WO2024034608A1 - 感光性樹脂組成物、硬化物、カラーフィルター及び画像表示装置 - Google Patents

感光性樹脂組成物、硬化物、カラーフィルター及び画像表示装置 Download PDF

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WO2024034608A1
WO2024034608A1 PCT/JP2023/028923 JP2023028923W WO2024034608A1 WO 2024034608 A1 WO2024034608 A1 WO 2024034608A1 JP 2023028923 W JP2023028923 W JP 2023028923W WO 2024034608 A1 WO2024034608 A1 WO 2024034608A1
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mass
group
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resin composition
photosensitive resin
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PCT/JP2023/028923
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English (en)
French (fr)
Japanese (ja)
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朋子 山川
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三菱ケミカル株式会社
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Priority to CN202380046339.2A priority Critical patent/CN119365827A/zh
Priority to KR1020247039377A priority patent/KR20250041100A/ko
Priority to JP2024540488A priority patent/JPWO2024034608A1/ja
Publication of WO2024034608A1 publication Critical patent/WO2024034608A1/ja

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]

Definitions

  • the present invention relates to a photosensitive resin composition, and further relates to a cured product obtained by curing the photosensitive resin composition, and a color filter and an image display device comprising the cured product.
  • Luminescent nanocrystal particles scatter the light that passes through the red and green pixels, but if the light from the blue pixels goes straight, the image will be unclear, so we are considering introducing scattering particles into the blue pixels for the purpose of scattering. has been done.
  • Patent Documents 1 and 2 metal oxides are used as scattering particles.
  • melamine resin fine particles are used as scattering particles in a resin composition for a light scattering layer in Patent Documents 3 and 4.
  • Patent Documents 5 and 6 melamine resin fine particles are used as scattering particles in quantum dot-containing compositions.
  • compositions described in Patent Documents 1 and 2 use a metal oxide with a high refractive index (titanium oxide) as scattering particles, so the light scattering property is low.
  • a metal oxide with a high refractive index titanium oxide
  • the composition described in Patent Document 3 uses melamine resin fine particles with an average primary particle diameter of 200 to 800 nm as scattering particles, and therefore has high light transmittance but low light scattering properties.
  • the composition described in Patent Document 4 uses titanium oxide as high refractive particles with a refractive index of 2.0 or more and melamine resin fine particles with a refractive index of 2.0 or less as scattering particles, so the composition has high light scattering properties. A problem was found in which the light transmittance decreased.
  • a non-alkali-soluble resin without an alkali-soluble component such as a carboxylic acid is mixed with melamine resin particles as a dispersion resin, and the photosensitive resin composition does not contain an alkali-soluble resin. It was found that pattern exposure tends to leave residues and the developability is low.
  • compositions containing an alkali-soluble resin having no ethylenic double bond in the side chain as a dispersant have a problem of low heat resistance after exposure.
  • the composition described in Patent Document 6 contains an acrylic resin having an acid value, but since the composition is an acrylic resin that does not have an ethylenic double bond in the side chain, a problem was found in that the composition has low heat resistance.
  • the present invention provides a photosensitive resin composition that has both high light scattering properties and high light transmittance, is developable, and has high heat resistance. Further, the present invention provides a cured product obtained by curing a photosensitive resin composition that is developable and has high heat resistance while achieving both high light scattering properties and high light transmittance, an organic electroluminescent device including the cured product, and a semiconductor.
  • the Company provides light emitting elements, color filters, light scattering films, and image display devices.
  • a photosensitive resin composition containing (a) resin particles, (b) an alkali-soluble resin, and (c) a photopolymerization initiator,
  • the resin particles (a) include resin particles (a1) having a refractive index of 1.56 or more and 2.00 or less and an average particle diameter of primary particles of 0.8 ⁇ m or more
  • the alkali-soluble resin (b) includes an alkali-soluble resin (b1) having an ethylenic double bond, further comprising at least one of (e) a polymerization inhibitor and (f) an ultraviolet absorber;
  • a photosensitive resin composition wherein a cured film having a thickness of 5 ⁇ m obtained by curing the photosensitive resin composition has an average transmittance of 70% or more in a wavelength range of 400 to 700 nm.
  • the present invention it is possible to provide a photosensitive resin composition that is developable and has high heat resistance while achieving both high light scattering properties and high light transmittance.
  • FIG. 1 is a schematic cross-sectional view of an example of a color filter including the cured product of the present invention.
  • (Co)polymer means to include both a single polymer (homopolymer) and a copolymer (copolymer), and "(acid) anhydride” and “(anhydride)...acid” , is meant to include both acids and their anhydrides.
  • the weight average molecular weight means the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
  • Acid value means an acid value in terms of effective solid content, unless otherwise specified, and is calculated by neutralization titration.
  • Photosensitive resin composition contains (a) resin particles, (b) an alkali-soluble resin, and (c) a photopolymerization initiator, and further contains (e) a polymerization inhibitor and (f) Contains at least one type of ultraviolet absorber.
  • Other components may be included as necessary, for example, (d) a photopolymerizable compound, (g) a dispersant, a solvent, and a chain transfer agent.
  • the photosensitive resin composition of the present invention contains (a) resin particles, and (a) the resin particles have a refractive index of 1.56 or more and 2.00 or less, and It contains resin particles (a1) whose primary particles have an average particle diameter of 0.8 ⁇ m or more.
  • resin particles include the resin particles (a1), light scattering properties can be increased while the light transmittance of the cured product formed from the photosensitive resin composition remains high.
  • resin particles refers to particles whose main component is resin.
  • the main component is a component that occupies the largest amount on a mass basis among the components constituting the particles, and is, for example, a component that occupies 50% by mass or more in the particles. It is preferable that the component accounts for 80% by mass or more and 90% by mass or more in the particles. Further, it is usually 100% by mass or less.
  • the resin particles and the resin particles (a1) may each have a particle shape or a non-particle shape. From the viewpoint of improving dispersion stability and light transmittance, resin particles (a) and resin particles (a1) each preferably have a particle shape. Examples of the particle shape include spherical, hollow, porous, rod-like, plate-like, fibrous, and irregular shapes, and preferably spherical.
  • the components constituting the resin particles (a1) include polystyrene (styrene resin), polyvinylidene chloride, polyimide, polyethylene terephthalate, polysulfone, phenol resin, melamine resin, benzoguanamine resin, and polycarbonate, which have high heat resistance. From the viewpoint of ease of making resin particles, benzoguanamine resin, melamine resin, and styrene resin are preferred. It is preferable that the resin particles (a1) contain at least one of benzoguanamine resin, melamine resin, and styrene resin. From the viewpoint of improving light scattering properties, melamine resins and benzoguanamine resins are particularly preferred. Styrene resin is particularly preferred from the viewpoint of increasing light transmittance.
  • benzoguanamine resin a benzoguanamine/formaldehyde condensate is preferred.
  • melamine resin a melamine/formaldehyde condensate is preferred.
  • styrene resin styrene or a resin having styrene having a substituent as a repeating unit is preferable. Examples of the styrene having a substituent include styrene having a substituent of an alkyl group having 1 to 6 carbon atoms, such as methylstyrene, ethylstyrene, and vinyltoluene.
  • Styrene a resin having styrene having a substituent as a repeating unit, styrene, or a copolymer with a repeating unit other than styrene having a substituent may be used.
  • repeating units other than styrene and styrene having substituents include (meth)acrylic acid, butadiene, maleic anhydride, and acrylonitrile. From the viewpoint of increasing transparency, styrene-(meth)acrylic acid copolymer is particularly preferred.
  • the average particle diameter of the primary particles of the resin particles (a1) is preferably 0.8 ⁇ m or more, more preferably 0.9 ⁇ m or more, even more preferably 1.0 ⁇ m or more, and particularly preferably 1.1 ⁇ m or more. Further, the thickness is preferably 5.0 ⁇ m or less, more preferably 4.0 ⁇ m or less, even more preferably 3.0 ⁇ m or less, even more preferably 2.0 ⁇ m or less, and particularly preferably 1.8 ⁇ m or less.
  • the average particle diameter of the primary particles is less than or equal to the above upper limit, light transmittance and sedimentation stability tend to increase. If it is more than the lower limit, the light scattering property tends to be high. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.8 to 5.0 ⁇ m, more preferably 0.9 to 4.0 ⁇ m, even more preferably 1.0 to 3.0 ⁇ m, even more preferably 1.1 to 2.0 ⁇ m, and even more preferably 1.1 to 2.0 ⁇ m. Particularly preferred is 1.8 ⁇ m.
  • the average particle diameter of the primary particles of the resin particles (a1) can be determined by directly measuring the size of the primary particles from an electron micrograph using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). Measure with. Specifically, the primary particle diameter of each particle is calculated as a circular equivalent diameter. The measurement is performed by imaging a range of 10 ⁇ m to 100 ⁇ m square and performing the measurement on all particles within the range. The average particle size is determined by imaging different areas several times, measuring the particle size of a total of 50 to 1000 primary particles, and taking the number average. The primary particle diameter can be measured, for example, on individual resin particles, a dispersion thereof, or a cured film of a photosensitive resin composition.
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • the measurement is carried out using the dispersion liquid immediately after dispersion and after evaporating the solvent.
  • a cured film measurement is performed by preparing a cured film using a photosensitive resin composition in which particles are uniformly dispersed, cutting the film in the thickness direction, and observing the cross section.
  • the average particle diameter of the dispersed particles of the resin particles (a1) can be determined using a dynamic light scattering method, a laser diffraction method, or a method of forming a coating film of a dispersion liquid, drying it, and then measuring the particle diameter with an SEM. , can be measured.
  • it is preferably 0.8 ⁇ m or more, more preferably 0.9 ⁇ m or more, even more preferably 1.0 ⁇ m or more, particularly preferably 1.1 ⁇ m or more.
  • it is preferably 5.0 ⁇ m or less, more preferably 4.0 ⁇ m or less, even more preferably 3.0 ⁇ m or less, particularly preferably 2.0 ⁇ m or less, and even more preferably 1.8 ⁇ m or less.
  • the average particle diameter of the primary particles is less than or equal to the above upper limit, dispersion stability tends to be high. If it is more than the lower limit, the light scattering property tends to be high.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.8 to 5.0 ⁇ m, more preferably 0.9 to 4.0 ⁇ m, even more preferably 1.0 to 3.0 ⁇ m, even more preferably 1.1 to 2.0 ⁇ m, and even more preferably 1.1 to 2.0 ⁇ m. Particularly preferred is 1.8 ⁇ m.
  • the refractive index of the resin particles (a1) is usually 1.56 or more, preferably 1.58 or more, more preferably 1.60 or more, even more preferably 1.61 or more, even more preferably 1.62 or more, It is particularly preferably 1.63 or more, even more preferably 1.64 or more, and most preferably 1.65 or more. Further, it is preferably 2.00 or less, more preferably 1.90 or less, even more preferably 1.80 or less, and even more preferably 1.70 or less.
  • the refractive index of the resin particles (a1) is less than or equal to the above upper limit, the light transmittance tends to be high. If it is above the lower limit, the light scattering property tends to be high. The above upper and lower limits can be arbitrarily combined.
  • the refractive index of the resin particles is measured by an extinction spectrum method, an extrapolation method, a Becke line method, an immersion method, or the like.
  • the refractive index value of the resin particles is evaluated for light with a wavelength of 400 to 650 nm.
  • the resin particles in addition to the resin particles (a1), other resin particles may be used in combination.
  • other resin particles include (meth)acrylic resin, polycarbonate, polyethylene, polyester, phenol resin, urethane resin, epoxy resin, polyvinyl chloride, polyamide, and silicone resin.
  • the average particle diameter of the primary particles of other resin particles is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, even more preferably 0.05 ⁇ m or more, and particularly preferably 0.1 ⁇ m or more.
  • the thickness is preferably 5.0 ⁇ m or less, more preferably 4.0 ⁇ m or less, even more preferably 3.0 ⁇ m or less, even more preferably 2.0 ⁇ m or less, and particularly preferably 1.8 ⁇ m or less.
  • the average particle diameter of the primary particles is less than or equal to the above upper limit, light transmittance and sedimentation stability tend to increase. If it is more than the lower limit, the light scattering property tends to be high.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.005 to 5.0 ⁇ m, more preferably 0.01 to 4.0 ⁇ m, even more preferably 0.05 to 3.0 ⁇ m, even more preferably 0.1 to 2.0 ⁇ m, and even more preferably 0.1 to 2.0 ⁇ m. Particularly preferred is 1.8 ⁇ m.
  • particles having the same constituent components as resin particles (a1) but having an average particle size outside the preferable range of the primary particles of resin particles (a1) may be used in combination as other resin particles.
  • it is 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, even more preferably 0.05 ⁇ m or more, particularly preferably 0.1 ⁇ m or more.
  • it is preferably 0.7 ⁇ m or less, more preferably 0.6 ⁇ m or less, and still more preferably 0.4 ⁇ m or less.
  • the thickness is preferably 0.005 to 0.7 ⁇ m, more preferably 0.01 to 0.6 ⁇ m, even more preferably 0.05 to 0.4 ⁇ m, even more preferably 0.1 to 0.4 ⁇ m.
  • the thickness is preferably 0.005 to 0.7 ⁇ m, more preferably 0.01 to 0.6 ⁇ m, even more preferably 0.05 to 0.4 ⁇ m, even more preferably 0.1 to 0.4 ⁇ m.
  • particles other than (a) resin particles may be used in combination with (a) resin particles.
  • the types of other particles are not particularly limited, and particles whose main component is an organic pigment other than resin, inorganic particles, and luminescent nanocrystal particles may be used in combination.
  • Organic pigments are not particularly limited, but include, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based.
  • the inorganic particles include particles whose main component is an inorganic pigment or a metal oxide.
  • inorganic pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black.
  • metal oxides include silicon dioxide, titanium oxide, zirconium oxide, aluminum oxide, and hafnium oxide. Titanium oxide is particularly preferred from the viewpoint of increasing light scattering properties.
  • particles other than resin particles from the viewpoint of durability, it is preferable to use particles whose main component is an inorganic pigment or a metal oxide.
  • particles whose main component is a metal oxide are preferable because they have high light transmittance. From the viewpoint of controlling the transmission wavelength of the photosensitive resin composition and curing it efficiently, it is preferable to use particles containing an organic pigment as a main component.
  • the content ratio of (a) resin particles is 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less based on the total solid content of the photosensitive resin composition. It is at most 50% by mass, more preferably at most 50% by mass, particularly preferably at most 40% by mass. Further, it is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 14% by mass or more. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 1 to 80% by weight, more preferably 5 to 70% by weight, even more preferably 10 to 60% by weight, even more preferably 14 to 50% by weight, and particularly preferably 14 to 40% by weight.
  • the content is equal to or more than the lower limit, light scattering properties tend to increase.
  • the upper limit value there is a tendency for light transmittance to become high.
  • the content ratio of the resin particles (a1) is 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less based on the total solid content of the photosensitive resin composition. It is at most 50% by mass, more preferably at most 50% by mass, particularly preferably at most 40% by mass. Further, it is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 14% by mass or more. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 1 to 80% by weight, more preferably 5 to 70% by weight, even more preferably 10 to 60% by weight, even more preferably 14 to 50% by weight, and particularly preferably 14 to 40% by weight.
  • the content is equal to or more than the lower limit, light scattering properties tend to increase.
  • the upper limit value there is a tendency for light transmittance to become high.
  • the photosensitive resin composition of the present invention has a content ratio of benzoguanamine resin, melamine resin, and styrene resin. It is 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less based on the total solid content of the photosensitive resin composition. . Further, it is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 14% by mass or more.
  • the content ratio of benzoguanamine resin, melamine resin, and styrene resin is the sum of both resins.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 80% by weight, more preferably 5 to 70% by weight, even more preferably 10 to 60% by weight, even more preferably 14 to 50% by weight, and particularly preferably 14 to 40% by weight.
  • the content is equal to or more than the lower limit, light scattering properties tend to increase. By setting it below the upper limit value, there is a tendency for light transmittance to become high.
  • the content ratio of the resin particles (a1) in the resin particles is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more based on the total mass of the resin particles (a). , more preferably 80% by mass or more, particularly preferably 90% by mass or more, and 100% by mass or less. When the content is equal to or more than the lower limit, light scattering properties tend to increase.
  • the photosensitive resin composition of the present invention contains (b) an alkali-soluble resin, and (b) the alkali-soluble resin is an alkali-soluble resin having an ethylenic double bond. It contains resin (b1) (hereinafter also referred to as alkali-soluble resin (b1)). Including the alkali-soluble resin (b1) tends to improve heat resistance.
  • the alkali-soluble resin (b) is not particularly limited as long as it can be developed with an alkaline developer.
  • Examples of the alkali-soluble resin include various resins having a carboxyl group or a hydroxyl group, and those having a carboxyl group are preferred from the viewpoint of excellent developability.
  • the alkali-soluble resin (b1) having an ethylenic double bond preferably has an ethylenic double bond in its side chain
  • the alkali-soluble resin (b1) having an ethylenic double bond in its side chain is, for example, Acrylic copolymer resin (b11) having an ethylenic double bond in the side chain (hereinafter also referred to as acrylic copolymer resin (b11)), epoxy (meth)acrylate resin having an ethylenic double bond in the side chain (b12) ) (hereinafter also referred to as epoxy (meth)acrylate resin (b12)), and the following alkali-soluble resin (b13) having an ethylenic double bond in the side chain (hereinafter also referred to as alkali-soluble resin (b13)).
  • Acrylic copolymer resin (b11) having an ethylenic double bond in the side chain hereinafter also referred to as acrylic copolymer resin (b11)
  • the alkali-soluble resin (b13) is a resin having a repeating unit represented by the following general formula (V) (hereinafter sometimes referred to as "repeat unit (V)").
  • R 1 to R 4 each independently represent a hydrogen atom or a hydrocarbon group.
  • n represents an integer from 0 to 2.
  • * represents a bond.
  • acrylic copolymer resin (b11) is preferred.
  • epoxy (meth)acrylate resin (b12) is preferred.
  • alkali-soluble resin (b13) is preferable.
  • the alkali-soluble resin (b1) contains both an acrylic copolymer resin (b11) and an epoxy (meth)acrylate resin (b12).
  • the acrylic copolymer resin (b11) is an acrylic copolymer resin having an ethylenic double bond in the side chain. It is thought that by having an ethylenic double bond in the side chain, photocuring occurs due to exposure to light, resulting in a stronger film and higher heat resistance.
  • the partial structure of the acrylic copolymer resin (b11) containing a side chain having an ethylenic double bond is not particularly limited, but from the viewpoint of ease of radical dispersion due to the flexibility of the membrane, for example, the following general formula: It is preferable to have a partial structure represented by (I).
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group. * represents a bond.
  • the partial structure represented by the formula (I) from the viewpoint of sensitivity and alkali developability, the partial structure represented by the following general formula (I') is preferable.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • R x represents a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue in formula (I') means a monovalent or divalent or more valent group obtained by subtracting one OH group from a polybasic acid.
  • polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene.
  • examples include one or more selected from tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid is more preferred.
  • Phthalic acid and biphenyltetracarboxylic acid are preferred.
  • the content ratio of the partial structure represented by formula (I) contained in the acrylic copolymer resin (b11) is not particularly limited, but is 10 mol% or more based on the total number of moles of the constituent units of the acrylic copolymer resin (b11). is preferably 30 mol% or more, more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, particularly preferably 80 mol% or more, and 99 mol% The following is preferable, 95 mol% or less is more preferable, and even more preferably 90 mol% or less. The above upper and lower limits can be arbitrarily combined.
  • heat resistance to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the content ratio is not particularly limited, but is 10% relative to the total number of moles of the constituent units of the acrylic copolymer resin (b11). It is preferably at least mol%, more preferably at least 30 mol%, even more preferably at least 50 mol%, even more preferably at least 60 mol%, even more preferably at least 70 mol%, particularly preferably at least 80 mol%, and The content is preferably 99 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less. The above upper and lower limits can be arbitrarily combined.
  • heat resistance to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the acrylic copolymer resin (b11) may have, for example, a partial structure represented by the following general formula (II).
  • R 3 represents a hydrogen atom or a methyl group
  • R 4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or a substituent. Represents an optional alkenyl group.
  • R 4 represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or an alkenyl group that may have a substituent.
  • alkyl group for R 4 include linear, branched, and cyclic alkyl groups.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and 14 or less. It is even more preferable, and 12 or less is particularly preferable.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 1 to 20, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 5 to 14, and particularly preferably 8 to 12.
  • the amount is equal to or more than the lower limit, the film strength tends to increase, and the development adhesion tends to improve.
  • the amount of residue is reduced by setting the amount to be less than or equal to the upper limit value.
  • Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. From the viewpoint of developability, a dicyclopentanyl group and a dodecanyl group are preferred, and a dicyclopentanyl group is more preferred.
  • substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • Examples of the aromatic ring group for R 4 include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
  • the number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 6 to 24, more preferably 6 to 22, even more preferably 6 to 20, even more preferably 6 to 18.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. There is a tendency for the amount of residue to be reduced by setting the amount to be less than or equal to the upper limit value.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and a pyrene ring.
  • ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring may be a single ring or a condensed ring, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and a pyrene ring.
  • the aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, and an imidazole ring.
  • oxadiazole ring indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, Examples include benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
  • a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.
  • substituents that the aromatic ring group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, and epoxy group.
  • oligoethylene glycol group, phenyl group, and carboxy group and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
  • alkenyl group for R 4 examples include linear, branched or cyclic alkenyl groups.
  • the number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, even more preferably 2 to 14.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. There is a tendency for the amount of residue to be reduced by setting the amount to be less than or equal to the upper limit value.
  • alkenyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferred.
  • R 4 is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
  • the acrylic copolymer resin (b11) has a partial structure represented by formula (II)
  • its content is not particularly limited, but is 1 mol based on the total number of moles of the constituent units of the acrylic copolymer resin (b11).
  • % or more more preferably 2 mol% or more, further preferably 5 mol% or more, even more preferably 10 mol% or more, particularly preferably 20 mol% or more, and preferably 70 mol% or less, 60 mol%
  • the following is more preferable, 50 mol% or less is even more preferable, and even more preferably 40 mol% or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 1 to 70 mol%, more preferably 2 to 70 mol%, even more preferably 5 to 60 mol%, even more preferably 10 to 50 mol%, particularly preferably 20 to 40 mol%.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve.
  • heat resistance is a tendency for heat resistance to be improved by setting it below the upper limit value.
  • the acrylic copolymer resin (b11) may have a partial structure represented by the following general formula (III) from the viewpoint of heat resistance and film strength.
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an alkenyl group that may have a substituent.
  • t represents an integer from 0 to 5.
  • Examples of the alkyl group for R 6 include linear, branched, or cyclic alkyl groups.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and even more preferably 12 or less. is particularly preferred.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 20, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 5 to 14.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. There is a tendency for the amount of residue to be reduced by setting the amount to be less than or equal to the upper limit value.
  • Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. From the viewpoint of developability and film strength, a dicyclopentanyl group or a dodecanyl group is preferred, and a dicyclopentanyl group is more preferred.
  • substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • alkenyl group for R 6 examples include linear, branched, or cyclic alkenyl groups.
  • the number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, even more preferably 2 to 14.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. There is a tendency for the amount of residue to be reduced by setting the amount to be less than or equal to the upper limit value.
  • alkenyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferred.
  • alkynyl group for R 6 examples include linear, branched or cyclic alkynyl groups.
  • the number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, even more preferably 2 to 14.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. There is a tendency for the amount of residue to be reduced by setting the amount to be less than or equal to the upper limit value.
  • alkynyl group may have examples include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferred.
  • halogen atom for R 6 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkoxy group for R 6 examples include linear, branched, or cyclic alkoxy groups.
  • the number of carbon atoms is 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, even more preferably 1 to 12.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. There is a tendency for the amount of residue to be reduced by setting the amount to be less than or equal to the upper limit value.
  • substituents that the alkoxy group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • alkyl sulfide group for R 6 examples include linear, branched or cyclic alkyl sulfide groups.
  • the number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, even more preferably 1 to 12.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. There is a tendency for the amount of residue to be reduced by setting the amount to be less than or equal to the upper limit value.
  • substituents that the alkyl group in the alkyl sulfide group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, and phenyl group. group, carboxy group, acryloyl group, and methacryloyl group, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
  • R 6 is preferably a hydroxy group or a carboxy group, and more preferably a carboxy group.
  • t represents an integer of 0 to 5, but from the viewpoint of ease of manufacture, t is preferably 0.
  • the acrylic copolymer resin (b11) has a partial structure represented by formula (III), its content is not particularly limited, but it is 0.00000000000000000 with respect to the total number of moles of the constituent units of the acrylic copolymerized resin (b11).
  • the content is preferably 5 mol% or more, more preferably 1 mol% or more, even more preferably 2 mol% or more, and particularly preferably 4 mol% or more.
  • it is preferably 50 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 6 mol% or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the amount is equal to or more than the lower limit, the uniformity of the film tends to improve.
  • the amount of residue is reduced by setting the amount to be less than or equal to the upper limit value.
  • the acrylic copolymer resin (b11) may have a partial structure represented by the following general formula (IV) from the viewpoint of developability.
  • R 7 represents a hydrogen atom or a methyl group.
  • the acrylic copolymer resin (b11) has a partial structure represented by formula (IV), its content is not particularly limited, but is 5 mol based on the total number of moles of the constituent units of the acrylic copolymer resin (b11). % or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and still more preferably 20 to 60 mol%.
  • heat resistance to be improved by setting it below the upper limit value.
  • the double bond equivalent of the acrylic copolymer resin (b11) is preferably 700 g/mol or less, more preferably 600 g/mol or less, and even more preferably 500 g/mol or less. Further, the amount is preferably 100 g/mol or more, more preferably 200 g/mol or more, even more preferably 300 g/mol or more, and particularly preferably 400 g/mol or more.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 100 to 700 g/mol, more preferably 200 to 600 g/mol, even more preferably 300 to 500 g/mol, and particularly preferably 400 to 500 g/mol.
  • developability to be improved by setting it below the upper limit value.
  • heat resistance to improve by setting it as the above-mentioned lower limit or more.
  • the double bond equivalent of the acrylic copolymer resin (b11) can be calculated from the following formula.
  • (Double bond equivalent of acrylic copolymer resin (b11)) (Weight average molecular weight of acrylic copolymer resin (b11))/(Number of ethylenic double bonds per molecule of acrylic copolymer resin (b11))
  • the acid value of the acrylic copolymer resin (b11) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, even more preferably 30 mgKOH/g or more, even more preferably 40 mgKOH/g or more, and even more preferably 50 mgKOH/g. It is particularly preferably at least 150 mgKOH/g, more preferably at most 120 mgKOH/g, even more preferably at most 100 mgKOH/g, even more preferably at most 90 mgKOH/g.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 10 to 150 mgKOH/g, more preferably 20 to 120 mgKOH/g, even more preferably 30 to 100 mgKOH/g, even more preferably 40 to 90 mgKOH/g, and particularly preferably 50 to 90 mgKOH/g.
  • the amount is equal to or more than the lower limit, developability tends to improve. There is a tendency for development adhesion to be improved by setting it below the upper limit value.
  • the weight average molecular weight (Mw) of the acrylic copolymer resin (b11) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, even more preferably 4000 or more, even more preferably 6000 or more, and particularly preferably 7000 or more. Further, it is preferably 30,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, and particularly preferably 10,000 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, even more preferably 4,000 to 20,000, even more preferably 6,000 to 15,000, even more preferably 7,000 to 15,000, and particularly preferably 7,000 to 10,000.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. There is a tendency for the amount of residue to be reduced by setting the amount to be less than or equal to the upper limit value.
  • the content ratio is not particularly limited, but the content ratio of the acrylic copolymer resin (b11) contained in the (b) alkali-soluble resin is particularly limited. However, it is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass, based on the total mass of the (b) alkali-soluble resin.
  • the above is particularly preferable, and also preferably 100% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and particularly preferably 85% by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 10 to 100% by weight, more preferably 20 to 95% by weight, even more preferably 30 to 90% by weight, even more preferably 40 to 85% by weight, and particularly preferably 50 to 85% by weight.
  • the amount is equal to or more than the lower limit, developability tends to improve.
  • the content is below the upper limit, heat resistance and outgas resistance tend to improve.
  • acrylic copolymer resin (b11) examples include, for example, the resins described in Japanese Unexamined Patent Publication No. 8-297366 and Japanese Unexamined Patent Publication No. 2001-89533.
  • Epoxy (meth)acrylate resin (b12) is produced by adding an ethylenically unsaturated monocarboxylic acid or ester compound to an epoxy resin, optionally reacting with an isocyanate group-containing compound, and then reacting with a polybasic acid or its anhydride.
  • epoxy (meth)acrylate resin (b12) is a resin obtained by reacting a compound having a functional group that can further react with the carboxy group of the resin obtained in the above reaction.
  • epoxy (meth)acrylate resin has virtually no epoxy groups due to its chemical structure, and is not limited to "(meth)acrylate", but it is made from an epoxy compound (epoxy resin) as a raw material. And since "(meth)acrylate” is a typical example, it is named this way according to common usage.
  • the epoxy (meth)acrylate resin (b12) one having an aromatic ring in the main chain can be more preferably used from the viewpoint of heat resistance.
  • the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Further, as the epoxy resin, a compound obtained by reacting a phenolic compound and epihalohydrin can be used.
  • the phenolic compound is preferably a compound having a divalent or more than divalent phenolic hydroxyl group, and may be a monomer or a polymer. Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, triglycidyl isocyanurate resin, combination of phenol and dicyclopentadiene.
  • Polymerized epoxy resin dihydroxylfluorene type epoxy resin, dihydroxylalkyleneoxylfluorene type epoxy resin, diglycidyl etherified product of 9,9-bis(4'-hydroxyphenyl)fluorene, 1,1-bis(4'- Examples include diglycidyl etherified products of hydroxyphenyl)adamantane and adamantyl group-containing phenol epoxy resins, and those having an aromatic ring in the main chain can be preferably used.
  • epoxy resin examples include bisphenol A epoxy resins (for example, "jER (registered trademark, hereinafter the same applies)” manufactured by Mitsubishi Chemical Corporation, “jER1001", “jER1002”, “jER1004", manufactured by Nippon Kayaku Co., Ltd.).
  • NER-1302 (epoxy equivalent: 323, softening point: 76°C), etc.), bisphenol F type resins (for example, “jER807”, “jER4004P”, “jER4005P”, “jER4007P” manufactured by Mitsubishi Chemical Corporation, Nippon Kayaku Co., Ltd.) "NER-7406” (epoxy equivalent: 350, softening point 66°C) manufactured by Mitsubishi Chemical Corporation), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "jERYX-4000” manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (For example, “EPPN (registered trademark, hereinafter the same)-201" manufactured by Nippon Kayaku Co., Ltd., "jER152", “jER154” manufactured by Mitsubishi Chemical Company, “DEN-438” manufactured by Dow Chemical Company), (o , m, p-) cresol novolac type epoxy resin (for example, "EOCN (registered trademark, hereinafter the same)-
  • ethylenically unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, pentaerythritol tri(meth)acrylate succinic anhydride adduct, and pentaerythritol tri(meth)acrylate succinic anhydride adduct.
  • Examples include phthalic anhydride adducts and reaction products of (meth)acrylic acid and ⁇ -caprolactone. From the viewpoint of sensitivity, (meth)acrylic acid is preferred.
  • polybasic acids examples include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, -Ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • succinic anhydride succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferred, and succinic anhydride and tetrahydrophthalic anhydride are more preferred.
  • the molecular weight of the epoxy (meth)acrylate resin (b12) can be increased and branching can be introduced into the molecule, which tends to balance the molecular weight and viscosity. Furthermore, the rate of introduction of acid groups into the molecule can be increased, and sensitivity, adhesion, etc. tend to be more balanced.
  • the polyhydric alcohol include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. It is preferable that
  • the acid value of the epoxy (meth)acrylate resin (b12) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even more preferably 50 mgKOH/g or more, even more preferably 70 mgKOH/g or more, It is particularly preferably at least 80 mgKOH/g, preferably at most 200 mgKOH/g, more preferably at most 180 mgKOH/g, even more preferably at most 150 mgKOH/g, even more preferably at most 120 mgKOH/g, and particularly preferably at most 110 mgKOH/g.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 10 to 200 mgKOH/g, more preferably 30 to 180 mgKOH/g, even more preferably 50 to 150 mgKOH/g, even more preferably 70 to 120 mgKOH/g, and particularly preferably 80 to 110 mgKOH/g.
  • the amount is equal to or more than the lower limit, developability tends to improve.
  • the film strength tends to improve.
  • the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (b12) is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, even more preferably 4,000 or more, and especially 5,000 or more. It is preferably 30,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, even more preferably 10,000 or less, and particularly preferably 8,000 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, even more preferably 3,000 to 15,000, even more preferably 4,000 to 10,000, and particularly preferably 5,000 to 8,000.
  • the amount is equal to or more than the lower limit, the film strength tends to improve. There is a tendency for the amount of residue to be reduced by setting the amount to be less than or equal to the upper limit value.
  • the double bond equivalent of the epoxy (meth)acrylate resin (b12) is not particularly limited, but is preferably 700 g/mol or less, more preferably 600 g/mol or less, even more preferably 500 g/mol or less, and particularly preferably 400 g/mol or less. , and preferably 100 g/mol or more, more preferably 200 g/mol or more, even more preferably 250 g/mol or more, and particularly preferably 300 g/mol or more.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 100 to 700 g/mol, more preferably 200 to 600 g/mol, even more preferably 250 to 500 g/mol, and particularly preferably 300 to 400 g/mol.
  • the double bond equivalent of the epoxy (meth)acrylate resin (b12) can be calculated in the same manner as the double bond equivalent of the acrylic copolymer resin (b11).
  • the content ratio is not particularly limited, but is preferably 10% by mass or more based on the total mass of the (b) alkali-soluble resin, and 20% by mass or more based on the total mass of the alkali-soluble resin (b). More preferably 30% by mass or more, even more preferably 35% by mass or more, particularly preferably 40% by mass or more, most preferably 50% by mass or more, and preferably 90% by mass or less, 70% by mass or more. It is more preferably at most 60% by mass, even more preferably at most 60% by mass. The above upper and lower limits can be arbitrarily combined.
  • it is preferably 10 to 90% by weight, more preferably 20 to 90% by weight, even more preferably 30 to 70% by weight, even more preferably 35 to 70% by weight, even more preferably 40 to 60% by weight, and even more preferably 50 to 70% by weight. Particularly preferred is 60% by weight.
  • outgas resistance tends to improve.
  • transparency tends to improve.
  • the epoxy (meth)acrylate resin (b12) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, the acid or ester compound having an ethylenically unsaturated bond is added thereto in the coexistence of a catalyst and a thermal polymerization inhibitor, and then the polybasic acid or its A method can be used in which the reaction is continued by adding an anhydride. Examples include methods described in Japanese Patent No. 3938375 and Japanese Patent No. 5169422.
  • Examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.
  • Examples of the above-mentioned catalysts include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine; Examples include one or more of quaternary ammonium salts, phosphorus compounds such as triphenylphosphine, and stibines such as triphenylstibine.
  • Examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone.
  • the amount of the acid or ester compound having an ethylenically unsaturated bond to be used is preferably 0.7 to 1.3 chemical equivalents, and 0.9 to 1.1 chemical equivalents per chemical equivalent of the epoxy group of the epoxy resin. Equivalent amounts are more preferred.
  • the temperature during the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C.
  • the amount of polybasic acid (anhydride) to be used is preferably 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents, per 1 chemical equivalent of the hydroxyl group generated in the addition reaction. preferable.
  • alkali-soluble resin (b13) is a resin having a repeating unit represented by the following general formula (V) (hereinafter sometimes referred to as "repeat unit (V)").
  • R 1 to R 4 each independently represent a hydrogen atom or a hydrocarbon group.
  • n represents an integer from 0 to 2.
  • * represents a bond.
  • the alkali-soluble resin (b13) has a repeating unit represented by the general formula (V) (hereinafter sometimes referred to as "repeat unit (V)"). Although it is not as rigid as aromatic hydrocarbons, it has a sterically bulky structure, and due to a certain degree of flexibility, the reaction points come close to each other during photo and/or heat curing reactions, and the curing reaction progresses. It is thought that heat resistance is improved without excessive inhibition and furthermore, due to its bulky structure after curing.
  • R 1 to R 4 are each independently a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an aromatic ring group, and an aralkyl group.
  • the alkyl group may be linear, branched, or cyclic.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 15 or less, more preferably 8 or less.
  • the amount is at least the lower limit, adhesion tends to improve, and when it is at most the upper limit, the developability tends to improve.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, and hexyl group. , heptyl group, octyl group, nonyl group, decyl group, adamantyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group.
  • the number of carbon atoms in the alkenyl group is not particularly limited, but is usually 2 or more, preferably 3 or more, preferably 10 or less, and more preferably 8 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be from 2 to 10, or from 3 to 8.
  • adhesion tends to improve, and when it is at most the upper limit, the developability tends to improve.
  • Specific examples of the alkenyl group include, for example, a vinyl group, an allyl group, a butenyl group, and a pentenyl group.
  • the number of carbon atoms in the alkynyl group is not particularly limited, but is usually 2 or more, preferably 3 or more, preferably 10 or less, and more preferably 8 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be from 2 to 10, or from 3 to 8.
  • adhesion tends to improve, and when it is at most the upper limit, the developability tends to improve.
  • Specific examples of alkynyl groups include, for example, ethynyl groups.
  • the aromatic ring group examples include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be between 4 and 20, between 5 and 15, and between 6 and 10.
  • the aromatic ring group include phenyl group, naphthyl group, anthracenyl group, tolyl group, and xylyl group.
  • the number of carbon atoms in the aralkyl group is not particularly limited, but is usually 5 or more, preferably 6 or more, more preferably 7 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be between 5 and 20, between 6 and 15, and between 7 and 10.
  • the aralkyl group include those in which one hydrogen atom of the alkyl group is substituted with the aromatic ring group.
  • Specific examples of the aralkyl group include benzyl group and phenethyl group.
  • R 1 to R 4 each independently represent a hydrogen atom or a hydrocarbon group, but R 1 and R 4 may be connected to form a cyclic structure, and similarly, R 2 and R 3 may be connected to each other to form a cyclic structure. may be used to form a cyclic structure.
  • any one of R 1 to R 4 is preferably a hydrogen atom, and more preferably all of R 1 to R 4 are hydrogen atoms.
  • n represents an integer of 0 to 2, but from the viewpoint of developability, n is preferably 0.
  • repeating unit (V) examples include those represented by the following general formulas (V-1) to (V-3). Among these, repeating units represented by the following general formula (V-1) are more preferred from the viewpoint of adhesion.
  • the alkali-soluble resin (b13) preferably has a repeating unit (VI) having a carboxy group (hereinafter sometimes referred to as "repeat unit (VI)").
  • the structure of the repeating unit (VI) having a carboxy group in the alkali-soluble resin (b13) is not particularly limited, and examples thereof include repeating units derived from unsaturated group-containing carboxylic acids and unsaturated group-containing carboxylic acid anhydrides. Among them, from the viewpoint of improving developability and adhesion, the alkali-soluble resin (b13) is a repeating unit represented by the following general formula (VI-1) (hereinafter referred to as "repeat unit (VI-1)"). ) is preferable.
  • R 5 represents a hydrogen atom or an organic group. * represents a bond.
  • Examples of the organic group include an alkyl group that may have a substituent and an aryl group that may have a substituent, and preferably has 1 to 18 carbon atoms.
  • R 5 is an alkyl group
  • the number of carbon atoms is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 9 or less, more preferably 7 or less.
  • the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, and heptyl group. , octyl group, nonyl group, decyl group, adamantyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group.
  • R 5 is an aryl group
  • the number of carbon atoms is not particularly limited, but is more preferably 6 or more, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the aryl group include phenyl group, naphthyl group, anthracenyl group, tolyl group, and xylyl group.
  • substituents that the alkyl group and aryl group may have include a hydroxyl group and a (meth)acryloyl group.
  • R 5 is more preferably a repeating unit represented by the following general formula (VI-2).
  • R 6 represents a hydrogen atom or a methyl group.
  • e represents an integer from 1 to 5.
  • * represents a bond.
  • e represents an integer of 1 to 5, but from the viewpoint of adhesion, e is preferably an integer of 1 to 3, more preferably an integer of 1 to 2.
  • any of the repeating units represented by the following general formulas (VI-3) to (VI-6) is more preferable, and the repeating units represented by the following general formula (VI-3) or the formula (VI-6) are more preferable.
  • the repeating unit represented by 4) is particularly preferred.
  • the alkali-soluble resin (b13) may have repeating units other than repeating units (V) and repeating units (VI).
  • Other repeating units include, for example, repeating units represented by the following general formulas (VII-1) to (VII-5) (hereinafter referred to as "repeating units (VII-1) to (VII-5)”) ), but are not limited to these.
  • R 5 has the same meaning as in formula (VII-1), and in formula (VII-1) and formula (VII-2), R 7 each independently represents a hydrogen atom or a methyl group. represent. * represents a bond.
  • R 8 represents an alkyl group which may have a substituent. * represents a bond.
  • alkyl group that may have a substituent in R 8 include methyl, ethyl, propyl, and benzyl.
  • the alkali-soluble resin (b13) preferably has a repeating unit (V), a repeating unit (VI-1), and a repeating unit (VII-1) from the viewpoint of surface smoothness and adhesion, and the repeating unit (V), It is more preferable to have a repeating unit (VI-1), a repeating unit (VII-1) and a repeating unit (VII-4).
  • the method for producing the alkali-soluble resin (b13) is not particularly limited, and conventionally known methods can be employed. For example, it can be produced by the following (step i) to (step iii). In addition, the following ring-opened precursor polymer obtained in (step ii) can also be used as the alkali-soluble resin (b13).
  • Step i A step of preparing a precursor polymer containing a repeating unit represented by the formula (V) and a repeating unit represented by the formula (VII-4).
  • Step ii Alcohols or water are allowed to act on the precursor polymer to open the acid anhydride skeleton in formula (VII-4), thereby generating a carboxyl group or its ester in the precursor polymer and opening the precursor polymer. Step of obtaining a ring precursor polymer.
  • the alcohol it is more preferable to use a compound represented by the following general formula (VI-2-1) from the viewpoint of adhesion.
  • Step iii a step of reacting the ring-opened precursor polymer with a compound having an epoxy group and an ethylenic double bond.
  • compounds having an epoxy group and an ethylenic double bond include glycidyl methacrylate.
  • the content ratio of the repeating unit (V) in the alkali-soluble resin (b13) is not particularly limited, but it is preferably 10% by mass or more, more preferably 20% by mass or more, and It is preferably 25% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be 10 to 50% by weight, 20 to 40% by weight, or 25 to 30% by weight. When the amount is at least the lower limit, adhesion tends to improve, and when it is at most the upper limit, the developability tends to improve.
  • the content ratio of the repeating unit (V) in the alkali-soluble resin (b13) is not particularly limited, but it is preferably 20 mol% or more, more preferably 30 mol% or more, and The content is preferably 40 mol% or more, more preferably 80 mol% or less, more preferably 70 mol% or less, even more preferably 60 mol% or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be 20 to 80 mol%, 30 to 70 mol%, or 40 to 60 mol%. When the amount is at least the lower limit, adhesion tends to improve, and when it is at most the upper limit, the developability tends to improve.
  • the alkali-soluble resin (b13) has a repeating unit (VI-1)
  • its content is not particularly limited, but it is preferably 5 mol% or more, more preferably The content is 10 mol% or more, more preferably 15 mol% or more, and preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be 5 to 40 mol%, 10 to 30 mol%, or 15 to 20 mol%.
  • the amount is at least the lower limit, developability tends to improve, and when it is at most the upper limit, the adhesion tends to improve.
  • the alkali-soluble resin (b13) has a repeating unit (VII-1)
  • its content is not particularly limited, but it is preferably 5 mol% or more in the total repeating units of the alkali-soluble resin (b13), and more It is preferably 10 mol% or more, more preferably 15 mol% or more, and preferably 40 mol% or less, more preferably 30 mol% or less, and still more preferably 20 mol% or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be 5 to 40 mol%, 10 to 30 mol%, or 15 to 20 mol%.
  • the amount is at least the lower limit, adhesion tends to improve, and when it is at most the upper limit, the developability tends to improve.
  • the alkali-soluble resin (b13) has a repeating unit (VII-4), its content is not particularly limited, but it is preferably 5 mol% or more in the total repeating units of the alkali-soluble resin (b13), and more It is preferably 10 mol% or more, more preferably 15 mol% or more, and preferably 40 mol% or less, more preferably 30 mol% or less, and still more preferably 20 mol% or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be 5 to 40 mol%, 10 to 30 mol%, or 15 to 20 mol%. Setting the content above the lower limit value tends to facilitate synthesis, and setting the content below the upper limit value tends to improve adhesion and developability.
  • the content ratio of repeating unit (VII-1) to the total content ratio of repeating unit (VII-1) and repeating unit (VII-4) is preferably 10 mol% or more, more preferably 20 mol% or more. , more preferably 30 mol% or more, preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 50 mol% or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it may be 10 to 90 mol%, 20 to 70 mol%, or 30 to 50 mol%.
  • the amount is at least the lower limit, developability tends to improve, and when it is at most the upper limit, the adhesion tends to improve.
  • the acid value of the alkali-soluble resin (b13) is not particularly limited, but preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even more preferably 50 mgKOH/g or more, and preferably 200 mgKOH/g or less, 150 mgKOH/g.
  • the following is more preferable, 100 mgKOH/g or less is even more preferable, and 80 mgKOH/g or less is particularly preferable.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be 10-200 mgKOH/g, it may be 10-150 mgKOH/g, it may be 30-100 mgKOH/g, it may be 50-80 mgKOH/g.
  • the amount is equal to or more than the lower limit, the developability tends to improve, and when it is equal to or less than the upper limit, the developer adhesion tends to improve.
  • the weight average molecular weight (Mw) of the alkali-soluble resin (b13) is not particularly limited, but is preferably 2000 or more, more preferably 3000 or more, even more preferably 4000 or more, even more preferably 5000 or more, and particularly preferably 6000 or more. , and preferably 35,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be 2,000 to 35,000, 3,000 to 35,000, 4,000 to 20,000, 5,000 to 20,000, and 6,000 to 15,000. When the amount is equal to or more than the lower limit, the development adhesion tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
  • the double bond equivalent of the alkali-soluble resin (b13) is not particularly limited, but is preferably 200 g/mol or more, more preferably 300 g/mol or more, even more preferably 400 g/mol or more, even more preferably 500 g/mol or more, especially It is preferably 600 g/mol or more, and preferably 800 g/mol or less, more preferably 700 g/mol or less, and still more preferably 600 g/mol or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be 200-800 g/mol, it may be 300-800 g/mol, it may be 400-700 g/mol, it may be 500-700 g/mol, it may be 600-700 g/mol.
  • the double bond equivalent of the alkali-soluble resin (b13) can be calculated in the same manner as the double bond equivalent of the acrylic copolymer resin (b11).
  • the content of the alkali-soluble resin (b13) is not particularly limited, but is preferably 10% by mass or more based on the total mass of the (b) alkali-soluble resin. , more preferably 20% by mass or more, further preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 50% by mass or more, and preferably 100% by mass or less, more preferably 95% by mass or less. , more preferably 90% by mass or less, particularly preferably 85% by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 10 to 100% by weight, more preferably 20 to 95% by weight, even more preferably 30 to 90% by weight, even more preferably 40 to 85% by weight, and particularly preferably 50 to 85% by weight.
  • the amount is equal to or more than the lower limit, developability tends to improve. Adhesion tends to improve when the content is below the upper limit.
  • the alkali-soluble resin (b) in the present invention may contain other alkali-soluble resins in addition to the alkali-soluble resin (b1).
  • the acid value of the alkali-soluble resin is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, even more preferably 25 mgKOH/g or more, and preferably 200 mgKOH/g or less, 150 mgKOH/g.
  • the following is more preferable, 100 mgKOH/g or less is even more preferable, and 80 mgKOH/g or less is particularly preferable.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 10 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g, even more preferably 25 to 100 mgKOH/g, particularly preferably 25 to 80 mgKOH/g.
  • the acid value means a weighted average value according to the content ratio.
  • the acid value of the alkali-soluble resin (b1) is not particularly limited, but preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, even more preferably 25 mgKOH/g or more, and preferably 200 mgKOH/g or less, 150 mgKOH/g.
  • the following is more preferable, 100 mgKOH/g or less is even more preferable, and 80 mgKOH/g or less is particularly preferable.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 10 to 200 mgKOH/g, more preferably 20 to 150 mgKOH/g, even more preferably 25 to 100 mgKOH/g, particularly preferably 25 to 80 mgKOH/g.
  • the acid value means a weighted average value according to the content ratio.
  • the double bond equivalent of the alkali-soluble resin is 700 g/mol or less, preferably 600 g/mol or less, and more preferably 500 g/mol or less. Further, the amount is preferably 100 g/mol or more, more preferably 200 g/mol or more, and even more preferably 300 g/mol or more.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 100 to 700 g/mol, more preferably 200 to 600 g/mol, even more preferably 300 to 500 g/mol. There is a tendency for developability to be improved by setting it below the upper limit value. There is a tendency for heat resistance to improve by setting it as the above-mentioned lower limit or more.
  • the double bond equivalent of the alkali-soluble resin can be calculated in the same way as for the acrylic copolymer resin (b11).
  • the double bond equivalent is , means a weighted average value according to its content ratio.
  • the double bond equivalent of the alkali-soluble resin (b1) is 700 g/mol or less, preferably 600 g/mol or less, and more preferably 500 g/mol or less. Further, the amount is preferably 100 g/mol or more, more preferably 200 g/mol or more, and even more preferably 300 g/mol or more.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 100 to 700 g/mol, more preferably 200 to 600 g/mol, even more preferably 300 to 500 g/mol. There is a tendency for developability to be improved by setting it below the upper limit value. There is a tendency for heat resistance to improve by setting it as the above-mentioned lower limit or more.
  • the double bond equivalent of the alkali-soluble resin (b1) can be calculated in the same manner as the acrylic copolymer resin (b11), and when the alkali-soluble resin (b1) is a mixture of two or more types, the double bond equivalent is , means a weighted average value according to its content ratio.
  • the content ratio of the alkali-soluble resin (b) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass or more based on the total solid content. is more preferably 30% by mass or more, even more preferably 40% by mass or more, further preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and 60% by mass. The following are particularly preferred. The above upper and lower limits can be arbitrarily combined.
  • the amount of residue is reduced by setting the amount to be equal to or more than the lower limit value.
  • heat resistance is improved by setting it below the upper limit value.
  • the content of the alkali-soluble resin (b1) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass or more based on the total solid content. is more preferably 30% by mass or more, even more preferably 40% by mass or more, further preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and 60% by mass. The following are particularly preferred. The above upper and lower limits can be arbitrarily combined.
  • the amount of residue is reduced by setting the amount to be equal to or more than the lower limit value.
  • heat resistance is improved by setting it below the upper limit value.
  • the content ratio of the alkali-soluble resin (b1) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, and 50% by mass or more based on the alkali-soluble resin (b). It is more preferably at least 70% by mass, even more preferably at least 90% by mass, and even more preferably at most 100% by mass, and more preferably at most 95% by mass.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 10 to 100% by weight, more preferably 30 to 100% by weight, even more preferably 50 to 100% by weight, even more preferably 70 to 100% by weight, even more preferably 90 to 95% by weight.
  • heat resistance to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the content of the alkali-soluble resin (b11) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more based on the total solid content of the photosensitive resin composition. It is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and 70% by mass or less. More preferably, 60% by mass or less is even more preferable.
  • the above upper and lower limits can be arbitrarily combined.
  • heat resistance to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the content of the alkali-soluble resin (b12) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more based on the total solid content of the photosensitive resin composition. It is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and 70% by mass or less. More preferably, 60% by mass or less is even more preferable.
  • the above upper and lower limits can be arbitrarily combined.
  • heat resistance to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the content ratio of the alkali-soluble resin (b13) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more based on the total solid content of the photosensitive resin composition. It is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and 70% by mass or less. More preferably, 60% by mass or less is even more preferable.
  • the above upper and lower limits can be arbitrarily combined.
  • content is equal to or more than the lower limit, dispersion stability and heat resistance tend to improve. There is a tendency for developability to be improved by setting it below the upper limit value.
  • the total content of (d) the photopolymerizable compound and (b) the alkali-soluble resin relative to the total solid content of the photosensitive resin composition is not particularly limited, but is preferably 10% by mass or more, and 30% by mass.
  • the above is more preferable, more preferably 60% by mass or more, particularly preferably 70% by mass or more, and preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 92% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 10 to 98% by weight, more preferably 30 to 95% by weight, even more preferably 60 to 92% by weight, even more preferably 70 to 92% by weight.
  • the amount is equal to or more than the lower limit, the adhesion to the base material tends to improve.
  • the content is below the upper limit, heat resistance tends to increase.
  • the photosensitive resin composition of the present invention contains (c) a photopolymerization initiator.
  • the photopolymerization initiator (c) is not particularly limited as long as it is a compound that polymerizes the photopolymerizable compound (d) with actinic rays.
  • a photopolymerization initiator those commonly used in the technical field of the present invention can be used.
  • Halomethylated oxadiazole derivatives halomethyl-s-triazine derivatives
  • N-aryl- ⁇ -amino acids such as N-phenylglycine
  • N-aryl- ⁇ - Examples include radical activators such as amino acid salts, N-aryl- ⁇ -amino acid esters, and alkylphenone derivatives (alkylphenone initiators).
  • metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, and dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl).
  • biimidazole derivatives examples include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, (4'-methoxyphenyl) )-4,5-diphenylimidazole dimer.
  • halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, Examples include 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
  • halomethyl-s-triazine derivatives examples include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine is mentioned.
  • alkylphenone initiators examples include benzyl ketal initiators such as 2,2-dimethoxy-2-phenylacetophenone; 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methylpropiophenone, and 2-hydroxy- 4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2,2'-dihydroxy-2,2'-dimethyl-1,1'-[methylenebis(4,1-phenylene)]bis(propane- Hydroxyalkylphenone initiators such as 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 ⁇ -aminoalkylphenone initiators such as -morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one; can be mentioned.
  • the photopolymerization initiator (c) contains an alkylphenone photopolymerization initiator.
  • alkylphenone photopolymerization initiators ⁇ -aminoalkylphenone photopolymerization initiators are preferred from the viewpoint of achieving both adhesion and developability, and 2-benzyl-2-dimethylamino-1-(4-morpholino More preferred are phenyl)butan-1-one and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one.
  • oxime ester photopolymerization initiators are effective in terms of sensitivity and plate-making properties.
  • the sensitivity is disadvantageous, so an oxime ester photopolymerization initiator with excellent sensitivity is particularly useful.
  • Oxime ester photopolymerization initiators have a high photoreaction quantum yield and a high activity of the generated radicals, so they have high sensitivity and are stable against thermal reactions. It is possible to obtain a resin composition.
  • Oxime ester photopolymerization initiators have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals, so they are highly sensitive even in small amounts and are resistant to thermal reactions. It is possible to obtain a highly sensitive photosensitive resin composition in a small amount.
  • oxime ester photopolymerization initiator examples include compounds represented by the following general formula (IV).
  • R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
  • R 21b represents an arbitrary substituent containing an aromatic ring.
  • R 22a represents an alkanoyl group which may have a substituent or an aroyl group which may have a substituent.
  • n represents an integer of 0 or 1.
  • the number of carbon atoms in the alkyl group in R21a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, 10 The following are more preferred.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.
  • substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2- Examples include a methylphenyl group and an N-acetyl-N-acetoxyamino group, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • Examples of the aromatic ring group for R 21a include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the colored photosensitive resin composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. The above upper and lower limits can be arbitrarily combined. For example, the number is preferably 5 to 30, more preferably 5 to 20, and even more preferably 5 to 12.
  • Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, from the viewpoint of developability, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
  • substituents that the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked, From the viewpoint of developability, an alkyl group, an alkoxy group, or a group formed by connecting these groups is preferable, and a connected alkoxy group is more preferable. From the viewpoint of sensitivity, R 21a is preferably an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
  • R21b is preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted diphenyl sulfide group, an optionally substituted fluorenyl group, or an optionally substituted fluorenyl group.
  • examples include indolyl group. From the viewpoint of sensitivity, an optionally substituted carbazolyl group is preferred.
  • the number of carbon atoms in the alkanoyl group in R22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 2 or more, preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, 5 The following are particularly preferred.
  • the alkanoyl group include an acetyl group, an ethyl group, a propanoyl group, and a butanoyl group.
  • substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, and amide groups, and from the viewpoint of ease of synthesis, unsubstituted It is preferable.
  • the number of carbon atoms in the aroyl group in R 22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 7 or more, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the aroyl group include benzoyl group and naphthoyl group.
  • substituents that the aroyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group. preferable.
  • R 22a is preferably an alkanoyl group that may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
  • the photopolymerization initiator may be used alone or in combination of two or more types.
  • the photopolymerization initiator may contain a sensitizing dye and a polymerization accelerator depending on the wavelength of the image exposure light source, if necessary, for the purpose of increasing sensitivity.
  • the sensitizing dye include xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958 and Japanese Patent Application Publication No. 4-219756, Japanese Patent Application Publication No. 3-239703, and Japanese Patent Application Publication No. 5-289335.
  • a sensitizing dye containing an amino group is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable.
  • a sensitizing dye a sensitizing dye containing an amino group is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable.
  • Benzophenone compounds such as benzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benz
  • polymerization accelerator examples include aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, and n-butylamine. , N-methyldiethanolamine, 2-dimethylaminoethyl benzoate, and the like can be used.
  • the polymerization accelerators may be used alone or in combination of two or more.
  • the content ratio of the photopolymerization initiator (c) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.01% by mass or more based on the total solid content of the photosensitive resin composition. 0.1% by mass or more, more preferably 1% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less. , particularly preferably at most 7% by weight, even more preferably at most 5% by weight, especially preferably at most 3% by weight, and most preferably at most 2% by weight.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.1 to 15% by mass, even more preferably 1 to 10% by mass, and even more preferably 1 to 7% by mass.
  • adhesion to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the content ratio is not particularly limited, but is preferably 0.01% by mass or more based on the total solid content of the photosensitive resin composition. , more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by weight or less, particularly preferably 7% by weight or less, even more preferably 5% by weight or less, particularly preferably 3% by weight or less, most preferably 2% by weight or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.1 to 15% by mass, even more preferably 1 to 10% by mass, and even more preferably 1 to 7% by mass.
  • adhesion to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the content ratio is not particularly limited, but is preferably 0.01% based on the total solid content of the photosensitive resin composition. % by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, It is more preferably 10% by weight or less, particularly preferably 7% by weight or less, even more preferably 5% by weight or less, particularly preferably 3% by weight or less, most preferably 2% by weight or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.1 to 15% by mass, even more preferably 1 to 10% by mass, and even more preferably 1 to 7% by mass.
  • adhesion to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the content ratio of the alkylphenone photopolymerization initiator in (c) the photopolymerization initiator is not particularly limited; It is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the polymerization initiator. Moreover, it is 100% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 30 to 100% by weight, more preferably 50 to 100% by weight, even more preferably 70 to 100% by weight, and particularly preferably 90 to 100% by weight.
  • the photosensitive resin composition of the present invention contains an ⁇ -aminoalkylphenone photopolymerization initiator
  • the content ratio of the ⁇ -aminoalkylphenone photopolymerization initiator in (c) the photopolymerization initiator is not particularly limited. However, it is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the photopolymerization initiator (c). Moreover, it is 100% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 30 to 100% by weight, more preferably 50 to 100% by weight, even more preferably 70 to 100% by weight, and particularly preferably 90 to 100% by weight.
  • the amount is equal to or more than the lower limit, the adhesion tends to improve. There is a tendency for developability to be improved by setting it below the upper limit value.
  • the blending ratio of (c) photopolymerization initiator to (d) photopolymerizable compound in the photosensitive resin composition is preferably 0.1 part by mass or more with respect to 100 parts by mass of (d) photopolymerizable compound. , more preferably 1 part by mass or more, further preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and preferably 200 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less. , 30 parts by mass or less is even more preferable, and even more preferably 20 parts by weight or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.1 to 200 parts by weight, more preferably 1 to 100 parts by weight, even more preferably 2 to 50 parts by weight, even more preferably 3 to 30 parts by weight, and particularly preferably 3 to 20 parts by weight.
  • adhesion to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the blending ratio of the alkylphenone photopolymerization initiator to (d) the photopolymerizable compound in the photosensitive resin composition is as follows: (d) With respect to 100 parts by mass of the photopolymerizable compound, the amount is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and It is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.1 to 200 parts by weight, more preferably 1 to 100 parts by weight, even more preferably 2 to 50 parts by weight, even more preferably 3 to 30 parts by weight, and particularly preferably 3 to 20 parts by weight.
  • adhesion to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the photosensitive resin composition of the present invention contains an ⁇ -aminoalkylphenone photopolymerization initiator
  • the ⁇ -aminoalkylphenone photopolymerization initiator for the photopolymerizable compound (d) in the photosensitive resin composition The blending ratio is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, and 3 parts by mass or more with respect to 100 parts by mass of the photopolymerizable compound (d). Even more preferably, it is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.1 to 200 parts by weight, more preferably 1 to 100 parts by weight, even more preferably 2 to 50 parts by weight, even more preferably 3 to 30 parts by weight, and particularly preferably 3 to 20 parts by weight.
  • adhesion to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • a chain transfer agent may be used in combination with the photopolymerization initiator.
  • chain transfer agents include mercapto group-containing compounds and carbon tetrachloride. Among these, mercapto group-containing compounds are more preferred because they tend to have a high chain transfer effect. This is thought to be because bond cleavage is likely to occur due to the small S--H bond energy, and hydrogen abstraction reactions and chain transfer reactions are likely to occur.
  • Use of a chain transfer agent is effective for improving sensitivity and surface hardening.
  • the mercapto group-containing compound may have a plurality of mercapto groups in the molecule, for example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4 -Mercapto group-containing compounds having an aromatic ring such as triazole, 2-mercapto-4(3H)-quinazoline, ⁇ -mercaptonaphthalene, 1,4-dimethylmercaptobenzene; Hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris( 3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyltristhiopropionate, pent
  • 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and among the aliphatic mercapto group-containing compounds, trimethylolpropane tris (3-mercaptopropionate) is preferred.
  • aliphatic mercapto group-containing compounds are preferred, and specifically, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred, and pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis ( 3-mercaptobutyrate) is more preferred. These may be used
  • 2-mercaptobenzothiazole 2-mercaptobenzimidazole
  • 2-mercaptobenzoxazole 2-mercaptobenzoxazole and a photopolymerization initiator
  • 2-mercaptobenzothiazole 2-mercaptobenzoimidazole
  • 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
  • pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate).
  • one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and pentaerythritol tetrakis (3-mercaptopropionate) It is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptobutyrate) in combination with a photopolymerization initiator.
  • the content of the chain transfer agent is not particularly limited, but is preferably 0.01% by mass or more based on the total solid content of the photosensitive resin composition. , more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, even more preferably 0.8% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less. , more preferably 3% by mass or less, even more preferably 2% by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.01 to 5% by weight, more preferably 0.1 to 4% by weight, even more preferably 0.5 to 3% by weight, and particularly preferably 0.8 to 2% by weight.
  • adhesion to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the photosensitive resin composition of the present invention may contain (d) a photopolymerizable compound.
  • (d) Containing a photopolymerizable compound is thought to increase the curability of the coating film and improve its adhesion.
  • the photopolymerizable compound (d) used here include compounds having one or more ethylenic double bonds in the molecule (hereinafter also referred to as ethylenically unsaturated compounds).
  • a compound having two or more ethylenic double bonds in the molecule is preferable from the viewpoint of polymerizability, crosslinkability, and the ability to widen the difference in developing solution solubility between exposed and non-exposed areas.
  • the unsaturated bond is derived from a (meth)acryloyloxy group, that is, a (meth)acrylate compound.
  • a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule is not particularly limited, but is preferably 2 or more, more preferably 3 or more, even more preferably 5 or more, and preferably 15.
  • the number is more preferably 10 or less, further preferably 8 or less, particularly preferably 7 or less.
  • the above upper and lower limits can be arbitrarily combined.
  • the number is preferably 2 to 15, more preferably 2 to 10, even more preferably 3 to 8, and particularly preferably 5 to 7.
  • ethylenically unsaturated compounds include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, etc.
  • esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
  • acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and methacrylic acid obtained by replacing the acrylate of these exemplary compounds with methacrylate.
  • esters such as itaconic esters in place of itaconate, crotonic esters in place of cronate or maleic esters in place of maleate.
  • esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
  • esters obtained by the esterification reaction of polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single products, but are typical examples.
  • condensates of acrylic acid, phthalic acid, and ethylene glycol examples include, for example, a condensate of acrylic acid, phthalic acid, and ethylene glycol, a condensate of acrylic acid, maleic acid, and diethylene glycol, a condensate of methacrylic acid, terephthalic acid, and pentaerythritol, acrylic acid, adipine Mention may be made of condensates of acids, butanediol and glycerin.
  • examples of the polyfunctional ethylenic monomer used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic ester, or a polyisocyanate compound, a polyol, and a hydroxyl group-containing (meth)acrylic ester.
  • Urethane (meth)acrylates such as those obtained; Epoxy acrylates such as addition reaction products of polyvalent epoxy compounds and hydroxy (meth)acrylate or (meth)acrylic acid; Acrylamides such as ethylene bisacrylamide; Diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate are useful.
  • urethane (meth)acrylates examples include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).
  • esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids or urethane (meth)acrylates are preferred.
  • acrylate dipentaerythritol penta(meth)acrylate, 2,2,2-tris(meth)acryloyloxymethylethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta
  • a dibasic acid anhydride adduct of (meth)acrylate and a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate may be used alone or in combination of two or more.
  • the molecular weight of the photopolymerizable compound (d) is not particularly limited, but is preferably 100 or more, more preferably 150 or more, even more preferably 200 or more, even more preferably 300 or more, particularly preferably 400 or more, Most preferably it is 500 or more, preferably 1000 or less, more preferably 700 or less.
  • adhesion to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 100 to 1000, more preferably 150 to 1000, even more preferably 200 to 1000, even more preferably 300 to 700, even more preferably 400 to 700, and particularly preferably 500 to 700.
  • the number of carbon atoms in the photopolymerizable compound is not particularly limited, but from the viewpoint of adhesion and residue suppression, it is preferably 7 or more, more preferably 10 or more, even more preferably 15 or more, even more preferably 20 or more, especially It is preferably 25 or more, preferably 50 or less, more preferably 40 or less, even more preferably 35 or less, particularly preferably 30 or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 7 to 50, more preferably 10 to 50, even more preferably 15 to 40, even more preferably 20 to 35, and particularly preferably 25 to 30.
  • ester (meth)acrylates from the viewpoint of achieving both adhesion and developability, ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates are preferred, and among them, pentaerythritol tetra(meth)acrylate and pentaerythritol tri(meth)acrylate.
  • Adducts of acid anhydrides to trifunctional or higher functional ester (meth)acrylates such as dibasic acid anhydride adducts of erythritol penta(meth)acrylate, are preferred
  • the content of the photopolymerizable compound (d) in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more based on the total solid content of the photosensitive resin composition. % by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, particularly preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably is 40% by mass or less, more preferably 30% by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 1 to 80% by weight, more preferably 5 to 80% by weight, even more preferably 10 to 60% by weight, even more preferably 15 to 40% by weight, and particularly preferably 20 to 30% by weight.
  • adhesion to improve by setting it as the above-mentioned lower limit or more.
  • developability to be improved by setting it below the upper limit value.
  • the content ratio of (d) photopolymerizable compound to 100 parts by mass of (b) alkali-soluble resin is not particularly limited, but is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and more. More preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, most preferably 40 parts by mass or more, and preferably 150 parts by mass or less, more preferably 100 parts by mass.
  • the amount is more preferably 70 parts by mass or less, even more preferably 60 parts by mass or less, particularly preferably 50 parts by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 1 to 150 parts by weight, more preferably 5 to 150 parts by weight, even more preferably 10 to 100 parts by weight, even more preferably 15 to 100 parts by weight, even more preferably 20 to 70 parts by weight, and even more preferably 30 to 100 parts by weight.
  • Particularly preferred is 60 parts by weight, most preferably 40 to 50 parts by weight.
  • the photosensitive resin composition of the present invention may contain (e) a polymerization inhibitor from the viewpoint of suppressing residues after development.
  • the photosensitive resin composition of the present invention does not contain (f) an ultraviolet absorber described below, the photosensitive resin composition of the present invention contains at least one type of (e) polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, 2,6-t-butyl-4-cresol, 2,6-di-t-butylphenol, 4-methoxyphenol, 2-methylhydroquinone, hydroquinone, benzoquinone, t -Butylcatechol and phenoxazine are included. From the viewpoint of developability and storage stability, 4-methoxyphenol and 2-methylhydroquinone are preferred, and 2-methylhydroquinone is more preferred.
  • the content ratio of (e) the polymerization inhibitor in the photosensitive resin composition is not particularly limited, but the total solid content of the photosensitive resin composition It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.08% by mass or more, particularly preferably 0.1% by mass or more, and preferably 5% by mass. % or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, even more preferably 1% by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, even more preferably 0.08 to 3% by mass, even more preferably 0.1 to 2% by mass, and even more preferably 0.1 to 2% by mass. 1% by weight is particularly preferred.
  • the amount is equal to or more than the lower limit, developability tends to improve. Adhesion tends to improve when the content is below the upper limit.
  • the content ratio of (e) polymerization inhibitor to 100 parts by mass of (c) photopolymerization initiator is not particularly limited, but is preferably 0. 1 part by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, even more preferably 5 parts by mass or more, and preferably 50 parts by mass or less, more preferably 40 parts by mass or less. , more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, even more preferably 10 parts by weight or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.1 to 50 parts by weight, more preferably 1 to 40 parts by weight, even more preferably 2 to 30 parts by weight, even more preferably 5 to 20 parts by weight, and even more preferably 5 to 10 parts by weight.
  • amount is equal to or more than the lower limit, developability tends to improve. Adhesion tends to improve when the content is below the upper limit.
  • the produced alkali-soluble resin may contain a polymerization inhibitor.
  • the alkali-soluble resin may be used while containing the polymerization inhibitor, or in addition to the polymerization inhibitor contained in the resin, the same or different polymerization inhibitor may be added during the production of the photosensitive resin composition. May be added.
  • the photosensitive resin composition of the present invention may contain (f) an ultraviolet absorber.
  • the photosensitive resin composition of the present invention does not contain (e) a polymerization inhibitor, the photosensitive resin composition of the present invention contains at least one type of (f) ultraviolet absorber.
  • the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, triazine ultraviolet absorbers, and benzoxazine ultraviolet absorbers.
  • benzophenone ultraviolet absorbers examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and 2-hydroxybenzophenone.
  • 4-Methoxybenzophenone-5-sulfonic acid 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'- Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, sodium 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sulfonate, bis(5-benzoyl-4-hydroxy- Examples include 2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.
  • benzotriazole ultraviolet absorbers examples include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy- 3,5-Dicumylphenyl)benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1, 3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2- Hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5- tert-butylphenyl)benzotriazole
  • cyanoacrylate ultraviolet absorbers examples include 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate, hexadecyl-2-cyano-3-(4- methylphenyl)acrylate, 2-cyano-3-(4-methylphenyl)acrylate, 1,3-bis(2'-cyano-3,3'-diphenylacryloyl)oxy)-2,2-bis(( (2'-cyano-3,3'-diphenylacryloyl)oxy)methyl)propane is mentioned.
  • triazine-based ultraviolet absorbers examples include 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-ethoxyphenyl)- 4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-propoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4- butoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2 -hydroxy-4-octyloxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-diphenyl-1,3,5- Triazine, 2-(2-hydroxy-4-benzyloxyphenyl)-4,6
  • benzoxazine ultraviolet absorbers examples include 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one), 2-methyl-3,1-benzoxazine- Examples include 4-one, 2-butyl-3,1-benzoxazin-4-one, and 2-phenyl-3,1-benzoxazin-4-one.
  • triazine-based, benzotriazole-based, and benzoxazine-based UV absorbers are preferred, and benzotriazole-based UV absorbers are more preferred.
  • One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.
  • the content ratio of (f) ultraviolet absorber in the photosensitive resin composition is not particularly limited, but the total solid content of the photosensitive resin composition It is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and preferably 10% by mass or less. , more preferably 5% by mass or less, still more preferably 3% by mass or less, even more preferably 2% by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, even more preferably 0.5 to 3% by weight, and even more preferably 1 to 2% by weight.
  • it is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, even more preferably 0.5 to 3% by weight, and even more preferably 1 to 2% by weight.
  • the content ratio of (f) ultraviolet absorber to 100 parts by mass of (c) photopolymerization initiator is not particularly limited, but is preferably 0. 1 part by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, and preferably 100 parts by mass or less, more preferably 50 parts by mass. parts by weight or less, more preferably 30 parts by weight or less, even more preferably 20 parts by weight or less, even more preferably 10 parts by weight or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, even more preferably 1 to 30 parts by weight, even more preferably 2 to 20 parts by weight, and even more preferably 2 to 10 parts by weight.
  • the amount is equal to or more than the lower limit, developability tends to improve. Adhesion tends to improve when the content is below the upper limit.
  • a surfactant may be used.
  • the surfactant can be used, for example, for the purpose of improving the coating properties of the photosensitive resin composition as a coating solution and the developability of the coating film, and among them, silicone-based and fluorine-based surfactants are preferred.
  • silicone-based surfactants are preferred, and polyether-modified silicone-based More preferred are surfactants.
  • fluorine-based surfactants are preferred.
  • a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain, and side chain is suitable.
  • These commercially available products include, for example, “BM-1000” and “BM-1100” manufactured by BM Chemie, “Megafac F142D”, “Megafac F172”, “Megafac F173”, and “Megafac F183” manufactured by DIC Corporation. ", “Megafac F470,””MegafacF475,””MegafacF554,””MegafacF559,””FC430” manufactured by 3M Japan, and “DFX-18” manufactured by Neos.
  • silicone surfactants examples include “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, “SH8400” manufactured by Dow Corning Toray Industries, Inc., and BIC Chemie Co., Ltd.
  • Commercially available products such as BYK (registered trademark, hereinafter the same) 323 and BYK330 can be mentioned.
  • the surfactant may include things other than fluorine-based surfactants and silicone-based surfactants, and other surfactants include nonionic, anionic, cationic, and amphoteric surfactants. .
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, and glycerin. Fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxyethylene Examples include sorbitol fatty acid esters. Examples of these commercially available products include polyoxyethylene surfactants such as "Emulgen (registered trademark, the same hereinafter) 104P" and "Emulgen A60" manufactured by Kao Corporation.
  • anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, higher alcohol sulfate ester salts, Aliphatic alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymer systems
  • surfactants include surfactants.
  • special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.
  • These commercially available products include alkyl sulfate ester salts such as “Emar (registered trademark, hereinafter the same applies) 10" manufactured by Kao Corporation, and alkylnaphthalene sulfonates such as “Perex (registered trademark)” manufactured by Kao Corporation.
  • alkyl sulfate ester salts such as "Emar (registered trademark, hereinafter the same applies) 10" manufactured by Kao Corporation
  • alkylnaphthalene sulfonates such as "Perex (registered trademark)” manufactured by Kao Corporation.
  • special polymer surfactants include “Homogenol (registered trademark, hereinafter the same) L-18" and “Homogenol L-100” manufactured by Kao Corporation.
  • Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts. Further, examples of the amphoteric surfactant include betaine type compounds, imidazolium salts, imidazolines, and amino acids. As the cationic surfactant, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. These commercially available products include alkylamine salts such as "Acetamine (registered trademark) 24" manufactured by Kao Corporation, and quaternary ammonium salts such as "Cortamine (registered trademark, hereinafter the same applies) 24P" manufactured by Kao Corporation. ” and “Cortamine 86W”.
  • One surfactant may be used alone, or two or more surfactants may be used in combination.
  • a combination of a silicone surfactant and a fluorine surfactant a combination of a silicone surfactant and a special polymer surfactant, a combination of a fluorine surfactant and a special polymer surfactant.
  • a combination of a silicone surfactant and a fluorine surfactant is preferred.
  • combinations of silicone surfactants and fluorosurfactants include "DFX-18" manufactured by Neos, "BYK-300" or “BYK-330" manufactured by BYK Chemie, and "S-" manufactured by AGC Seimi Chemical.
  • a liquid repellent may be used in the photosensitive resin composition of the present invention.
  • ink repellency can be imparted to the surface of the photosensitive resin composition. Therefore, when forming another composition after curing the photosensitive resin composition, it is possible to prevent compositions from being mixed with each other.
  • the liquid repellent contains a compound having a fluorine atom and/or a siloxane chain, and may have a crosslinking group. From the viewpoint of improving ink repellency, it is preferable to have a crosslinking group.
  • the liquid repellent described in Japanese Patent Application No. 2022-020652 can be used.
  • the photosensitive resin composition of the present invention contains (g) a dispersant in order to (a) finely disperse the resin particles and stabilize the dispersion state. It is preferable to do so.
  • the photosensitive resin composition of the present invention may contain a dispersant in addition to the alkali-soluble resin (b1).
  • a polymeric dispersant having a functional group is preferable, and from the viewpoint of dispersion stability, a carboxy group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary or tertiary Polymer dispersants having functional groups such as amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine are preferred.
  • pigments are dispersed by polymeric dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine. It is particularly preferred from the viewpoint that it can be dispersed with a small amount of dispersant.
  • polymeric dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of monomers and macromonomers having amino groups, and polyoxyethylene alkyl ether-based dispersants.
  • examples include dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
  • polymer dispersants include, for example, the trade names EFKA (registered trademark, manufactured by BASF Corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie Corporation), Disparlon (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), Examples include SOLSPERSE (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Ltd.).
  • One type of polymer dispersant may be used alone, or two or more types may be used in combination.
  • the weight average molecular weight (Mw) of the polymer dispersant is preferably 700 or more, more preferably 1000 or more. Further, it is preferably 100,000 or less, more preferably 50,000 or less. The above upper and lower limits can be arbitrarily combined.
  • the weight average molecular weight (Mw) of the polymer dispersant is preferably 700 to 100,000, more preferably 1,000 to 50,000.
  • the dispersant (g) preferably contains an acrylic polymer dispersant having a functional group. From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and one or both of a polyester bond and a polyether bond is preferred.
  • the acrylic polymer dispersant includes an unsaturated group-containing monomer having a functional group (the functional group referred to herein is the functional group described above as a functional group contained in the polymer dispersant); It is preferable to use a random copolymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by known methods.
  • the acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block not having a functional group.
  • the block may also contain partial structures derived from unsaturated group-containing monomers that do not contain the above-mentioned functional groups. may be contained in the A block in either random copolymerization or block copolymerization.
  • the content of the partial structure that does not contain a functional group in the A block is preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 30% by mass or less.
  • the B block consists of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but one B block contains partial structures derived from two or more types of monomers. These may be contained in the B block in either random copolymerization or block copolymerization.
  • the AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below. Living polymerization methods include anionic living polymerization methods, cationic living polymerization methods, and radical living polymerization methods.
  • the amount of quaternary ammonium base in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. By keeping it within the above range, there is a tendency that good dispersibility can be ensured.
  • the amine value is preferably 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g. g or more, more preferably 50 mgKOH/g or more, and preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH/g or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 100 mgKOH/g, more preferably 10 to 90 mgKOH/g, even more preferably 30 to 80 mgKOH/g, and particularly preferably 50 to 75 mgKOH/g.
  • the amine value is expressed as the base amount and the equivalent mass of KOH per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method. Accurately weigh 0.5 to 1.5 g of the dispersant sample into a 100 mL beaker and dissolve it in 50 mL of acetic acid. This solution is neutralized and titrated with a 0.1 mol/L HClO 4 acetic acid solution using an automatic titrator equipped with a pH electrode. The inflection point of the titration pH curve is taken as the titration end point, and the amine value is determined by the following formula.
  • Amine value [mgKOH/g] (561 ⁇ V) / (W ⁇ S) [However, W: Dispersant sample weighed amount [g], V: Titration amount at the titration end point [mL], S: Dispersant Represents the solid content concentration [mass%] of the sample. ]
  • the acid value of the block copolymer depends on the presence or absence and type of acidic groups that are the source of the acid value, it is preferably lower, and is preferably 10 mgKOH/g or less.
  • the weight average molecular weight (Mw) of the block copolymer is preferably in the range of 1,000 to 100,000. By keeping it within the above range, there is a tendency that good dispersibility can be ensured.
  • the photosensitive resin composition of the present invention contains (g) a dispersant
  • its content is not particularly limited, but is preferably 0.1% by mass or more based on the total solid content of the photosensitive resin composition.
  • the content is more preferably 0.5% by mass or more, preferably 8% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.1 to 8% by weight, more preferably 0.1 to 5% by weight, even more preferably 0.5 to 3% by weight, and particularly preferably 0.5 to 2% by weight.
  • the amount is equal to or more than the lower limit, aggregates tend to be suppressed and a uniform coating film can be formed.
  • the content is below the upper limit, heat resistance and developability tend to improve.
  • the content ratio of the (g) dispersant is preferably 1 part by mass or more, and 3 parts by mass based on 100 parts by mass of the resin particles (a1).
  • the above is more preferable, 5 parts by weight or more is even more preferable, 100 parts by weight or less is more preferable, 50 parts by weight or less is more preferable, even more preferably 25 parts by weight or less, even more preferably 20 parts by weight or less, 15 parts by weight or less.
  • the following is particularly preferred, and 12 parts by mass or less is particularly preferred.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, even more preferably 1 to 25 parts by weight, even more preferably 3 to 20 parts by weight, particularly preferably 5 to 15 parts by weight, and even more preferably 5 to 12 parts by weight. Parts by mass are particularly preferred.
  • Thermal polymerization initiator The photosensitive resin composition of the present invention may contain a thermal polymerization initiator. Containing a thermal polymerization initiator tends to increase the degree of crosslinking of the membrane. Specific examples of such thermal polymerization initiators include azo compounds, organic peroxides, and hydrogen peroxide. One type of thermal polymerization initiator may be used alone, or two or more types may be used in combination.
  • the total content ratio of these components must be the total solid content of the photosensitive resin composition. It is preferable to adjust the content ratio of the photopolymerization initiator to In addition, when a thermal polymerization initiator is used in combination with a photopolymerization initiator, the proportion of the photopolymerization initiator and thermal polymerization initiator used should be determined from the viewpoint of heat resistance. Preferably, the amount of initiator is 5 to 300 parts by mass.
  • the photosensitive resin composition of the present invention may contain a silane coupling agent in order to improve the adhesion to the substrate.
  • a silane coupling agent for example, epoxy-based, methacrylic-based, amino-based, or imidazole-based silane coupling agents can be used. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are particularly preferred.
  • the photosensitive resin composition of the present invention contains a silane coupling agent, its content is preferably 20% by mass or less, more preferably 20% by mass or less based on the total solid content of the photosensitive resin composition, from the viewpoint of adhesion.
  • it is 15% by weight or less, more preferably 10% by weight or less, even more preferably 5% by weight or less, even more preferably 2% by weight or less, preferably 0.1% by weight or more, more preferably 0.5% by weight. It is at least 1% by mass, more preferably at least 1% by mass.
  • the above upper and lower limits can be arbitrarily combined. For example, it may be 0.1% by mass or more and 20% by mass or less, 0.1% by mass or more and 15% by mass or less, 0.5% by mass or more and 10% by mass or less, and 0.5% by mass or more and 10% by mass or less. It may be at least 1% by mass and at most 5% by mass, and at least 1% by mass and at most 2% by mass.
  • Inorganic filler The photosensitive resin composition of the present invention not only has improved strength as a cured product, but also has an excellent coating film due to moderate interaction with the alkali-soluble resin (formation of matrix structure).
  • an inorganic filler may be contained for the purpose of improving verticality and taper angle. Examples of the inorganic filler include talc, barium sulfate, and those surface-treated with various silane coupling agents.
  • the average particle diameter of the inorganic filler is preferably 0.005 to 2 ⁇ m, more preferably 0.01 to 1 ⁇ m.
  • the average particle diameter is a value measured using a laser diffraction scattering particle size distribution analyzer manufactured by Beckman Coulter.
  • silica sol and modified silica sol are particularly preferable because they tend to have excellent dispersion stability and an excellent effect of improving the taper angle.
  • the photosensitive resin composition of the present invention contains an inorganic filler, the content thereof is preferably 5% by mass based on the total solid content of the photosensitive resin composition from the viewpoint of crack resistance of the cured product.
  • % or more more preferably 10% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 80% by weight, more preferably 10 to 70% by weight.
  • the photosensitive resin composition of the present invention may contain an adhesion improver for the purpose of imparting adhesion to the substrate.
  • adhesion improver include phosphoric acid-based ethylenic monomers.
  • phosphoric acid-based ethylenic monomer (meth)acryloyloxy group-containing phosphates are preferred, and those represented by the following general formulas (g1), (g2), and (g3) are preferred.
  • R 51 represents a hydrogen atom or a methyl group
  • l and l' are integers of 1 to 10
  • m is 1, 2, or 3.
  • phosphoric acid-based ethylenic monomers may be used alone or in combination of two or more.
  • the content thereof is 0.02% by mass or more based on the total solid content of the photosensitive resin composition. is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, and preferably 4% by mass or less, more preferably 3% by mass or less, It is more preferably 2% by mass or less, particularly preferably 1% by mass or less.
  • the above upper and lower limits can be arbitrarily combined.
  • it is preferably 0.02 to 4% by weight, more preferably 0.05 to 3% by weight, even more preferably 0.1 to 2% by weight, and particularly preferably 0.2 to 1% by weight.
  • the amount is equal to or more than the lower limit, the effect of improving adhesion to the substrate tends to be sufficient.
  • the upper limit there is a tendency to easily suppress deterioration of adhesiveness with the substrate.
  • the photosensitive resin composition of the present invention usually contains a solvent in addition to each component contained in the photosensitive resin composition described above, and each of the components contained in the photosensitive resin composition It is used with the components dissolved or dispersed in a solvent.
  • the solvent is not particularly limited, but includes, for example, the organic solvents described below.
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, Glycol monoalkyl ethers such as triethylene glycol monoethyl ether and tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
  • solvents include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2.
  • Solvesso #150 Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names).
  • the solvent can dissolve or disperse each component contained in the photosensitive resin composition, and is selected depending on the method of using the photosensitive resin composition of the present invention.
  • the boiling point of the solvent under atmospheric pressure is preferably 60 to 280°C, more preferably 70 to 260°C.
  • propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferred.
  • the total solid content of the solvent in the photosensitive resin composition solution is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 25% by mass or more, Further, it is preferably used in an amount of 90% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, particularly preferably 35% by mass or less.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably used in an amount of 10 to 90% by weight, more preferably 15 to 50% by weight, even more preferably 20 to 40% by weight, particularly preferably 25 to 35% by weight.
  • the photosensitive resin composition of the present invention has an average transmittance of 70% or more in the wavelength range of 400 to 700 nm in a cured film with a thickness of 5 ⁇ m obtained by curing the photosensitive resin composition. Since the average transmittance in the wavelength range of 400 to 700 nm is 70% or more, the light transmittance is high mainly in the visible light region, and pixels and light scattering films are formed using the photosensitive resin composition of the present invention. In this case, luminous efficiency tends to be maintained.
  • the average transmittance in the wavelength range of 400 to 700 nm in a cured film with a thickness of 5 ⁇ m obtained by curing the photosensitive resin composition is 70% or more, preferably 80% or more, more preferably 90% or more, 95% or more. is even more preferred. Usually it is 100% or less.
  • the average transmittance in the wavelength range of 400 to 700 nm can be measured using a spectrophotometer.
  • the transmittance is measured at a pitch of 1 nm in the wavelength range of 400 to 700 nm, and the arithmetic mean value is taken as the average transmittance. be able to.
  • the photosensitive resin composition of the present invention is prepared by mixing each component contained in the photosensitive resin composition using a stirrer.
  • a stirrer for example, (a) when containing solvent-insoluble components such as resin particles, dispersion treatment may be performed in advance using a stirrer, three-one motor, paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. is preferred.
  • dispersion treatment (a) resin particles, organic pigments, and inorganic particles are made into fine particles, so that the coating characteristics of the photosensitive resin composition are improved.
  • Dispersion treatment usually involves a system in which (a) resin particles, organic pigments, inorganic particles, a solvent, and (g) a dispersant are used in combination, or (b) a part or all of an alkali-soluble resin is optionally used in combination with them.
  • the mixture subjected to dispersion treatment and the composition obtained by dispersion treatment may be referred to as "ink” or "resin particle dispersion”).
  • a polymer dispersant as the dispersant (g) because the obtained ink and photosensitive resin composition have excellent dispersion stability and increase in viscosity over time is suppressed.
  • a particle dispersion containing at least (a) resin particles, an organic pigment, an inorganic particle, a solvent, and (g) a dispersant.
  • resin particles, organic pigments, inorganic particles, organic solvents, and (g) dispersants that can be used in the particle dispersion those described as those that can be used in the photosensitive resin composition are preferably used.
  • dispersants those described as those that can be used in the photosensitive resin composition are preferably used.
  • the content ratio of the resin particles (a) in the resin particle dispersion the ratio described as the content ratio in the photosensitive resin composition can be preferably adopted.
  • the temperature is preferably from 0°C to 100°C, more preferably from room temperature to 80°C.
  • the appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, etc., and is therefore adjusted as appropriate.
  • a guideline for dispersion is to control the gloss of the ink so that the 20 degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300.
  • the dispersed particle size of the resin particles (a) dispersed in the ink is preferably 0.8 to 5 ⁇ m.
  • the dispersed particle size of the organic pigment and inorganic particles dispersed in the ink is preferably 0.01 to 5 ⁇ m, more preferably 0.03 to 5 ⁇ m.
  • the dispersed particle size of (a) resin particles, organic pigments, and inorganic particles in the ink is measured by a dynamic light scattering method or the like.
  • the ink obtained by the dispersion treatment and other components contained in the photosensitive resin composition are mixed to form a uniform solution or dispersion.
  • fine dust may be mixed into the liquid, so it is desirable to filter the obtained photosensitive resin composition using a filter or the like.
  • the cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention.
  • the photosensitive resin composition of the present invention can be used as a cured product within a partition wall, and for example, the cured product of the present invention can be suitably used as a material that scatters light from an organic electroluminescent device or a semiconductor light emitting device. .
  • the method for forming a cured product using the photosensitive resin composition of the present invention is not particularly limited, and conventionally known methods can be employed.
  • the method for forming the cured product includes, for example, a coating step in which a photosensitive resin composition is applied onto a substrate to form a photosensitive resin composition layer, and an exposure step in which the photosensitive resin composition layer is exposed.
  • a coating step in which a photosensitive resin composition is applied onto a substrate to form a photosensitive resin composition layer
  • an exposure step in which the photosensitive resin composition layer is exposed. Examples include methods including: Specific examples of methods for forming such a cured product include an inkjet method and a photolithography method.
  • a photosensitive resin composition whose viscosity has been adjusted by dilution with a solvent is used as ink, and ink droplets are ejected onto the substrate along a predetermined pattern by the inkjet method. Coat on top to form an uncured pattern. Then, the uncured pattern is exposed to light to form a cured product on the substrate. The uncured pattern is exposed to light in the same manner as the exposure step in the photolithography method described later, except that a mask is not used.
  • a photosensitive resin composition is applied to the entire area on a substrate where a pattern is to be formed to form a photosensitive resin composition layer. After exposing the formed photosensitive resin composition layer according to a predetermined pattern, the exposed photosensitive resin composition layer is developed to form a cured product on the substrate.
  • a contact transfer type such as a roll coater, reverse coater, bar coater, die coater, screen printing, etc. is applied to the substrate on which a cured product is to be formed.
  • the photosensitive resin composition is applied using a non-contact coating device such as a coating device, a spinner (rotary coating device), or a curtain flow coater, and if necessary, the solvent is removed by drying to coat the photosensitive resin composition. form a material layer.
  • the photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays and excimer laser light using a negative mask, and the photosensitive resin composition layer is partially exposed according to the pattern. do.
  • active energy rays such as ultraviolet rays and excimer laser light using a negative mask
  • a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp, can be used.
  • the exposure amount varies depending on the composition of the photosensitive resin composition, it is preferably about 10 to 3000 mJ/cm 2 , for example.
  • the photosensitive resin composition layer exposed according to the pattern is developed with a developer to form a cured product.
  • the developing method is not particularly limited, and a dipping method, a spray method, etc. can be used.
  • Specific examples of developing solutions include organic ones such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. Can be mentioned.
  • an antifoaming agent and a surfactant can also be added to the developer.
  • the post-baking conditions are preferably 80°C or higher, more preferably 90°C or higher, even more preferably 100°C or higher, and even more preferably 120°C or higher.
  • the temperature is preferably 250°C or lower, more preferably 200°C or lower, even more preferably 180°C or lower, even more preferably 160°C or lower.
  • the temperature is preferably 80 to 250°C, more preferably 90 to 200°C, even more preferably 100 to 180°C, even more preferably 120 to 160°C.
  • the post-bake time is preferably 5 minutes or more, more preferably 10 minutes or more, even more preferably 20 minutes or more, particularly preferably 30 minutes or more, and preferably 180 minutes or less, more preferably 150 minutes or less, and 120 minutes.
  • the following is more preferable, 100 minutes or less is particularly preferable, and 60 minutes or less is particularly preferable.
  • the time is preferably 15 to 180 minutes, more preferably 10 to 150 minutes, even more preferably 20 to 120 minutes, particularly preferably 30 to 100 minutes, and even more preferably 30 to 60 minutes.
  • Heat resistance and solvent resistance tend to be good when the lower limit value is exceeded, and by lowering the upper limit value or below, the impact on manufacturing costs and compatibility with substrates and elements with limited heat resistance, such as plastic substrates, tends to be reduced.
  • the post-bake time is preferably 5 minutes or more, more preferably 10 minutes or more, even more preferably 20 minutes or more, particularly preferably 30 minutes or more, and preferably 180 minutes or less, more preferably 150 minutes or less, and 120 minutes
  • the substrate used for forming the cured product is not particularly limited, and is appropriately selected depending on the type of organic electroluminescent device or semiconductor light emitting device to be manufactured using the substrate on which the cured product is formed.
  • Suitable materials for the substrate include glass and various resin materials.
  • Specific examples of the resin material include polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonate; poly(meth)methacrylic resin; polysulfone; and polyimide.
  • glass and polyimide are preferred because they have excellent heat resistance.
  • a transparent electrode layer of ITO, ZnO, or the like may be provided in advance on the surface of the substrate on which the cured product is formed.
  • the film thickness of the cured product of the present invention is preferably 0.1 ⁇ m or more, preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, even more preferably 3 ⁇ m or more, particularly preferably 5 ⁇ m or more, and more preferably 1 mm or less. is 100 ⁇ m or less, more preferably 50 ⁇ m or less, even more preferably 30 ⁇ m or less, particularly preferably 20 ⁇ m or less, even more preferably 10 ⁇ m or less.
  • the film thickness of the cured product is measured using a step/surface roughness/fine shape measuring device, a scanning white interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, and an electron microscope.
  • Color filter containing luminescent nanocrystal particles of the present invention is not particularly limited as long as it includes the cured product of the present invention, and the color filter includes pixels in the region partitioned by partition walls. Examples include those that have been formed.
  • FIG. 1 is a schematic cross-sectional view of an example of a color filter comprising the cured product of the present invention.
  • the color filter 100 includes a substrate 10, a partition wall 20 provided on the substrate, a red pixel 30, a green pixel 40, and a blue pixel 50.
  • the red pixel 30, the green pixel 40, and the blue pixel 50 are arranged in a grid pattern so as to be repeated in this order.
  • the partition wall 20 is provided between these adjacent pixels. In other words, these adjacent pixels are separated by the partition wall 20.
  • the red pixel 30 contains red light-emitting nanocrystal particles 1
  • the green pixel 40 contains green light-emitting nanocrystal particles 2.
  • the blue pixel 50 is a pixel that transmits blue light from a light source. Particles 3 are included that scatter light from the light source.
  • the photosensitive resin composition of the present invention can be preferably used for forming a blue pixel portion, and the cured product of the present invention can be preferably used for a blue pixel portion.
  • Red-emitting and green-emitting nanocrystal particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, for example, the largest particle measured by a transmission electron microscope or a scanning electron microscope. It is a crystalline substance with a diameter of 100 nm or less.
  • Luminescent nanocrystal particles are particles that can emit light (fluorescence or phosphorescence) at a wavelength different from the absorbed wavelength by absorbing light at a predetermined wavelength; for example, red luminescent nanocrystal particles 1 emits light (red light) having an emission peak wavelength in the range of 605 to 665 nm, and green-emitting nanocrystal particles 2 emit light (green light) having an emission peak wavelength in the range of 500 to 560 nm. ).
  • the wavelength of light emitted by a luminescent nanocrystal particle depends on the size of the luminescent nanocrystal particle (for example, particle diameter). It also depends on the energy gap that the crystal grains have. Therefore, the color of the emitted light can be selected by changing the constituent material and size of the luminescent nanocrystal particles used. Examples of the luminescent nanocrystal particles include quantum dots and the like.
  • the method for manufacturing a color filter containing luminescent nanocrystal particles is not particularly limited, but a substrate with partition walls is prepared, and a layer containing luminescent nanocrystal particles or a blue pixel is coated with the photosensitive material of the present invention in a region defined by the partition walls.
  • Examples include a method of forming a layer containing a synthetic resin composition.
  • the method for forming the layer containing luminescent nanocrystal particles and the layer containing the photosensitive resin composition of the present invention is not particularly limited, but for example, it is selectively deposited by an inkjet method and cured by irradiation with active energy rays or heating. It can be manufactured by a method or a photolithography method.
  • Light-scattering film The cured product of the present invention can be used as a light-scattering film.
  • a light scattering film of an image display device including an organic electroluminescent device, a semiconductor light emitting device, etc. it tends to improve luminous efficiency.
  • organic electroluminescent devices and semiconductor light emitting devices since the light emitting layer has a high refractive index, the emitted light is likely to be totally reflected at the interface, and the efficiency of extracting light to the outside is likely to decrease. Therefore, there are applications in which the traveling direction of light generated by a light scattering film is changed, suppressing the reflection of light at the interface, and improving the light extraction efficiency.
  • the light scattering film of the present invention can be used to improve light extraction efficiency by suppressing reflection of light. Further, in order to suppress unevenness due to reflection of external light, it can be preferably used as a light scattering film of an image display device including an organic electroluminescent device, a semiconductor light emitting device, etc. By changing the traveling direction of the reflected external light using the light scattering film, unevenness due to the external light reflection can be suppressed. Furthermore, in order to improve the viewing angle, it can be preferably used as a light scattering film of an image display device including an organic electroluminescent device, a semiconductor light emitting device, etc.
  • the image display device of the present invention includes a color filter containing the cured product of the present invention in a pixel region, and a light scattering film using the cured product of the present invention.
  • a color filter containing the cured product of the present invention in a pixel region and a light scattering film using the cured product of the present invention.
  • an organic electroluminescent device, a semiconductor light emitting device, or the like can be used as the light source.
  • examples of the image display device of the present invention include an image display device including a color filter containing the luminescent nanocrystal particles according to the present invention.
  • Examples of types of image display devices include liquid crystal display devices, organic electroluminescent devices, and image display devices including semiconductor light emitting devices.
  • Examples of liquid crystal display devices include ones that include a light source including a blue LED and a liquid crystal layer including electrodes that control blue light emitted from the light source for each pixel portion.
  • Other examples include those in which a blue-emitting organic electroluminescent element or a semiconductor light-emitting element is arranged at a position corresponding to each pixel portion of the color filter.
  • methods described in Japanese Patent Application Publication No. 2019-87746 and Japanese Patent Application Publication No. 2021-089433 can be mentioned.
  • the photosensitive resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples unless the gist thereof is exceeded.
  • the constituent components of the photosensitive resin compositions used in the following Examples and Comparative Examples are as follows.
  • the weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 9000, the solid content acid value was 80 mgKOH/g, and the double bond equivalent was 470 g/mol. This corresponds to an alkali-soluble resin (b1) having an ethylenic double bond.
  • Alkali-soluble resin-II> An alkali-soluble acrylic copolymer resin whose constituent monomers are benzyl methacrylate/methacrylic acid (molar ratio: 0.73/0.27).
  • the weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 12,300, and the solid content acid value was 98 mgKOH/g. It does not fall under the alkali-soluble resin (b1) having an ethylenic double bond.
  • ⁇ Photopolymerizable compound-I> DPHA: Nippon Kayaku Co., Ltd. A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.
  • DPHA Nippon Kayaku Co., Ltd. A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate.
  • M-933 Manufactured by Toagosei Co., Ltd. A mixture of pentaerythritol diacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate.
  • Photopolymerization initiator-III> A compound having the following chemical structure was used. This compound can be created by the synthesis method described in International Publication No. 2019/131189.
  • KAYAMER PM-21 methacryloyl group-containing phosphate manufactured by Nippon Kayaku Co., Ltd.
  • ⁇ Resin particles-II> Eposter S12 manufactured by Nippon Shokubai Co., Ltd. (melamine formaldehyde condensate (melamine resin), average particle size 1.4 ⁇ m, refractive index 1.66).
  • resin particles (a1) having a refractive index of 1.56 or more and 2.00 or less and an average primary particle diameter of 0.8 ⁇ m or more.
  • resin particles (a1) with a refractive index of 1.56 or more and 2.00 or less and an average primary particle diameter of 0.8 ⁇ m or more.
  • Pigment-I amine-based polymeric acrylic dispersant (dispersant-I), and solvent were mixed at the mass ratio shown in Table 1.
  • This mixed solution was subjected to a dispersion treatment using a paint shaker at a temperature of 25 to 45° C. for 6 hours. Zirconia beads with a diameter of 0.3 mm were used as beads, and 2.5 times the mass of the mixed solution was added. After the dispersion was completed, the beads and the dispersion liquid were separated using a filter to prepare a pigment dispersion liquid 1.
  • the blending ratio of the dispersant in Table 1 is shown in terms of solid content, and the blending ratio of the solvent also includes the amount of the solvent derived from the dispersant.
  • Pigment-II ⁇ Pigment dispersion-II> Pigment-II, alkali-soluble resin-I, and solvent were mixed at the mass ratio shown in Table 1.
  • Pigment Dispersion-II was prepared in the same manner as Pigment Dispersion-I except that the dispersion time was 8 hours.
  • Resin particles-V, dispersant-I, and solvent were mixed at the mass ratio shown in Table 1.
  • Resin particle dispersion-I was prepared in the same manner as pigment dispersion-I except that the dispersion time was 2 hours and 0.1 mm diameter zirconia beads were used.
  • Each of the obtained photosensitive resin compositions was evaluated by the method described below. The blending ratios of the pigment dispersion liquid and the alkali-soluble resin in Table 2 are shown in terms of solid content.
  • ⁇ Transmittance measurement on a cured film with a film thickness of 5 ⁇ m> The photosensitive resin composition was applied onto a glass substrate using a spinner so that the thickness of the cured film after heat curing was 5 ⁇ m. This coated substrate was vacuum dried for 1 minute, and then heated and dried on a hot plate at 100° C. for 120 seconds to obtain a coated substrate. Next, using a high-pressure mercury lamp, wavelengths of 330 nm or less were cut and the entire surface was exposed at 50 mJ/cm 2 . At this time, the light intensity at a wavelength of 365 nm was 45 mW/cm 2 .
  • this substrate was spray developed at 24°C for 70 seconds using an aqueous solution containing 0.03% by mass of KOH and 0.07% by mass of Emulgen A-60 (a surfactant manufactured by Kao Corporation) as a developer. Washed with pure water for 10 seconds. Finally, this substrate was heated and cured in an oven at 150° C. for 30 minutes to obtain a substrate for transmittance measurement on which a cured film with a thickness of 5 ⁇ m was formed.
  • Emulgen A-60 a surfactant manufactured by Kao Corporation
  • the transmittance of the substrate for transmittance measurement was measured using a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.) using the glass substrate as a reference, and the transmittance was measured at a pitch of 1 nm in the wavelength range of 400 to 700 nm. The average value was calculated. Tables 2 to 4 show the results of evaluating the average transmittance in the wavelength range of 400 to 700 nm based on the following criteria.
  • Haze measurement was performed using the same operating procedure as for the transmittance measurement substrate, except that the photosensitive resin composition was coated on the glass substrate using a spinner so that the cured film after heating and curing had a predetermined thickness. A substrate for use was obtained. The haze of the haze measurement substrate was measured using a haze meter (NDH5000SP manufactured by Nippon Denshoku Industries). A D65 light source was used. The measurement results and the results evaluated based on the following criteria are shown in Tables 2 to 4. The higher the haze, the higher the light scattering property.
  • Tables 2 to 4 show the results of measuring the thickness of the cured film on the haze measurement substrate using a stylus-type step film thickness meter (Alpha-Step IQ manufactured by KLA-Tencor).
  • ⁇ Developability evaluation> During exposure, a photomask having linear openings of various widths with an opening width of 5 to 50 ⁇ m (5 to 20 ⁇ m: every 1 ⁇ m, 25 to 50 ⁇ m: every 5 ⁇ m) and an opening length of 2 mm was used, and the exposure gap was 100 ⁇ m.
  • a line-shaped patterned substrate was produced using the same operating procedure as for producing the haze measurement substrate except for this. The entire line (2 mm) on the line-patterned substrate was observed with an optical microscope to confirm whether there were any lines that were in close contact with the substrate without chipping or peeling, and whether there were any residues remaining on the substrate other than the lines. The evaluation criteria for line presence and residue are shown below. Further, the film thickness of the line pattern substrate was measured using a stylus type step film thickness meter (Alpha-Step IQ manufactured by KLA-Tencor).
  • Heat resistance evaluation> A heat resistance evaluation substrate was produced using a square glass substrate of 5 cm on a side in the same manner as in the production of the haze measurement substrate. The heat resistance evaluation substrate was placed against the oven floor at an angle of 80° and heated in the oven at 150° C. for 30 minutes.
  • the film thickness at a position moved 1.5 cm from the center of the substrate for heat resistance evaluation (the end farthest from the oven floor) toward the center of the substrate when it is propped up in an oven and heated is 1, and the film thickness at the bottom (
  • Film thickness change (%)
  • the alkali-soluble resin (b1) having a double bond has high solubility in the developer, the unexposed area is easily dissolved in the developer, while the exposed area has a high degree of curing and is therefore difficult to dissolve in the developer. It is considered that this is because the properties were lowered, lines could be formed, and high developability was exhibited.
  • the haze could be increased by containing the resin particles (a1) with a refractive index of 1.56 or more and 2.00 or less. This is considered to be because the use of resin particles (a1) with a refractive index of 1.56 or more increases the scattering intensity at the interface between the resin in the coating film and the resin particles, resulting in an increase in haze.
  • the haze could be increased by containing resin particles (a1) with an average particle diameter of 0.8 ⁇ m or more. This is considered to be because when the average particle diameter of the resin particles is 0.8 ⁇ m or more, the scattering intensity becomes large with respect to the D65 light source during haze measurement, and the haze becomes high. Moreover, by containing the resin particles (a1) having an average particle diameter of 0.8 ⁇ m or more, lines could be formed without any residue after development, and the developability could be improved.
  • Examples 1 to 11 and Comparative Example 5 by containing (e) a polymerization inhibitor and/or (f) an ultraviolet absorber, a line can be formed without a residue after development, and the developability is improved. I was able to increase it.
  • a photosensitive resin composition containing resin particles, exposed light is scattered in unexposed areas, so that a residue tends to remain in unexposed areas after development.
  • the photosensitive resin composition contains (e) a polymerization inhibitor and/or (f) an ultraviolet absorber, and suppresses photocuring due to scattered light in unexposed areas, thereby suppressing residues in unexposed areas. , it is thought that it showed high developability.
  • Red-emitting nanocrystal particles Green-emitting nanocrystal particles 3 Particles that scatter light from a light source 10
  • Substrate 20 Partition Red pixel 40 Green pixel 50 Blue pixel 100 Color filter

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TWI766941B (zh) 2017-03-31 2022-06-11 南韓商東友精細化工有限公司 藍色感光性樹脂組成物以及利用彼製造之彩色濾光片與影像顯示裝置

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JP2001290021A (ja) * 2000-04-05 2001-10-19 Dainippon Printing Co Ltd カラーフィルタ
JP2008202042A (ja) * 2007-01-25 2008-09-04 Fujifilm Corp 有機顔料ナノ粒子分散物の製造方法、それにより得られる有機顔料ナノ粒子分散物、並びに、それを含有するインクジェットインク、着色感光性樹脂組成物、及び感光性樹脂転写材料、それらを用いたカラーフィルタ及び液晶表示装置
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