その両末端ジカルボキシポリマーのモノ（メタ）アクリレートであってもよく、例えば、ω－カルボキシポリカプロラクトンモノアクリレート、ω－カルボキシポリカプロラクトンモノメタクリレートなどが挙げられる。また、不飽和カルボン酸としては、アクリル酸－２－カルボキシエチルエステル、メタクリル酸－２－カルボキシエチルエステル、マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、４－カルボキシスチレン等も用いることができる。
　中でも、現像性の観点から、上記分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）を形成するためには、アクリル酸、メタクリル酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチルフタル酸、又は、不飽和多価カルボン酸の無水物等を用いることが好ましく、アクリル酸、メタクリル酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、を用いることがより好ましい。
　上記分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）は、１種単独で構成されていてもよいし、２種以上で構成されていてもよい。 <<< (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>
Examples of 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, α-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. Moreover, 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. Further, 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. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the 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.
Among them, from the viewpoint of developability, in order to form 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.
＜＜＜（ａ１－１－２）エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位＞＞＞
　エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位（ａ１－１－２）は、エチレン性不飽和基を有する構成単位中に存在する水酸基と酸無水物とを反応させて得られたモノマーに由来する単位であることが好ましい。
　上記酸無水物としては、公知のものが使用でき、具体的には、無水マレイン酸、無水コハク酸、無水イタコン酸、無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水クロレンド酸等の二塩基酸無水物；無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物、ビフェニルテトラカルボン酸無水物などの酸無水物が挙げられる。これらの中では、現像性の観点から、無水フタル酸、テトラヒドロ無水フタル酸、又は、無水コハク酸が好ましい。
　上記酸無水物の水酸基に対する反応率は、現像性の観点から、好ましくは１０～１００モル％、より好ましくは３０～１００モル％である。 <<< (a1-1-2) a structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride >>>
The structural unit (a1-1-2) 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.
As 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. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, 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.
－構成単位（ａ１－１）に用いることができる酸分解性基－
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）に用いることができる上記酸分解性基としては上述の酸分解性基を用いることができる。
　これらの酸分解性基の中でもカルボキシル基がアセタールの形で保護された保護カルボキシル基であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、コンタクトホールの形成性、感光性樹脂組成物の保存安定性の観点から好ましい。更に酸分解性基の中でもカルボキシル基が下記式（ａ１－１０）で表されるアセタールの形で保護された保護カルボキシル基であることが、感度の観点からより好ましい。なお、カルボキシル基が下記式（ａ１－１０）で表されるアセタールの形で保護された保護カルボキシル基である場合、保護カルボキシル基の全体としては、－（Ｃ＝Ｏ）－Ｏ－ＣＲ101Ｒ102（ＯＲ103）の構造となっている。 -Acid-decomposable group that can be used for the structural unit (a1-1)-
As the acid-decomposable group that can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group, the above-mentioned acid-decomposable groups can be used.
Among these acid-decomposable groups, it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal. Basic properties of the photosensitive resin composition, in particular, sensitivity and pattern shape, contact hole formation, photosensitive resin It is preferable from the viewpoint of the storage stability of the composition. Furthermore, among the acid-decomposable groups, 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. When 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 ).
Figure JPOXMLDOC01-appb-C000003
 （式（ａ１－１０）中、Ｒ101及びＲ102はそれぞれ独立に、水素原子又はアルキル基を表し、ただし、Ｒ101とＲ102とが共に水素原子の場合を除く。Ｒ103は、アルキル基を表す。Ｒ101又はＲ102と、Ｒ103とが連結して環状エーテルを形成してもよい。）
Figure JPOXMLDOC01-appb-C000003
 (In formula (a1-10), R 101 and R 102 each independently represents a hydrogen atom or an alkyl group, except that R 101 and R 102 are both hydrogen atoms, and R 103 represents an alkyl group. R 101 or R 102 and R 103 may be linked to form a cyclic ether.)
　上記式（ａ１－１０）中、Ｒ101～Ｒ103はそれぞれ独立に、水素原子又はアルキル基を表し、上記アルキル基は直鎖状、分岐鎖状、環状のいずれでもよい。ここで、Ｒ101及びＲ102の双方が水素原子を表すことはなく、Ｒ101及びＲ102の少なくとも一方はアルキル基を表す。 In the above formula (a1-10), R 101 to R 103 each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic. Here, 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.
　上記式（ａ１－１０）において、Ｒ101、Ｒ102及びＲ103がアルキル基を表す場合、上記アルキル基は直鎖状、分岐鎖状又は環状のいずれであってもよい。
　上記直鎖状又は分岐鎖状のアルキル基としては、炭素数１～１２であることが好ましく、炭素数１～６であることがより好ましく、炭素数１～４であることが更に好ましい。具体的には、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｎ－ヘキシル基、テキシル基（２，３－ジメチル－２－ブチル基）、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基、ｎ－ノニル基、ｎ－デシル基等を挙げることができる。 In the above formula (a1-10), when 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. Specifically, 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.
　上記環状アルキル基としては、炭素数３～１２であることが好ましく、炭素数４～８であることがより好ましく、炭素数４～６であることが更に好ましい。上記環状アルキル基としては、例えばシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルニル基、イソボルニル基等を挙げることができる。 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.
　上記アルキル基は、置換基を有していてもよく、置換基としては、ハロゲン原子、アリール基、アルコキシ基が例示できる。置換基としてハロゲン原子を有する場合、Ｒ101、Ｒ102、Ｒ103はハロアルキル基となり、置換基としてアリール基を有する場合、Ｒ101、Ｒ102、Ｒ103はアラルキル基となる。
　上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が例示され、これらの中でも、フッ素原子又は塩素原子が好ましい。
　また、上記アリール基としては、炭素数６～２０のアリール基が好ましく、炭素数６～１２のアリール基がより好ましい。具体的には、フェニル基、α－メチルフェニル基、ナフチル基等が例示でき、アリール基で置換されたアルキル基全体、すなわち、アラルキル基としては、ベンジル基、α－メチルベンジル基、フェネチル基、ナフチルメチル基等が例示できる。
　上記アルコキシ基としては、炭素数１～６のアルコキシ基が好ましく、炭素数１～４のアルコキシ基がより好ましく、メトキシ基又はエトキシ基が更に好ましい。
　また、上記アルキル基がシクロアルキル基である場合、上記シクロアルキル基は置換基として炭素数１～１０の直鎖状又は分岐鎖状のアルキル基を有していてもよく、アルキル基が直鎖状又は分岐鎖状のアルキル基である場合には、置換基として炭素数３～１２のシクロアルキル基を有していてもよい。
　これらの置換基は、上記置換基で更に置換されていてもよい。 The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. 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.
Examples of 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 α-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 α-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.
Further, when 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.
　上記式（ａ１－１０）において、Ｒ101、Ｒ102及びＲ103がアリール基を表す場合、上記アリール基は炭素数６～１２であることが好ましく、炭素数６～１０であることがより好ましい。上記アリール基は置換基を有していてもよく、上記置換基としては炭素数１～６のアルキル基が好ましく例示できる。アリール基としては、例えば、フェニル基、トリル基、キシリル基、クメニル基、１－ナフチル基等が例示できる。 In the above formula (a1-10), when 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.
　また、Ｒ101、Ｒ102及びＲ103は互いに結合して、それらが結合している炭素原子と一緒になって環を形成することができる。Ｒ101とＲ102、Ｒ101とＲ103又はＲ102とＲ103が結合した場合の環構造としては、例えばシクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、テトラヒドロフラニル基、アダマンチル基及びテトラヒドロピラニル基等を挙げることができる。 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.
　なお、上記式（ａ１－１０）において、Ｒ101及びＲ102のいずれか一方が、水素原子又はメチル基であることが好ましい。 Note that in the above formula (a1-10), any one of R 101 and R 102 is preferably a hydrogen atom or a methyl group.
　上記式（ａ１－１０）で表される保護カルボキシル基を有する構成単位を形成するために用いられるラジカル重合性単量体は、市販のものを用いてもよいし、公知の方法で合成したものを用いることもできる。例えば、特開２０１１－２２１４９４号公報の段落００３７～００４０に記載の合成方法などで合成することができる。 As the 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.
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）の第一の好ましい態様は、下記式で表される構成単位である。 The 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.
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ1及びＲ2はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、少なくともＲ1及びＲ2のいずれか一方がアルキル基又はアリール基であり、Ｒ3は、アルキル基又はアリール基を表し、Ｒ1又はＲ2と、Ｒ3とが連結して環状エーテルを形成してもよく、Ｒ4は、水素原子又はメチル基を表し、Ｘは単結合又はアリーレン基を表す。）
Figure JPOXMLDOC01-appb-C000004
 (In the 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. .)
　Ｒ1及びＲ2がアルキル基の場合、炭素数は１～１０のアルキル基が好ましい。Ｒ1及びＲ2がアリール基の場合、フェニル基が好ましい。Ｒ1及びＲ2はそれぞれ独立に、水素原子又は炭素数１～４のアルキル基が好ましい。
　Ｒ3は、アルキル基又はアリール基を表し、炭素数１～１０のアルキル基が好ましく、１～６のアルキル基がより好ましい。
　Ｘは、単結合又はアリーレン基を表し、単結合が好ましい。 When 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.
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）の第二の好ましい態様は、下記式で表される構成単位である。 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.
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ121は水素原子又は炭素数１～４のアルキル基を表し、Ｌ1はカルボニル基又はフェニレン基を表し、Ｒ122～Ｒ128はそれぞれ独立に、水素原子又は炭素数１～４のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000005
 Wherein R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 1 represents a carbonyl group or a phenylene group, and R 122 to R 128 each independently represents a hydrogen atom or 1 to 4 carbon atoms. Represents an alkyl group of
　Ｒ121は水素原子又はメチル基が好ましい。
　Ｌ1はカルボニル基が好ましい。
　Ｒ122～Ｒ128は、水素原子が好ましい。 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.
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）の好ましい具体例としては、下記の構成単位が例示できる。なお、Ｒは水素原子又はメチル基を表す。 As preferred specific examples of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group, the following structural units can be exemplified. R represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
＜＜（ａ１－２）酸分解性基で保護された保護フェノール性水酸基を有する構成単位＞＞
　上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）は、フェノール性水酸基を有する構成単位が、以下で詳細に説明する酸分解性基によって保護された保護フェノール性水酸基を有する構成単位である。 << (a1-2) Structural Unit Having Protected Phenolic Hydroxyl Group Protected with Acid-Decomposable 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. A structural unit having a hydroxyl group.
＜＜＜（ａ１－２－１）フェノール性水酸基を有する構成単位＞＞＞
　上記フェノール性水酸基を有する構成単位としては、ヒドロキシスチレン系構成単位やノボラック系の樹脂における構成単位が挙げられるが、これらの中では、ヒドロキシスチレン又はα－メチルヒドロキシスチレンに由来する構成単位が、感度の観点から好ましい。また、フェノール性水酸基を有する構成単位として、下記式（ａ１－２０）で表される構成単位も、感度の観点から好ましい。 << ((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 α-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.
Figure JPOXMLDOC01-appb-C000007
 （式（ａ１－２０）中、Ｒ220は水素原子又はメチル基を表し、Ｒ221は単結合又は二価の連結基を表し、Ｒ222はハロゲン原子又は炭素数１～５の直鎖若しくは分岐鎖状のアルキル基を表し、ａは１～５の整数を表し、ｂは０～４の整数を表し、ａ＋ｂは５以下である。なお、Ｒ222が２以上存在する場合、これらのＲ222は相互に異なっていてもよいし同じでもよい。）
Figure JPOXMLDOC01-appb-C000007
 (In the formula (a1-20), R 220 represents a hydrogen atom or a methyl group, R 221 represents a single bond or a divalent linking group, and R 222 represents a halogen atom or a linear or branched group having 1 to 5 carbon atoms. Represents a chain alkyl group, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less, and when R 222 is 2 or more, these R 222 May be different from each other or the same.)
　上記式（ａ１－２０）中、Ｒ220は水素原子又はメチル基を表し、メチル基であることが好ましい。
　また、Ｒ221は単結合又は二価の連結基を表す。単結合である場合には、感度を向上させることができ、更に硬化膜の透明性を向上させることができるので好ましい。Ｒ221の二価の連結基としてはアルキレン基が例示でき、Ｒ221がアルキレン基である具体例としては、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ｎ－ブチレン基、イソブチレン基、ｔｅｒｔ－ブチレン基、ペンチレン基、イソペンチレン基、ネオペンチレン基、ヘキシレン基等が挙げられる。中でも、Ｒ221が単結合、メチレン基、又は、エチレン基であることが好ましい。また、上記二価の連結基は、置換基を有していてもよく、置換基としては、ハロゲン原子、水酸基、アルコキシ基等が挙げられる。また、ａは１～５の整数を表すが、本発明の効果の観点や、製造が容易であるという点から、ａは１又は２であることが好ましく、ａが１であることがより好ましい。
　また、ベンゼン環における水酸基の結合位置は、Ｒ221と結合している炭素原子を基準（１位）としたとき、４位に結合していることが好ましい。
　Ｒ222はそれぞれ独立に、ハロゲン原子又は炭素数１～５の直鎖若しくは分岐鎖状のアルキル基を表す。具体的には、フッ素原子、塩素原子、臭素原子、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。中でも製造が容易であるという点から、塩素原子、臭素原子、メチル基又はエチル基であることが好ましい。
　また、ｂは０又は１～４の整数を表す。 In the above formula (a1-20), 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. The divalent linking group of R 221 may be exemplified alkylene groups, specific examples R 221 is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among these, R 221 is preferably a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
R 222 each independently represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. It is done. Among these, 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;
－構成単位（ａ１－２）に用いることができる酸分解性基－
　上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）に用いることができる上記酸分解性基としては、上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）に用いることができる上記酸分解性基と同様に、公知のものを使用でき、特に限定されない。酸分解性基の中でもアセタールで保護された保護フェノール性水酸基を有する構成単位であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、感光性樹脂組成物の保存安定性、コンタクトホールの形成性の観点から好ましい。更に、酸分解性基の中でもフェノール性水酸基が上記式（ａ１－１０）で表されるアセタールの形で保護された保護フェノール性水酸基であることが、感度の観点からより好ましい。なお、フェノール性水酸基が上記式（ａ１－１０）で表されるアセタールの形で保護された保護フェノール性水酸基である場合、保護フェノール性水酸基の全体としては、－Ａｒ－Ｏ－ＣＲ101Ｒ102（ＯＲ103）の構造となっている。なお、Ａｒはアリーレン基を表す。 -Acid-decomposable group that can be used for the structural unit (a1-2)-
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. Among the acid-decomposable groups, 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. Furthermore, among the acid-decomposable groups, 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. When 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.
　フェノール性水酸基のアセタールエステル構造の好ましい例は、Ｒ101＝Ｒ102＝Ｒ103＝メチル基の組み合わせやＲ101＝Ｒ102＝メチル基でＲ103＝ベンジル基の組み合わせが例示できる。 Preferred examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R 101 = R 102 = R 103 = methyl group and a combination of R 101 = R 102 = methyl group and R 103 = benzyl group.
　また、フェノール性水酸基がアセタールの形で保護された保護フェノール性水酸基を有する構成単位を形成するために用いられるラジカル重合性単量体としては、例えば、特開２０１１－２１５５９０号公報の段落００４２に記載のものなどが挙げられる。
　これらの中で、４－ヒドロキシフェニルメタクリレートの１－アルコキシアルキル保護体、４－ヒドロキシフェニルメタクリレートのテトラヒドロピラニル保護体が透明性の観点から好ましい。 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.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
　フェノール性水酸基のアセタール保護基の具体例としては、１－アルコキシアルキル基が挙げられ、例えば、１－エトキシエチル基、１－メトキシエチル基、１－ｎ－ブトキシエチル基、１－イソブトキシエチル基、１－（２－クロロエトキシ）エチル基、１－（２－エチルヘキシルオキシ）エチル基、１－ｎ－プロポキシエチル基、１－シクロヘキシルオキシエチル基、１－（２－シクロヘキシルエトキシ）エチル基、１－ベンジルオキシエチル基などを挙げることができ、これらは１種単独又は２種類以上を組み合わせて使用することができる。 Specific examples of the acetal protecting group for the phenolic hydroxyl group 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.
　上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）を形成するために用いられるラジカル重合性単量体は、市販のものを用いてもよいし、公知の方法で合成したものを用いることもできる。例えば、フェノール性水酸基を有する化合物を酸触媒の存在下でビニルエーテルと反応させることにより合成することができる。上記の合成はフェノール性水酸基を有するモノマーをその他のモノマーと予め共重合させておき、その後に酸触媒の存在下でビニルエーテルと反応させてもよい。 As 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.
　上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）の好ましい具体例としては、下記の構成単位が例示できるが、本発明はこれらに限定されるものではない。下記具体例中、Ｒは水素原子又はメチル基を表す。 As preferred specific examples of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group, the following structural units can be exemplified, but the present invention is not limited thereto. In the following specific examples, R represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
－構成単位（ａ１）の好ましい態様－
　上記構成単位（ａ１）を有する重合体が、実質的に、構成単位（ａ２）を有しない場合、構成単位（ａ１）は、該構成単位（ａ１）を有する重合体中、２０～１００モル％が好ましく、３０～９０モル％がより好ましい。
　上記構成単位（ａ１）を有する重合体が、下記構成単位（ａ２）を有する場合、単構成単位（ａ１）は、該構成単位（ａ１）と構成単位（ａ２）とを有する重合体中、感度の観点から３～７０モル％が好ましく、１０～６０モル％がより好ましい。また、特に上記構成単位（ａ１）が、カルボキシル基がアセタールの形で保護された保護カルボキシル基を有する構成単位である場合、２０～５０モル％が好ましい。
　なお、本発明において、「構成単位」の含有量をモル比で規定する場合、当該「構成単位」は「モノマー単位」と同義であるものとする。また、本発明において当該「モノマー単位」は、高分子反応等により重合後に修飾されていてもよい。以下においても同様である。 -Preferred embodiment of the structural unit (a1)-
When the polymer having the structural unit (a1) does not substantially have the structural unit (a2), the structural unit (a1) is 20 to 100 mol% in the polymer having the structural unit (a1). It is preferably 30 to 90 mol%.
When the polymer having the structural unit (a1) has the following structural unit (a2), the single structural unit (a1) is sensitive to the polymer having the structural unit (a1) and the structural unit (a2). From this viewpoint, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%. In particular, when 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.
In the present invention, when the content of the “structural unit” is defined in terms of molar ratio, the “structural unit” is synonymous with the “monomer unit”. In the present invention, the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）は、上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）に比べると、現像が速いという特徴がある。よって、速く現像したい場合には酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）が好ましい。逆に現像を遅くしたい場合には酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）を用いることが好ましい。
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）は、上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）に比べると、現像が速いという特徴がある。よって、速く現像したい場合には酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）が好ましい。逆に現像を遅くしたい場合には酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）を用いることが好ましい。 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.
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.
＜（ａ２）架橋性基を有する構成単位＞
　成分Ｄは、架橋性基を有する構成単位（ａ２）を有する重合体を含有する。上記架橋性基は、加熱処理で硬化反応を起こす基であれば特に限定はされない。好ましい架橋性基を有する構成単位の態様としては、エポキシ基、オキセタニル基、－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは水素原子又は炭素数１～２０のアルキル基を表す。）で表される基及びエチレン性不飽和基よりなる群から選ばれた少なくとも１つを含む構成単位が挙げられ、エポキシ基、オキセタニル基、及び、－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは水素原子又は炭素数１～２０のアルキル基を表す。）で表される基よりなる群から選ばれた少なくとも１種であることが好ましい。その中でも、本発明の感光性樹脂組成物は、上記成分Ｄが、エポキシ基及びオキセタニル基のうち少なくとも１つを含む構成単位を含むことがより好ましい。より詳細には、以下のものが挙げられる。 <(A2) Structural unit having a crosslinkable 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). And a structural unit containing at least one selected from the group consisting of an ethylenically unsaturated group, an epoxy group, an oxetanyl group, and —NH—CH 2 —O—R (R represents a hydrogen atom or a carbon number) It is preferably at least one selected from the group consisting of groups represented by 1 to 20 alkyl groups). Among them, in the photosensitive resin composition of the present invention, it is more preferable that the component D includes a structural unit including at least one of an epoxy group and an oxetanyl group. In more detail, the following are mentioned.
＜＜（ａ２－１）エポキシ基及び／又はオキセタニル基を有する構成単位＞＞
　成分Ｄは、エポキシ基及び／又はオキセタニル基を有する構成単位（構成単位（ａ２－１））を有する重合体を含有することが好ましい。上記３員環の環状エーテル基はエポキシ基とも呼ばれ、４員環の環状エーテル基はオキセタニル基とも呼ばれる。
　上記エポキシ基及び／又はオキセタニル基を有する構成単位（ａ２－１）は、１つの構成単位中にエポキシ基又はオキセタニル基を少なくとも１つ有していればよく、１つ以上のエポキシ基及び１つ以上オキセタニル基、２つ以上のエポキシ基、又は、２つ以上のオキセタニル基を有していてもよく、特に限定されないが、エポキシ基及び／又はオキセタニル基を合計１～３つ有することが好ましく、エポキシ基及び／又はオキセタニル基を合計１又は２つ有することがより好ましく、エポキシ基又はオキセタニル基を１つ有することが更に好ましい。 << (a2-1) Structural Unit Having Epoxy Group and / or 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. The 3-membered cyclic ether group is also called an epoxy group, and the 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.
　エポキシ基を有する構成単位を形成するために用いられるラジカル重合性単量体の具体例としては、例えば、アクリル酸グリシジル、メタクリル酸グリシジル、α－エチルアクリル酸グリシジル、α－ｎ－プロピルアクリル酸グリシジル、α－ｎ－ブチルアクリル酸グリシジル、アクリル酸－３，４－エポキシブチル、メタクリル酸－３，４－エポキシブチル、アクリル酸－３，４－エポキシシクロヘキシルメチル、メタクリル酸－３，４－エポキシシクロヘキシルメチル、α－エチルアクリル酸－３，４－エポキシシクロヘキシルメチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、特許第４１６８４４３号公報の段落００３１～００３５に記載の脂環式エポキシ骨格を含有する化合物などが挙げられる。
　オキセタニル基を有する構成単位を形成するために用いられるラジカル重合性単量体の具体例としては、例えば、特開２００１－３３０９５３号公報の段落００１１～００１６に記載のオキセタニル基を有する（メタ）アクリル酸エステルなどが挙げられる。
　上記エポキシ基及び／又はオキセタニル基を有する構成単位（ａ２－１）を形成するために用いられるラジカル重合性単量体の具体例としては、メタクリル酸エステル構造を含有するモノマー、アクリル酸エステル構造を含有するモノマーであることが好ましい。 Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic epoch Compounds containing shea skeleton, and the like.
Specific examples of the 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. Examples include acid esters.
Specific examples of the 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.
　これらの中でも好ましいものは、メタクリル酸グリシジル、アクリル酸３，４－エポキシシクロヘキシルメチル、メタクリル酸３，４－エポキシシクロヘキシルメチル、３－エチル－３－オキセタニルメチルアクリレート、及び、３－エチル－３－オキセタニルメチルメタクリレートである。これらの構成単位は、１種単独又は２種類以上を組み合わせて使用することができる。 Among these, preferred are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-ethyl-3-oxetanylmethyl acrylate, and 3-ethyl-3-oxetanyl. Methyl methacrylate. These structural units can be used individually by 1 type or in combination of 2 or more types.
　エポキシ基及び／又はオキセタニル基を有する構成単位（ａ２－１）の好ましい具体例としては、下記の構成単位が例示できる。なお、Ｒは、水素原子又はメチル基を表す。 As preferred specific examples of the structural unit (a2-1) having an epoxy group and / or oxetanyl group, the following structural units can be exemplified. R represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
＜＜（ａ２－２）エチレン性不飽和基を有する構成単位＞＞
　上記架橋性基を有する構成単位（ａ２）の１つとして、エチレン性不飽和基を有する構成単位（ａ２－２）が挙げられる（以下、「構成単位（ａ２－２）」ともいう。）。上記エチレン性不飽和基を有する構成単位（ａ２－２）としては、側鎖にエチレン性不飽和基を有する構成単位が好ましく、末端にエチレン性不飽和基を有し、炭素数３～１６の側鎖を有する構成単位がより好ましく、下記式（ａ２－２－１）で表される側鎖を有する構成単位が更に好ましい。 << (a2-2) Structural unit having an ethylenically unsaturated group >>
One example of the structural unit (a2) having a crosslinkable 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, and a structural unit having a side chain represented by the following formula (a2-2-1) is still more preferred.
Figure JPOXMLDOC01-appb-C000010
 （式（ａ２－２－１）中、Ｒ301は炭素数１～１３の二価の連結基を表し、Ｒ302は水素原子又はメチル基を表し、波線部分は架橋性基を有する構成単位（ａ２）の主鎖に連結する部位を表す。）
Figure JPOXMLDOC01-appb-C000010
 (In the formula (a2-2-1), R 301 represents a divalent linking group having 1 to 13 carbon atoms, R 302 represents a hydrogen atom or a methyl group, and the wavy line part represents a structural unit having a crosslinkable group ( It represents a site linked to the main chain of a2).
　Ｒ301は、炭素数１～１３の二価の連結基であって、アルケニル基、シクロアルケニル基、アリーレン基又はこれらを組み合わせた基を含み、エステル結合、エーテル結合、アミド結合、ウレタン結合等の結合を含んでいてもよい。また、二価の連結基は、任意の位置にヒドロキシ基、カルボキシル基等の置換基を有していてもよい。Ｒ301の具体例としては、下記の二価の連結基が挙げられる。 R 301 is a divalent linking group having 1 to 13 carbon atoms, and includes an alkenyl group, a cycloalkenyl group, an arylene group, or a combination thereof, and includes an ester bond, an ether bond, an amide bond, a urethane bond, and the like. Bonds may be included. The divalent linking group may have a substituent such as a hydroxy group or a carboxyl group at an arbitrary position. Specific examples of R 301 include the following divalent linking groups.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記式（ａ２－２－１）で表される側鎖の中でも、上記Ｒ301で表される２価の連結基を含めて脂肪族の側鎖が好ましい。 Among the side chains represented by the formula (a2-2-1), an aliphatic side chain including the divalent linking group represented by R 301 is preferable.
　その他、（ａ２－２）エチレン性不飽和基を有する構成単位については、特開２０１１－２１５５８０号公報の段落００７２～００９０の記載を参酌できる。 In addition, for the structural unit having (a2-2) an ethylenically unsaturated group, the description in paragraphs 0072 to 0090 of JP2011-215580A can be referred to.
＜＜（ａ２－３）－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは水素原子又は炭素数１～２０のアルキル基を表す。）で表される基を有する構成単位＞＞
　本発明で用いる共重合体は、－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは水素原子又は炭素数１～２０のアルキル基を表す。）で表される基を有する構成単位（ａ２－３）も好ましい。構成単位（ａ２－３）を有することで、緩やかな加熱処理で硬化反応を起こすことができ、諸特性に優れた硬化膜を得ることができる。ここで、Ｒは炭素数１～２０のアルキル基が好ましく、炭素数１～９のアルキル基がより好ましく、炭素数１～４のアルキル基が更に好ましい。また、アルキル基は、直鎖、分岐又は環状のアルキル基のいずれであってもよいが、直鎖又は分岐のアルキル基であることが好ましい。構成単位（ａ２）は、下記式（ａ２－３０）で表される基を有する構成単位であることがより好ましい。 << (a2-3) -NH-CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)}
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. By having the structural unit (a2-3), a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, 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).
Figure JPOXMLDOC01-appb-C000012
 （式（ａ２－３０）中、Ｒ31は水素原子又はメチル基を表し、Ｒ32は炭素数１～２０のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000012
 (In the formula (a2-30), R 31 represents a hydrogen atom or a methyl group, and R 32 represents an alkyl group having 1 to 20 carbon atoms.)
　Ｒ32は、炭素数１～９のアルキル基が好ましく、炭素数１～４のアルキル基が更に好ましい。また、アルキル基は、直鎖、分岐又は環状のアルキル基のいずれであってもよいが、好ましくは、直鎖又は分岐のアルキル基である。
　Ｒ32の具体例としては、メチル基、エチル基、ｎ－ブチル基、ｉ－ブチル基、シクロヘキシル基、及び、ｎ－ヘキシル基を挙げることができる。中でも、ｉ－ブチル基、ｎ－ブチル基、メチル基が好ましい。 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 a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl group, n-butyl group and methyl group are preferable.
－構成単位（ａ２）の好ましい態様－
　上記構成単位（ａ２）を有する重合体が、実質的に、構成単位（ａ１）を有しない場合、構成単位（ａ２）は、該構成単位（ａ２）を有する重合体中、５～９０モル％が好ましく、２０～８０モル％がより好ましい。
　上記構成単位（ａ２）を有する重合体が、上記構成単位（ａ１）を有する場合、単構成単位（ａ２）は、該構成単位（ａ１）と構成単位（ａ２）を有する重合体中、薬品耐性の観点から３～７０モル％が好ましく、１０～６０モル％がより好ましい。
　本発明では、更に、いずれの態様にかかわらず、成分Ｄの全構成単位中、構成単位（ａ２）を３～７０モル％含有することが好ましく、１０～６０モル％含有することがより好ましい。
　上記の数値の範囲内であると、感光性樹脂組成物から得られる硬化膜の透明性及び薬品耐性が良好となる。 -Preferred embodiment of the structural unit (a2)-
When the polymer having the structural unit (a2) does not substantially have the structural unit (a1), the structural unit (a2) is 5 to 90 mol% in the polymer having the structural unit (a2). Is preferable, and 20 to 80 mol% is more preferable.
When the polymer having the structural unit (a2) has the structural unit (a1), the single structural unit (a2) has chemical resistance in the polymer having the structural unit (a1) and the structural unit (a2). From this viewpoint, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
In the present invention, 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.
Within the above numerical range, the cured film obtained from the photosensitive resin composition has good transparency and chemical resistance.
＜（ａ３）その他の構成単位＞
　本発明において、成分Ｄは、上記構成単位（ａ１）及び／又は（ａ２）に加えて、これら以外の他の構成単位（ａ３）を有していてもよい。これらの構成単位は、上記重合体成分（１）及び／又は（２）が含んでいてもよい。また、上記重合体成分（１）又は（２）とは別に、実質的に構成単位（ａ１）及び構成単位（ａ２）を含まずに他の構成単位（ａ３）を有する重合体成分を有していてもよい。上記重合体成分（１）又は（２）とは別に、実質的に構成単位（ａ１）及び構成単位（ａ２）を有さずに他の構成単位（ａ３）を有する重合体成分を含む場合、該重合体成分の配合量は、全重合体成分中、６０質量％以下であることが好ましく、４０質量％以下であることがより好ましく、２０質量％以下であることが更に好ましい。 <(A3) Other structural units>
In the present invention, the component D may have another structural unit (a3) in addition to the structural units (a1) and / or (a2). These structural units may be contained in the polymer component (1) and / or (2). In addition to the polymer component (1) or (2), the polymer component has another structural unit (a3) substantially free from the structural unit (a1) and the structural unit (a2). It may be. Apart from the polymer component (1) or (2), in the case of containing a polymer component having other structural unit (a3) substantially without the structural unit (a1) and the structural unit (a2), The blending amount of the polymer component is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in all polymer components.
　その他の構成単位（ａ３）となるモノマーとしては、特に制限はなく、例えば、スチレン類、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸環状アルキルエステル、（メタ）アクリル酸アリールエステル、不飽和ジカルボン酸ジエステル、ビシクロ不飽和化合物類、マレイミド化合物類、不飽和芳香族化合物、共役ジエン系化合物、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和ジカルボン酸無水物、その他の不飽和化合物を挙げることができる。また、後述するとおり、酸基を有する構成単位を有していてもよい。その他の構成単位（ａ３）となるモノマーは、１種単独又は２種類以上を組み合わせて使用することができる。 There is no restriction | limiting in particular as 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. Moreover, you may have the structural unit which has an acid group so that it may mention later. The monomer which becomes another structural unit (a3) can be used individually by 1 type or in combination of 2 or more types.
　以下に、本発明における重合体成分の好ましい実施形態を挙げるが、本発明はこれらに限定されるものではない。
－第１の実施形態－
　重合体成分（１）が、更に、１種又は２種以上のその他の構成単位（ａ３）を有する態様。
－第２の実施形態－
　重合体成分（２）の（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体が、更に、１種又は２種以上のその他の構成単位（ａ３）を有する態様。
－第３の実施形態－
　重合体成分（２）の（ａ２）架橋性基を有する構成単位を有する重合体が、更に、１種又は２種以上のその他の構成単位（ａ３）を有する態様。 Hereinafter, preferred embodiments of the polymer component in the present invention will be described, but the present invention is not limited thereto.
-First embodiment-
The aspect in which the polymer component (1) further has one or more other structural units (a3).
-Second Embodiment-
The polymer having a structural unit in which the (a1) acid group of the polymer component (2) has a group protected with an acid-decomposable group further has one or more other structural units (a3). Aspect.
-Third embodiment-
The aspect which the polymer which has a structural unit which has a (a2) crosslinkable group of a polymer component (2) further has 1 type, or 2 or more types of other structural units (a3).
－第４の実施形態－
　上記第１～第３の実施形態のいずれかにおいて、その他の構成単位（ａ３）として、少なくとも酸基を含む構成単位をいずれかの重合体に有する態様。
－第５の実施形態－
　上記重合体成分（１）又は（２）とは別に、更に、実質的に構成単位（ａ１）及び構成単位（ａ２）を有さずに他の構成単位（ａ３）を有する重合体を有する態様。
－第６の実施形態－
　上記第１～第５の実施形態の２以上の組み合わせからなる態様。 -Fourth Embodiment-
In any one of the first to third embodiments, any polymer includes a structural unit containing at least an acid group as the other structural unit (a3).
-Fifth embodiment-
In addition to the polymer component (1) or (2), an embodiment having a polymer having another structural unit (a3) substantially not having the structural unit (a1) and the structural unit (a2). .
-Sixth embodiment-
A mode comprising a combination of two or more of the first to fifth embodiments.
　構成単位（ａ３）は、具体的には、スチレン、ｔｅｒｔ－ブトキシスチレン、メチルスチレン、ヒドロキシスチレン、α－メチルスチレン、アセトキシスチレン、メトキシスチレン、エトキシスチレン、クロロスチレン、ビニル安息香酸メチル、ビニル安息香酸エチル、４－ヒドロキシ安息香酸（３－メタクリロイルオキシプロピル）エステル、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸イソボルニル、アクリロニトリル、エチレングリコールモノアセトアセテートモノ（メタ）アクリレートなどによる構成単位を挙げることができる。この他、特開２００４－２６４６２３号公報の段落００２１～００２４に記載の化合物を挙げることができる。 The structural unit (a3) specifically includes styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid. Ethyl, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid Isopropyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate Mention may be made of a structural unit due to theft. In addition, compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.
　また、その他の構成単位（ａ３）としては、スチレン類、又は、脂肪族環式骨格を有するモノマー由来の構成単位が、電気特性の観点で好ましい。具体的にはスチレン、ｔｅｒｔ－ブトキシスチレン、メチルスチレン、ヒドロキシスチレン、α－メチルスチレン、ジシクロペンタニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート等が挙げられる。 As the other structural unit (a3), a structural unit derived from a monomer having a styrene or an aliphatic cyclic skeleton is preferable from the viewpoint of electrical characteristics. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.
　更にまた、その他の構成単位（ａ３）としては、（メタ）アクリル酸アルキルエステル由来の構成単位が、密着性の観点で好ましい。具体的には（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ｎ－ブチル等が挙げられ、（メタ）アクリル酸メチルがより好ましい。重合体を構成する構成単位中、上記の構成単位（ａ３）の含有率は、６０モル％以下が好ましく、５０モル％以下がより好ましく、４０モル％以下が更に好ましい。下限値としては、０モル％でもよいが、例えば、１モル％以上とすることが好ましく、５モル％以上とすることがより好ましい。上記の数値の範囲内であると、感光性樹脂組成物から得られる硬化膜の諸特性が良好となる。 Furthermore, as 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. In the structural unit constituting the polymer, 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. As a lower limit, although 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. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.
　成分Ｄに含まれる重合体は、その他の構成単位（ａ３）として、酸基を有する構成単位を有することが好ましい。重合体が酸基を有することにより、アルカリ性の現像液に溶けやすくなり、本発明の効果がより効果的に発揮される。本発明における酸基とは、ｐＫａが１０．５より小さいプロトン解離性基を意味する。また、上記ｐＫａは、－１５以上であることが好ましい。酸基は、通常、酸基を形成しうるモノマーを用いて、酸基を有する構成単位として、重合体に組み込まれる。このような酸基を有する構成単位を重合体中に含めることにより、アルカリ性の現像液に対して溶けやすくなる傾向にある。
　本発明で用いられる酸基としては、カルボン酸基、スルホンアミド基、ホスホン酸基、スルホン酸基、フェノール性水酸基、スルホンアミド基、スルホニルイミド基、並びに、これらの酸基の酸無水物基、及び、これらの酸基を中和し塩構造とした基等が例示され、カルボン酸基及び／又はフェノール性水酸基が好ましい。上記塩としては、特に制限はないが、アルカリ金属塩、アルカリ土類金属塩、及び、有機アンモニウム塩が好ましく例示できる。
　本発明で用いられる酸基を有する構成単位は、スチレン化合物に由来する構成単位や、ビニル化合物に由来する構成単位、（メタ）アクリル酸及び／又はそのエステルに由来する構成単位であることがより好ましい。
　本発明では、特に、カルボキシル基を有する構成単位、又は、フェノール性水酸基を有する構成単位を含有することが、感度の観点で好ましい。 The polymer contained in Component D preferably has a structural unit having an acid group as the other structural unit (a3). When the polymer has an acid group, the polymer easily dissolves in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa of less than 10.5. The pKa is preferably −15 or more. The acid group is usually incorporated into the polymer as a structural unit having an acid group using a monomer capable of forming an acid group. By including such a structural unit having 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. Although there is no restriction | limiting in particular as said salt, An alkali metal salt, alkaline-earth metal salt, and organic ammonium salt can illustrate preferably.
The structural unit having an acid group used in the present invention is more preferably a structural unit derived from a styrene compound, a structural unit derived from a vinyl compound, (meth) acrylic acid and / or an ester thereof. preferable.
In the present invention, it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.
　酸基を含む構成単位は、全重合体成分の構成単位の１～８０モル％が好ましく、１～５０モル％がより好ましく、５～４０モル％が更に好ましく、５～３０モル％が特に好ましく、５～２０モル％が特に好ましい。 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.
　本発明では、上記重合体成分（１）又は（２）とは別に、実質的に構成単位（ａ１）及び構成単位（ａ２）を含まずに他の構成単位（ａ３）を有する重合体を含んでいてもよい。
　このような重合体としては、側鎖にカルボキシル基を有する樹脂が好ましい。例えば、特開昭５９－４４６１５号、特公昭５４－３４３２７号、特公昭５８－１２５７７号、特公昭５４－２５９５７号、特開昭５９－５３８３６号、特開昭５９－７１０４８号の各公報に記載されているような、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体等、並びに側鎖にカルボキシル基を有する酸性セルロース誘導体、水酸基を有するポリマーに酸無水物を付加させたもの等が挙げられ、更に側鎖に（メタ）アクリロイル基を有する高分子重合体も好ましいものとして挙げられる。 In the present invention, apart from the polymer component (1) or (2), 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.
As such a polymer, a resin having a carboxyl group in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and 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.
　例えば、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、２－ヒドロキシエチル（メタ）アクリレート／ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、特開平７－１４０６５４号公報に記載の、２－ヒドロキシプロピル（メタ）アクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシ－３－フェノキシプロピルアクリレート／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／メチルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体などが挙げられる。
　その他にも、特開平７－２０７２１１号公報、特開平８－２５９８７６号公報、特開平１０－３００９２２号公報、特開平１１－１４０１４４号公報、特開平１１－１７４２２４号公報、特開２０００－５６１１８号公報、特開２００３－２３３１７９号公報、特開２００９－５２０２０号公報等に記載の公知の高分子化合物を使用することができる。
　これらの重合体は、１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。 For example, 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 Copolymer and the like.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used.
These polymers may contain only 1 type and may contain 2 or more types.
　これらの重合体として、市販されている、ＳＭＡ　１０００Ｐ、ＳＭＡ　２０００Ｐ、ＳＭＡ　３０００Ｐ、ＳＭＡ　１４４０Ｆ、ＳＭＡ　１７３５２Ｐ、ＳＭＡ　２６２５Ｐ、ＳＭＡ　３８４０Ｆ（以上、サートマー社製）、ＡＲＵＦＯＮ　ＵＣ－３０００、ＡＲＵＦＯＮ　ＵＣ－３５１０、ＡＲＵＦＯＮ　ＵＣ－３９００、ＡＲＵＦＯＮ　ＵＣ－３９１０、ＡＲＵＦＯＮ　ＵＣ－３９２０、ＡＲＵＦＯＮ　ＵＣ－３０８０（以上、東亞合成（株）製）、ＪＯＮＣＲＹＬ　６９０、ＪＯＮＣＲＹＬ　６７８、ＪＯＮＣＲＹＬ　６７、ＪＯＮＣＲＹＬ　５８６（以上、ＢＡＳＦ社製）等を用いることもできる。 As these polymers, commercially available 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.
－成分Ｄにおける重合体の分子量－
　成分Ｄにおける重合体の分子量は、ポリスチレン換算重量平均分子量で、１，０００～２００，０００であることが好ましく、２，０００～５０，０００であることがより好ましい。上記の数値の範囲内であると、諸特性が良好である。数平均分子量Ｍｎと重量平均分子量Ｍｗとの比（分散度、Ｍｗ／Ｍｎ）は１．０～５．０が好ましく、１．５～３．５がより好ましい。 -Molecular weight of polymer in component D-
The molecular weight of the polymer in Component D is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000 in terms of polystyrene-converted weight average molecular weight. 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.
－成分Ｄにおける重合体の製造方法－
　また、成分Ｄにおける重合体の合成法についても、様々な方法が知られているが、一例を挙げると、少なくとも上記構成単位（ａ１）及び上記構成単位（ａ３）を形成するために用いられるラジカル重合性単量体を含むラジカル重合性単量体混合物を有機溶剤中、ラジカル重合開始剤を用いて重合することにより合成することができる。また、いわゆる高分子反応で合成することもできる。 -Method for producing polymer in component D-
Various methods for synthesizing the polymer in component D are also known. To give an example, radicals used to form at least the structural unit (a1) and the structural unit (a3). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
　本発明の感光性樹脂組成物中における成分Ｄの含有量は、感光性樹脂組成物の全固形分に対して、２０～９９．９質量％であることが好ましく、５０～９８質量％であることがより好ましく、７０～９５質量％であることが更に好ましい。含有量がこの範囲であると、現像した際のパターン形成性が良好となり、また、より高屈折率の硬化物が得られる。 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.
（成分Ｅ）光酸発生剤
　本発明の感光性樹脂組成物は、（成分Ｅ）光酸発生剤を含有する。
　本発明で使用される光酸発生剤としては、波長３００ｎｍ以上、好ましくは波長３００～４５０ｎｍの活性光線に感応し、酸を発生する化合物が好ましいが、その化学構造に制限されるものではない。また、波長３００ｎｍ以上の活性光線に直接感応しない光酸発生剤についても、増感剤と併用することによって波長３００ｎｍ以上の活性光線に感応し、酸を発生する化合物であれば、増感剤と組み合わせて好ましく用いることができる。本発明で使用される光酸発生剤としては、ｐＫａが４以下の酸を発生する光酸発生剤が好ましく、ｐＫａが３以下の酸を発生する光酸発生剤がより好ましく、ｐＫａが２以下の酸を発生する光酸発生剤が最も好ましい。また、上記ｐＫａは、－１５以上であることが好ましい。 (Component E) Photoacid Generator 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. Further, 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. The pKa is preferably −15 or more.
　光酸発生剤の例として、トリクロロメチル－ｓ－トリアジン類、スルホニウム塩やヨードニウム塩、第四級アンモニウム塩類、ジアゾメタン化合物、イミドスルホネート化合物、及び、オキシムスルホネート化合物などを挙げることができる。これらの中でも、絶縁性、感度の観点から、オキシムスルホネート化合物を用いることが好ましい。これら光酸発生剤は、１種単独又は２種類以上を組み合わせて使用することができる。トリクロロメチル－ｓ－トリアジン類、ジアリールヨードニウム塩類、トリアリールスルホニウム塩類、第四級アンモニウム塩類、及び、ジアゾメタン誘導体の具体例としては、特開２０１１－２２１４９４号公報の段落００８３～００８８に記載の化合物が例示できる。 Examples of the photoacid generator 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. These photoacid generators can be used singly or in combination of two or more. Specific examples of 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.
　オキシムスルホネート化合物、すなわち、オキシムスルホネート構造を有する化合物としては、下記式（Ｅ１）で表されるオキシムスルホネート構造を含有する化合物が好ましく例示できる。 Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following formula (E1).
Figure JPOXMLDOC01-appb-C000013
 （式（Ｅ１）中、Ｒ21は、アルキル基又はアリール基を表し、波線部分は他の基との結合箇所を表す。）
Figure JPOXMLDOC01-appb-C000013
 (In the formula (E1), R 21 represents an alkyl group or an aryl group, the wavy line portion represents a bonding site to another group.)
　いずれの基も置換されてもよく、Ｒ21におけるアルキル基は直鎖状でも分岐状でも環状でもよい。許容される置換基は以下に説明する。
　Ｒ21のアルキル基としては、炭素数１～１０の、直鎖状又は分岐状アルキル基が好ましい。Ｒ21のアルキル基は、炭素数６～１１のアリール基、炭素数１～１０のアルコキシ基、又は、シクロアルキル基（７，７－ジメチル－２－オキソノルボルニル基などの有橋式脂環基を含む、好ましくはビシクロアルキル基等）で置換されてもよい。
　Ｒ21のアリール基としては、炭素数６～１１のアリール基が好ましく、フェニル基又はナフチル基がより好ましい。Ｒ21のアリール基は、炭素数１～１０のアルキル基、炭素数１～１０のアルコキシ基又はハロゲン原子で置換されてもよい。 Any group may be substituted, and the alkyl group in R 21 may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R 21 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like). It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
As the 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.
　上記式（Ｅ１）で表されるオキシムスルホネート構造を含有する上記化合物は、下記式（Ｅ２）で表されるオキシムスルホネート化合物であることも好ましい。 The above compound containing an oxime sulfonate structure represented by the above formula (E1) is also preferably an oxime sulfonate compound represented by the following formula (E2).
Figure JPOXMLDOC01-appb-C000014
 （式（Ｅ２）中、Ｒ42は、アルキル基又はアリール基を表し、Ｘは、アルキル基、アルコキシ基又はハロゲン原子を表し、ｍ４は、０～３の整数を表し、ｍ４が２又は３であるとき、複数のＸは同一でも異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000014
 (In the formula (E2), R 42 represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents an integer of 0 to 3, and m4 is 2 or 3. In some cases, multiple Xs may be the same or different.)
　Ｘとしてのアルキル基は、炭素数１～４の直鎖状又は分岐状アルキル基が好ましい。
　Ｘとしてのアルコキシ基は、炭素数１～４の直鎖状又は分岐状アルコキシ基が好ましい。
　Ｘとしてのハロゲン原子は、塩素原子又はフッ素原子が好ましい。
　ｍ４は、０又は１が好ましい。上記式（Ｅ２）中、ｍ４が１であり、Ｘがメチル基であり、Ｘの置換位置がオルト位であり、Ｒ42が炭素数１～１０の直鎖状アルキル基、７，７－ジメチル－２－オキソノルボルニルメチル基、又は、ｐ－トルイル基である化合物が特に好ましい。 The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1. In the above formula (E2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl A compound having a -2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.
　上記式（Ｅ１）で表されるオキシムスルホネート構造を含有する化合物は、下記式（Ｅ３）で表されるオキシムスルホネート化合物であることも好ましい。 The compound containing an oxime sulfonate structure represented by the above formula (E1) is also preferably an oxime sulfonate compound represented by the following formula (E3).
Figure JPOXMLDOC01-appb-C000015
 （式（Ｅ３）中、Ｒ43は式（Ｅ２）におけるＲ42と同義であり、Ｘ1は、ハロゲン原子、水酸基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、シアノ基又はニトロ基を表し、ｎ４は０～５の整数を表す。）
Figure JPOXMLDOC01-appb-C000015
 (In the formula (E3), R 43 has the same meaning as R 42 in the formula (E2). X 1 represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and n4 represents an integer of 0 to 5.)
　上記式（Ｅ３）におけるＲ43としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－オクチル基、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロ－ｎ－プロピル基、パーフルオロ－ｎ－ブチル基、ｐ－トリル基、４－クロロフェニル基又はペンタフルオロフェニル基が好ましく、ｎ－オクチル基が特に好ましい。
　Ｘ1としては、炭素数１～５のアルコキシ基が好ましく、メトキシ基がより好ましい。
　ｎ４としては、０～２の整数が好ましく、０又は１が特に好ましい。 R 43 in the above formula (E3) is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-octyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoro-n-propyl group, A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferred, and an n-octyl group is particularly preferred.
X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
n4 is preferably an integer of 0 to 2, particularly preferably 0 or 1.
　上記式（Ｅ３）で表される化合物の具体例としては、α－（メチルスルホニルオキシイミノ）ベンジルシアニド、α－（エチルスルホニルオキシイミノ）ベンジルシアニド、α－（ｎ－プロピルスルホニルオキシイミノ）ベンジルシアニド、α－（ｎ－ブチルスルホニルオキシイミノ）ベンジルシアニド、α－（４－トルエンスルホニルオキシイミノ）ベンジルシアニド、α－〔（メチルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（エチルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（ｎ－プロピルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（ｎ－ブチルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（４－トルエンスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリルを挙げることができる。 Specific examples of the compound represented by the above formula (E3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) Benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α -[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4-methoxy Phenyl] acetonitrile, α-[(4-to Can be exemplified ene sulfonyl) -4-methoxyphenyl] acetonitrile.
　好ましいオキシムスルホネート化合物の具体例としては、下記化合物（i）～（viii）等が挙げられ、１種単独で使用、又は、２種類以上を併用することができる。化合物（i）～（viii）は、市販品として、入手することができる。また、他の種類の（成分Ｅ）光酸発生剤と組み合わせて使用することもできる。 Specific examples of preferred oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used alone or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. It can also be used in combination with other types of (component E) photoacid generators.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　上記式（Ｅ１）で表されるオキシムスルホネート構造を含有する化合物としては、下記式（ＯＳ－１）で表される化合物であることも好ましい。 The compound containing an oxime sulfonate structure represented by the above formula (E1) is also preferably a compound represented by the following formula (OS-1).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記式（ＯＳ－１）中、Ｒ101は、水素原子、アルキル基、アルケニル基、アルコキシ基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基、又は、ヘテロアリール基を表す。Ｒ102は、アルキル基、又は、アリール基を表す。
　Ｘ101は－Ｏ－、－Ｓ－、－ＮＨ－、－ＮＲ105－、－ＣＨ2－、－ＣＲ106Ｈ－、又は、－ＣＲ105Ｒ107－を表し、Ｒ105～Ｒ107はアルキル基、又は、アリール基を表す。
　Ｒ121～Ｒ124はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基、又は、アリール基を表す。Ｒ121～Ｒ124のうち２つは、それぞれ互いに結合して環を形成してもよい。
　Ｒ121～Ｒ124としてはそれぞれ独立に、水素原子、ハロゲン原子、又は、アルキル基が好ましく、また、Ｒ121～Ｒ124のうち少なくとも２つが互いに結合してアリール基を形成する態様もまた、好ましく挙げられる。中でも、Ｒ121～Ｒ124がいずれも水素原子である態様が感度の観点から好ましい。
　既述の官能基は、いずれも、更に置換基を有していてもよい。 In the above formula (OS-1), R 101 represents a hydrogen atom, alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, aryl group, or hetero Represents an aryl group. R102 represents an alkyl group or an aryl group.
X 101 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups. Or an aryl group.
R 121 to R 124 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or Represents an aryl group. Two of R 121 to R 124 may be bonded to each other to form a ring.
R 121 to R 124 are each independently preferably a hydrogen atom, a halogen atom or an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferable. Can be mentioned. Among these, an embodiment in which R 121 to R 124 are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.
　上記式（ＯＳ－１）で表される化合物は、下記式（ＯＳ－２）で表される化合物であることがより好ましい。 The compound represented by the above formula (OS-1) is more preferably a compound represented by the following formula (OS-2).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記式（ＯＳ－２）中、Ｒ101、Ｒ102、Ｒ121～Ｒ124は、それぞれ式（ＯＳ－１）におけるものと同義であり、好ましい例もまた同様である。
　これらの中でも、上記式（ＯＳ－１）及び上記式（ＯＳ－２）におけるＲ101がシアノ基、又は、アリール基である態様がより好ましく、上記式（ＯＳ－２）で表され、Ｒ101がシアノ基、フェニル基又はナフチル基である態様が最も好ましい。 In the above formula (OS-2), R 101 , R 102 and R 121 to R 124 have the same meanings as those in the formula (OS-1), and preferred examples thereof are also the same.
Among them, the formulas (OS-1) and the formula (OS-2) in R 101 is a cyano group, or, more preferably embodiment an aryl group is represented by the above formula (OS-2), R 101 The embodiment in which is a cyano group, a phenyl group or a naphthyl group is most preferred.
　また、本発明におけるオキシムスルホネート化合物において、オキシムやベンゾチアゾール環の立体構造（Ｅ，Ｚ等）のついてはそれぞれ、どちらか一方であっても、混合物であってもよい。 In the oxime sulfonate compound of the present invention, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
　本発明に好適に用いうる上記式（ＯＳ－１）で表される化合物の具体例としては、特開２０１１－２２１４９４号公報の段落０１２８～０１３２に記載の化合物（例示化合物ｂ－１～ｂ－３４）が挙げられるが、本発明はこれに限定されない。 Specific examples of the compound represented by the formula (OS-1) that can be suitably used in the present invention include compounds described in paragraphs 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to b- 34), but the present invention is not limited to this.
　本発明では、上記式（Ｅ１）で表されるオキシムスルホネート構造を含有する化合物としては、下記式（ＯＳ－３）、下記式（ＯＳ－４）又は下記式（ＯＳ－５）で表されるオキシムスルホネート化合物であることが好ましい。 In the present invention, the compound having an oxime sulfonate structure represented by the above formula (E1) is represented by the following formula (OS-3), the following formula (OS-4) or the following formula (OS-5). It is preferably an oxime sulfonate compound.
Figure JPOXMLDOC01-appb-C000019
 （式（ＯＳ－３）～式（ＯＳ－５）中、Ｒ22、Ｒ25及びＲ28はそれぞれ独立に、アルキル基、アリール基又はヘテロアリール基を表し、Ｒ23、Ｒ26及びＲ29はそれぞれ独立に、水素原子、アルキル基、アリール基又はハロゲン原子を表し、Ｒ24、Ｒ27及びＲ30はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表し、Ｘ1～Ｘ3はそれぞれ独立に、酸素原子又は硫黄原子を表し、ｎ1～ｎ3はそれぞれ独立に、１又は２を表し、ｍ1～ｍ3はそれぞれ独立に、０～６の整数を表す。）
Figure JPOXMLDOC01-appb-C000019
 (In the formulas (OS-3) to (OS-5), R 22 , R 25 and R 28 each independently represents an alkyl group, an aryl group or a heteroaryl group, and R 23 , R 26 and R 29 are Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxy group. Represents a sulfonyl group, X 1 to X 3 each independently represents an oxygen atom or a sulfur atom, n 1 to n 3 each independently represents 1 or 2, and m 1 to m 3 each independently represents 0 Represents an integer of ~ 6)
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25及びＲ28におけるアルキル基、アリール基又はヘテロアリール基は、置換基を有していてもよい。
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25及びＲ28におけるアルキル基としては、置換基を有していてもよい総炭素数１～３０のアルキル基であることが好ましい。
　また、上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25及びＲ28におけるアリール基としては、置換基を有してもよい総炭素数６～３０のアリール基が好ましい。
　また、上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25及びＲ28におけるヘテロアリール基としては、置換基を有してもよい総炭素数４～３０のヘテロアリール基が好ましい。
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25及びＲ28におけるヘテロアリール基は、少なくとも１つの環が複素芳香環であればよく、例えば、複素芳香環とベンゼン環とが縮環していてもよい。 In the above formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R 22 , R 25 and R 28 may have a substituent.
In the above formulas (OS-3) to (OS-5), the alkyl group in R 22 , R 25 and R 28 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.
In the above formulas (OS-3) to (OS-5), the aryl group in R 22 , R 25 and R 28 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent. .
In the above formulas (OS-3) to (OS-5), the heteroaryl group in R 22 , R 25 and R 28 is a heteroaryl group having a total of 4 to 30 carbon atoms which may have a substituent. Is preferred.
In the above formulas (OS-3) to (OS-5), at least one of the heteroaryl groups in R 22 , R 25 and R 28 may be a heteroaromatic ring, such as a heteroaromatic ring and a benzene ring. And may be condensed.
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ23、Ｒ26及びＲ29は、水素原子、アルキル基又はアリール基であることが好ましく、水素原子又はアルキル基であることがより好ましい。
　上記式（ＯＳ－３）～（ＯＳ－５）中、化合物中に２以上存在するＲ23、Ｒ26及びＲ29のうち、１つ又は２つがアルキル基、アリール基又はハロゲン原子であることが好ましく、１つがアルキル基、アリール基又はハロゲン原子であることがより好ましく、１つがアルキル基であり、かつ残りが水素原子であることが特に好ましい。 In the above formulas (OS-3) to (OS-5), R 23 , R 26 and R 29 are preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group. .
In the above formulas (OS-3) to (OS-5), one or two of R 23 , R 26 and R 29 present in the compound may be an alkyl group, an aryl group or a halogen atom. More preferably, one is an alkyl group, an aryl group or a halogen atom, more preferably one is an alkyl group and the rest is a hydrogen atom.
　Ｒ23、Ｒ26及びＲ29におけるアルキル基としては、置換基を有してもよい総炭素数１～１２のアルキル基であることが好ましく、置換基を有してもよい総炭素数１～６のアルキル基であることがより好ましい。 The alkyl group for R 23 , R 26 and R 29 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.
　Ｒ23、Ｒ26及びＲ29におけるアリール基としては、置換基を有してもよい総炭素数６～３０のアリール基であることが好ましい。 The aryl group for R 23 , R 26 and R 29 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｘ1～Ｘ3はそれぞれ独立に、Ｏ又はＳを表し、Ｏであることが好ましい。
　上記式（ＯＳ－３）～（ＯＳ－５）において、Ｘ1～Ｘ3を環員として含む環は、５員環又は６員環である。
　上記式（ＯＳ－３）～（ＯＳ－５）中、ｎ1～ｎ3はそれぞれ独立に、１又は２を表し、Ｘ1～Ｘ3がＯである場合、ｎ1～ｎ3はそれぞれ独立に、１であることが好ましく、また、Ｘ1～Ｘ3がＳである場合、ｎ1～ｎ3はそれぞれ独立に、２であることが好ましい。 In the above formulas (OS-3) to (OS-5), X 1 to X 3 each independently represents O or S, and is preferably O.
In the above formulas (OS-3) to (OS-5), the ring containing X 1 to X 3 as a ring member is a 5-membered ring or a 6-membered ring.
In the formulas (OS-3) to (OS-5), n 1 to n 3 each independently represents 1 or 2, and when X 1 to X 3 are O, n 1 to n 3 are each independently In addition, it is preferably 1, and when X 1 to X 3 are S, n 1 to n 3 are each independently preferably 2.
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ24、Ｒ27及びＲ30はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表す。その中でも、Ｒ24、Ｒ27及びＲ30はそれぞれ独立に、アルキル基又はアルキルオキシ基であることが好ましい。
　Ｒ24、Ｒ27及びＲ30におけるアルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基及びアルコキシスルホニル基は、置換基を有していてもよい。
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ24、Ｒ27及びＲ30におけるアルキル基としては、置換基を有していてもよい総炭素数１～３０のアルキル基であることが好ましい。
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ24、Ｒ27及びＲ30におけるアルキルオキシ基としては、置換基を有してもよい総炭素数１～３０のアルキルオキシ基であることが好ましい。 In the above formulas (OS-3) to (OS-5), R 24 , R 27 and R 30 each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. To express. Among these, R 24 , R 27 and R 30 are preferably each independently an alkyl group or alkyloxy group.
The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R 24 , R 27 and R 30 may have a substituent.
In the above formulas (OS-3) to (OS-5), the alkyl group in R 24 , R 27 and R 30 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.
In the above formulas (OS-3) to (OS-5), the alkyloxy group in R 24 , R 27 and R 30 is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. It is preferable.
　また、上記式（ＯＳ－３）～（ＯＳ－５）中、ｍ1～ｍ3はそれぞれ独立に、０～６の整数を表し、０～２の整数であることが好ましく、０又は１であることがより好ましく、０であることが特に好ましい。
　また、上記式（ＯＳ－３）～（ＯＳ－５）のそれぞれの置換基について、特開２０１１－２２１４９４号公報の段落００９２～０１０９に記載の（ＯＳ－３）～（ＯＳ－５）の置換基の好ましい範囲も同様に好ましい。 In the above formulas (OS-3) to (OS-5), m 1 to m 3 each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0.
In addition, for each substituent of the above formulas (OS-3) to (OS-5), the substitution of (OS-3) to (OS-5) described in paragraphs 0092 to 0109 of JP2011-221494A The preferred range of groups is likewise preferred.
　また、上記式（Ｅ１）で表されるオキシムスルホネート構造を含有する化合物は、下記式（ＯＳ－６）～（ＯＳ－１１）のいずれかで表されるオキシムスルホネート化合物であることが特に好ましい。 The compound containing an oxime sulfonate structure represented by the above formula (E1) is particularly preferably an oxime sulfonate compound represented by any of the following formulas (OS-6) to (OS-11).
Figure JPOXMLDOC01-appb-C000020
 （式（ＯＳ－６）～（ＯＳ－１１）中、Ｒ301～Ｒ306はアルキル基、アリール基又はヘテロアリール基を表し、Ｒ307は、水素原子又は臭素原子を表し、Ｒ308～Ｒ310、Ｒ313、Ｒ316及びＲ318はそれぞれ独立に、水素原子、炭素数１～８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、Ｒ311及びＲ314はそれぞれ独立に、水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、Ｒ312、Ｒ315、Ｒ317及びＲ319はそれぞれ独立には、水素原子又はメチル基を表す。）
Figure JPOXMLDOC01-appb-C000020
 (In the formulas (OS-6) to (OS-11), R 301 to R 306 represent an alkyl group, an aryl group, or a heteroaryl group, R 307 represents a hydrogen atom or a bromine atom, and R 308 to R 310 , R 313 , R 316 and R 318 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group. , R 311 and R 314 each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R 312 , R 315 , R 317 and R 319 each independently represent a hydrogen atom or a methyl group. )
　上記式（ＯＳ－６）～（ＯＳ－１１）における好ましい範囲は、特開２０１１－２２１４９４号公報の段落０１１０～０１１２に記載される（ＯＳ－６）～（ＯＳ－１１）の好ましい範囲と同様である。 Preferred ranges in the above formulas (OS-6) to (OS-11) are the same as the preferred ranges of (OS-6) to (OS-11) described in paragraphs 0110 to 0112 of JP2011-221494A. It is.
　上記式（ＯＳ－３）～上記式（ＯＳ－５）で表されるオキシムスルホネート化合物の具体例としては、特開２０１１－２２１４９４号公報の段落０１１４～０１２０に記載の化合物が挙げられるが、本発明は、これらに限定されるものではない。 Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-3) to (OS-5) include the compounds described in paragraphs 0114 to 0120 of JP2011-221494A. The invention is not limited to these.
　本発明の感光性樹脂組成物において、（成分Ｅ）光酸発生剤は、感光性樹脂組成物中の成分Ｄ１００質量部に対して、０．１～１０質量部使用することが好ましく、０．５～１０質量部使用することがより好ましい。
　また、成分Ｅは、１種単独で使用してもよいし、２種以上を併用することもできる。 In the photosensitive resin composition of the present invention, (Component E) 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.
Moreover, the component E may be used individually by 1 type, and can also use 2 or more types together.
（成分Ｆ）熱架橋剤
　本発明の感光性樹脂組成物は、必要に応じ、熱架橋剤を含有することが好ましい。熱架橋剤を添加することにより、本発明の感光性樹脂組成物により得られる硬化膜をより強固な膜とすることができる。
　熱架橋剤としては、熱によって架橋反応が起こるものであれば制限はない（ただし、成分Ｄを除く。）。例えば、以下に述べる分子内に２個以上のエポキシ基若しくはオキセタニル基を有する化合物、アルコキシメチル基含有架橋剤、少なくとも１個のエチレン性不飽和二重結合を有する化合物、又は、ブロックイソシアネート化合物等を添加することができる。
　本発明の感光性樹脂組成物中における熱架橋剤の添加量は、感光性樹脂組成物の全固形分１００質量部に対し、０．０１～５０質量部であることが好ましく、０．１～３０質量部であることがより好ましく、０．５～２０質量部であることが更に好ましい。この範囲で添加することにより、機械的強度及び耐溶剤性に優れた硬化膜が得られる。熱架橋剤は複数を併用することもでき、その場合は熱架橋剤を全て合算して含有量を計算する。 (Component F) Thermal crosslinking agent It is preferable that the photosensitive resin composition of the present invention contains a thermal crosslinking agent, if necessary. 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 crosslinking agent is not limited as long as it causes a crosslinking reaction by heat (excluding component D). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing 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.
＜分子内に２個以上のエポキシ基又はオキセタニル基を有する化合物＞
　分子内に２個以上のエポキシ基を有する化合物の具体例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂肪族エポキシ樹脂等を挙げることができる。 <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.
　これらは市販品として入手できる。例えば、ＪＥＲ１５７Ｓ７０、ＪＥＲ１５７Ｓ６５（三菱化学（株）製）など、特開２０１１－２２１４９４号公報の段落０１８９に記載の市販品などが挙げられる。
　その他にも、ＡＤＥＫＡ　ＲＥＳＩＮ　ＥＰ－４０００Ｓ、同ＥＰ－４００３Ｓ、同ＥＰ－４０１０Ｓ、同ＥＰ－４０１１Ｓ（以上、（株）ＡＤＥＫＡ製）、ＮＣ－２０００、ＮＣ－３０００、ＮＣ－７３００、ＸＤ－１０００、ＥＰＰＮ－５０１、ＥＰＰＮ－５０２（以上、（株）ＡＤＥＫＡ製）、デナコールＥＸ－６１１、ＥＸ－６１２、ＥＸ－６１４、ＥＸ－６１４Ｂ、ＥＸ－６２２、ＥＸ－５１２、ＥＸ－５２１、ＥＸ－４１１、ＥＸ－４２１、ＥＸ－３１３、ＥＸ－３１４、ＥＸ－３２１、ＥＸ－２１１、ＥＸ－２１２、ＥＸ－８１０、ＥＸ－８１１、ＥＸ－８５０、ＥＸ－８５１、ＥＸ－８２１、ＥＸ－８３０、ＥＸ－８３２、ＥＸ－８４１、ＥＸ－９１１、ＥＸ－９４１、ＥＸ－９２０、ＥＸ－９３１、ＥＸ－２１２Ｌ、ＥＸ－２１４Ｌ、ＥＸ－２１６Ｌ、ＥＸ－３２１Ｌ、ＥＸ－８５０Ｌ、ＤＬＣ－２０１、ＤＬＣ－２０３、ＤＬＣ－２０４、ＤＬＣ－２０５、ＤＬＣ－２０６、ＤＬＣ－３０１、ＤＬＣ－４０２（以上、ナガセケムテックス（株）製）、ＹＨ－３００、ＹＨ－３０１、ＹＨ－３０２、ＹＨ－３１５、ＹＨ－３２４、ＹＨ－３２５（以上、新日鐵化学（株）製）などが挙げられる。
　これらは１種単独又は２種以上を組み合わせて使用することができる。 These are available as commercial products. Examples thereof include commercially available products described in paragraph 0189 of JP 2011-221494, such as JER157S70 and JER157S65 (manufactured by Mitsubishi Chemical Corporation).
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX- 832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX- 14L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (above, Nagase ChemteX Corporation) YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.).
These can be used alone or in combination of two or more.
　これらの中でも、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂及び脂肪族エポキシ樹脂がより好ましく挙げられ、ビスフェノールＡ型エポキシ樹脂が特に好ましく挙げられる。 Among these, 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.
　分子内に２個以上のオキセタニル基を有する化合物の具体例としては、アロンオキセタンＯＸＴ－１２１、ＯＸＴ－２２１、ＯＸ－ＳＱ、ＰＮＯＸ（以上、東亞合成（株）製）を用いることができる。
　また、オキセタニル基を含む化合物は、単独で又はエポキシ基を含む化合物と混合して使用することが好ましい。 As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.
　また、その他の熱架橋剤としては、特開２０１２－８２２３号公報の段落０１０７～０１０８に記載のアルコキシメチル基含有架橋剤、及び、少なくとも１個のエチレン性不飽和二重結合を有する化合物なども好ましく用いることができる。アルコキシメチル基含有架橋剤としては、アルコキシメチル化グリコールウリルが好ましい。 Other thermal crosslinking agents include alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A, and compounds having at least one ethylenically unsaturated double bond. It can be preferably used. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.
＜ブロックイソシアネート化合物＞
　本発明の感光性樹脂組成物では、熱架橋剤として、ブロックイソシアネート化合物も好ましく採用できる。ブロックイソシアネート化合物は、ブロックイソシアネート基を有する化合物であれば特に制限はないが、硬化性の観点から、１分子内に２以上のブロックイソシアネート基を有する化合物であることが好ましい。
　なお、本発明におけるブロックイソシアネート基とは、熱によりイソシアネート基を生成することが可能な基であり、例えば、ブロック剤とイソシアネート基とを反応させイソシアネート基を保護した基が好ましく例示できる。また、上記ブロックイソシアネート基は、９０℃～２５０℃の熱によりイソシアネート基を生成することが可能な基であることが好ましい。
　また、ブロックイソシアネート化合物としては、その骨格は特に限定されるものではなく、１分子中にイソシアネート基を２個有するものであればどのようなものでもよく、脂肪族、脂環族又は芳香族のポリイソシアネートであってよいが、例えば２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、イソホロンジイソシアネート、１，６－ヘキサメチレンジイソシアネート、１，３－トリメチレンジイソシアネート、１，４－テトラメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、１，９－ノナメチレンジイソシアネート、１，１０－デカメチレンジイソシアネート、１，４－シクロヘキサンジイソシアネート、２，２’－ジエチルエーテルジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、ｏ－キシレンジイソシアネート、ｍ－キシレンジイソシアネート、ｐ－キシレンジイソシアネート、メチレンビス（シクロヘキシルイソシアネート）、シクロヘキサン－１，３－ジメチレンジイソシアネート、シクロヘキサン－１，４－ジメチレレンジイソシアネート、１，５－ナフタレンジイソシアネート、ｐ－フェニレンジイソシアネート、３，３’－メチレンジトリレン－４，４’－ジイソシアネート、４，４’－ジフェニルエーテルジイソシアネート、テトラクロロフェニレンジイソシアネート、ノルボルナンジイソシアネート、水素化１，３－キシリレンジイソシアネート、水素化１，４－キシリレンジイソシアネート等のイソシアネート化合物及びこれらの化合物から派生するプレポリマー型の骨格の化合物を好適に用いることができる。これらの中でも、トリレンジイソシアネート（ＴＤＩ）やジフェニルメタンジイソシアネート（ＭＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）が特に好ましい。 <Block isocyanate compound>
In the photosensitive resin composition of the present invention, 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.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, 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.
Further, 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 is aliphatic, alicyclic or aromatic. Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1, 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, Isocyanate compounds such as hydrogenated 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate And prepolymer-type skeleton compounds derived from these compounds can be suitably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
　本発明の感光性樹脂組成物におけるブロックイソシアネート化合物の母構造としては、ビウレット型、イソシアヌレート型、アダクト型、２官能プレポリマー型等を挙げることができる。
　上記ブロックイソシアネート化合物のブロック構造を形成するブロック剤としては、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物、メルカプタン化合物、イミダゾール系化合物、イミド系化合物等を挙げることができる。これらの中でも、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物から選ばれるブロック剤が特に好ましい。 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. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
　上記オキシム化合物としては、アルドキシム、及び、ケトオキシムが挙げられ、具体的には、アセトキシム、ホルムアルドキシム、シクロヘキサンオキシム、メチルエチルケトンオキシム、シクロヘキサノンオキシム、ベンゾフェノンオキシム、アセトキシム等が例示できる。
　上記ラクタム化合物としては、ε－カプロラクタム、γ－ブチロラクタム等が例示できる。
　上記フェノール化合物としては、フェノール、ナフトール、クレゾール、キシレノール、ハロゲン置換フェノール等が例示できる。
　上記アルコール化合物としては、メタノール、エタノール、プロパノール、ブタノール、シクロヘキサノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、乳酸アルキル等が例示できる。
　上記アミン化合物としては、１級アミン及び２級アミンが上げられ、芳香族アミン、脂肪族アミン、脂環族アミンいずれでもよく、アニリン、ジフェニルアミン、エチレンイミン、ポリエチレンイミン等が例示できる。
　上記活性メチレン化合物としては、マロン酸ジエチル、マロン酸ジメチル、アセト酢酸エチル、アセト酢酸メチル等が例示できる。
　上記ピラゾール化合物としては、ピラゾール、メチルピラゾール、ジメチルピラゾール等が例示できる、
　上記メルカプタン化合物としては、アルキルメルカプタン、アリールメルカプタン等が例示できる。 Examples of the oxime compound include aldoxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-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.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
　本発明の感光性樹脂組成物に使用できるブロックイソシアネート化合物は、市販品として入手可能であり、例えば、コロネートＡＰステーブルＭ、コロネート２５０３、２５１５、２５０７、２５１３、２５５５、ミリオネートＭＳ－５０（以上、日本ポリウレタン工業（株）製）、タケネートＢ－８３０、Ｂ－８１５Ｎ、Ｂ－８２０ＮＳＵ、Ｂ－８４２Ｎ、Ｂ－８４６Ｎ、Ｂ－８７０Ｎ、Ｂ－８７４Ｎ、Ｂ－８８２Ｎ（以上、三井化学（株）製）、デュラネート１７Ｂ－６０ＰＸ、１７Ｂ－６０Ｐ、ＴＰＡ－Ｂ８０Ｘ、ＴＰＡ－Ｂ８０Ｅ、ＭＦ－Ｂ６０Ｘ、ＭＦ－Ｂ６０Ｂ、ＭＦ－Ｋ６０Ｘ、ＭＦ－Ｋ６０Ｂ、Ｅ４０２－Ｂ８０Ｂ、ＳＢＮ－７０Ｄ、ＳＢＢ－７０Ｐ、Ｋ６０００（以上、旭化成ケミカルズ（株）製）、デスモジュールＢＬ１１００、ＢＬ１２６５　ＭＰＡ／Ｘ、ＢＬ３５７５／１、ＢＬ３２７２ＭＰＡ、ＢＬ３３７０ＭＰＡ、ＢＬ３４７５ＢＡ／ＳＮ、ＢＬ５３７５ＭＰＡ、ＶＰＬＳ２０７８／２、ＢＬ４２６５ＳＮ、ＰＬ３４０、ＰＬ３５０、スミジュールＢＬ３１７５（以上、住化バイエルウレタン（株）製）等を好ましく使用することができる。 The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, 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, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) etc. are preferably used can do.
（成分Ｇ）酸化防止剤
　本発明の感光性樹脂組成物は、酸化防止剤を含有することが好ましい。
　酸化防止剤としては、公知の酸化防止剤を含有することができる。酸化防止剤を添加することにより、硬化膜の着色を防止できる、又は、分解による膜厚減少を低減でき、また、耐熱透明性に優れるという利点がある。
　このような酸化防止剤としては、例えば、リン系酸化防止剤、アミド類、ヒドラジド類、ヒンダードアミン系酸化防止剤、イオウ系酸化防止剤、フェノール系酸化防止剤、アスコルビン酸類、硫酸亜鉛、糖類、亜硝酸塩、亜硫酸塩、チオ硫酸塩、ヒドロキシルアミン誘導体等を挙げることができる。これらの中では、硬化膜の着色、膜厚減少の観点から特にフェノール系酸化防止剤、アミド系酸化防止剤、ヒドラジド系酸化防止剤、イオウ系酸化防止剤が好ましい。これらは１種単独で用いてもよいし、２種以上を混合してもよい。
　フェノール系酸化防止剤の市販品としては、例えば、アデカスタブＡＯ－１５、アデカスタブＡＯ－１８、アデカスタブＡＯ－２０、アデカスタブＡＯ－２３、アデカスタブＡＯ－３０、アデカスタブＡＯ－３７、アデカスタブＡＯ－４０、アデカスタブＡＯ－５０、アデカスタブＡＯ－５１、アデカスタブＡＯ－６０、アデカスタブＡＯ－７０、アデカスタブＡＯ－８０、アデカスタブＡＯ－３３０、アデカスタブＡＯ－４１２Ｓ、アデカスタブＡＯ－５０３、アデカスタブＡ－６１１、アデカスタブＡ－６１２、アデカスタブＡ－６１３、アデカスタブＰＥＰ－４Ｃ、アデカスタブＰＥＰ－８、アデカスタブＰＥＰ－８Ｗ、アデカスタブＰＥＰ－２４Ｇ、アデカスタブＰＥＰ－３６、アデカスタブＰＥＰ－３６Ｚ、アデカスタブＨＰ－１０、アデカスタブ２１１２、アデカスタブ２６０、アデカスタブ５２２Ａ、アデカスタブ１１７８、アデカスタブ１５００、アデカスタブＣ、アデカスタブ１３５Ａ、アデカスタブ３０１０、アデカスタブＴＰＰ、アデカスタブＣＤＡ－１、アデカスタブＣＤＡ－６、アデカスタブＺＳ－２７、アデカスタブＺＳ－９０、アデカスタブＺＳ－９１（以上、（株）ＡＤＥＫＡ製）、イルガノックス２４５ＦＦ、イルガノックス１０１０ＦＦ、イルガノックス１０１０、イルガノックスＭＤ１０２４、イルガノックス１０３５ＦＦ、イルガノックス１０３５、イルガノックス１０９８、イルガノックス１３３０、イルガノックス１５２０Ｌ、イルガノックス３１１４、イルガノックス１７２６、イルガフォス１６８、イルガモッド２９５（ＢＡＳＦ社製）、チヌビン４０５（ＢＡＳＦ社製）などが挙げられる。中でも、アデカスタブＡＯ－６０、アデカスタブＡＯ－８０、イルガノックス１７２６、イルガノックス１０３５、イルガノックス１０９８、チヌビン４０５を好適に使用することができる。 (Component G) Antioxidant The photosensitive resin composition of the present invention preferably contains an antioxidant.
As 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.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Among these, 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. These may be used individually by 1 type and may mix 2 or more types.
Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO. -50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 13510, ADK STAB 3010, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS-90 -91 (above, manufactured by ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Company, Ltd.), Tinuvin 405 (manufactured by BASF), and the like. Among them, ADK STAB AO-60, ADK STAB AO-80, Irganox 1726, Irganox 1035, Irganox 1098, and Tinuvin 405 can be preferably used.
　酸化防止剤の含有量は、感光性樹脂組成物の全固形分に対して、０．１～１０質量％であることが好ましく、０．２～５質量％であることがより好ましく、０．５～４質量％であることが特に好ましい。この範囲にすることで、形成された膜の十分な透明性が得られ、かつ、パターン形成時の感度も良好となる。
　また、酸化防止剤以外の添加剤として、“高分子添加剤の新展開（（株）日刊工業新聞社）”に記載の各種紫外線吸収剤や、金属不活性化剤等を本発明の感光性樹脂組成物に添加してもよい。 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.
As additives other than antioxidants, 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.
＜その他の成分＞
　本発明の感光性樹脂組成物には、上記成分に加えて、必要に応じて、（成分Ｈ）増感剤、（成分Ｉ）密着改良剤、（成分Ｊ）塩基性化合物、（成分Ｋ）界面活性剤を好ましく加えることができる。更に本発明の感光性樹脂組成物には、上記紫外線吸収剤、金属不活性化剤や、酸増殖剤、現像促進剤、可塑剤、熱ラジカル発生剤、熱酸発生剤、増粘剤、及び、有機又は無機の沈殿防止剤などの公知の添加剤を加えることができる。 <Other ingredients>
In the photosensitive resin composition of the present invention, in addition to the above components, as necessary, (Component H) sensitizer, (Component I) adhesion improver, (Component J) basic compound, (Component K) A surfactant can be preferably added. Furthermore, the photosensitive resin composition of the present invention includes the ultraviolet absorber, metal deactivator, acid multiplier, development accelerator, plasticizer, thermal radical generator, thermal acid generator, thickener, and Known additives such as organic or inorganic suspending agents can be added.
（成分Ｈ）増感剤
　本発明の感光性樹脂組成物は、（成分Ｅ）光酸発生剤との組み合わせにおいて、その分解を促進させるために、増感剤を含有することが好ましい。増感剤は、活性光線又は放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、光酸発生剤と接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより光酸発生剤は化学変化を起こして分解し、酸を生成する。好ましい増感剤の例としては、以下の化合物類に属しており、かつ３５０ｎｍから４５０ｎｍの波長域のいずれかに吸収波長を有する化合物を挙げることができる。 (Component H) Sensitizer The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (Component E) a photoacid generator. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
　多核芳香族類（例えば、ピレン、ペリレン、トリフェニレン、アントラセン、９，１０－ジブトキシアントラセン、９，１０－ジエトキシアントラセン，３，７－ジメトキシアントラセン、９，１０－ジプロピルオキシアントラセン）、キサンテン類（例えば、フルオレッセイン、エオシン、エリスロシン、ローダミンＢ、ローズベンガル）、キサントン類（例えば、キサントン、チオキサントン、ジメチルチオキサントン、ジエチルチオキサントン）、シアニン類（例えばチアカルボシアニン、オキサカルボシアニン）、メロシアニン類（例えば、メロシアニン、カルボメロシアニン）、ローダシアニン類、オキソノール類、チアジン類（例えば、チオニン、メチレンブルー、トルイジンブルー）、アクリジン類（例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン）、アクリドン類（例えば、アクリドン、１０－ブチル－２－クロロアクリドン）、アントラキノン類（例えば、アントラキノン）、スクアリウム類（例えば、スクアリウム）、スチリル類、ベーススチリル類（例えば、２－｛２－［４－（ジメチルアミノ）フェニル］エテニル｝ベンゾオキサゾール）、クマリン類（例えば、７－ジエチルアミノ－４－メチルクマリン、７－ヒドロキシ－４－メチルクマリン、２，３，６，７－テトラヒドロ－９－メチル－１Ｈ，５Ｈ，１１Ｈ［１］ベンゾピラノ［６，７，８－ｉｊ］キノリジン－１１－ノン）。
　これら増感剤の中でも、多核芳香族類、アクリドン類、スチリル類、ベーススチリル類、クマリン類が好ましく、多核芳香族類がより好ましい。 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, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), styryls, base styryls ( For example, 2- {2- [4- (dimethylamino) phenyl] ethenyl} benzoxazole), coumarins (eg, 7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 2, 3, 6 , 7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolidine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.
　本発明の感光性樹脂組成物中における増感剤の添加量は、感光性樹脂組成物の光酸発生剤１００質量部に対し、０～１，０００質量部であることが好ましく、１０～５００質量部であることがより好ましく、５０～２００質量部であることが更に好ましい。
　また、増感剤は、１種単独で使用してもよいし、２種以上を併用することもできる。 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.
Moreover, a sensitizer may be used individually by 1 type and can also use 2 or more types together.
（成分Ｉ）密着改良剤
　本発明の感光性樹脂組成物は、密着改良剤を含有してもよい。
　本発明の感光性樹脂組成物に用いることができる密着改良剤は、基材となる無機物、例えば、シリコン、酸化シリコン、窒化シリコン等のシリコン化合物、金、銅、アルミニウム等の金属と絶縁膜との密着性を向上させる化合物である。具体的には、シランカップリング剤、チオール系化合物等が挙げられる。これらの中でも、シランカップリング剤が好ましい。
　本発明で使用される密着改良剤としてのシランカップリング剤は、界面の改質を目的とするものであり、特に限定することなく、公知のものを使用することができる。 (Component I) Adhesion improving agent The photosensitive resin composition of the present invention may contain an adhesion improving agent.
The adhesion improver that can be used in the photosensitive resin composition of the present invention is an inorganic material serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum, and an insulating film. It is a compound that improves the adhesion. Specific examples include silane coupling agents and thiol compounds. Among these, a silane coupling agent is preferable.
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.
　好ましいシランカップリング剤としては、例えば、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－グリシドキシプロピルトリアコキシシラン、γ－グリシドキシプロピルアルキルジアルコキシシラン、γ－メタクリロキシプロピルトリアルコキシシラン、γ－メタクリロキシプロピルアルキルジアルコキシシラン、γ－クロロプロピルトリアルコキシシラン、γ－メルカプトプロピルトリアルコキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリアルコキシシラン、ビニルトリアルコキシシランが挙げられる。
　これらのうち、γ－グリシドキシプロピルトリアルコキシシランやγ－メタクリロキシプロピルトリアルコキシシランがより好ましく、γ－グリシドキシプロピルトリアルコキシシランが更に好ましい。 Preferred examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned.
Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.
　これらは１種単独又は２種以上を組み合わせて使用することができる。これらは基板との密着性の向上に有効であるとともに、基板とのテーパー角の調整にも有効である。
　本発明の感光性樹脂組成物における密着改良剤の含有量は、成分Ｄ１００質量部に対して、０．１～２０質量部が好ましく、０．５～１０質量部がより好ましい。 These can be used alone or in combination of two or more. These are effective for improving the adhesion to the substrate and also for adjusting the taper angle with the substrate.
The content of the adhesion improving agent 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.
（成分Ｊ）塩基性化合物
　本発明の感光性樹脂組成物は、塩基性化合物を含有してもよい。
　塩基性化合物としては、化学増幅レジストで用いられるものの中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、カルボン酸の第四級アンモニウム塩等が挙げられる。これらの具体例としては、特開２０１１－２２１４９４号公報の段落０２０４～０２０７に記載の化合物が挙げられる。 (Component J) Basic Compound The photosensitive resin composition of the present invention may contain 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.
　具体的には、脂肪族アミンとしては、例えば、トリメチルアミン、ジエチルアミン、トリエチルアミン、ジ－ｎ－プロピルアミン、トリ－ｎ－プロピルアミン、ジ－ｎ－ペンチルアミン、トリ－ｎ－ペンチルアミン、ジエタノールアミン、トリエタノールアミン、ジシクロヘキシルアミン、ジシクロヘキシルメチルアミンなどが挙げられる。
　芳香族アミンとしては、例えば、アニリン、ベンジルアミン、Ｎ，Ｎ－ジメチルアニリン、ジフェニルアミンなどが挙げられる。
　複素環式アミンとしては、例えば、ピリジン、２－メチルピリジン、４－メチルピリジン、２－エチルピリジン、４－エチルピリジン、２－フェニルピリジン、４－フェニルピリジン、Ｎ－メチル－４－フェニルピリジン、４－ジメチルアミノピリジン、イミダゾール、ベンズイミダゾール、４－メチルイミダゾール、２－フェニルベンズイミダゾール、２，４，５－トリフェニルイミダゾール、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、８－オキシキノリン、ピラジン、ピラゾール、ピリダジン、プリン、ピロリジン、ピペリジン、ピペラジン、モルホリン、４－メチルモルホリン、Ｎ－シクロヘキシル－Ｎ’－［２－（４－モルホリニル）エチル］チオ尿素、１，５－ジアザビシクロ［４．３．０］－５－ノネン、１，８－ジアザビシクロ［５．３．０］－７－ウンデセンなどが挙げられる。
　第四級アンモニウムヒドロキシドとしては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラ－ｎ－ブチルアンモニウムヒドロキシド、テトラ－ｎ－ヘキシルアンモニウムヒドロキシドなどが挙げられる。
　カルボン酸の第四級アンモニウム塩としては、例えば、テトラメチルアンモニウムアセテート、テトラメチルアンモニウムベンゾエート、テトラ－ｎ－ブチルアンモニウムアセテート、テトラ－ｎ－ブチルアンモニウムベンゾエートなどが挙げられる。 Specific examples of the aliphatic amine 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.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine 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 [5.3.0] -7-undecene.
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.
　本発明に用いることができる塩基性化合物は、１種単独で使用しても、２種以上を併用してもよい。
　本発明の感光性樹脂組成物における塩基性化合物の含有量は、感光性樹脂組成物中の全固形分１００質量部に対して、０．００１～３質量部であることが好ましく、０．００５～１質量部であることがより好ましい。 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.
（成分Ｋ）界面活性剤
　本発明の感光性樹脂組成物は、界面活性剤を含有してもよい。
　界面活性剤としては、アニオン系、カチオン系、ノニオン系又は両性のいずれでも使用することができるが、好ましい界面活性剤は、ノニオン界面活性剤である。
　ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリオキシエチレングリコールの高級脂肪酸ジエステル類、シリコーン系、フッ素系界面活性剤を挙げることができる。フッ素系界面活性剤、シリコーン系界面活性剤の例として具体的には、特開昭６２－３６６６３号、特開昭６１－２２６７４６号、特開昭６１－２２６７４５号、特開昭６２－１７０９５０号、特開昭６３－３４５４０号、特開平７－２３０１６５号、特開平８－６２８３４号、特開平９－５４４３２号、特開平９－５９８８号、特開２００１－３３０９５３号等の各公報記載の界面活性剤を挙げることができ、市販の界面活性剤を用いることもできる。また、以下商品名で、ＫＰ（信越化学工業（株）製）、ポリフロー（共栄社化学（株）製）、エフトップ（三菱マテリアル電子化成（株）製）、メガファック（ＤＩＣ（株）製）、フロラード（住友スリーエム（株）製）、アサヒガード（旭硝子（株）製）、サーフロン（ＡＧＣセイミケミカル（株）製）、ＰｏｌｙＦｏｘ（ＯＭＮＯＶＡ社製）、ＳＨ－８４００（東レ・ダウコーニング（株）製）等の各シリーズを挙げることができる。
　これらの中でも、フッ素系界面活性剤又はシリコーン系界面活性剤が好ましく、フッ素系界面活性剤がより好ましく、フッ素系ノニオン界面活性剤が更に好ましく、パーフルオロ基含有ノニオン界面活性剤が特に好ましい。
　また、界面活性剤として、下記式（Ｋ－１）で表される構成単位Ａ及び構成単位Ｂを含み、テトラヒドロフラン（ＴＨＦ）を溶媒とした場合のゲルパーミエーションクロマトグラフィで測定されるポリスチレン換算の重量平均分子量（Ｍｗ）が１，０００以上１０，０００以下である共重合体を好ましい例として挙げることができる。 (Component K) Surfactant The photosensitive resin composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of 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. . Specific examples of fluorine surfactants and silicone surfactants include JP-A Nos. 62-36663, 61-226746, 61-226745, and 62-170950. The interfaces described in JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, JP-A-2001-330953, etc. An activator can be mentioned and a commercially available surfactant can also be used. In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.), MegaFuck (manufactured by DIC Corporation) Fluorard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard (manufactured by Asahi Glass Co., Ltd.), Surflon (manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Co., Ltd.) And other series).
Among these, a fluorine-based surfactant or a silicone-based surfactant is preferable, a fluorine-based surfactant is more preferable, a fluorine-based nonionic surfactant is further preferable, and a perfluoro group-containing nonionic surfactant is particularly preferable.
Further, the surfactant includes a structural unit A and a structural unit B represented by the following formula (K-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.
Figure JPOXMLDOC01-appb-C000021
 （式（Ｋ－１）中、Ｒ401及びＲ403はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ402は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ404は水素原子又は炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐ及びｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。）
Figure JPOXMLDOC01-appb-C000021
 (In Formula (K-1), 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, and 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, and p is 10 mass% to 80 mass%. A numerical value is represented, q represents a numerical value of 20 mass% or more and 90 mass% or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.)
　上記Ｌは、下記式（Ｋ－２）で表される分岐アルキレン基であることが好ましい。式（Ｋ－２）におけるＲ405は、炭素数１以上４以下のアルキル基を表し、相溶性と被塗布面に対する濡れ性の点で、炭素数１以上３以下のアルキル基が好ましく、炭素数２又は３のアルキル基がより好ましい。ｐとｑとの和（ｐ＋ｑ）は、ｐ＋ｑ＝１００、すなわち、１００質量％であることが好ましい。 L is preferably a branched alkylene group represented by the following formula (K-2). R 405 in formula (K-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 sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　上記共重合体の重量平均分子量（Ｍｗ）は、１，５００以上５，０００以下がより好ましい。 The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
　これらの界面活性剤は、１種単独で又は２種以上を混合して使用することができる。
　本発明の感光性樹脂組成物における界面活性剤の添加量は、感光性樹脂組成物中の全固形分１００質量部に対して、１０質量部以下であることが好ましく、０．００１～１０質量部であることがより好ましく、０．０１～３質量部であることが更に好ましい。 These surfactants can be used individually by 1 type or in mixture of 2 or more types.
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.
（成分Ｌ）酸増殖剤
　本発明の感光性樹脂組成物は、感度向上を目的に、酸増殖剤を含有してもよい。
　本発明に用いることができる酸増殖剤は、酸触媒反応によって更に酸を発生して反応系内の酸濃度を上昇させることができる化合物であり、酸が存在しない状態では安定に存在する化合物である。このような化合物は、１回の反応で１つ以上の酸が増えるため、反応の進行に伴って加速的に反応が進むが、発生した酸自体が自己分解を誘起するため、ここで発生する酸の強度は、酸解離定数、ｐＫａとして３以下であることが好ましく、２以下であることが特に好ましい。また、上記ｐＫａは、－１５以上であることが好ましい。
　酸増殖剤の具体例としては、特開平１０－１５０８号公報の段落０２０３～０２２３、特開平１０－２８２６４２号公報の段落００１６～００５５、及び、特表平９－５１２４９８号公報第３９頁１２行目～第４７頁２行目に記載の化合物を挙げることができる。
　本発明で用いることができる酸増殖剤としては、酸発生剤から発生した酸によって分解し、ジクロロ酢酸、トリクロロ酢酸、メタンスルホン酸、ベンゼンスルホン酸、トリフルオロメタンスルホン酸、フェニルホスホン酸などのｐＫａが３以下の酸を発生させる化合物を挙げることができる。
　具体的には、以下の化合物等を挙げることができる。 (Component L) Acid Proliferating Agent The photosensitive resin composition of the present invention may contain an acid proliferating agent 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. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The strength of the acid is preferably 3 or less, particularly preferably 2 or less, as the acid dissociation constant, pKa. The pKa is preferably −15 or more.
Specific examples of the acid proliferating agent include paragraphs 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39, line 12 of JP-A-9-512498. Examples of the compounds described on page 47, line 2 are listed.
Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
Specific examples include the following compounds.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　酸増殖剤の感光性組成物への含有量は、光酸発生剤１００質量部に対して、１０～１，０００質量部とするのが、露光部と未露光部との溶解コントラストの観点から好ましく、２０～５００質量部とするのが更に好ましい。 The content of the acid proliferating agent in the photosensitive 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 and unexposed parts. It is preferably 20 to 500 parts by mass.
（成分Ｍ）現像促進剤
　本発明の感光性樹脂組成物は、現像促進剤を含有してもよい。
　現像促進剤としては、現像促進効果のある任意の化合物を使用できるが、カルボキシル基、フェノール性水酸基、及び、アルキレンオキシ基よりなる群から選ばれた少なくとも一種の構造を有する化合物であることが好ましく、カルボキシル基又はフェノール性水酸基を有する化合物がより好ましく、フェノール性水酸基を有する化合物が最も好ましい。
　現像促進剤としては、特開２０１２－０４２８３７号公報の段落０１７１～０１７２の記載を参酌でき、かかる内容は本願明細書に組み込まれる。
　また、現像促進剤の分子量は、１００～２，０００が好ましく、１５０～１，５００がより好ましく、１５０～１，０００が更に好ましい。 (Component M) Development accelerator The photosensitive resin composition of the present invention may contain a development accelerator.
As the development accelerator, any compound having a development acceleration effect can be used, but a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an alkyleneoxy group is preferable. A compound having a carboxyl group or a phenolic hydroxyl group is more preferred, and a compound having a phenolic hydroxyl group is most preferred.
As the development accelerator, the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
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.
　現像促進剤は、１種を単独で用いてもよいし、２種以上を併用することも可能である。
　本発明の感光性樹脂組成物における現像促進剤の添加量は、感度と残膜率の観点から、感光性組成物の全固形分１００質量部に対し、０～３０質量部が好ましく、０．１～２０質量部がより好ましく、０．５～１０質量部であることが最も好ましい。 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 composition, from the viewpoint of sensitivity and residual film ratio. 1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
（成分Ｎ）可塑剤
　本発明の樹脂組成物は、可塑剤を含有してもよい。
　可塑剤としては、例えば、ジブチルフタレート、ジオクチルフタレート、ジドデシルフタレート、ポリエチレングリコール、グリセリン、ジメチルグリセリンフタレート、酒石酸ジブチル、アジピン酸ジオクチル、トリアセチルグリセリンなどが挙げられる。
　本発明の樹脂組成物における可塑剤の含有量は、成分Ｄの含有量１００質量部に対して、０．１～３０質量部であることが好ましく、１～１０質量部であることがより好ましい。 (Component N) Plasticizer The resin composition of the present invention may contain a plasticizer.
Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerin phthalate, dibutyl tartrate, dioctyl adipate, and triacetyl glycerin.
The plasticizer content in the resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component D content. .
　また、その他の添加剤としては特開２０１２－８２２３号公報の段落０１２０～０１２１に記載の熱ラジカル発生剤、国際公開第２０１１／１３６０７４号に記載の窒素含有化合物及び熱酸発生剤も用いることができる。 As other additives, the 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. it can.
（硬化膜の製造方法）
　次に、本発明の硬化膜（「樹脂パターン」ともいう。）の製造方法を説明する。
　本発明の硬化膜の製造方法は、以下の（１）～（５）の工程を含むことが好ましい。
　（１）本発明の感光性樹脂組成物を基板上に塗布する塗布工程；
　（２）塗布された樹脂組成物から溶剤を除去する溶剤除去工程；
　（３）溶剤が除去された樹脂組成物を活性光線によりパターン状に露光する露光工程；
　（４）露光された樹脂組成物を水性現像液により現像する現像工程；
　（５）現像された樹脂組成物を熱処理する熱処理工程。
　以下に各工程を順に説明する。 (Method for producing cured film)
Next, a method for producing the cured film (also referred to as “resin pattern”) of the present invention will be described.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) A coating process for coating the photosensitive resin composition of the present invention on a substrate;
(2) a solvent removal step of removing the solvent from the applied resin composition;
(3) An exposure step of exposing the resin composition from which the solvent has been removed to a pattern with actinic rays;
(4) Development step of developing the exposed resin composition with an aqueous developer;
(5) A heat treatment step of heat-treating the developed resin composition.
Each step will be described below in order.
　（１）の塗布工程では、本発明の感光性樹脂組成物を基板上に塗布して溶剤を含む湿潤膜とすることが好ましい。感光性樹樹脂組成物を基板へ塗布する前にアルカリ洗浄やプラズマ洗浄といった基板の洗浄を行うことが好ましく、更に基板洗浄後にヘキサメチルジシラザンで基板表面を処理することがより好ましい。この処理を行うことにより、感光性樹脂組成物の基板への密着性が向上する。ヘキサメチルジシラザンで基板表面を処理する方法としては、特に限定されないが、例えば、ヘキサメチルジシラザン蒸気に中に基板を晒しておく方法等が挙げられる。
　上記の基板としては、無機基板、樹脂、樹脂複合材料、ＩＴＯ、Ｃｕ基板、ポリエチレンテレフタレート、セルローストリアセテート（ＴＡＣ）などのプラスチック基板が挙げられる。
　無機基板としては、例えばガラス、石英、シリコーン、シリコンナイトライド、及び、それらのような基板上にモリブデン、チタン、アルミ、銅などを蒸着した複合基板が挙げられる。
　樹脂としては、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリスチレン、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリアリレート、アリルジグリコールカーボネート、ポリアミド、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリベンズアゾール、ポリフェニレンサルファイド、ポリシクロオレフィン、ノルボルネン樹脂、ポリクロロトリフルオロエチレン等のフッ素樹脂、液晶ポリマー、アクリル樹脂、エポキシ樹脂、シリコーン樹脂、アイオノマー樹脂、シアネート樹脂、架橋フマル酸ジエステル樹脂、環状ポリオレフィン、芳香族エーテル樹脂、マレイミド－オレフィン樹脂、セルロース、エピスルフィド樹脂等の合成樹脂からなる基板が挙げられる。
　これらの基板は、上記の形態のまま用いられる場合は少なく、最終製品の形態によって、例えばＴＦＴ素子のような多層積層構造が形成されている場合が通常である。
　基板への塗布方法は特に限定されず、例えば、スリットコート法、スプレーコート法、ロールコート法、回転塗布法、流延塗布法、スリットアンドスピン法等の方法を用いることができる。更に、特開２００９－１４５３９５号公報に記載されているような、所謂プリウェット法を適用することも可能である。
　塗布膜厚は特に限定されるものではなく、用途に応じた膜厚で塗布することができるが、０．５～１０μｍの範囲で使用されることが好ましい。 In the application step (1), 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.
Examples of the substrate include inorganic substrates, resins, resin composite materials, ITO, Cu substrates, polyethylene terephthalate, and plastic substrates such as cellulose triacetate (TAC).
Examples of the inorganic substrate 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. A substrate made of, and the like.
These substrates are rarely used in the above-described form, and usually have a multilayer laminated structure such as a TFT element formed depending on the form of the final product.
The coating method on the substrate is not particularly limited, and for example, methods such as a slit coating method, a spray coating method, a roll coating method, a spin coating method, a casting coating method, and a slit and spin method 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 μm.
　（１）の塗布工程では、本発明の感光性樹脂組成物の優れた効果を十分に発揮させるため、本発明の感光性樹脂組成物を基板上に省液コーター法により塗布することが好ましく、本発明の感光性樹脂組成物を基板上にスリットコート法又はスプレーコート法により塗布することがより好ましい。
　スリットコートや、スプレーコートなどの省液コーターは、塗布液使用量が大幅に削減され、かつ、スピンコート法によった際に付着するミストなどの影響が低減され、異物発生が抑制されるなど、総合的な観点からも好ましい。
　例えば、スリットコート法による塗布条件は、硬化性樹脂組成物の組成や、製造する塗膜の種類などによって適宜選択すればよい。例えば、ノズル先端のリップ幅は５０～５００μｍとし、ノズル先端と基板面との間隔は３０～３００μｍとするのが好ましい。塗布膜の厚さを調節するためには、リップの走行速度、及び、リップからの液状の硬化性樹脂組成物の吐出量を調整すればよい。
　スプレーコート法に用いられるスプレーコーターとしては、特に制限はなく、公知のスプレー塗布方法及び噴射装置を適用すればよい。具体的には、超音波スプレーコーティング装置、二流体スプレーコーティング装置、一流体スプレーコーティング装置などが挙げられる。 In the application step (1), in order to sufficiently exhibit the excellent effect of the photosensitive resin composition of the present invention, it is preferable to apply the photosensitive resin composition of the present invention on a substrate by a liquid-saving coater method, It is more preferable to apply the photosensitive resin composition of the present invention on a substrate by a slit coat method or a spray coat method.
Liquid-saving coaters such as slit coat and spray coat greatly reduce the amount of coating solution used, reduce the influence of mist that adheres when using the spin coat method, and suppress foreign matter generation. This is also preferable from a comprehensive viewpoint.
For example, the coating conditions by the slit coating method may be appropriately selected depending on the composition of the curable resin composition, the type of coating film to be manufactured, and the like. For example, the lip width at the nozzle tip is preferably 50 to 500 μm, and the distance between the nozzle tip and the substrate surface is preferably 30 to 300 μm. In order to adjust the thickness of the coating film, the running speed of the lip and the discharge amount of the liquid curable resin composition from the lip may be adjusted.
There is no restriction | limiting in particular as a spray coater used for the spray coat method, What is necessary is just to apply a well-known spray coating method and injection apparatus. Specific examples include an ultrasonic spray coating apparatus, a two-fluid spray coating apparatus, and a one-fluid spray coating apparatus.
　（２）の溶剤除去工程では、適用された上記の膜から、真空、或いは、減圧（バキューム）及び／又は加熱により、溶剤を除去して基板上に乾燥塗膜を形成させる。溶剤除去工程の加熱条件は、好ましくは７０～１３０℃で３０～３００秒間程度である。温度と時間が上記範囲である場合、パターンの密着性が良好で、かつ残渣も低減できる。 (2) In the solvent removal step (2), the solvent is removed from the applied film by vacuum or reduced 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.
　（３）の露光工程では、塗膜を設けた基板に所定のパターンを有するマスクを介して、活性光線を照射する。この工程では、光酸発生剤が分解し酸が発生する。発生した酸の触媒作用により、塗膜成分中に含まれる酸分解性基が加水分解されて、酸基、例えば、カルボキシル基又はフェノール性水酸基が生成する。
　活性光線による露光光源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ＬＥＤ光源、エキシマレーザー発生装置などを用いることができ、ｇ線（４３６ｎｍ）、ｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）などの波長３００ｎｍ以上４５０ｎｍ以下の波長を有する活性光線が好ましく使用できる。また、必要に応じて長波長カットフィルター、短波長カットフィルター、バンドパスフィルターのような分光フィルターを通して照射光を調整することもできる。
　露光装置としては、ミラープロジェクションアライナー、ステッパー、スキャナー、プロキシミティ、コンタクト、マイクロレンズアレイ、レーザー露光など各種方式の露光機を用いることができる。
　酸触媒の生成した領域において、上記の加水分解反応を加速させるために、露光後加熱処理：Post Exposure Bake（以下、「ＰＥＢ」ともいう。）を行うことができる。ＰＥＢにより、酸分解性基からのカルボキシル基又はフェノール性水酸基の生成を促進させることができる。ＰＥＢを行う場合の温度は、３０℃以上１３０℃以下であることが好ましく、４０℃以上１１０℃以下がより好ましく、５０℃以上１００℃以下が特に好ましい。
　ただし、本発明における酸分解性基は、酸分解の活性化エネルギーが低く、露光による酸発生剤由来の酸により容易に分解し、酸基、例えば、カルボキシル基又はフェノール性水酸基を生じるため、必ずしもＰＥＢを行うことなく、現像によりポジ画像を形成することもできる。 In the exposure step (3), the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated 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.
As 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. can be used, and 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. Moreover, 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.
As the exposure apparatus, 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.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment (Post Exposure Bake (hereinafter also referred to as “PEB”)) can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. 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.
However, 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 generate an acid group, for example, a carboxyl group or a phenolic hydroxyl group. A positive image can be formed by development without performing PEB.
　（４）の現像工程では、遊離したカルボキシル基又はフェノール性水酸基を有する共重合体を、アルカリ性現像液を用いて現像する。アルカリ性現像液に溶解しやすい酸基、例えば、カルボキシル基又はフェノール性水酸基を有する樹脂組成物を含む露光部領域を除去することにより、ポジ画像が形成される。
　現像工程で使用する現像液には、塩基性化合物が含まれることが好ましい。塩基性化合物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物類；炭酸ナトリウム、炭酸カリウムなどのアルカリ金属炭酸塩類；重炭酸ナトリウム、重炭酸カリウムなどのアルカリ金属重炭酸塩類；テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリンヒドロキシド等のアンモニウムヒドロキシド類；ケイ酸ナトリウム、メタケイ酸ナトリウムなどの水溶液を使用することができる。また、上記アルカリ類の水溶液にメタノールやエタノールなどの水溶性有機溶剤や界面活性剤を適当量添加した水溶液を現像液として使用することもできる。
　好ましい現像液として、テトラエチルアンモニウムヒドロキシドの０．４質量％水溶液、０．５質量％水溶液、０．７質量％水溶液、又は、２．３８質量％水溶液を挙げることができる。
　現像液のｐＨは、好ましくは１０．０～１４．０である。
　現像時間は、好ましくは３０～５００秒間であり、また、現像の手法は液盛り法、ディップ法等のいずれでもよい。現像後は、流水洗浄を３０～３００秒間行い、所望のパターンを形成させることができる。
　現像の後に、リンス工程を行うこともできる。リンス工程では、現像後の基板を純水などで洗うことで、付着している現像液除去、現像残渣除去を行う。リンス方法は公知の方法を用いることができる。例えばシャワーリンスやディップリンスなどを挙げることができる。 In the developing step (4), 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.
　（５）の熱処理工程（ポストベーク）では、得られたポジ画像を加熱することにより、酸分解性基を熱分解し酸基、例えば、カルボキシル基又はフェノール性水酸基を生成させ、架橋性基、架橋剤等と架橋させることにより、硬化膜を形成することができる。この加熱は、ホットプレートやオーブン等の加熱装置を用いて、所定の温度、例えば１８０℃～２５０℃で所定の時間、例えばホットプレート上なら５～９０分間、オーブンならば３０～１２０分間、加熱処理をすることが好ましい。架橋反応を進行させることにより、耐熱性、硬度等に優れた保護膜や層間絶縁膜を形成することができる。また、加熱処理を行う際は窒素雰囲気下で行うことにより透明性を向上させることもできる。プラスチック基板を用いたときは、８０℃～１４０℃で５分～１２０分間、加熱処理をすることが好ましい。
　熱処理工程（ポストベーク）の前に、比較的低温でベークを行った後に熱処理工程を行うこともできる（ミドルベーク工程の追加）。ミドルベークを行う場合は、９０～１５０℃で１～６０分加熱した後に、２００℃以上の高温でポストベークすることが好ましい。また、ミドルベーク、ポストベークを３段階以上の多段階に分けて加熱することもできる。このようなミドルベーク、ポストベークの工夫により、パターンのテーパー角を調整することができる。これらの加熱は、ホットプレート、オーブン、赤外線ヒーターなど、公知の加熱方法を使用することができる。
　なお、ポストベークに先立ち、パターンを形成した基板に活性光線により全面再露光（ポスト露光）した後、ポストベークすることにより未露光部分に存在する光酸発生剤から酸を発生させ、架橋工程を促進する触媒として機能させることができ、膜の硬化反応を促進することができる。ポスト露光工程を含む場合の好ましい露光量としては、１００～３，０００ｍＪ／ｃｍ2が好ましく、１００～５００ｍＪ／ｃｍ2が特に好ましい。 In the heat treatment step (post-bake) of (5), 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, and a crosslinkable group, A cured film can be formed by crosslinking with a 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. By proceeding with the crosslinking reaction, it is possible to form a protective film or an interlayer insulating film excellent in heat resistance, hardness and the like. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere. When a plastic substrate is used, heat treatment is preferably performed at 80 to 140 ° C. for 5 to 120 minutes.
Prior to the heat treatment step (post-bake), the heat treatment step can be performed after baking at a relatively low temperature (addition of a middle bake step). When middle baking is performed, 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.
Prior to post-baking, 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.
　更に、本発明の感光性樹脂組成物より得られた硬化膜は、ドライエッチングレジストとして使用することもできる。熱処理工程により熱硬化して得られた硬化膜をドライエッチングレジストとして使用する場合、エッチング処理としてはアッシング、プラズマエッチング、オゾンエッチングなどのドライエッチング処理を行うことができる。 Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. In the case where a cured film obtained by thermal curing in a heat treatment step is 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.
（硬化膜）
　本発明の硬化膜は、本発明の感光性樹脂組成物を硬化して得られた硬化膜である。
　本発明の硬化膜は、層間絶縁膜として好適に用いることができる。また、本発明の硬化膜は、本発明の硬化膜の形成方法により得られた硬化膜であることが好ましい。
　本発明の感光性樹脂組成物により、絶縁性に優れ、高温でベークされた場合においても高い透明性を有する層間絶縁膜が得られる。本発明の感光性樹脂組成物を用いてなる層間絶縁膜は、高い透明性を有し、硬化膜物性に優れるため、有機ＥＬ表示装置や液晶表示装置の用途に有用である。 (Cured film)
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. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
With the photosensitive resin composition of the present 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.
（硬化物及びその製造方法）
　本発明の硬化物は、本発明の感光性樹脂組成物を硬化して得られた硬化物であり、上記のように、その形状は、膜でなくともよく、任意の形状であればよい。
　本発明の硬化物の製造方法は、特に制限はないが、少なくとも以下の工程（ａ）～（ｃ）をこの順に含むことが好ましい。
　（ａ）本発明の感光性樹脂組成物を基板上に塗布する塗布工程；
　（ｂ）塗布された樹脂組成物から溶剤を除去する溶剤除去工程；
　（ｃ）溶剤が除去された樹脂組成物を熱処理する熱処理工程。 (Hardened product and manufacturing method thereof)
The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. As described above, 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.
(A) A coating process for coating the photosensitive resin composition of the present invention on a substrate;
(B) a solvent removal step of removing the solvent from the applied resin composition;
(C) A heat treatment step of heat treating the resin composition from which the solvent has been removed.
　工程（ａ）及び工程（ｂ）はそれぞれ、上記塗布工程及び上記溶剤除去工程と同義であり、好ましい態様も同様である。
　工程（ｃ）は、熱処理する対象が工程（ｂ）で得られた溶剤が除去された樹脂組成物であること以外は、上記熱処理工程と同様の工程であり、上記熱処理工程における加熱温度、加熱時間、加熱手段等の好ましい態様も同様に好ましい。 Process (a) and process (b) are synonymous with the said application | coating process and the said solvent removal process, respectively, A preferable aspect is also the same.
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.
　本発明の硬化物又は硬化膜は、マイクロレンズ、光導波路、反射防止膜、ＬＥＤ用封止材及びＬＥＤ用チップコート材等の光学部材、又は、タッチパネルに使用される配線電極の視認性低減用硬化物として好適に用いることができる。
　また、本発明の硬化物又は硬化膜は、例えば、後述するような、液晶表示装置又は有機ＥＬ装置等における平坦化膜や層間絶縁膜、カラーフィルターの保護膜、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサー、ＭＥＭＳ（Micro Electro Mechanical Systems）デバイスの構造部材等に好適に用いることができる。 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. Can be suitably used for spacers for holding the substrate constant, structural members of MEMS (Micro Electro Mechanical Systems) devices, and the like.
（液晶表示装置）
　本発明の液晶表示装置は、本発明の硬化膜を具備することを特徴とする。
　本発明の液晶表示装置としては、本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の液晶表示装置を挙げることができる。
　例えば、本発明の液晶表示装置が具備するＴＦＴ（Thin-Film Transistor）の具体例としては、アモルファスシリコン－ＴＦＴ、低温ポリシリコン－ＴＦＴ、酸化物半導体ＴＦＴ等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのＴＦＴに組み合わせて好ましく用いることができる。
　また、本発明の液晶表示装置が取りうる液晶駆動方式としてはＴＮ（Twisted Nematic）方式、ＶＡ（Virtical Alignment）方式、ＩＰＳ（In-Place-Switching）方式、ＦＦＳ（Frings Field Switching）方式、ＯＣＢ（Optical Compensated Bend）方式などが挙げられる。
　パネル構成においては、ＣＯＡ（Color Filter on Allay）方式の液晶表示装置でも本発明の硬化膜を用いることができ、例えば、特開２００５－２８４２９１号公報に記載の有機絶縁膜（１１５）や、特開２００５－３４６０５４号公報に記載の有機絶縁膜（２１２）として用いることができる。
　また、本発明の液晶表示装置が取りうる液晶配向膜の具体的な配向方式としてはラビング配向法、光配向方などが挙げられる。また、特開２００３－１４９６４７号公報や特開２０１１－２５７７３４号公報に記載のＰＳＡ（Polymer Sustained Alignment）技術によってポリマー配向支持されていてもよい。
　また、本発明の感光性樹脂組成物及び本発明の硬化膜は、上記用途に限定されず種々の用途に使用することができる。例えば、平坦化膜や層間絶縁膜以外にも、カラーフィルターの保護膜や、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサーや固体撮像素子においてカラーフィルター上に設けられるマイクロレンズ等に好適に用いることができる。 (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.
For example, 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.
Further, liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtical Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (OCB). Optical Compensated Bend) method.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Allay) type liquid crystal display device. For example, 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.
Specific examples of 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. Further, 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.
Moreover, 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. For example, in addition to the planarization film and interlayer insulating film, 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.
　図１は、アクティブマトリックス方式の液晶表示装置１０の一例を示す概念的断面図である。このカラー液晶表示装置１０は、背面にバックライトユニット１２を有する液晶パネルであって、液晶パネルは、偏光フィルムが貼り付けられた２枚のガラス基板１４，１５の間に配置されたすべての画素に対応するＴＦＴ１６の素子が配置されている。ガラス基板上に形成された各素子には、硬化膜１７中に形成されたコンタクトホール１８を通して、画素電極を形成するＩＴＯ透明電極１９が配線されている。ＩＴＯ透明電極１９の上には、液晶２０の層とブラックマトリックスを配置したＲＧＢカラーフィルター２２が設けられている。
　バックライトの光源としては、特に限定されず公知の光源を用いることができる。例えば白色ＬＥＤ、青色・赤色・緑色などの多色ＬＥＤ、蛍光灯（冷陰極管）、有機ＥＬなどを挙げることができる。
　また、液晶表示装置は、３Ｄ（立体視）型のものとしたり、タッチパネル型のものとしたりすることも可能である。更にフレキシブル型にすることも可能であり、特開２０１１－１４５６８６号公報に記載の第２相間絶縁膜（４８）や、特開２００９－２５８７５８号公報に記載の相間絶縁膜（５２０）として用いることができる。 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. On the ITO transparent electrode 19, 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. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, 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.
（有機ＥＬ表示装置）
　本発明の有機ＥＬ表示装置は、本発明の硬化膜を具備することを特徴とする。
　本発明の有機ＥＬ表示装置としては、本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の各種有機ＥＬ表示装置や液晶表示装置を挙げることができる。
　例えば、本発明の有機ＥＬ表示装置が具備するＴＦＴ（Thin-Film Transistor）の具体例としては、アモルファスシリコン－ＴＦＴ、低温ポリシリコン－ＴＦＴ、酸化物半導体ＴＦＴ等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのＴＦＴに組み合わせて好ましく用いることができる。
　図２は、有機ＥＬ表示装置の一例の構成概念図である。ボトムエミッション型の有機ＥＬ表示装置における基板の模式的断面図を示し、平坦化膜４を有している。
　ガラス基板６上にボトムゲート型のＴＦＴ１を形成し、このＴＦＴ１を覆う状態でＳｉ3Ｎ4から成る絶縁膜３が形成されている。絶縁膜３に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してＴＦＴ１に接続される配線２（高さ１．０μｍ）が絶縁膜３上に形成されている。配線２は、ＴＦＴ１間、又は、後の工程で形成される有機ＥＬ素子とＴＦＴ１とを接続するためのものである。
　更に、配線２の形成による凹凸を平坦化するために、配線２による凹凸を埋め込む状態で絶縁膜３上に平坦化層４が形成されている。
　平坦化膜４上には、ボトムエミッション型の有機ＥＬ素子が形成されている。すなわち、平坦化膜４上に、ＩＴＯからなる第一電極５が、コンタクトホール７を介して配線２に接続させて形成されている。また、第一電極５は、有機ＥＬ素子の陽極に相当する。
　第一電極５の周縁を覆う形状の絶縁膜８が形成されており、この絶縁膜８を設けることによって、第一電極５とこの後の工程で形成する第二電極との間のショートを防止することができる。
　更に、図２には図示していないが、所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設け、次いで、基板上方の全面にＡｌから成る第二電極を形成し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止し、各有機ＥＬ素子にこれを駆動するためのＴＦＴ１が接続されてなるアクティブマトリックス型の有機ＥＬ表示装置が得られる。 (Organic EL display device)
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.
For example, 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 μm) 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.
Further, in order to flatten the unevenness due to the formation of the wiring 2, a planarizing layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. 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. 2, 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.
　本発明の感光性樹脂組成物は、硬化性及び硬化膜特性に優れるため、ＭＥＭＳデバイスの構造部材として、本発明の感光性樹脂組成物を用いて形成されたレジストパターンを隔壁としたり、機械駆動部品の一部として組み込んで使用される。このようなＭＥＭＳ用デバイスとしては、例えば、ＳＡＷ（surface acoustic wave）フィルター、ＢＡＷ（bulk acoustic wave）フィルター、ジャイロセンサー、ディスプレイ用マイクロシャッター、イメージセンサー、電子ペーパー、インクジェットヘッド、バイオチップ、封止剤等の部品が挙げられる。より具体的な例は、特表２００７－５２２５３１号公報、特開２００８－２５０２００号公報、特開２００９－２６３５４４号公報等に例示されている。 Since the photosensitive resin composition of the present invention is excellent in curability and cured film characteristics, 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. Such 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.
　本発明の感光性樹脂組成物は、平坦性や透明性に優れるため、例えば、特開２０１１－１０７４７６号公報の図２に記載のバンク層（１６）及び平坦化膜（５７）、特開２０１０－９７９３号公報の図４（ａ）に記載の隔壁（１２）及び平坦化膜（１０２）、特開２０１０－２７５９１号公報の図１０に記載のバンク層（２２１）及び第３層間絶縁膜（２１６ｂ）、特開２００９－１２８５７７号公報の図４（ａ）に記載の第２層間絶縁膜（１２５）及び第３層間絶縁膜（１２６）、特開２０１０－１８２６３８号公報の図３に記載の平坦化膜（１２）及び画素分離絶縁膜（１４）などの形成に用いることもできる。 Since 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.
（タッチパネル表示装置）
　本発明のタッチパネル表示装置は、本発明の硬化膜を有する静電容量型入力装置を具備する。また、本発明の静電容量型入力装置は、本発明の硬化膜を有することを特徴とする。
　本発明の静電容量型入力装置は、前面板と、上記前面板の非接触側に、少なくとも下記（１）～（５）の要素を有し、上記（４）が本発明の硬化物であることが好ましい。
　（１）マスク層
　（２）複数のパッド部分が接続部分を介して第一の方向に延在して形成された複数の第一の透明電極パターン
　（３）上記第一の透明電極パターンと電気的に絶縁され、上記第一の方向に交差する方向に延在して形成された複数のパッド部分からなる複数の第二の透明電極パターン
　（４）上記第一の透明電極パターンと上記第二の透明電極パターンとを電気的に絶縁する絶縁層
　（５）上記第一の透明電極パターン及び上記第二の透明電極パターンの少なくとも一方に電気的に接続され、上記第一の透明電極パターン及び上記第二の透明電極パターンとは別の導電性要素
　本発明の静電容量型入力装置は、更に上記（１）～（５）の要素の全て又は一部を覆うように透明保護層を設置することが好ましく、上記透明保護層が本発明の硬化膜であることがより好ましい。 (Touch panel display)
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. (4) The first transparent electrode pattern and the second An insulating layer that electrically insulates the transparent electrode pattern of (5) electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and the first transparent electrode pattern and the above Conductive element different from the second transparent electrode pattern In the capacitive input device of the present invention, 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.
　まず、静電容量型入力装置の構成について説明する。図３は、静電容量型入力装置の構成を示す断面図である。図３において静電容量型入力装置３０は、前面板３１と、マスク層３２と、第一の透明電極パターン３３と、第二の透明電極パターン３４と、絶縁層３５と、導電性要素３６と、透明保護層３７と、から構成されている。 First, the configuration of the capacitive input device will be described. FIG. 3 is a cross-sectional view showing the configuration of the capacitive input device. In FIG. 3, 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.
　前面板３１は、ガラス基板等の透光性基板で構成されており、コーニング社のゴリラガラスに代表される強化ガラスなどを用いることができる。また、図３において、前面板３１の各要素が設けられている側を非接触面と称する。本発明の静電容量型入力装置３０においては、前面板３１の接触面（非接触面の反対の面）に指などを接触などさせて入力が行われる。以下、前面板を、「基材」と称する場合がある。 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. Hereinafter, the front plate may be referred to as a “base material”.
　また、前面板３１の非接触面上にはマスク層３２が設けられている。マスク層３２は、タッチパネル前面板の非接触側に形成された表示領域周囲の額縁状のパターンであり、引回し配線等が見えないようにするために形成される。
　本発明の静電容量型入力装置には、図４に示すように、前面板３１の一部の領域（図４においては入力面以外の領域）を覆うようにマスク層３２が設けられている。更に、前面板３１には、図４に示すように一部に開口部３８を設けることができる。開口部３８には、押圧によるメカニカルなスイッチを設置することができる。 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.
In the capacitive input device of the present invention, as shown in FIG. 4, 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). . Further, 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.
　図５に示すように、前面板３１の接触面には、複数のパッド部分が接続部分を介して第一の方向に延在して形成された複数の第一の透明電極パターン３３と、第一の透明電極パターン３３と電気的に絶縁され、第一の方向に交差する方向に延在して形成された複数のパッド部分からなる複数の第二の透明電極パターン３４と、第一の透明電極パターン３３と第二の透明電極パターン３４を電気的に絶縁する絶縁層３５とが形成されている。上記第一の透明電極パターン３３と、第二の透明電極パターン３４と、後述する導電性要素３６とは、例えば、ＩＴＯ（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ）やＩＺＯ（Ｉｎｄｉｕｍ　Ｚｉｎｃ　Ｏｘｉｄｅ）などの透光性の導電性金属酸化膜で作製することができる。このような金属膜としては、ＩＴＯ膜；Ａｌ、Ｚｎ、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｏ等の金属膜；ＳｉＯ2等の金属酸化膜などが挙げられる。この際、各要素の、膜厚は１０～２００ｎｍとすることができる。また、焼成により、アモルファスのＩＴＯ膜を多結晶のＩＴＯ膜とするため、電気的抵抗を低減することもできる。また、上記第一の透明電極パターン３３と、第二の透明電極パターン３４と、後述する導電性要素３６とは、上記導電性繊維を用いた硬化性樹脂組成物を有する感光性転写材料を用いて製造することもできる。その他、ＩＴＯ等によって第一の導電性パターン等を形成する場合には、特許第４５０６７８５号公報の段落［００１４］～［００１６］等を参考にすることができる。 As shown in FIG. 5, on the contact surface of the front plate 31, 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. Examples of such metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO 2 . At this time, the film thickness of each element can be set to 10 to 200 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced. In addition, 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. In addition, when the first conductive pattern or the like is formed of ITO or the like, paragraphs [0014] to [0016] of Japanese Patent No. 4506785 can be referred to.
　また、第一の透明電極パターン３３及び第二の透明電極パターン３４の少なくとも一方は、前面板３１の非接触面及びマスク層３２の前面板３１とは逆側の面の両方の領域にまたがって設置することができる。図３においては、第二の透明電極パターンが、前面板３１の非接触面及びマスク層３２の前面板３１とは逆側の面の両方の領域にまたがって設置されている図が示されている。 In addition, 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. In 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.
　図５を用いて第一の透明電極パターン３３及び第二の透明電極パターン３４について説明する。図５は、本発明における第一の透明電極パターン及び第二の透明電極パターンの一例を示す説明図である。図５に示すように、第一の透明電極パターン３３は、パッド部分３３ａが接続部分３３ｂを介して第一の方向に延在して形成されている。また、第二の透明電極パターン３４は、第一の透明電極パターン３３と絶縁層３５によって電気的に絶縁されており、第一の方向に交差する方向（図５における第二の方向）に延在して形成された複数のパッド部分によって構成されている。ここで、第一の透明電極パターン３３を形成する場合、上記パッド部分３３ａと接続部分３３ｂとを一体として作製してもよいし、接続部分３３ｂのみを作製して、パッド部分３３ａと第二の透明電極パターン３４とを一体として作製（パターニング）してもよい。パッド部分３３ａと第二の透明電極パターン３４とを一体として作製（パターニング）する場合、図５に示すように接続部分３３ｂの一部とパッド部分３３ａの一部とが連結され、かつ、絶縁層３５によって第一の透明電極パターン３３と第二の透明電極パターン３４とが電気的に絶縁されるように各層が形成される。 The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. 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. As shown in FIG. 5, 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. Here, when the first transparent electrode pattern 33 is 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). When 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.
　図３において、マスク層３２の前面板３１とは逆側の面側には導電性要素３６が設置されている。導電性要素３６は、第一の透明電極パターン３３及び第二の透明電極パターン３４の少なくとも一方に電気的に接続され、かつ、第一の透明電極パターン３３及び第二の透明電極パターン３４とは別の要素である。図３においては、導電性要素３６が第二の透明電極パターン３４に接続されている図が示されている。 In FIG. 3, 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. In FIG. 3, a view in which the conductive element 36 is connected to the second transparent electrode pattern 34 is shown.
　また、図３においては、各構成要素の全てを覆うように透明保護層３７が設置されている。透明保護層３７は、各構成要素の一部のみを覆うように構成されていてもよい。絶縁層３５と透明保護層３７とは、同一材料であってもよいし、異なる材料であってもよい。 Moreover, in FIG. 3, 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.
＜静電容量型入力装置、及び、静電容量型入力装置を具備したタッチパネル表示装置＞
　本発明の製造方法によって得られる静電容量型入力装置、及び、当該静電容量型入力装置を構成要素として備えたタッチパネル表示装置は、「最新タッチパネル技術」（２００９年７月６日発行（株）テクノタイムズ）、三谷雄二監修、“タッチパネルの技術と開発”、シーエムシー出版（２００４，１２）、ＦＰＤ　Ｉｎｔｅｒｎａｔｉｏｎａｌ　２００９　Ｆｏｒｕｍ　Ｔ－１１講演テキストブック、Ｃｙｐｒｅｓｓ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ　Ｃｏｒｐｏｒａｔｉｏｎ　アプリケーションノートＡＮ２２９２等に開示されている構成を適用することができる。 <Capacitance type input device and touch panel display device provided with capacitance type input device>
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.
　以下に実施例を挙げて本発明を更に具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。したがって、本発明の範囲は以下に示す具体例に限定されるものではない。なお、特に断りのない限り、「部」、「％」は質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.
　以下の実施例において、以下の符号はそれぞれ以下の化合物を表す。
　ＭＡＴＨＦ：メタクリル酸テトラヒドロフラン－２－イル（合成品）
　ＯＸＥ－３０：３－エチル－３－オキセタニルメチルメタクリレート（大阪有機化学工業（株）製）
　ＧＭＡ：グリシジルメタクリレート（和光純薬工業（株）製）
　ＭＡＡ：メタクリル酸（和光純薬工業（株）製）
　ＭＭＡ：メチルメタクリレート（和光純薬工業（株）製）
　Ｓｔ：スチレン（和光純薬工業（株）製）
　ＤＣＰＭ：ジシクロペンタニルメタクリレート（日立化成工業（株）製）
　Ｖ－６０１：ジメチル　２，２’－アゾビス（２－メチルプロピオネート）（和光純薬工業（株）製）
　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
　ＥＥＰ：３－エトキシプロピオン酸エチル（三協化学（株）製）
　ＭＥＤＧ：ジエチレングリコールエチルメチルエーテル（商品名：ハイソルブＥＤＭ、東邦化学工業（株）製） In the following examples, the following symbols represent the following compounds, respectively.
MATHF: tetrahydrofuran-2-yl methacrylate (synthetic product)
OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate EEP: Ethyl 3-ethoxypropionate (manufactured by Sankyo Chemical Co., Ltd.)
MEDG: Diethylene glycol ethyl methyl ether (trade name: Hisolv EDM, manufactured by Toho Chemical Industry Co., Ltd.)
＜ＭＡＴＨＦの合成＞
　メタクリル酸（８６ｇ、１ｍｏｌ）を１５℃に冷却しておき、カンファースルホン酸（４．６ｇ，０．０２ｍｏｌ）添加した。その溶液に、２－ジヒドロフラン（７１ｇ、１ｍｏｌ、１．０当量）を滴下した。１時間撹拌した後に、飽和炭酸水素ナトリウム（５００ｍＬ）を加え、酢酸エチル（５００ｍＬ）で抽出し、硫酸マグネシウムで乾燥後、不溶物をろ過後４０℃以下で減圧濃縮し、残渣の黄色油状物を減圧蒸留して沸点（ｂｐ．）５４～５６℃／３．５ｍｍＨｇ留分のメタクリル酸テトラヒドロフラン－２－イル（ＭＡＴＨＦ）１２５ｇを無色油状物として得た（収率８０％）。 <Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium hydrogen carbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, filtered to insoluble matter and concentrated under reduced pressure at 40 ° C. or lower to give a yellow oily residue. Distillation under reduced pressure gave 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.
＜酸価の測定方法＞
　重合体の酸価は、水酸化カリウムを用いた滴定により測定した。 <Method for measuring acid value>
The acid value of the polymer was measured by titration using potassium hydroxide.
＜分散液Ｄ１の調製＞
　下記組成の分散液を調合し、これをジルコニアビーズ（０．３ｍｍφ）１７，０００部と混合し、ペイントシェーカーを用いて１２時間分散を行った。ジルコニアビ－ズ（０．３ｍｍφ）をろ別し、分散液Ｄ１を得た。
・二酸化チタン（石原産業（株）製、商品名：ＴＴＯ－５１（Ｃ）、平均一次粒径：１０～３０ｎｍ）：１，８７５部
・分散剤（ＤＩＳＰＥＲＢＹＫ－１１１：ビックケミー・ジャパン（株）製の３０％ＰＧＭＥＡ溶液）：２，２００部
・溶剤　ＰＧＭＥＡ：２，８２５部
・溶剤　ＥＥＰ：６００部 <Preparation of dispersion D1>
A dispersion having the following composition was prepared, mixed with 17,000 parts of zirconia beads (0.3 mmφ), and dispersed for 12 hours using a paint shaker. Zirconia beads (0.3 mmφ) were filtered off to obtain dispersion D1.
・ Titanium dioxide (made by Ishihara Sangyo Co., Ltd., trade name: TTO-51 (C), average primary particle size: 10 to 30 nm): 1,875 parts ・ Dispersant (DISPERBYK-111: manufactured by Big Chemie Japan Co., Ltd.) 30% PGMEA solution): 2,200 parts / solvent PGMEA: 2,825 parts / solvent EEP: 600 parts
＜分散液Ｄ２～Ｄ６の調製＞
　ＴＴＯ－５１（Ｃ）及びＤＩＳＰＥＲＢＹＫ－１１１を、表１に記載のものにそれぞれ変更した以外は、分散液Ｄ１の調製と同様にして、分散液Ｄ２～Ｄ６をそれぞれ得た。
　なお、使用溶剤については、感光性樹脂組成物の溶剤組成に合わせるよう、ＥＥＰ、ＭＥＤＧに適宜変更をした。 <Preparation of dispersions D2 to D6>
Dispersions D2 to D6 were obtained in the same manner as the dispersion D1, except that TTO-51 (C) and DISPERBYK-111 were changed to those shown in Table 1, respectively.
In addition, about the solvent to be used, it changed into EEP and MEDG suitably so that it might match with the solvent composition of the photosensitive resin composition.
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
　なお、表１に記載の分散液に使用した前述した以外の略号は、以下に示す通りである。－酸化チタン（ＴｉＯ2）粒子顔料（２種類）－
　ＴＴＯ－５５（Ｃ）：二酸化チタン、石原産業（株）製、平均一次粒径：３０～５０ｎｍ
　ＴＴＯ－５５（Ａ）：二酸化チタン、石原産業（株）製、平均一次粒径：３０～５０ｎｍ In addition, abbreviations other than those used in the dispersions described in Table 1 are as shown below. -Titanium oxide (TiO 2 ) particle pigment (2 types)-
TTO-55 (C): Titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd., average primary particle size: 30-50 nm
TTO-55 (A): Titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd., average primary particle size: 30-50 nm
－分散剤（３種類）－
　ＤＩＳＰＥＲＢＹＫ－１１１：分散剤、ビックケミー・ジャパン（株）製
　ＤＩＳＰＥＲＢＹＫ－２００１：分散剤、ビックケミー・ジャパン（株）製
　ソルスパース４１０００：分散剤、Ｌｕｂｒｉｚｏｌ社製 -Dispersant (3 types)-
DISPERBYK-111: Dispersant, manufactured by Big Chemie Japan Co., Ltd. DISPERBYK-2001: Dispersant, manufactured by Big Chemie Japan Co., Ltd. Solsperse 41000: Dispersant, manufactured by Lubrizol
－重合体（３種類）－
＜重合体Ｐ１の合成＞
　メタクリル酸テトラヒドロフラン－２－イル（０．４０モル当量）、
　メタクリル酸（０．１０モル当量）、
　３－エチル－３－オキセタニルメチルメタクリレート（０．５０モル当量）を合計で１００部、及び、
　プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）（１２０部）の混合溶液を窒素気流下、７０℃に加熱した。この混合溶液を撹拌しながら、ラジカル重合開始剤Ｖ－６０１（ジメチル　２，２’－アゾビス（２－メチルプロピオネート））、和光純薬工業（株）製、１２．０部）及びＰＧＭＥＡ（８０部）の混合溶液を３．５時間かけて滴下した。滴下が終了してから、７０℃で２時間反応させることにより重合体Ｐ１のＰＧＭＥＡ溶液を得た。更にＰＧＭＥＡを添加して固形分濃度４０質量％に調整した。
　得られた重合体Ｐ１のゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定した重量平均分子量（Ｍｗ）は、１５，０００であった。酸価は、４５ｍｇＫＯＨ／ｇであった。 -Polymer (3 types)-
<Synthesis of Polymer P1>
Tetrahydrofuran-2-yl methacrylate (0.40 molar equivalent),
Methacrylic acid (0.10 molar equivalent),
100 parts of 3-ethyl-3-oxetanylmethyl methacrylate (0.50 molar equivalent) in total, and
A mixed solution of propylene glycol monomethyl ether acetate (PGMEA) (120 parts) was heated to 70 ° C. under a nitrogen stream. While stirring this mixed solution, radical polymerization initiator V-601 ( dimethyl 2,2′-azobis (2-methylpropionate)), manufactured by Wako Pure Chemical Industries, Ltd., 12.0 parts) and PGMEA ( 80 parts) was added dropwise over 3.5 hours. After the completion of dropping, the PGMEA solution of polymer P1 was obtained by reacting at 70 ° C. for 2 hours. Further, PGMEA was added to adjust the solid content concentration to 40% by mass.
The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the obtained polymer P1 was 15,000. The acid value was 45 mg KOH / g.
＜重合体Ｐ２及びＰ３の合成＞
　モノマー組成を以下に変更した以外は、重合体Ｐ１と同様の方法により、重合体Ｐ２、Ｐ３のＰＧＭＥＡ溶液をそれぞれ得た。更にＰＧＭＥＡを添加して固形分濃度４０質量％に調整した。なお、使用溶剤については、感光性樹脂組成物の溶剤組成に合わせるよう、ＥＥＰ、ＭＥＤＧに適宜変更をした。 <Synthesis of Polymers P2 and P3>
PGMEA solutions of polymers P2 and P3 were obtained by the same method as polymer P1, except that the monomer composition was changed to the following. Further, PGMEA was added to adjust the solid content concentration to 40% by mass. In addition, about the solvent to be used, it changed into EEP and MEDG suitably so that it might match with the solvent composition of the photosensitive resin composition.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
（実施例１）
＜感光性樹脂組成物の調製＞
　下記組成にて、配合し混合して均一な溶液とした後、０．２μｍのポアサイズを有するポリエチレン製フィルターを用いてろ過して、実施例１の感光性樹脂組成物を調製した。得られた感光性樹脂組成物を用い、後述する各種評価を行った。評価結果を後述の表３に示す。
・下記化合物（東洋化成工業（株）製、ＣＭＴＵ）の０．２％ＰＧＭＥＡ溶液：２５．７部
・重合体Ｐ１の３０％ＰＧＭＥＡ溶液：２６３．３部
・光酸発生剤Ｅ－１（下記化合物）：５．１部
・ＪＥＲ１５７Ｓ６５（エポキシ樹脂、三菱化学（株）製、エポキシ当量：２００～２２０ｇ／ｅｑ）：１７．９部
・３－グリシドキシプロピルトリメトキシシラン（ＫＢＭ－４０３、信越化学工業（株）製）：４．５部
・イルガノックス１７２６（酸化防止剤、ＢＡＳＦ社製）：３．０部
・パーフルオロアルキル基含有ノニオン界面活性剤（Ｆ－５５４、ＤＩＣ（株）製）の２．０％ＰＧＭＥＡ溶液：１１．０部
・分散液Ｄ１：４７８．４部
・溶剤（下記表３の溶剤種、溶剤比、使用量、含有量にて、所望粘度の組成物が得られるよう適宜調整して添加した。なお、表３に記載の溶剤の総使用量は、今回の感光性樹脂組成物の調製において追加した溶剤量だけでなく、使用した分散液等に含まれる溶剤の量も含む値である。） (Example 1)
<Preparation of photosensitive resin composition>
After mixing and mixing with the following composition to make a uniform solution, the mixture was filtered using a polyethylene filter having a pore size of 0.2 μm to prepare a photosensitive resin composition of Example 1. Various evaluations described later were performed using the obtained photosensitive resin composition. The evaluation results are shown in Table 3 described later.
-0.2% PGMEA solution of the following compound (Toyo Kasei Kogyo Co., Ltd., CMTU): 25.7 parts-30% PGMEA solution of polymer P1: 263.3 parts-Photoacid generator E-1 (below Compound): 5.1 parts JER157S65 (epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 200 to 220 g / eq): 17.9 parts 3-glycidoxypropyltrimethoxysilane (KBM-403, Shin-Etsu) Chemical Industry Co., Ltd.): 4.5 parts Irganox 1726 (Antioxidant, manufactured by BASF): 3.0 parts Perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC Corporation) ) 2.0% PGMEA solution: 11.0 parts-Dispersion D1: 478.4 parts-Solvent (Solvent type, solvent ratio, amount used and content in Table 3 below give a composition having the desired viscosity) Adjust as appropriate In addition, the total amount of solvent used in Table 3 is a value that includes not only the amount of solvent added in the preparation of the photosensitive resin composition this time, but also the amount of solvent contained in the used dispersion. is there.)
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
＜塗布性の評価＞
　得られた組成物を、表３に記載の各塗布法によりガラス基板に塗布し、８０℃で１２０秒乾燥することによって厚さ２．５μｍの膜を形成した。
　スリット塗布は、スリットコートにより、塗布速度５０ｍｍ／ｓ、塗布ギャップ５０μｍの条件で枚葉塗布した。
　スプレー塗布は、二流体方式のスプレー塗布装置を用いて塗布した。
　これらの基板をＮａランプにて観察し、以下の基準で目視評価を行ったところ、表３の結果となった。なお、１又は２が実用範囲である。
　　１：塗布スジ及びムラが無く、均一な塗布膜である。
　　２：塗布スジ及び／又はムラがわずかに発生しているが、ほぼ均一な塗布膜である。
　　３：塗布スジ及び／又はムラが部分的に発生している。
　　４：塗布スジ及び／又はムラが全面的に発生している。 <Evaluation of coatability>
The obtained composition was applied to a glass substrate by the application methods described in Table 3, and dried at 80 ° C. for 120 seconds to form a 2.5 μm thick film.
For slit coating, single wafer coating was performed by slit coating under the conditions of a coating speed of 50 mm / s and a coating gap of 50 μm.
The spray coating was performed using a two-fluid type spray coating apparatus.
When these substrates were observed with a Na lamp and visually evaluated according to the following criteria, the results shown in Table 3 were obtained. In addition, 1 or 2 is a practical range.
1: A uniform coating film with no coating stripes and unevenness.
2: Although coating stripes and / or unevenness are slightly generated, the coating film is almost uniform.
3: Application stripes and / or unevenness partially occurs.
4: Coating streaks and / or unevenness occurs entirely.
＜塗布性の経時評価＞
　表３に記載の各塗布法により、ガラス基板への塗布を５０枚実施した後に、スリット刃先又はスプレーノズルの先端を目視又は拡大鏡にて確認した。なお、スリット塗布及びスプレー塗布は、上記塗布性の評価に記載の方法と同様に行った。評価基準は、以下の通りである。
　　１：目詰まり及び異物凝集の発生が無い。
　　２：目詰まり及び／又は異物凝集がスリット刃先の一部又はスプレーノズル先端に部分的に発生している。
　　３：目詰まり及び／又は異物凝集がスリット刃先の大部分又はスプレーノズル先端の大部分に発生している。 <Evaluation of applicability over time>
After 50 coatings on the glass substrate were carried out by each coating method described in Table 3, the slit blade edge or the tip of the spray nozzle was confirmed visually or with a magnifying glass. In addition, slit application | coating and spray application were performed similarly to the method as described in the said applicability | paintability evaluation. The evaluation criteria are as follows.
1: No clogging or foreign matter aggregation occurs.
2: Clogging and / or agglomeration of foreign matter partially occurs at a part of the slit blade edge or at the tip of the spray nozzle.
3: Clogging and / or foreign matter aggregation occurs in most of the slit blade edge or most of the tip of the spray nozzle.
＜屈折率の評価＞
　得られた感光性樹脂組成物を、シリコンウエハ基板上に塗布し、８０℃で１２０秒乾燥することによって厚さ０．５μｍの膜を形成した。この基板を、超高圧水銀灯を用いて２００ｍＪ／ｃｍ2（ｉ線で測定）で露光し、その後オーブンにて２２０℃で４５分加熱した。
　エリプソメーターＶＵＶ－ＶＡＳＥ（ジェー・エー・ウーラム・ジャパン（株）製）を用いて、５８９ｎｍでの硬化膜の屈折率を測定した。屈折率が高いほうが好ましく、１．７０以上がより好ましい。 <Evaluation of refractive index>
The obtained photosensitive resin composition was applied on a silicon wafer substrate and dried at 80 ° C. for 120 seconds to form a film having a thickness of 0.5 μm. 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.
＜ＩＴＯ視認性の評価＞
　１００ｍｍ×１００ｍｍのガラス基板（商品名：ＸＧ、コーニング社製）上に、あらかじめＩＴＯのパターンを形成しておき、得られた感光性樹脂組成物を膜厚１．０μｍとなるように塗布し、９０℃のホットプレート上で１２０秒乾燥（プリベーク）した。
　次に、基板全面にｇｈｉ線高圧水銀灯露光機を用いて、照度２０ｍＷ／ｃｍ2、２００ｍＪ／ｃｍ2にて、露光した。
　続いて２２０℃４５分加熱してＩＴＯパターン上に感光性組樹脂組成物の乾燥膜を設けた。得られた基板を明室内において肉眼で、傾斜をかけながら観察し、ＩＴＯパターン上に感光性樹脂組成物を設けなかった時と比較して、視認性の評価を行った。なお、評価基準は、以下の通りであり、ＩＴＯのパターンが見えにくいほどよい。１又は２が実用範囲である。
　　１：ＩＴＯのラインが見えない、又は、ほぼ見えない。
　　２：ＩＴＯのラインがうっすら見える。
　　３：ＩＴＯのラインがはっきり見える。 <Evaluation of ITO visibility>
An ITO pattern was previously formed on a 100 mm × 100 mm glass substrate (trade name: XG, manufactured by Corning), and the obtained photosensitive resin composition was applied to a film thickness of 1.0 μm. It was dried (prebaked) for 120 seconds on a 90 ° C. hot plate.
Next, the entire surface of the substrate was exposed at an illuminance of 20 mW / cm 2 and 200 mJ / cm 2 using a ghi-line high-pressure mercury lamp exposure machine.
Subsequently, it was heated at 220 ° C. for 45 minutes to provide a dry film of the photosensitive resin composition on the ITO pattern. The obtained substrate was observed with the naked eye in the bright room while tilting, and the visibility was evaluated as compared with the case where the photosensitive resin composition was not provided on the ITO pattern. The evaluation criteria are as follows, and it is better that the ITO pattern is less visible. 1 or 2 is a practical range.
1: The ITO line is not visible or almost invisible.
2: The ITO line is slightly visible.
3: The ITO line is clearly visible.
（実施例２～１９及び比較例１～６）
　実施例２～１９及び比較例１～６においては、分散液、重合体、溶剤、及び／又は、塗布方法をそれぞれ表３に記載のものに変更した以外は、実施例１と同様に感光性樹脂組成物を調製し、各評価を行った。評価結果を表３に合わせて示す。
　なお、比較例２及び３については、分散液Ｄ１中の溶剤を全てＥＥＰ、又は、ＭＥＤＧに変更して調製した。 (Examples 2 to 19 and Comparative Examples 1 to 6)
In Examples 2 to 19 and Comparative Examples 1 to 6, the dispersion, the polymer, the solvent, and / or the photosensitivity were the same as in Example 1 except that the coating methods were changed to those shown in Table 3, respectively. Resin compositions were prepared and evaluated. The evaluation results are shown in Table 3.
Comparative Examples 2 and 3 were prepared by changing all the solvents in the dispersion D1 to EEP or MEDG.
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
　上記表３に記載の「沸点１６０℃以上の溶剤の含有量Ａ」は、感光性樹脂組成物中の全溶剤量に対する沸点１６０℃以上の溶剤の含有量を表し、「沸点１６０℃以上の溶剤の含有量Ｂ」は、感光性樹脂組成物の全質量に対する沸点１６０℃以上の溶剤の含有量を表す。 “Solvent content A having a boiling point of 160 ° C. or higher” in Table 3 above represents the content of a solvent having a boiling point of 160 ° C. or higher relative to the total amount of solvent in the photosensitive resin composition. "Content B" represents the content of a solvent having a boiling point of 160 ° C or higher with respect to the total mass of the photosensitive resin composition.
（実施例２０）
　特許第３３２１００３号公報の図１に記載のアクティブマトリクス型液晶表示装置において、層間絶縁膜として硬化膜１７を以下のようにして形成し、実施例２０の液晶表示装置を得た。すなわち、実施例３の感光性樹脂組成物を基板上にスリット塗布し、ホットプレート上でプリベーク（９０℃／１２０秒）した後、マスク上から高圧水銀灯を用いてｉ線（３６５ｎｍ）を４５ｍＪ／ｃｍ2（照度２０ｍＷ／ｃｍ2）照射した後、アルカリ水溶液にて現像してパターンを形成し、２３０℃／３０分間の加熱処理を行い、層間絶縁膜として硬化膜１７を形成した。 (Example 20)
In the active matrix type liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 20 was obtained. That is, the photosensitive resin composition of Example 3 was slit-coated on a substrate, pre-baked (90 ° C./120 seconds) on a hot plate, and then i-line (365 nm) was 45 mJ / mm using a high-pressure mercury lamp from above the mask. After irradiation with cm 2 (illuminance 20 mW / cm 2 ), development was performed with an alkaline aqueous solution to form a pattern, and heat treatment was performed at 230 ° C./30 minutes to form a cured film 17 as an interlayer insulating film.
　得られた液晶表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 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.
（実施例２１）
　薄膜トランジスター（ＴＦＴ）を用いた有機ＥＬ表示装置を以下の方法で作製した（図２参照）。
　ガラス基板６上にボトムゲート型のＴＦＴ１を形成し、このＴＦＴ１を覆う状態でＳｉ3Ｎ4から成る絶縁膜３を形成した。次に、この絶縁膜３に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してＴＦＴ１に接続される配線２（高さ１．０μｍ）を絶縁膜３上に形成した。この配線２は、ＴＦＴ１間、又は、後の工程で形成される有機ＥＬ素子とＴＦＴ１とを接続するためのものである。 (Example 21)
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. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) 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.
　更に、配線２の形成による凹凸を平坦化するために、配線２による凹凸を埋め込む状態で絶縁膜３上へ平坦化膜４を形成した。絶縁膜３上への平坦化膜４の形成は、実施例１２の感光性樹脂組成物を基板上にスリット塗布し、ホットプレート上でプリベーク（９０℃／１２０秒）した後、マスク上から高圧水銀灯を用いてｉ線（３６５ｎｍ）を４５ｍＪ／ｃｍ2（照度２０ｍＷ／ｃｍ2）照射した後、アルカリ水溶液にて現像してパターンを形成し、２３０℃／３０分間の加熱処理を行った。
　感光性樹脂組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。更に、配線２の平均段差は５００ｎｍ、作製した平坦化膜４の膜厚は２，０００ｎｍであった。 Further, in order to flatten the unevenness due to the formation of the wiring 2, 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 planarization film 4 is formed on the insulating film 3 by slit coating the photosensitive resin composition of Example 12 on the 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.
　次に、得られた平坦化膜４上に、ボトムエミッション型の有機ＥＬ素子を形成した。まず、平坦化膜４上に、ＩＴＯからなる第一電極５を、コンタクトホール７を介して配線２に接続させて形成した。その後、レジストを塗布、プリベークし、所望のパターンのマスクを介して露光し、現像した。このレジストパターンをマスクとして、ＩＴＯエッチャント用いたウエットエッチングによりパターン加工を行った。その後、レジスト剥離液（リムーバ１００、ＡＺエレクトロニックマテリアルズ社製）を用いて上記レジストパターンを５０℃で剥離した。こうして得られた第一電極５は、有機ＥＬ素子の陽極に相当する。 Next, a bottom emission type organic EL element was formed on the obtained flattening film 4. First, 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. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, 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.
　次に、第一電極５の周縁を覆う形状の絶縁膜８を形成した。絶縁膜８には、実施例１２の感光性樹脂組成物を用い、上記と同様の方法で絶縁膜８を形成した。この絶縁膜８を設けることによって、第一電極５とこの後の工程で形成する第二電極との間のショートを防止することができる。 Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition of Example 12 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.
　更に、真空蒸着装置内で所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設けた。次いで、基板上方の全面にＡｌから成る第二電極を形成した。得られた上記基板を蒸着機から取り出し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止した。 Further, 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. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | 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.
　以上のようにして、各有機ＥＬ素子にこれを駆動するためのＴＦＴ１が接続してなるアクティブマトリックス型の有機ＥＬ表示装置が得られた。駆動回路を介して電圧を印加したところ、良好な表示特性を示し、信頼性の高い有機ＥＬ表示装置であることが分かった。 As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving it was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.
（実施例２２）
　以下に述べる方法により本発明の高屈折率の感光性樹脂組成物を用いてタッチパネル表示装置を作成した。 (Example 22)
A touch panel display device was prepared using the high refractive index photosensitive resin composition of the present invention by the method described below.
＜第一の透明電極パターンの形成＞
［透明電極層の形成］
　あらかじめマスク層が形成された強化処理ガラス（３００ｍｍ×４００ｍｍ×０．７ｍｍ）の前面板を、真空チャンバー内に導入し、ＳｎＯ2含有率が１０質量％のＩＴＯターゲット（インジウム：錫＝９５：５（モル比））を用いて、ＤＣマグネトロンスパッタリング（条件：基材の温度２５０℃、アルゴン圧０．１３Ｐａ、酸素圧０．０１Ｐａ）により、厚さ４０ｎｍのＩＴＯ薄膜を形成し、透明電極層を形成した前面板を得た。ＩＴＯ薄膜の表面抵抗は８０Ω／□であった。 <Formation of first transparent electrode pattern>
[Formation of transparent electrode layer]
A front plate of tempered glass (300 mm × 400 mm × 0.7 mm) with a mask layer formed in advance is introduced into a vacuum chamber, and an ITO target (indium: tin = 95: 5) with a SnO 2 content of 10% by mass. (Molar ratio)) was used to form an ITO thin film having a thickness of 40 nm by DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent electrode layer was formed. A formed front plate was obtained. The surface resistance of the ITO thin film was 80Ω / □.
　次いで、市販のエッチングレジストをＩＴＯ上に塗布・乾燥し、エッチングレジスト層を形成した。露光マスク（透明電極パターンを有す石英露光マスク）面と該エッチングレジスト層との間の距離を１００μｍに設定し、露光量５０ｍＪ／ｃｍ2（ｉ線）でパターン露光したのち、専用の現像液で現像を行い、更に１３０℃３０分間のポストベーク処理を行って、透明電極層とエッチング用光硬化性樹脂層パターンとを形成した前面板を得た。 Next, a commercially available etching resist was applied onto ITO and dried to form an etching resist layer. The distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the etching resist layer is set to 100 μm, pattern exposure is performed at an exposure amount of 50 mJ / cm 2 (i-line), and then a dedicated developer And a post-bake treatment at 130 ° C. for 30 minutes to obtain a front plate on which a transparent electrode layer and a photocurable resin layer pattern for etching were formed.
　透明電極層とエッチング用光硬化性樹脂層パターンとを形成した前面板を、ＩＴＯエッチャント（塩酸、塩化カリウム水溶液。液温３０℃）を入れたエッチング槽に浸漬し、１００秒処理し、エッチングレジスト層で覆われていない露出した領域の透明電極層を溶解除去し、エッチングレジスト層パターンのついた透明電極層パターン付の前面板を得た。
　次に、エッチングレジスト層パターンのついた透明電極層パターン付の前面板を、専用のレジスト剥離液に浸漬し、エッチング用光硬化性樹脂層を除去し、マスク層と第一の透明電極パターンとを形成した前面板を得た。 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. 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.
Next, 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.
［絶縁層の形成］
　マスク層と第一の透明電極パターンとを形成した前面板の上に、実施例１の感光性樹脂組成物を塗布・乾燥（膜厚１μｍ、９０℃１２０秒）し、感光性樹脂組成物層を得た。露光マスク（絶縁層用パターンを有す石英露光マスク）面と該感光性樹脂組成物層との間の距離を３０μｍに設定し、露光量５０ｍＪ／ｃｍ2（ｉ線）でパターン露光した。
　次に、２．３８質量％のテトラメチルアンモニウムヒドロキシド水溶液により２３℃で１５秒間浸液盛り法にて現像し、更に超純水で１０秒間リンスした。続いて２２０℃４５分のポストベーク処理を行って、マスク層、第一の透明電極パターン、絶縁層パターンを形成した前面板を得た。 [Formation of insulating layer]
On the front plate on which the mask layer and the first transparent electrode pattern were formed, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm, 90 ° C., 120 seconds) to form a photosensitive resin composition layer. Got. The distance between the exposure mask (quartz exposure mask having an insulating layer pattern) surface and the photosensitive resin composition layer was set to 30 μm, and pattern exposure was performed at an exposure amount of 50 mJ / cm 2 (i-line).
Next, 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. Subsequently, 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.
＜第二の透明電極パターンの形成＞
［透明電極層の形成］
　上記第一の透明電極パターンの形成と同様にして、絶縁層パターンまで形成した前面板をＤＣマグネトロンスパッタリング処理し（条件：基材の温度５０℃、アルゴン圧０．１３Ｐａ、酸素圧０．０１Ｐａ）、厚さ８０ｎｍのＩＴＯ薄膜を形成し、透明電極層を形成した前面板を得た。ＩＴＯ薄膜の表面抵抗は１１０Ω／□であった。
　第一の透明電極パターンの形成と同様にして、市販のエッチングレジストを用いて、第一の透明電極パターン、実施例１の感光性樹脂組成物を用いて形成した絶縁層パターン、透明電極層、エッチングレジストパターンを形成した前面板を得た（ポストベーク処理；１３０℃３０分間）。
　更に、第一の透明電極パターンの形成と同様にして、エッチングし、エッチングレジスト層を除去することにより、マスク層、第一の透明電極パターン、実施例１の感光性樹脂組成物用いて形成した絶縁層パターン、第二の透明電極パターンを形成した前面板を得た。 <Formation of second transparent electrode pattern>
[Formation of transparent electrode layer]
In the same manner as the formation of the first transparent electrode pattern, the front plate formed up to the insulating layer pattern was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa). An ITO thin film having a thickness of 80 nm was formed to obtain a front plate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 110Ω / □.
Similarly to the formation of the first transparent electrode pattern, using a commercially available etching resist, the first transparent electrode pattern, an insulating layer pattern formed using the photosensitive resin composition of Example 1, a transparent electrode layer, A front plate on which an etching resist pattern was formed was obtained (post-baking treatment; 130 ° C. for 30 minutes).
Further, etching was performed in the same manner as the formation of the first transparent electrode pattern, and the etching resist layer was removed to form the mask layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. A front plate on which an insulating layer pattern and a second transparent electrode pattern were formed was obtained.
＜第一及び第二の透明電極パターンとは別の導電性要素の形成＞
　上記第一、及び、第二の透明電極パターンの形成と同様にして、第一の透明電極パターン、実施例１の感光性樹脂組成物を用いて形成した絶縁層パターン、第二の透明電極パターンを形成した前面板をＤＣマグネトロンスパッタリング処理し、厚さ２００ｎｍのアルミニウム（Ａｌ）薄膜を形成した前面板を得た。
　上記第一、及び、第二の透明電極パターンの形成と同様にして、市販のエッチングレジストを用いて、第一の透明電極パターン、実施例１の感光性樹脂組成物を用いて形成した絶縁層パターン、第二の透明電極パターン、エッチングレジストパターンを形成した前面板を得た。（ポストベーク処理；１３０℃３０分間）。
　更に、第一の透明電極パターンの形成と同様にして、エッチング（３０℃５０秒間）し、エッチングレジスト層を除去（４５℃２００秒間）することにより、マスク層、第一の透明電極パターン、実施例１の感光性樹脂組成物を用いて形成した絶縁層パターン、第二の透明電極パターン、第一及び第二の透明電極パターンとは別の導電性要素を形成した前面板を得た。 <Formation of Conductive Element Different from First and Second Transparent Electrode Pattern>
Similar to the formation of the first and second transparent electrode patterns, the first transparent electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 1, and the second transparent electrode pattern The front plate on which was formed was subjected to DC magnetron sputtering to obtain a front plate on which an aluminum (Al) thin film having a thickness of 200 nm was formed.
Insulating layer formed using the first transparent electrode pattern, the photosensitive resin composition of Example 1, using a commercially available etching resist in the same manner as the formation of the first and second transparent electrode patterns. 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 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). A front plate on which a conductive element different from the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns formed using the photosensitive resin composition of Example 1 was obtained was obtained.
＜透明保護層の形成＞
　絶縁層の形成と同様にして、上記第一及び第二の透明電極パターンとは別の導電性要素まで形成した前面板に、実施例１の感光性樹脂組成物を塗布・乾燥（膜厚１μｍ、９０℃１２０秒）し、感光性樹脂組成物膜を得た。更に、露光マスクを介さずに露光量５０ｍＪ／ｃｍ2（ｉ線）で前面露光し、現像、ポスト露光（１，０００ｍＪ／ｃｍ2）、ポストベーク処理を行って、マスク層、第一の透明電極パターン、実施例１の感光性樹脂組成物を用いて形成した絶縁層パターン、第二の透明電極パターン、第一及び第二の透明電極パターンとは別の導電性要素の全てを覆うように実施例１の感光性樹脂組成物を用いて形成した絶縁層（透明保護層）を積層した前面板を得た。 <Formation of transparent protective layer>
In the same manner as the formation of the insulating layer, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm) 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. Furthermore, 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. The front board which laminated | stacked the insulating layer (transparent protective layer) formed using the photosensitive resin composition of Example 1 was obtained.
＜画像表示装置（タッチパネル）の作製＞
　特開２００９－４７９３６号公報に記載の方法で製造した液晶表示素子に、先に製造した前面板を貼り合わせ、公知の方法で静電容量型入力装置を構成要素として備えた画像表示装置を作製した。 <Production of image display device (touch panel)>
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.
＜前面板、及び、画像表示装置の評価＞
　第一の透明電極パターン、第二の透明電極パターン、及び、これらとは別の導電性要素の、各々の導電性には問題がなく、一方で、第一の透明電極パターンと第二の透明電極パターンの間では絶縁性を有してあり、タッチパネルとして良好な表示特性が得られた。更に、第一及び第二の透明電極パターンは視認されにくく、表示特性に優れた画像表示装置が得られた。 <Evaluation of front plate and image display device>
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and other conductive elements, while the first transparent electrode pattern and the second transparent electrode pattern Between the electrode patterns, there was insulation, and good display characteristics as a touch panel were obtained. Furthermore, the first and second transparent electrode patterns were hardly visible and an image display device having excellent display characteristics was obtained.
　１：ＴＦＴ（薄膜トランジスタ）、２：配線、３：絶縁膜、４：平坦化膜、５：第一電極、６：ガラス基板、７：コンタクトホール、８：絶縁膜、１０：液晶表示装置、１２：バックライトユニット、１４，１５：ガラス基板、１６：ＴＦＴ、１７：硬化膜、１８：コンタクトホール、１９：ＩＴＯ透明電極、２０：液晶、２２：カラーフィルター
３０：静電容量型入力装置、３１：前面板、３２：マスク層、３３：第一の透明電極パターン、３３ａ：パッド部分、３３ｂ：接続部分、３４：第二の透明電極パターン、３５：絶縁層、３６：導電性要素、３７：透明保護層、３８：開口部 1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: flattening 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

Claims (18)

  1. 　（成分Ａ）無機粒子、
    　（成分Ｂ）分散剤、
    　（成分Ｃ）溶剤、
    　（成分Ｄ）酸基が酸分解性基で保護された基を有する構成単位を含む重合体、及び、
    　（成分Ｅ）光酸発生剤を含有し、
    　成分Ｃが、沸点１６０℃以上の溶剤を含み、
    　前記沸点１６０℃以上の溶剤の含有量が、感光性樹脂組成物中の全溶剤量に対し、３質量％以上４０質量％以下であることを特徴とする
    　感光性樹脂組成物。     (Component A) inorganic particles,
    (Component B) Dispersant,
    (Component C) solvent,
    (Component D) a polymer containing a structural unit having a group in which an acid group is protected with an acid-decomposable group, and
    (Component E) contains a photoacid generator,
    Component C contains a solvent having a boiling point of 160 ° C. or higher,
    Content of the said solvent whose boiling point is 160 degreeC or more is 3 to 40 mass% with respect to the total amount of solvent in the photosensitive resin composition, The photosensitive resin composition characterized by the above-mentioned.
  2. 　成分Ｃが、プロピレングリコールモノメチルエーテルアセテート、３－エトキシプロピオン酸エチル、及び／又は、ジエチレングリコールエチルメチルエーテルを含む、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein Component C comprises propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, and / or diethylene glycol ethyl methyl ether.
  3. 　成分Ｃが、沸点１６０℃未満の溶剤としてプロピレングリコールモノメチルエーテルアセテートと、沸点１６０℃以上の溶剤として３－エトキシプロピオン酸エチル及び／又はジエチレングリコールエチルメチルエーテルとを含む、請求項１又は２に記載の感光性樹脂組成物。 The component C comprises propylene glycol monomethyl ether acetate as a solvent having a boiling point of less than 160 ° C and ethyl 3-ethoxypropionate and / or diethylene glycol ethyl methyl ether as a solvent having a boiling point of 160 ° C or higher. Photosensitive resin composition.
  4. 　成分Ｃの含有量が、７０質量％以上９５質量％以下である、請求項１～３のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of Component C is 70% by mass or more and 95% by mass or less.
  5. 　粘度が、１５ｍＰａ・ｓ以下である、請求項１～４のいずれか１項に記載の感光性樹脂組成物。 5. The photosensitive resin composition according to claim 1, wherein the viscosity is 15 mPa · s or less.
  6. 　成分Ａが、金属酸化物粒子である、請求項１～５のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 5, wherein Component A is metal oxide particles.
  7. 　成分Ａが、酸化チタン粒子又は酸化ジルコニウム粒子である、請求項１～６のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 6, wherein Component A is titanium oxide particles or zirconium oxide particles.
  8. 　前記酸基が酸分解性基で保護された基を有する構成単位が、下記式で表される構成単位である、請求項１～７のいずれか１項に記載の感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ121は水素原子又は炭素数１～４のアルキル基を表し、Ｌ1はカルボニル基又はフェニレン基を表し、Ｒ122～Ｒ128はそれぞれ独立に、水素原子又は炭素数１～４のアルキル基を表す。）     The photosensitive resin composition according to any one of claims 1 to 7, wherein the structural unit having a group in which the acid group is protected by an acid-decomposable group is a structural unit represented by the following formula.
    Figure JPOXMLDOC01-appb-C000001
     Wherein R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 1 represents a carbonyl group or a phenylene group, and R 122 to R 128 each independently represents a hydrogen atom or 1 to 4 carbon atoms. Represents an alkyl group of
  9. 　（成分Ｆ）熱架橋剤を更に含む、請求項１～８のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, further comprising (Component F) a thermal crosslinking agent.
  10. 　（成分Ｇ）酸化防止剤を更に含む、請求項１～９のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 9, further comprising (Component G) an antioxidant.
  11. 　少なくとも工程（ａ）～（ｃ）をこの順に含むことを特徴とする硬化物の製造方法。
    　（ａ）請求項１～１０のいずれか１項に記載の感光性樹脂組成物を基板上に塗布する塗布工程
    　（ｂ）塗布された樹脂組成物から溶剤を除去する溶剤除去工程
    　（ｃ）溶剤が除去された樹脂組成物を熱処理する熱処理工程     A method for producing a cured product, comprising at least steps (a) to (c) in this order.
    (A) a coating step of applying the photosensitive resin composition according to any one of claims 1 to 10 on a substrate; (b) a solvent removal step of removing a solvent from the applied resin composition; (c) a solvent; Heat treatment step of heat treating the resin composition from which the resin has been removed
  12. 　少なくとも工程（１）～（５）をこの順に含むことを特徴とする樹脂パターン製造方法。
    　（１）請求項１～１０のいずれか１項に記載の感光性樹脂組成物を基板上に塗布する塗布工程
    　（２）塗布された樹脂組成物から溶剤を除去する溶剤除去工程
    　（３）溶剤が除去された樹脂組成物を活性光線によりパターン状に露光する露光工程
    　（４）露光された樹脂組成物を水性現像液により現像する現像工程
    　（５）現像された樹脂組成物を熱処理する熱処理工程     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 claims 1 to 10 on a substrate (2) Solvent removal step of removing the solvent from the applied resin composition (3) Solvent (4) Development step of developing the exposed resin composition with an aqueous developer (5) Heat treatment step of heat-treating the developed resin composition
  13. 　請求項１１に記載の硬化物の製造方法、又は、請求項１２に記載の樹脂パターン製造方法により得られた硬化物。 The hardened | cured material obtained by the manufacturing method of the hardened | cured material of Claim 11, or the resin pattern manufacturing method of Claim 12.
  14. 　請求項１～１０のいずれか１項に記載の感光性樹脂組成物を硬化してなる硬化膜。 A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 10.
  15. 　層間絶縁膜である、請求項１４に記載の硬化膜。 The cured film according to claim 14, which is an interlayer insulating film.
  16. 　請求項１４又は１５に記載の硬化膜を有する液晶表示装置。 A liquid crystal display device having the cured film according to claim 14 or 15.
  17. 　請求項１４又は１５に記載の硬化膜を有する有機ＥＬ表示装置。 An organic EL display device having the cured film according to claim 14 or 15.
  18. 　請求項１４又は１５に記載の硬化膜を有するタッチパネル表示装置。 A touch panel display device having the cured film according to claim 14 or 15.
PCT/JP2013/078766 2012-10-26 2013-10-24 Photosensitive resin composition, cured product and method for producing same, method for producing resin pattern, cured film, organic el display device, liquid crystal display device, and touch panel display device WO2014065351A1 (en)

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