Classifications

• • 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
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • G—PHYSICS
  • G02—OPTICS
  • 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
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—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
• • 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
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/10—OLED displays
  • H10K59/12—Active-matrix OLED [AMOLED] displays
  • H10K59/122—Pixel-defining structures or layers, e.g. banks
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/114—Initiator containing

Definitions

• the present invention relates to a photosensitive colored resin composition.
• the present invention also relates to a cured product obtained by curing the photosensitive colored resin composition, partition walls formed of the cured product, and an image display device comprising the partition walls.
• An image display device including an organic electroluminescent element (also called organic electroluminescence or organic EL) has excellent visibility and responsiveness such as contrast and viewing angle, low power consumption, reduction in thickness and weight, and display main body. It is attracting attention as a next-generation flat panel display (FPD) because it can be made flexible.
• An organic electroluminescent element has a structure in which an organic layer including a light-emitting layer or various functional layers is sandwiched between a pair of electrodes, at least one of which is translucent. 2. Description of the Related Art
• An image display device displays an image by driving a panel in which an organic electroluminescence element is arranged for each pixel. Conventionally, such an organic electroluminescence device is manufactured by forming partition walls (banks) on a substrate and then laminating a light-emitting layer or various functional layers in a region surrounded by the partition walls.
• Patent Document 1 describes a photosensitive colored resin composition in which a specific organic pigment, a specific dispersant and a specific resin are combined.
• Patent Document 2 describes a photosensitive colored resin composition containing a specific resin and a specific initiator.
• Patent Document 3 describes a photosensitive colored resin composition in which two specific resins are combined.
• Patent Document 4 describes a photosensitive colored resin composition in which a specific resin and an organic pigment having a specific specific surface area are combined.
• the photosensitive colored resin composition When producing colored barrier ribs by photolithography, the photosensitive colored resin composition is coated on a substrate, dried under reduced pressure in a vacuum drying apparatus, then heated and dried on a hot plate, further image-exposed, and developed. It is cured by high temperature treatment.
• a vacuum drying apparatus In the above-described development process, depending on the combination of the developer and the photosensitive colored resin composition, film-like peeling occurs, causing problems such as clogging of the piping of the developing device.
• TMAH tetramethylammonium hydroxide
• the partition walls In order to suppress display defects of the image display device, the partition walls must have low surface roughness and excellent surface smoothness.
• the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive colored resin composition capable of forming a cured product excellent in development form and surface smoothness.
• An object of the present invention is to provide a cured product obtained by curing a photosensitive colored resin composition, partition walls formed from the cured product, and an image display device comprising the partition walls.
• the present inventors found that the above problems can be solved by including a specific alkali-soluble resin in the photosensitive colored resin composition, leading to the present invention.
• a photosensitive colored resin composition containing (a) an alkali-soluble resin, (b) a photopolymerization initiator, (c) an ethylenically unsaturated compound and (d) a coloring agent,
• the (a) alkali-soluble resin is characterized by containing an alkali-soluble resin (a1) having a cardo skeleton and an alkali-soluble resin (a2) having a partial structure represented by the following general formula (a2-1).
• a photosensitive colored resin composition containing an alkali-soluble resin, (b) a photopolymerization initiator, (c) an ethylenically unsaturated compound and (d) a coloring agent.
• the benzene ring in formula (a1-1) may be further substituted with any substituent.
• R 1 represents a hydrogen atom or a methyl group.
• X represents O, S, CO, or a direct bond.
• n represents an integer of 0 to 4 and * represents a bond.
• a photosensitive colored resin composition capable of forming a cured product having excellent development form and surface smoothness.
• it comprises a cured product with excellent development form and surface smoothness, partition walls formed from a cured product with excellent development form and surface smoothness, and partition walls formed from a cured product with excellent development form and surface smoothness.
• An image display device can be provided.
• (meth)acryl means “one or both of acryl and methacryl”.
• Total solid content means all components other than the solvent in the photosensitive colored resin composition. Even if a component other than the solvent is liquid at normal temperature, the component is not included in the solvent but is included in the total solid content.
• a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
• a partition wall material means a bank material, a wall material, and a wall material, and similarly, a partition wall means a bank, a wall, and a wall.
• a partition wall is for partitioning a functional layer (organic layer) in, for example, an active drive type organic electroluminescence device. It is used to form pixels and the like comprising a functional layer and partition walls by applying and drying by means of the above.
• the weight average molecular weight refers to the polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
• the acid value represents an acid value in terms of effective solid content, unless otherwise specified, and is calculated by neutralization titration.
• the photosensitive colored resin composition of the present invention is (a) an alkali-soluble resin (b) a photopolymerization initiator (c) an ethylenically unsaturated compound (d) a colorant, and optionally, for example, a dispersant, a pigment derivative, a surfactant, and a liquid repellent , ultraviolet absorbers, polymerization inhibitors, thermal polymerization initiators, amino compounds, silane coupling agents, inorganic fillers, adhesion improvers, and other compounding ingredients. Each compounding component is usually used in a state of being dissolved or dispersed in a solvent.
• the photosensitive colored resin composition of the present invention contains (a) an alkali-soluble resin.
• an alkali-soluble resin By containing an alkali-soluble resin, it becomes possible to develop with an alkali developer, and patterns such as partition walls can be formed.
• the (a) alkali-soluble resin in the photosensitive colored resin composition of the present invention includes an alkali-soluble resin (a1) having a cardo skeleton, and an alkali-soluble resin having a partial structure represented by the following general formula (a2-1) ( Contains a2).
• R 2 in formula (a2-1) represents a hydrogen atom or a methyl group. * represents a bond.
• the development form and surface smoothness during development are improved.
• alkali-soluble resin (a1) is not particularly limited as long as it contains a cardo skeleton, but from the viewpoint of surface smoothness, it preferably has a partial structure represented by the following general formula (a1-1). .
• the benzene ring in formula (a1-1) may be further substituted with any substituent.
• R 1 represents a hydrogen atom or a methyl group.
• X represents O, S, CO, or a direct bond.
• n represents an integer of 0 to 4, and * represents a bond.
• R 1 is preferably a hydrogen atom.
• X is preferably a direct bond from the viewpoint of surface smoothness.
• the benzene ring in formula (a1-1) may be unsubstituted or further substituted with any substituent.
• Optional substituents include, for example, a methyl group and a methoxy group. From the viewpoint of surface roughness, a methyl group is preferred.
• repeating unit structure represented by formula (a1-1) is preferably a repeating unit structure represented by general formula (a1-2) below.
• the benzene ring in formula (a1-2) may be unsubstituted or optionally substituted with any substituent.
• R 1 , X, n, and the optional substituents are the same as in formula (a1-1).
• R X1 , R X2 and R X3 each independently represent a hydrogen atom or a polybasic acid residue. * represents a bond.
• a polybasic acid residue means a monovalent group obtained by removing 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. Tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid.
• maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are preferred. is more preferred, and tetrahydrophthalic acid is even more preferred.
• the acid value of the alkali-soluble resin (a1) is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, still more preferably 60 mgKOH/g or more, even more preferably 80 mgKOH/g or more, and 100 mgKOH/g.
• the above are particularly preferred.
• it is preferably 150 mgKOH/g or less, more preferably 140 mgKOH/g or less, still more preferably 130 mgKOH/g or less, and even more preferably 120 mgKOH/g or less.
• the above upper and lower limits can be combined arbitrarily. For example, 20 to 150 mgKOH/g is preferred, 40 to 150 mgKOH/g is more preferred, 60 to 140 mgKOH/g is even more preferred, 80 to 130 mgKOH/g is even more preferred, and 100 to 120 mgKOH/g is particularly preferred.
• the weight average molecular weight (Mw) of the alkali-soluble resin (a1) is not particularly limited, it is preferably 1000 or more, more preferably 2000 or more, even more preferably 3000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more. Also, it is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 6,000 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily. For example, 1,000 to 20,000 is preferred, 2,000 to 15,000 is more preferred, 3,000 to 10,000 is even more preferred, 4,000 to 8,000 is even more preferred, and 5,000 to 6,000 is particularly preferred.
• the content of the alkali-soluble resin (a1) relative to the total amount of the alkali-soluble resin is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and even more preferably 40% by mass or more.
• 60% by mass or more is particularly preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, 75% by mass or less is even more preferable, and 70% by mass or less is particularly preferable.
• the surface smoothness tends to be improved by setting it to the above lower limit or more, and the developing form tends to be improved by setting it to the above upper limit or less.
• the above upper and lower limits can be combined arbitrarily. For example, 10 to 90% by mass is preferable, 20 to 80% by mass is more preferable, 40 to 75% by mass is even more preferable, and 60 to 70% by mass is particularly preferable.
• alkali-soluble resin (a2) The alkali-soluble resin (a2) in the photosensitive colored resin composition of the present invention has a partial structure represented by the following general formula (a2-1).
• R 2 in formula (a2-1) represents a hydrogen atom or a methyl group. * represents a bond.
• R 2 is preferably a methyl group from the viewpoint of reducing residues.
• repeating unit structure represented by formula (a2-1) is preferably a repeating unit structure represented by general formula (a2-2) below.
• R 2 in formula (a2-2) has the same definition as R 2 in formula (a2-1). * represents a bond. RY represents a hydrogen atom or a polybasic acid residue.
• Polybasic acid residue is synonymous with formula (a1-2).
• Examples of 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. Tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid.
• maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are preferred. is more preferred, and tetrahydrophthalic acid is even more preferred.
• the acid value of the alkali-soluble resin (a2) is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, still more preferably 60 mgKOH/g or more, even more preferably 80 mgKOH/g or more, and 90 mgKOH/g.
• the above are particularly preferred.
• it is preferably 150 mgKOH/g or less, more preferably 140 mgKOH/g or less, still more preferably 130 mgKOH/g or less, and even more preferably 120 mgKOH/g or less.
• the above upper and lower limits can be combined arbitrarily. For example, 20 to 150 mgKOH/g is preferred, 40 to 150 mgKOH/g is more preferred, 60 to 140 mgKOH/g is even more preferred, 80 to 130 mgKOH/g is even more preferred, and 90 to 120 mgKOH/g is particularly preferred.
• the weight average molecular weight (Mw) of the alkali-soluble resin (a2) is not particularly limited, it is preferably 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, even more preferably 2500 or more, and particularly preferably 3000 or more. Also, it is preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 6,000 or less, and particularly preferably 4,000 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily. For example, 1,000 to 20,000 is preferred, 1,500 to 15,000 is more preferred, 2,000 to 10,000 is even more preferred, 2,500 to 6,000 is even more preferred, and 3,000 to 4,000 is particularly preferred.
• the content of the alkali-soluble resin (a2) with respect to the total amount of the alkali-soluble resin is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and particularly preferably 30% by mass or more.
• the content is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass or less, and particularly preferably 40% by mass or less.
• the content is at least the above lower limit, the development pattern tends to be improved, and when the content is at most the above upper limit, the surface smoothness tends to be improved.
• the above upper and lower limits can be combined arbitrarily. For example, 10 to 90% by mass is preferable, 20 to 70% by mass is more preferable, 25 to 50% by mass is even more preferable, and 30 to 40% by mass is particularly preferable.
• the content ratio of the alkali-soluble resin (a2) to the alkali-soluble resin (a1) is not particularly limited, but is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, relative to 100 parts by mass of the alkali-soluble resin (a1). It is more preferably 30 parts by mass or more, preferably 300 parts by mass or less, more preferably 150 parts by mass or less, and even more preferably 100 parts by mass or less.
• the content is at least the above lower limit, the development pattern tends to be improved, and when the content is at most the above upper limit, the surface smoothness tends to be improved.
• the above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 300 parts by mass, more preferably 15 to 150 parts by mass, and even more preferably 30 to 100 parts by mass.
• the (a) alkali-soluble resin in the photosensitive colored resin composition of the present invention is an alkali-soluble resin other than the alkali-soluble resin (a1) and the alkali-soluble resin (a2) (hereinafter, sometimes referred to as "other alkali-soluble resin" There is.) may be contained.
• acrylic copolymer resin (A11) having an ethylenically unsaturated group in the side chain (hereinafter, sometimes abbreviated as "acrylic copolymer resin (A11)") .) is preferably included. From the viewpoint of the linearity of the pattern, it is preferable that the epoxy (meth)acrylate resin (A12) is included.
• the (a) alkali-soluble resin includes an acrylic copolymer resin (A11) and an epoxy (meth)acrylate resin (A12).
• Acrylic copolymer resin (A11) has an ethylenically unsaturated group in a side chain. By having an ethylenically unsaturated group, it is believed that photocuring by exposure occurs to form a stronger film, thermal deformation during post-baking after development is suppressed, and resolution is improved. In addition, since photocuring by exposure occurs to form a strong film, there is a tendency to reduce the residue generated when weakly hardenable portions in the film are scraped off during development and adhere to the substrate.
• the partial structure containing a side chain having an ethylenically unsaturated group, which the acrylic copolymer resin (A11) has, is not particularly limited. It preferably has a partial structure represented by (I).
• R 111 and R 112 each independently represent a hydrogen atom or a methyl group. * represents a bond.
• partial structures represented by formula (I) partial structures represented by the following general formula (I') are preferable from the viewpoint of sensitivity and alkali developability.
• R 111 and R 112 each independently represent a hydrogen atom or a methyl group.
• R x represents a hydrogen atom or a polybasic acid residue. * represents a bond.
• R x represents a hydrogen atom or a polybasic acid residue.
• a polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
• polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene. Tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid.
• maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and succinic acid are more preferred. preferable.
• the content ratio is not particularly limited, but 10 mol with respect to the total number of moles of the structural units of the acrylic copolymer resin (A11). % or more, more preferably 20 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, and preferably 90 mol% or less, 85 mol%
• 80 mol% or less is more preferable
• 75 mol% or less is even more preferable
• 70 mol% or less is particularly preferable.
• the content of the partial structure represented by formula (I) is preferably 10 to 90 mol%, preferably 20 to 85 mol. %, more preferably 30 to 80 mol %, even more preferably 40 to 75 mol %, and particularly preferably 50 to 70 mol %.
• the content is not particularly limited, but 10 mol% or more is preferable, 20 mol% or more is more preferable, 25 mol% or more is more preferable, 30 mol% or more is even more preferable, 35 mol% or more is particularly preferable, and 80 mol% or less is preferable, and 75 mol % or less, more preferably 70 mol % or less, and particularly preferably 65 mol % or less.
• the content is at least the above lower limit, the alkali developability tends to be improved, and when the content is at most the above upper limit, development adhesion tends to be easily ensured.
• the above upper and lower limits can be combined arbitrarily.
• the content of the partial structure represented by formula (I') is preferably 10 to 80 mol%, and 20 to 80 mol % is more preferred, 25 to 75 mol % is more preferred, 30 to 70 mol % is even more preferred, and 35 to 65 mol % is particularly preferred.
• R 113 represents a hydrogen atom or a methyl group
• R 114 represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or a substituent represents an alkenyl group which may be present.
• * represents a bond.
• R 114 represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group.
• the alkyl group for R 114 includes 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, It is more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less.
• the content is equal to or higher than the lower limit, the film strength tends to increase and the development adhesion tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 3-18, even more preferably 5-16, even more preferably 8-14, and particularly preferably 8-12.
• alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. 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, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group and carboxy group. , acryloyl group, and methacryloyl group. A hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.
• the aromatic ring group for R 114 includes monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic groups.
• the carbon number 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 aromatic ring group preferably has 6 to 24 carbon atoms, more preferably 6 to 22 carbon atoms, still more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 18 carbon atoms.
• the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
• Examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
• the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring, such as furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring and imidazole ring.
• oxadiazole ring indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, 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, azulene ring .
• a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.
• Substituents which the aromatic ring group may have include, for example, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group and epoxy group. , an oligoethylene glycol group, a phenyl group, and a carboxy group. A hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.
• Alkenyl groups for R 114 include linear, branched and cyclic alkenyl groups.
• the number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, even more preferably 16 or less, and 14 or less. is particularly preferred.
• the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
• the above upper and lower limits can be combined arbitrarily.
• the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 18 carbon atoms, even more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.
• Substituents that the alkenyl group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxy group. is mentioned.
• a hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.
• R 114 represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkenyl group, from the viewpoint of developability and film strength. , an alkyl group and an alkenyl group are preferred, and an alkyl group is more preferred.
• the content ratio is not particularly limited, but 1 mol with respect to the total number of moles of the structural units of the acrylic copolymer resin (A11) % or more, more preferably 5 mol% or more, more preferably 10 mol% or more, particularly preferably 20 mol% or more, and preferably 70 mol% or less, more preferably 60 mol% or less, and 50 mol% or less. is more preferable, and 40 mol % or less is particularly preferable.
• the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
• the acrylic copolymer resin (A11) contains the partial structure represented by formula (II), for example, the content of the partial structure represented by formula (II) is preferably 1 to 70 mol%, and 5 to 60 mol. %, more preferably 10 to 50 mol %, particularly preferably 20 to 40 mol %.
• R 115 represents a hydrogen atom or a methyl group
• R 116 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted represents an optionally substituted alkynyl group, a hydroxy group, a carboxy group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group.
• t represents an integer of 0 to 5; * represents a bond.
• R 116 is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxy group, a carboxy group, represents a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group.
• the alkyl group for R 116 includes 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, preferably 20 or less, more preferably 18 or less, It is more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less.
• the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 3-18, even more preferably 5-16, even more preferably 5-14, and particularly preferably 5-12.
• alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of developability and film strength, a dicyclopentanyl group and a dodecanyl group are preferred, and a dicyclopentanyl group is more preferred.
• Substituents that the alkyl group may have include, for example, 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, a methacryloyl group, and the like. A hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.
• Alkenyl groups for R 116 include linear, branched and cyclic alkenyl groups.
• the number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, even more preferably 16 or less, and 14 or less. is particularly preferred.
• the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
• the above upper and lower limits can be combined arbitrarily.
• the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 18 carbon atoms, even more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.
• Substituents that the alkenyl group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxy group. is mentioned.
• a hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.
• Alkynyl groups for R 116 include linear, branched and cyclic alkynyl groups.
• the number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, even more preferably 16 or less, and 14 or less. is particularly preferred.
• the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
• the above upper and lower limits can be combined arbitrarily.
• the alkynyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 18 carbon atoms, even more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.
• alkynyl group may have include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group and carboxy group. is mentioned.
• a hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.
• Halogen atoms for R 116 include, for example, fluorine, chlorine, bromine and iodine atoms.
• a fluorine atom is preferable from the viewpoint of resolution.
• the alkoxy group for R 116 includes linear, branched and cyclic alkoxy groups.
• the number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and 12 or less. is particularly preferred.
• the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
• the above upper and lower limits can be combined arbitrarily.
• the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 16 carbon atoms, even more preferably 1 to 14 carbon atoms, and particularly preferably 1 to 12 carbon atoms.
• Substituents that the alkoxy group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxy group. , acryloyl group, and methacryloyl group. A hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.
• the alkylsulfide group for R 116 includes linear, branched and cyclic alkylsulfide groups.
• the number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less.
• the alkylsulfide group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 16 carbon atoms, even more preferably 1 to 14 carbon atoms, and particularly preferably 1 to 12 carbon atoms.
• substituents that the alkyl group in the alkylsulfide group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl group, carboxy group, acryloyl group, and methacryloyl group.
• a hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.
• R 116 is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group; , a hydroxyalkyl group, a thiol group, or an optionally substituted alkylsulfide group, preferably a hydroxy group or a carboxy group, more preferably a carboxy group, from the viewpoint of developability.
• t represents an integer of 0 to 5, but t is preferably 0 from the viewpoint of ease of production.
• the content is not particularly limited, but it is 0.00 to the total number of moles of the structural units of the acrylic copolymer resin (A11). 5 mol % or more is preferable, 1 mol % or more is more preferable, and 2 mol % or more is even more preferable. Also, it is preferably 50 mol % or less, more preferably 30 mol % or less, even more preferably 20 mol % or less, still more preferably 10 mol % or less, and particularly preferably 5 mol % or less.
• the acrylic copolymer resin (A11) contains the partial structure represented by formula (III), for example, the content of the partial structure represented by formula (III) is preferably 0.5 to 50 mol %, and 0.5 to 50 mol %. 5 to 30 mol % is more preferable, 1 to 20 mol % is more preferable, 1 to 10 mol % is even more preferable, and 2 to 5 mol % is particularly preferable.
• R 117 represents a hydrogen atom or a methyl group. * represents a bond.
• the content ratio is not particularly limited, but 5 mol relative to the total number of moles of the structural units of the acrylic copolymer resin (A11) % or more, more preferably 10 mol % or more, still more preferably 20 mol % or more, preferably 80 mol % or less, more preferably 70 mol % or less, and even more preferably 60 mol % or less.
• the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the development adhesion tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the content of the partial structure represented by formula (IV) is preferably 5 to 80 mol%, and 10 to 70 mol. %, more preferably 20 to 60 mol %.
• the acid value of the acrylic copolymer resin (A11) is not particularly limited, but is preferably 30 mgKOH/g or more, more preferably 40 mgKOH/g or more, still more preferably 50 mgKOH/g or more, even more preferably 60 mgKOH/g or more, and 150 mgKOH/g or less is preferable, 140 mgKOH/g or less is more preferable, 130 mgKOH/g or less is still more preferable, and 120 mgKOH/g or less is even more preferable.
• the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the development adhesion tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the acid value of the acrylic copolymer resin (A11) is preferably 30-150 mgKOH/g, more preferably 40-140 mgKOH/g, even more preferably 50-130 mgKOH/g, and particularly preferably 60-120 mgKOH/g.
• the weight average molecular weight (Mw) of the acrylic copolymer resin (A11) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, still more preferably 4000 or more, even more preferably 6000 or more, and even more preferably 7000 or more. , 8000 or more is particularly preferable, 30000 or less is preferable, 20000 or less is more preferable, 15000 or less is more preferable, and 10000 or less is particularly preferable.
• the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the amount of residue tends to be reduced.
• the above upper and lower limits can be combined arbitrarily.
• the weight average molecular weight (Mw) of the acrylic copolymer resin (A11) is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, still more preferably 4,000 to 15,000, even more preferably 6,000 to 15,000, and preferably 7,000 to 10,000. More preferably, 8,000 to 10,000 is particularly preferred.
• the content of the acrylic copolymer resin (A11) with respect to the total amount of the alkali-soluble resin is not particularly limited, but is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and 10% by mass. % or more is particularly preferable, 70% by mass or less is preferable, 50% by mass or less is more preferable, 30% by mass or less is even more preferable, and 20% by mass or less is particularly preferable.
• the content is equal to or higher than the lower limit, there is a tendency for the amount of residue to be reduced, and when the content is equal to or lower than the upper limit, there is a tendency for adhesion to improve.
• the above upper and lower limits can be combined arbitrarily.
• the content of the acrylic copolymer resin (A11) contained in (a) the alkali-soluble resin is preferably 3 to 70% by mass, more preferably 5 to 50% by mass, even more preferably 8 to 30% by mass, and 10 to 20% by weight is particularly preferred.
• acrylic copolymer resin (A11) examples include, for example, the resins described in Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.
• Epoxy (meth)acrylate resin (A12) is obtained by adding an ethylenically unsaturated monocarboxylic acid or an ester compound to an epoxy resin, optionally reacting an isocyanate group-containing compound, and then reacting a polybasic acid or its anhydride. It is a resin that has been Among them, an epoxy (meth)acrylate resin having an aromatic ring in the main chain can be preferably used.
• ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin results in addition of an ethylenically unsaturated bond to the epoxy compound via an ester bond (-COO-),
• One carboxyl group of the polybasic acid anhydride is added to the hydroxyl group generated at that time.
• adding a polybasic acid anhydride the thing added by adding a polyhydric alcohol simultaneously is mentioned.
• a resin obtained by further reacting a compound having a reactive functional group with the carboxy group of the resin obtained by the above reaction is also included in the epoxy (meth)acrylate resin (A12).
• the epoxy (meth)acrylate resin has substantially no epoxy group due to its chemical structure, and is not limited to "(meth)acrylate", but an epoxy compound (epoxy resin) is a raw material. and "(meth)acrylate” is a typical example, so it is named in this way according to common practice.
• the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected and used from known epoxy resins.
• 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 divalent phenolic hydroxyl group, and may be a monomer or a polymer.
• bisphenol A epoxy resin bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolak epoxy resin, trisphenol epoxy resin, dihydroxylfluorene type epoxy resin
• examples include dihydroxylalkyleneoxylfluorene type epoxy resins and diglycidyl etherified products of 1,1-bis(4′-hydroxyphenyl)adamantane, and those having an aromatic ring in the main chain can be preferably used.
• epoxy resins include bisphenol A type epoxy resins (e.g., "jER (registered trademark, hereinafter the same) 828", “jER1001", “jER1002”, “jER1004" manufactured by Mitsubishi Chemical Corporation, manufactured by Nippon Kayaku Co., Ltd.).
• NER-1302 epoxy equivalent 323, softening point 76 ° C.
• bisphenol F type resin for example, Mitsubishi Chemical "jER807”, “jER4004P”, “jER4005P”, “jER4007P”, Nippon Kayaku "NER-7406” (epoxy equivalent 350, softening point 66 ° C.), etc.
• EOCN triglycidyl isocyanate Nurate
• TEPIC trisphenolmethane type epoxy resin
• EPPN-501 e.g., "EPPN-502”, “EPPN-503” manufactured by Nippon Kayaku Co., Ltd.
• alicyclic epoxy resin e.g., "Celoxide (registered trademark, hereinafter the same) 2021P” and “Celoxide EHPE” manufactured by Daicel
• a resin can be preferably used.
• NC-3000 manufactured by Nippon Kayaku Co., Ltd. can be mentioned as an epoxy resin represented by the following general formula (i-12).
• b is an average value and represents a number from 0 to 10.
• Each R 121 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R 121 in one molecule may be the same or different.
• X represents a linking group represented by general formula (i-13-1) or (i-13-2) below. However, it contains one or more adamantane structures in its molecular structure.
• c represents 2 or 3;
• R 131 to R 134 and R 135 to R 137 each independently represent an optionally substituted adamantyl group, a hydrogen atom, It represents an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group. * represents a bond.
• Examples of 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, penta Erythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate phthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydro 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, 4 - 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 their anhydrides.
• succinic anhydride succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferable, and succinic anhydride and tetrahydrophthalic anhydride are more preferable.
• the molecular weight of the epoxy (meth)acrylate resin (A12) can be increased, branching can be introduced into the molecule, and the molecular weight and viscosity can be improved. I tend to be able to strike a balance.
• the rate of introduction of acid groups into the molecule can be increased, and there is a tendency to easily balance sensitivity, adhesion, and the like.
• Preferred polyhydric alcohols include, for example, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol.
• epoxy (meth)acrylate resins examples include those described in Korean Patent Publication No. 10-2013-0022955, in addition to those described above.
• the acid value of the epoxy (meth)acrylate resin (A12) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 30 mgKOH/g or more, and even more preferably 40 mgKOH/g or more. Especially preferably 50 mgKOH/g or more, preferably 200 mgKOH/g or less, more preferably 180 mgKOH/g or less, still more preferably 150 mgKOH/g or less, even more preferably 120 mgKOH/g or less, and particularly preferably 110 mgKOH/g or less.
• the acid value of the epoxy (meth)acrylate resin (A12) is preferably 10 to 200 mgKOH/g, more preferably 20 to 180 mgKOH/g, still more preferably 30 to 150 mgKOH/g, even more preferably 40 to 120 mgKOH/g. , 50 to 110 mg KOH/g are particularly preferred.
• the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (A12) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, still more preferably 3000 or more, particularly preferably 3500 or more, and 30000 or less. It is preferably 15,000 or less, more preferably 10,000 or less, even more preferably 8,000 or less, and particularly preferably 6,000 or less.
• Mw weight average molecular weight
• the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (A12) is preferably 1,000 to 30,000, more preferably 2,000 to 15,000, still more preferably 3,000 to 10,000, even more preferably 3,500 to 8,000, and 3,500 to 6,000. is particularly preferred.
• the content of the epoxy (meth)acrylate resin (A12) relative to the total amount of (a) the alkali-soluble resin is not particularly limited, but is 3% by mass. is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 15% by mass or more, and preferably 90% by mass or less, more preferably 50% by mass or less, and 30% by mass or less. More preferred.
• the content is equal to or higher than the lower limit, there is a tendency to reduce the amount of residue, and when the content is equal to or lower than the upper limit, there is a tendency to improve the resolution.
• the above upper and lower limits can be combined arbitrarily. For example, 3 to 90% by mass is preferable, 5 to 90% by mass is more preferable, 10 to 50% by mass is even more preferable, and 15 to 30% by mass is particularly preferable.
• Epoxy (meth)acrylate resin (A12) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having the ethylenically unsaturated bond is added for addition reaction, and further polybasic acid or its A method of continuing the reaction by adding anhydride can be used. For example, the methods described in Japanese Patent No. 3938375 and Japanese Patent No. 5169422 can be mentioned.
• Examples of the organic solvent used for 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 catalysts include tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine; One or more of class ammonium salts, phosphorus compounds such as triphenylphosphine, stibines such as triphenylstibine, and the like can be used.
• Examples of thermal polymerization inhibitors include one or more of hydroquinone, hydroquinone monomethyl ether, and methylhydroquinone.
• 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, more preferably 0.9 to 1 chemical equivalent, with respect to 1 chemical equivalent of the epoxy group of the epoxy resin. .1 chemical equivalent.
• the temperature during the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C.
• the amount of the polybasic acid (anhydride) to be used is preferably 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.5 chemical equivalents, relative to 1 chemical equivalent of the hydroxyl group produced by the addition reaction. The amount can be set to 1 chemical equivalent.
• epoxy (meth)acrylate resins (A12) from the viewpoint of film strength and linearity, the following general formula (i), the following general formula (ii-1), the following general formula (ii-2), the following general formula ( Epoxy (meth)acrylate resins having at least one of the partial structures represented by iii) are preferred.
• R a represents a hydrogen atom or a methyl group.
• R b is an optionally substituted linear or branched divalent aliphatic group, an optionally substituted divalent aromatic cyclic group, or an optionally substituted It represents a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.
• the benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.
• each R c independently represents a hydrogen atom or a methyl group.
• R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
• n is an integer of 1 or more.
• the benzene ring in formula (ii-1) may be further substituted with any substituent.
• each R c independently represents a hydrogen atom or a methyl group.
• R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
• the benzene ring in formula (ii-2) may be further substituted with any substituent.
• R e represents a hydrogen atom or a methyl group.
• ⁇ represents a single bond, —CO—, an optionally substituted alkylene group, or an optionally substituted divalent cyclic hydrocarbon group.
• the benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.
• epoxy (meth)acrylate resin having a partial structure represented by the following general formula (i) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (A12-1)") will be described in detail.
• R a represents a hydrogen atom or a methyl group.
• R b is an optionally substituted linear or branched divalent aliphatic group, an optionally substituted divalent aromatic cyclic group, or an optionally substituted It represents a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.
• the benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.
• R b is an optionally substituted linear or branched divalent aliphatic group, an optionally substituted divalent aromatic cyclic group, or a substituted It represents a group in which one or more divalent aliphatic groups which may have a group and one or more divalent aromatic ring groups are linked.
• Divalent aliphatic groups include linear and branched aliphatic groups.
• the number of carbon atoms is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
• the film strength tends to be improved
• the resolution tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the number of carbon atoms in the divalent aliphatic group is preferably 1-20, more preferably 1-15, even more preferably 1-10.
• divalent linear aliphatic groups examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group and n-heptylene group.
• a methylene group is preferred from the viewpoint of resolution and production cost.
• the divalent branched aliphatic group includes, for example, the aforementioned divalent straight-chain aliphatic group, and side chains of methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. structures having a group, a sec-butyl group, and a tert-butyl group.
• substituents that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
• Divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups.
• the number of carbon atoms is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
• the divalent aromatic ring group preferably has 4 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.
• the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring.
• the divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
• the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring.
• divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences.
• substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of curability, non-substitution is preferred.
• one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring groups is linked to one or more.
• the number of divalent aliphatic groups is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
• the number of divalent aliphatic groups is preferably 1-10, more preferably 1-5, even more preferably 1-3.
• the number of divalent aromatic ring groups is not particularly limited, it is preferably 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less.
• the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the number of divalent aromatic ring groups is preferably 1-10, more preferably 1-5, even more preferably 1-3.
• groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked are represented by the following general formulas (iA) to (iF).
• group a group represented by the following general formula (iA) is preferable from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.
• the benzene ring in formula (i) may be further substituted with any substituent.
• Substituents include, for example, hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups.
• the number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.
• the partial structure represented by formula (i) is preferably a partial structure represented by the following general formula (i-1) from the viewpoint of development solubility.
• R a and R b have the same definitions as R a and R b in formula (i).
• R y represents a hydrogen atom or a polybasic acid residue. * represents a bond.
• the benzene ring in formula (i-1) may be further substituted with any substituent.
• ( Ry ) Ry represents a hydrogen atom or a polybasic acid residue.
• a polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
• polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene. Tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid.
• maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are preferred. is more preferred.
• the number of repeating unit structures represented by formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-1) may be one or two or more.
• the number of partial structures represented by formula (i) contained in one molecule of the epoxy (meth)acrylate resin (A12-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 3 or more. More preferably, 10 or less is preferable, and 8 or less is even more preferable.
• concentration is equal to or higher than the lower limit, the developability tends to be improved, and when the concentration is equal to or lower than the upper limit, the film strength tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the number of partial structures represented by formula (i) contained in one molecule of the epoxy (meth)acrylate resin (A12-1) is preferably 1 to 10, more preferably 2 to 8, and 3 to 8. More preferred.
• the number of partial structures represented by formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 3. Above is more preferable, 10 or less is preferable, and 8 or less is more preferable. When the concentration is equal to or higher than the lower limit, the developability tends to be improved, and when the concentration is equal to or lower than the upper limit, the film strength tends to be improved. The above upper and lower limits can be combined arbitrarily.
• the number of partial structures represented by formula (i-1) contained in one molecule of epoxy (meth)acrylate resin (A12-1) is preferably 1 to 10, more preferably 2 to 8, and 3 to 8 is more preferred.
• epoxy (meth)acrylate resin (A12-1) Specific examples of the epoxy (meth)acrylate resin (A12-1) are given below.
• epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii-1) and the epoxy (meth)acrylate resin having a partial structure represented by general formula (ii-2) are described in detail. do. (Hereinafter, both may be collectively referred to as "epoxy (meth)acrylate resin (A12-2)".)
• R c represents a hydrogen atom or a methyl group.
• R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
• n is an integer of 1 or more.
• the benzene ring in formula (ii-1) may be further substituted with any substituent.
• R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
• the monovalent cyclic hydrocarbon group for R ⁇ includes an aliphatic ring group and an aromatic ring group.
• the number of rings possessed by the aliphatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.
• the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the number of rings possessed by the aliphatic ring group is preferably 1-6, more preferably 1-4, still more preferably 1-3, and particularly preferably 2-3.
• the number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less.
• the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the number of carbon atoms in the aliphatic ring group is preferably 4-40, more preferably 4-30, still more preferably 6-20, and particularly preferably 8-15.
• Examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring.
• An adamantane ring is preferable from the viewpoint of compatibility between film strength and developability.
• the number of rings possessed by the aromatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 10 or less, more preferably 5 or less.
• the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the number of rings possessed by the aromatic ring group is preferably 1-10, more preferably 1-5, even more preferably 2-5.
• Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
• the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
• the number of carbon atoms in the aromatic ring group is preferably 4-30, more preferably 5-20, even more preferably 6-15.
• aromatic ring in the aromatic ring group examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and fluorene ring.
• a fluorene ring is preferable from the viewpoint of achieving both film strength and developability.
• Substituents that the cyclic hydrocarbon group may have include, for example, hydroxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, Alkyl groups having 1 to 5 carbon atoms such as amyl group and isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; and carboxy group. Unsubstituted is preferred from the viewpoint of ease of synthesis.
• n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less.
• concentration is equal to or higher than the lower limit, the developability tends to be improved, and when the concentration is equal to or lower than the upper limit, the film strength tends to be improved.
• n is preferably an integer of 1 or more and 3 or less, more preferably an integer of 2 or more and 3 or less.
• R ⁇ is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group.
• the benzene ring in formula (ii-1) may be further substituted with any substituent.
• Substituents include, for example, hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups.
• the number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.
• R c represents a hydrogen atom or a methyl group.
• R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
• the benzene ring in formula (ii-2) may be further substituted with any substituent.
• R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
• the divalent cyclic hydrocarbon group for R ⁇ includes a divalent aliphatic cyclic group and a divalent aromatic cyclic group.
• the number of rings possessed by the divalent aliphatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less.
• the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the number of rings possessed by the divalent aliphatic cyclic group is preferably 1-10, more preferably 1-5, even more preferably 2-5.
• the number of carbon atoms in the divalent aliphatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less.
• the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the divalent aliphatic cyclic group preferably has 4 to 40 carbon atoms, more preferably 6 to 35 carbon atoms, and even more preferably 8 to 30 carbon atoms.
• Examples of the aliphatic ring in the divalent aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring.
• An adamantane ring is preferable from the viewpoint of compatibility between film strength and developability.
• the number of rings possessed by the divalent aromatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 10 or less, more preferably 5 or less.
• the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the number of rings possessed by the divalent aromatic ring group is preferably 1-10, more preferably 1-5, still more preferably 2-5, and particularly preferably 3-5.
• Divalent aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
• the number of carbon atoms in the divalent aromatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, particularly preferably 10 or more, preferably 40 or less, more preferably 30 or less, and 20 The following is more preferable, and 15 or less is particularly preferable.
• the divalent aromatic ring group preferably has 4 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, still more preferably 8 to 20 carbon atoms, and particularly preferably 10 to 15 carbon atoms.
• aromatic ring in the divalent aromatic ring group examples include benzene ring, naphthalene ring, anthracene ring, and phenanthrene ring.
• a benzene ring is preferred from the viewpoint of film strength and developability.
• Substituents which the divalent cyclic hydrocarbon group may have include a hydroxy group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. , an amyl group, an isoamyl group, and other C1-5 alkyl groups; a C1-5 alkoxy group, such as a methoxy group and an ethoxy group; a nitro group; a cyano group; and a carboxy group. Unsubstituted is preferred from the viewpoint of ease of synthesis.
• R ⁇ is preferably a divalent aliphatic cyclic group, more preferably a divalent adamantane cyclic group.
• the benzene ring in formula (ii-2) may be further substituted with any substituent.
• Substituents include, for example, hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups.
• the number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.
• the partial structure represented by formula (ii-1) is preferably a partial structure represented by general formula (ii-3) below.
• R c , R ⁇ and n have the same meanings as in formula (ii-1) above.
• R z1 and R z2 each independently represent a hydrogen atom or a polybasic acid residue.
• the partial structure represented by formula (ii-2) is preferably a partial structure represented by general formula (ii-4) below.
• R c and R ⁇ have the same definitions as R c and R ⁇ in formula (ii-2).
• R v1 and R v2 each independently represent a hydrogen atom or a polybasic acid residue.
• a polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
• polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene. Tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid.
• maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are preferred. is more preferred.
• the partial structure may be of one type or two or more types.
• the number of partial structures represented by formula (ii-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and , is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
• the resolution tends to improve
• the content is at the upper limit or less
• the developability tends to improve.
• the above upper and lower limits can be combined arbitrarily.
• the number of partial structures represented by formula (ii-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 to 10 is more preferred.
• the number of partial structures represented by formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and , is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
• the resolution tends to improve
• the content is at the upper limit or less
• the developability tends to improve.
• the above upper and lower limits can be combined arbitrarily.
• the number of partial structures represented by formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 to 10 is more preferred.
• the number of partial structures represented by formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and , is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
• the resolution tends to improve
• the content is at the upper limit or less
• the developability tends to improve.
• the above upper and lower limits can be combined arbitrarily.
• the number of partial structures represented by formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 to 10 is more preferred.
• the number of partial structures represented by formula (ii-4) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and , is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
• the resolution tends to improve
• the content is at the upper limit or less
• the developability tends to improve.
• the above upper and lower limits can be combined arbitrarily.
• the number of partial structures represented by formula (ii-4) contained in one molecule of the epoxy (meth)acrylate resin (A12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 to 10 is more preferred.
• epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (A12-3)") will be described in detail. .
• R e represents a hydrogen atom or a methyl group.
• ⁇ represents a single bond, —CO—, an optionally substituted alkylene group, or an optionally substituted divalent cyclic hydrocarbon group.
• the benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.
• ⁇ represents a single bond, —CO—, an optionally substituted alkylene group, or an optionally substituted divalent cyclic hydrocarbon group.
• the alkylene group in ⁇ may be linear or branched, preferably linear from the viewpoint of development solubility, and preferably branched from the viewpoint of development adhesion.
• the number of carbon atoms is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, and more preferably 4 or less.
• the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the number of carbon atoms in the alkylene group is preferably 1-6, more preferably 1-4, even more preferably 2-4.
• alkylene groups examples include methylene, ethylene, propylene, butylene, hexylene, and heptylene groups. From the viewpoint of achieving both film strength and developability, an ethylene group and a propylene group are preferred, and a propylene group is more preferred.
• substituents that the alkylene group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
• the divalent cyclic hydrocarbon group for ⁇ includes a divalent aliphatic ring group and a divalent aromatic ring group.
• the number of rings possessed by the divalent aliphatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less.
• the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the number of rings possessed by the divalent aliphatic cyclic group is preferably 1-10, more preferably 1-5, even more preferably 2-5.
• the number of carbon atoms in the divalent aliphatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less.
• the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the divalent aliphatic cyclic group preferably has 4 to 40 carbon atoms, more preferably 6 to 35 carbon atoms, and even more preferably 8 to 30 carbon atoms.
• Examples of the aliphatic ring in the divalent aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring.
• An adamantane ring is preferable from the viewpoint of compatibility between film strength and developability.
• the number of rings possessed by the divalent aromatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 10 or less, more preferably 5 or less.
• the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the number of rings possessed by the divalent aromatic ring group is preferably 1-10, more preferably 1-5, still more preferably 2-5, and particularly preferably 3-5.
• the divalent aromatic ring group includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
• the number of carbon atoms in the divalent aromatic ring group is preferably 4 or more, more preferably 6 or more, more preferably 8 or more, particularly preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and 20 or less. More preferably, 15 or less is particularly preferable.
• the divalent aromatic ring group preferably has 4 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, still more preferably 8 to 20 carbon atoms, and particularly preferably 10 to 15 carbon atoms.
• aromatic ring in the divalent aromatic ring group examples include benzene ring, naphthalene ring, anthracene ring, and phenanthrene ring.
• a benzene ring is preferred from the viewpoint of achieving both film strength and developability.
• Substituents that the divalent cyclic hydrocarbon group may have include, for example, hydroxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- C1-5 alkyl groups such as butyl group, amyl group and isoamyl group; C1-5 alkoxy groups such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; Unsubstituted is preferred from the viewpoint of ease of synthesis.
• ⁇ is preferably an optionally substituted alkylene group, more preferably a dimethylmethylene group.
• the benzene ring in formula (iii) may be further substituted with any substituent.
• Substituents include, for example, hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups.
• the number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.
• the partial structure represented by formula (iii) is preferably a partial structure represented by the following general formula (iii-1) from the viewpoint of development solubility.
• R e and ⁇ have the same definitions as R e and ⁇ in formula (iii) above.
• R W represents a hydrogen atom or a polybasic acid residue. * represents a bond.
• the benzene ring in formula (iii-1) may be further substituted with any substituent.
• a polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
• polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene. Tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid.
• maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are preferred. is more preferred.
• the number of repeating unit structures represented by formula (iii) contained in one molecule of the epoxy (meth)acrylate resin (A12-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and 10 or more. is more preferred, 18 or less is preferred, and 15 or less is even more preferred.
• the resolution tends to improve
• the content is at the upper limit or less, the developability tends to improve.
• the above upper and lower limits can be combined arbitrarily.
• the number of repeating unit structures represented by the formula (iii) contained in one molecule of the epoxy (meth)acrylate resin (A12-3) is preferably 1 to 18, more preferably 5 to 15, and 10 to 15 is more preferred.
• the number of repeating unit structures represented by formula (iii-1) contained in one molecule of the poxy(meth)acrylate resin (A12-3) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, 5 or more is more preferable, 18 or less is preferable, and 15 or less is more preferable.
• the resolution tends to improve
• the content is at the upper limit or less, the developability tends to improve.
• the above upper and lower limits can be combined arbitrarily.
• the number of repeating unit structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-3) is preferably 1 to 18, more preferably 3 to 15, 5 to 15 are more preferred.
• epoxy (meth)acrylate resin (A12-3) Specific examples of the epoxy (meth)acrylate resin (A12-3) are given below.
• the content of (a) the alkali-soluble resin in the photosensitive colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, and 10% by mass, based on the total solid content of the photosensitive colored resin composition. 20% by mass or more is more preferable, 30% by mass or more is even more preferable, 40% by mass or more is particularly preferable, 50% by mass or more is particularly preferable, and 90% by mass or less is preferable, and 80% by mass % or less is more preferable, and 70% by mass or less is even more preferable.
• the content is equal to or higher than the lower limit, the resolution tends to be improved, and when the content is equal to or lower than the upper limit, the surface hardness tends to be improved.
• the content of (a) alkali-soluble resin relative to the total solid content of the photosensitive colored resin composition is preferably 5 to 90% by mass, more preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and 30 ⁇ 80% by mass is more preferable, 40 to 70% by mass is particularly preferable, and 50 to 70% by mass is particularly preferable.
• the total content of (c) ethylenically unsaturated compound and (a) alkali-soluble resin relative to the total solid content of the photosensitive colored resin composition is not particularly limited, but is preferably 10% by mass or more, and 30% by mass. % or more, more preferably 50% by mass or more, particularly preferably 60% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and 75% by mass. More preferred are: Adhesion tends to be improved by making it equal to or higher than the lower limit, and the shape of the partition wall tends to be improved by making it equal to or lower than the upper limit. The above upper and lower limits can be combined arbitrarily.
• the sum of the content ratio of (c) ethylenically unsaturated compound and the content ratio of (a) alkali-soluble resin with respect to the total solid content of the photosensitive colored resin composition is preferably 10 to 90% by mass, and 30 to 80% by mass. is more preferable, 50 to 80% by mass is more preferable, and 60 to 75% by mass is particularly preferable.
• the photosensitive colored resin composition of the present invention contains (b) a photopolymerization initiator.
• the photopolymerization initiator is a component that has the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating polymerization active radicals. If necessary, in addition to the photopolymerization initiator (b), additives such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may be added for use.
• the photosensitive colored resin composition of the present invention can use a photopolymerization initiator commonly used in this field as (b) the photopolymerization initiator.
• photopolymerization initiators include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; JP-A-2000-56118. Hexaarylbiimidazole derivatives described in JP-A-10-39503; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-aryl- ⁇ -amino acids such as N-phenylglycine described in JP-A-10-39503.
• N-aryl- ⁇ -amino acid salts radical activators such as N-aryl- ⁇ -amino acid esters, ⁇ -aminoalkylphenone derivatives; Examples thereof include oxime ester compounds described in publications and the like.
• Titanocene derivatives include, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl), dicyclo Pentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di(2,6- difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl) titanium bis(2,3,4,5,6-pentafluorophenyl), di(methylcyclo pentadienyl) titanium bis(2,6-difluorophenyl), dicyclopentadienyl titanium [2,6-di-fluoro-3-(pyro-1-
• Biimidazole derivatives include, for example, 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, 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-triazines.
• ⁇ -aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate -, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4 -diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone.
• an oxime ester compound As a photopolymerization initiator, an oxime ester compound is effective in terms of sensitivity and plate-making properties. In the case of using an alkali-soluble resin containing a phenolic hydroxyl group, the sensitivity is disadvantageous, so an oxime ester compound having excellent sensitivity is particularly useful.
• Oxime ester compounds have a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals. Since the activity of is high, it is possible to obtain a photosensitive colored resin composition which is highly sensitive and stable against thermal reaction, and which is highly sensitive even in a small amount.
• oxime ester compounds examples include compounds represented by the following general formula (b1).
• R 21a represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group.
• R 21b represents any substituent containing an aromatic ring.
• R 22a represents an optionally substituted alkanoyl group or an optionally substituted aryloyl group.
• n represents an integer of 0 or 1;
• R 21a represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group.
• the number of carbon atoms in the alkyl group in R 21a 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, and 10. More preferred are: Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl and cyclohexylethyl groups.
• the aromatic ring group for R 21a includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
• the number of carbon atoms in the aromatic ring group is not particularly limited, it is preferably 5 or more from the viewpoint of solubility in the photosensitive colored resin composition. 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 combined arbitrarily.
• the number of carbon atoms in the aromatic ring group is preferably 5-30, more preferably 5-20, even more preferably 5-12.
• aromatic ring groups examples include phenyl, naphthyl, pyridyl and furyl groups. From the viewpoint of developability, a phenyl group and a naphthyl group are preferred, and a phenyl group is more preferred.
• substituents that the aromatic ring group may have include hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amido groups, alkyl groups, alkoxy groups, and groups in which these substituents are linked. From the viewpoint of developability, an alkyl group, an alkoxy group, or a group in which these are linked is preferable, and a linked alkoxy group is more preferable.
• R 21b represents any substituent containing an aromatic ring.
• R 21b is preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted fluorenyl group, an optionally substituted diphenylsulfide group, an optionally substituted A fluorenyl group or an optionally substituted indolyl group can be mentioned.
• An optionally substituted carbazolyl group is preferred from the viewpoint of sensitivity.
• R 22a represents an optionally substituted alkanoyl group or an optionally substituted aryloyl group.
• the number of carbon atoms in the alkanoyl group in R 22a 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, and 10. The following are more preferable, and 5 or less are particularly preferable.
• Alkanoyl groups include, for example, an acetyl group, an ethyloyl group, a propanoyl group, and a butanoyl group.
• alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
• the number of carbon atoms in the aryloyl group in R 22a is not particularly limited, it is preferably 7 or more, preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less, from the viewpoint of solubility in solvents and sensitivity.
• the aryloyl group includes, for example, a benzoyl group and a naphthoyl group.
• substituents that the aryloyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
• R 22a is preferably an optionally substituted alkanoyl group, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
• Photopolymerization initiators may be used singly or in combination of two or more.
• the photopolymerization initiator may optionally contain a sensitizing dye and a polymerization accelerator suitable for the wavelength of the image exposure light source for the purpose of increasing sensitivity.
• sensitizing dyes include the xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703 and JP-A-5-289335. JP-A-3-239703, 3-ketocoumarin compounds described in JP-A-5-289335, and JP-A-6-19240.
• pyrromethene dye, and others Japanese Patent Laid-Open Publication No. 47-2528, Japanese Patent Laid-Open Publication No. 54-155292, Japanese Patent Publication No.
• Japanese Patent Laid-Open Publication No. 48-84183 Japan Japanese Unexamined Patent Publication No. 52-112681, Japanese Unexamined Patent Publication No. 58-15503, Japanese Unexamined Patent Publication No. 60-88005, Japanese Unexamined Patent Publication No. 59-56403, Japanese Unexamined Patent Publication No. 2-69 JP, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. can be mentioned.
• an amino group-containing sensitizing dye is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable.
• 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3,4-diamino Benzophenone compounds such as benzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2- (p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1
• polymerization accelerators examples include aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, and n-butylamine. , N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate are used.
• a polymerization accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.
• a chain transfer agent may be used in combination with the photopolymerization initiator.
• chain transfer agents include mercapto group-containing compounds and carbon tetrachloride.
• a mercapto group-containing compound is more preferable because it tends to have a high chain transfer effect. It is believed that this is because bond cleavage is likely to occur due to the small SH bond energy, and hydrogen abstraction reaction and chain transfer reaction are likely to occur, which is effective in improving sensitivity and surface curability.
• Mercapto group-containing compounds include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, ⁇ - Mercapto group-containing compounds having an aromatic ring such as mercaptonaphthalene and 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, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis (3-mercaptoprop
• 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and among aliphatic mercapto group-containing compounds, 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 are preferred.
• a chain transfer agent may be used individually by 1 type, or may be used in combination of 2 or more type.
• the chain transfer agent from the viewpoint of increasing the taper angle, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and a photopolymerization initiator. It is preferred to use them in combination as a photoinitiator system.
• 2-mercaptobenzothiazole may be used
• 2-mercaptobenzimidazole may be used
• 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 photopolymerization initiator (b) in the photosensitive colored resin composition of the present invention is not particularly limited, but the total solid content of the photosensitive colored resin composition is preferably 0.01% by mass or more, and 0 .1% by mass or more is more preferable, 1% by mass or more is more preferable, 2% by mass or more is even more preferable, 3% by mass or more is particularly preferable, 25% by mass or less is preferable, and 20% by mass or less is more preferable. % by mass or less is more preferable, 10% by mass or less is even more preferable, 7% by mass or less is particularly preferable, and 5% by mass or less is particularly preferable.
• the surface smoothness tends to be improved by making it equal to or higher than the lower limit, and the resolution tends to be improved by making it equal to or lower than the upper limit.
• the above upper and lower limits can be combined arbitrarily. For example, 0.01 to 25% by mass is preferable, 0.01 to 20% by mass is more preferable, 0.1 to 15% by mass is more preferable, 1 to 10% by mass is even more preferable, and 2 to 7% by mass is More preferably, 3 to 5% by mass is particularly preferable.
• the mixing ratio of the (b) photopolymerization initiator to the (c) ethylenically unsaturated compound in the photosensitive colored resin composition is 5 parts by mass or more with respect to 100 parts by mass of the (c) ethylenically unsaturated compound.
• 10 parts by mass or more is more preferable, 20 parts by mass or more is more preferable, 25 parts by mass or more is even more preferable, 30 parts by mass or more is particularly preferable, and 200 parts by mass or less is preferable, and 100 parts by mass or less is more preferable. It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less.
• the surface smoothness tends to be improved by making it equal to or higher than the lower limit, and the resolution tends to improve by making it equal to or lower than the upper limit.
• the above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, even more preferably 20 to 100 parts by mass, even more preferably 25 to 50 parts by mass, and particularly preferably 30 to 40 parts by mass.
• the photosensitive colored resin composition of the present invention contains (c) an ethylenically unsaturated compound. (c) It is thought that the inclusion of the ethylenically unsaturated compound increases the curability of the coating film and improves the adhesion.
• the ethylenically unsaturated compound means a compound having one or more ethylenically unsaturated bonds in the molecule, and expands the difference in polymerizability, crosslinkability, and accompanying developer solubility between exposed and unexposed areas.
• a compound having two or more ethylenically unsaturated bonds in the molecule is preferred because it can be used.
• the unsaturated bond is preferably derived from a (meth)acryloyloxy group, that is, the ethylenically unsaturated compound is preferably a (meth)acrylate compound.
• the ethylenically unsaturated compound it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule.
• the number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and preferably 15 or less, more preferably 10. Below, more preferably 8 or less, particularly preferably 6 or less.
• the content is at least the lower limit, the surface smoothness tends to improve, and when the content is at most the upper limit, the developability tends to be better.
• the above upper and lower limits can be combined arbitrarily.
• the number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is preferably 2 to 15, more preferably 2 to 10, still more preferably 2 to 8, even more preferably 3 to 8. , 3 to 6 are particularly preferred.
• Ethylenically unsaturated compounds include, for example, 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. and esters obtained by an esterification reaction of polyhydric hydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.
• esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
• pentaerythritol tetraacrylate dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate
• acrylic acid esters of aliphatic polyhydroxy compounds such as glycerol acrylate, methacrylic acid esters obtained by replacing these acrylates with methacrylates
• methacrylic acid esters obtained by replacing these acrylates with methacrylates examples include itaconic acid esters obtained by replacing these acrylates with itaconates, crotonic acid esters obtained by replacing these acrylates with crotonates, and maleic acid esters obtained by replacing these acrylates with maleates.
• Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacryl esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. acid esters. Esters obtained by the esterification reaction of polyvalent hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single substances, but are representative.
• condensates of acrylic acid, phthalic acid and ethylene glycol condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid and adipic acid.
• condensates of butanediol and glycerin condensates of butanediol and glycerin.
• polyfunctional ethylenic monomer used in the present invention include, for example, a reaction of a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester.
• urethane (meth)acrylates such as those obtained by exfoliation
• epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxy (meth)acrylate or (meth)acrylic acid
• acrylamides such as ethylenebisacrylamide
• allyl esters such as diallyl acid
• vinyl group-containing compounds such as divinyl phthalate.
• Urethane (meth)acrylates include, for example, 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, Examples include UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).
• esters or urethane (meth)acrylates of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid as the (c) ethylenically unsaturated compound, trimethylolpropane triacrylate, Dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2,2,2-tris(meth)acryloyloxymethylethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth) It is more preferable to use an acrylate, a dibasic anhydride adduct of dipentaerythritol penta(meth)acrylate, or a dibasic anhydride adduct of pentaerythritol tri(meth)acrylate.
• the molecular weight of (c) the ethylenically unsaturated compound is not particularly limited, but from the viewpoint of resolution, it is preferably 100 or more, more preferably 150 or more, still more preferably 200 or more, and still more preferably 300 or more. , particularly preferably 400 or more, most preferably 500 or more, and preferably 1000 or less, more preferably 700 or less.
• the above upper and lower limits can be combined arbitrarily.
• the molecular weight of the (c) ethylenically unsaturated compound is preferably 100 to 1000, more preferably 150 to 1000, still more preferably 200 to 1000, even more preferably 300 to 700, even more preferably 400 to 700, particularly preferably 500 to 700 is particularly preferred.
• the number of carbon atoms in the ethylenically unsaturated compound is not particularly limited, but from the viewpoint of resolution, it is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, and more preferably 50 or less. is 40 or less, more preferably 30 or less, and particularly preferably 20 or less.
• the above upper and lower limits can be combined arbitrarily.
• the (c) ethylenically unsaturated compound preferably has 7 to 50 carbon atoms, more preferably 10 to 40 carbon atoms, still more preferably 15 to 30 carbon atoms, and even more preferably 15 to 20 carbon atoms.
• the content of the (c) ethylenically unsaturated compound in the photosensitive colored resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more with respect to the total solid content of the photosensitive colored resin composition, 5% by mass or more is more preferable, 8% by mass or more is more preferable, 12% by mass or more is particularly preferable, 80% by mass or less is preferable, 60% by mass or less is more preferable, and 40% by mass or less is even more preferable. % by mass or less is particularly preferred.
• the content is at least the lower limit, the surface smoothness tends to be improved, and when the content is at most the upper limit, the developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the content of the (c) ethylenically unsaturated compound relative to the total solid content of the photosensitive colored resin composition is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and even more preferably 8 to 40% by mass. , 12 to 20% by weight are particularly preferred.
• the content ratio of the ethylenically unsaturated compound (c) to 100 parts by mass of the alkali-soluble resin is not particularly limited, but is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more. More preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, preferably 150 parts by mass or less, more preferably 100 parts by mass or less, further preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less , 40 parts by mass or less is particularly preferred.
• the content is at least the lower limit, the surface smoothness tends to be good, and when the content is at most the upper limit, the developability tends to be good.
• the content ratio of (c) ethylenically unsaturated compound to 100 parts by mass of (a) alkali-soluble resin is preferably 1 to 150 parts by mass, more preferably 5 to 100 parts by mass, further preferably 10 to 70 parts by mass, 15 to 50 parts by mass is more preferable, and 20 to 40 parts by mass is particularly preferable.
• the photosensitive colored resin composition of the present invention contains (d) a colorant.
• a coloring agent By containing a coloring agent, it is possible to obtain an appropriate light-absorbing property, particularly an appropriate light-shielding property when used for forming a light-shielding member such as a colored partition wall.
• the content of the coloring agent is not particularly limited, but from the viewpoint of light-shielding properties, it is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content of the photosensitive colored resin composition. 20% by mass or more is more preferable, and 25% by mass or more is particularly preferable. From the viewpoint of surface smoothness and developability, it is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 35% by mass or less, and particularly preferably 30% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 60% by mass is preferable, 5 to 50% by mass is more preferable, 10 to 40% by mass is more preferable, 20 to 35% by mass is even more preferable, and 25 to 30% by mass is particularly preferable.
• the coloring agent is not particularly limited, but from the viewpoint of dielectric constant and resolution, it is preferable to contain an organic pigment.
• organic pigment is not particularly limited, but from the viewpoint of light-shielding properties, organic black pigments and organic coloring pigments are preferable, and organic black pigments are more preferable.
• the organic coloring pigment means an organic pigment exhibiting a color other than black, and examples thereof include red pigment, orange pigment, blue pigment, purple pigment, green pigment, and yellow pigment.
• the organic coloring pigments may be used singly or in combination of two or more.
• the chemical structure of the organic pigment is not particularly limited, examples thereof include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments. Specific examples of pigments that can be used are shown below by pigment number. In the following, terms such as "C.I. Pigment Red 2" refer to the Color Index (C.I.).
• red pigments examples include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200
• C.I. I. Pigment Red 48 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 may be mentioned.
• C.I. I. Pigment Red 177, 254, 272 is preferably used, and when the photosensitive colored resin composition is cured with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate. . I. Pigment Red 254, 272 is more preferably used.
• an orange (orange) pigment for example, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned.
• C.I. I. Pigment Orange 13, 43, 64, 72 is preferably used, and when the photosensitive colored resin composition is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate.
• C.I. I. Pigment Orange 64 and 72 are more preferred, and C.I. I. Pigment Orange 64 is more preferably used.
• blue pigments examples include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. From the viewpoint of light-shielding properties, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, more preferably C.I. I. Pigment Blue 15:6 may be mentioned. C.I. I.
• Pigment Blue 15:6, 16, 60 is preferably used, and when the photosensitive colored resin composition is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. is C.I. I. Pigment Blue 60 is more preferably used.
• Examples of purple pigments include C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned. From the viewpoint of light-shielding properties, C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 may be mentioned. C.I. I. Pigment Violet 23, 29 is preferably used, and when the photosensitive colored resin composition is cured with ultraviolet rays, it is preferable to use a purple pigment having a low ultraviolet absorption rate. I. Pigment Violet 29 is more preferably used.
• organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and violet pigments include green pigments and yellow pigments.
• green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 can be mentioned.
• C.I. I. Pigment Green 7, 36 can be mentioned.
• yellow pigments include C.I. I.
• C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.
• Red pigment C.I. I. Pigment Red 177, 254, 272
• Orange pigment C.I. I. Pigment Orange 43, 64, 72
• Blue pigment C.I. I. pigment blue 15:6,60 Purple pigment: C.I. I. Pigment Violet 23, 29
• the organic black pigment is not particularly limited, but from the viewpoint of light-shielding properties, a compound represented by the following general formula (1) (hereinafter also referred to as “compound (1)”), and geometric isomerism of compound (1) an organic black pigment containing at least one selected from the group consisting of isomers, salts of compound (1), and salts of geometric isomers of compound (1) (hereinafter referred to as “organic black pigment represented by general formula (1) ) is preferably used.
• R 11 and R 16 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom, or a chlorine atom;
• compound (1) When compound (1) is anionic, its charge can be transferred to any known suitable cation such as metallic, organic, inorganic or metal-organic cations, particularly alkali metals, alkaline earth metals, transition metals, primary ammonium , secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium or a salt compensated by an organometallic complex. When the geometric isomers of compound (1) are anionic, similar salts are preferred.
• suitable cation such as metallic, organic, inorganic or metal-organic cations, particularly alkali metals, alkaline earth metals, transition metals, primary ammonium , secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium or a salt compensated by an organometallic complex.
• suitable cation such as metallic, organic, inorgan
• R 12 , R 14 , R 15 , R 17 , R 19 and R 20 are each independently preferably hydrogen, fluorine or chlorine, more preferably hydrogen.
• R 13 and R 18 are each independently preferably hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N(CH 3 ) 2 , N(CH 3 ) (C 2 H 5 ), N(C 2 H 5 ) 2 , ⁇ -naphthyl, ⁇ -naphthyl, SO 3 H, or SO 3 - , more preferably a hydrogen atom or SO 3 H, especially A hydrogen atom is preferred.
• R 11 and R 16 are each independently preferably a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.
• at least one combination selected from the group consisting of R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 is the same, more preferably is the same as R 16 , R 12 is the same as R 17 , R 13 is the same as R 18 , R 14 is the same as R 19 , and R 15 is the same as R 20 are identical.
• Alkyl groups having 1 to 12 carbon atoms are, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n -pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group and dodecyl group.
• Cycloalkyl groups having 3 to 12 carbon atoms are, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, thuzyl, norbornyl, bornyl and norcalyl groups. , karyl group, menthyl group, norpinyl group, pinyl group, adamantan-1-yl group and adamantan-2-yl group.
• Alkenyl groups having 2 to 12 carbon atoms are, for example, vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 1,3-butadiene -2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-methyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, 3-methyl-2-buten-1-yl group, 1,4-pentadien-3-yl group, hexenyl group, octenyl group, nonenyl group, decenyl group and dodecenyl group.
• Cycloalkenyl groups having 3 to 12 carbon atoms are, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2 , 4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4(10)-thugen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -yl group, 7,7-dimethyl-2,4-norcaladien-3-yl group, and camphenyl group.
• Alkynyl groups having 2 to 12 carbon atoms are, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl group, 1,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, 1-decyn-10-yl group and 1-dodecyn-12-yl group.
• a halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
• the organic black pigment represented by formula (1) is preferably a compound represented by the following general formula (2) (hereinafter also referred to as "compound (2)”), and a geometric isomer of compound (2)
• compound (2) a compound represented by the following general formula (2)
• organic black pigment is Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
• This organic black pigment is preferably used by dispersing it with a dispersant, solvent, and method, which will be described later.
• a sulfonic acid derivative of compound (1) particularly a sulfonic acid derivative of compound (2), is present during dispersion, the dispersibility and storage stability may be improved. It is preferred to include
• organic black pigments other than the organic black pigment represented by formula (1) include aniline black and perylene black.
• Inorganic pigments may be contained in addition to these organic pigments.
• As an inorganic pigment it is preferable to contain an inorganic black pigment from a light-shielding viewpoint.
• inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black.
• carbon black can be preferably used from the viewpoint of light shielding properties and image characteristics.
• examples of carbon black include the following carbon blacks.
• Carbon black that is coated with resin may be used.
• the use of resin-coated carbon black has the effect of improving the adhesion to the glass substrate and the volume resistivity.
• resin-coated carbon black for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used.
• Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.
• the total content of Na and Ca is preferably 100 ppm or less as the carbon black to be coated with the resin.
• Carbon black usually contains Na, Ca, K, Mg, Al, Fe, etc. mixed from raw material oil, combustion oil (or gas), reaction stop water and granulation water at the time of production, and furnace materials of reactors. Contains ash with a composition of Of these, Na and Ca are generally contained in amounts of several hundred ppm or more, respectively. tend to prevent short circuits.
• carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide solution, and then a solvent that is sparingly soluble in water is added. Carbon black migrates to the solvent side and is completely separated from water. Most of Na and Ca present in the carbon black together with the carbon black are dissolved and removed in water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, it may be possible to use the carbon black manufacturing process alone with carefully selected raw materials, or the water or acid dissolution method alone. The total amount of Na and Ca can be easily made 100 ppm or less.
• the resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water becomes small, it is possible to coat even fine units, which is preferable. Furthermore, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption amount is 140 mL/100 g or less. Within the above range, there is a tendency to obtain a coating film having good light-shielding properties.
• the average particle diameter means the number average particle diameter. Particle image analysis is performed by taking photographs taken at tens of thousands of times by electron microscope observation and measuring about 2000 to 3000 particles in these photographs with an image processing device. means the equivalent circle diameter determined by
• a carboxylic acid such as maleic acid or fumaric acid is dissolved in the solvent exemplified above, carbon black is added, mixed and dried, the solvent is removed to obtain a carboxylic acid-impregnated carbon black, and a resin is added thereto. 4.
• a reactive group-containing monomer component constituting the resin to be coated and water are stirred at high speed to prepare a suspension, which is cooled after polymerization to obtain a reactive group-containing resin from the polymer suspension.
• a method of adding carbon black, kneading, reacting the carbon black with a reactive group (grafting the carbon black), cooling, and pulverizing can be adopted.
• the type of resin to be coated is not particularly limited, but synthetic resins are common, and resins having a benzene ring in the structure have a stronger amphoteric surfactant-like action. It is preferable in terms of dispersibility and dispersion stability.
• thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, Thermoplastic resins such as modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, and polyetheretherketone can be used.
• the amount of coating resin is preferably 1 to 30% by mass with respect to the total amount of carbon black and resin.
• the coverage can be made sufficient by making it equal to or higher than the above lower limit.
• the content is equal to or less than the above upper limit, there is a tendency that adhesion between resins can be prevented and dispersibility can be improved.
• Carbon black coated with a resin in this way can be used as a coloring agent for colored partition walls according to a conventional method.
• carbon black When such carbon black is used, there is a tendency that colored partition walls having a high light shielding rate and a low surface reflectance can be formed at low cost. It is also presumed that the coating of the carbon black surface with a resin has a function of confining ash containing Na and Ca in the carbon black.
• the average particle size of the pigment is preferably 0.2 ⁇ m or less, more preferably 0.1 ⁇ m or less, and even more preferably 0.05 ⁇ m or less.
• the average primary particle size of the pigment is measured by using a transmission electron microscope (TEM) or a scanning electron microscope (SEM) and directly measuring the size of the primary particles from the electron micrograph.
• a dye may be used in addition to an organic coloring pigment and a black pigment.
• Dyes that can be used as colorants include, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
• azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I.
• Direct Orange 26 C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordan Tread 7, C.I. I. Mordant Yellow 5, C.I. I. Mordant Black 7 is mentioned.
• anthraquinone dyes examples include C.I. I. bat blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 may be mentioned.
• phthalocyanine dyes examples include C.I. I. Bat Blue 5 is mentioned.
• quinone imine dyes examples include C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 is mentioned.
• quinoline dyes examples include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 is mentioned.
• nitro-based dyes examples include C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 is mentioned.
• the photosensitive colored resin composition of the present invention preferably contains (d) a dispersant in order to finely disperse the colorant and stabilize its dispersion state.
• a dispersant in the present invention a polymeric dispersant having a functional group is preferable.
• Polymeric 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.
• polymer 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 disperse pigments. It is particularly preferable from the viewpoint that it can be dispersed with a small amount of dispersant.
• Polymer dispersants include, for example, urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ether dispersants. agents, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
• dispersants examples include trade names such as EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Kasei), and SOLSPERSE (registered trademark). Lubrizol Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, Ajinomoto Co.). Polymer dispersants may be used alone or in combination of two or more.
• the weight average molecular weight (Mw) of the polymeric dispersant is preferably 700 or more, more preferably 1000 or more, and preferably 100,000 or less, more preferably 50,000 or less.
• the above upper and lower limits can be combined arbitrarily.
• the weight average molecular weight (Mw) of the polymeric dispersant is preferably 700-100,000, more preferably 1,000-50,000.
• the dispersant preferably contains one or both of a functional group-containing urethane polymer dispersant and an acrylic polymer dispersant, and may contain an acrylic polymer dispersant.
• a polymer dispersant having a basic functional group and either one or both of a polyester bond and a polyether bond is preferred.
• Urethane-based and acrylic-based polymer dispersants include, for example, DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116 (all acrylic-based) (all manufactured by BYK-Chemie) ).
• the urethane polymer dispersant for example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the molecule, and active hydrogen and a tertiary amino group in the same molecule.
• examples thereof include dispersion resins having a weight average molecular weight of 1,000 to 200,000 obtained by reacting with a compound. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino groups can be converted to quaternary ammonium bases.
• polyisocyanate compounds include aromatic compounds such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate.
• Aliphatic diisocyanates such as diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), ⁇ , ⁇ ′- Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane, xylylene diisocyanate, aliphatic diisocyanates having aromatic rings such as ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11- Triisocyanates such as undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane
• the polyisocyanate is preferably a trimer of organic diisocyanate, more preferably a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate.
• Polyisocyanate compounds may be used alone or in combination of two or more.
• trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. to convert the isocyanate group part
• trimerization is terminated by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate.
• Compounds having a number average molecular weight of 300 to 10000 and having one or two hydroxyl groups in the same molecule include, for example, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and one terminal hydroxyl group of these compounds has a carbon number. Examples include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more of these.
• Polyether glycols include, for example, polyether diols, polyether ester diols, and mixtures of two or more thereof.
• polyether diols examples include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and polyoxyoctamethylene glycol. and mixtures of two or more thereof.
• polyether ester diols include those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly (Polyoxytetramethylene) adipate and the like.
• polyether glycol polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or compounds obtained by alkoxylating one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms are particularly preferable.
• Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 ,6-hexanediol, 2-methyl-2,4-pentane
• polycarbonate glycols examples include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate
• polyolefin glycols examples include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. are mentioned.
• One type of polycarbonate glycol may be used alone, or two or more types may be used in combination.
• the compound having one or two hydroxyl groups in the same molecule preferably has a number average molecular weight of 300 to 10,000, more preferably 500 to 6,000, and even more preferably 1,000 to 4,000.
• Active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group, a thiol group, an amino group, particularly a primary A hydrogen atom of an amino group is preferred.
• the tertiary amino group is not particularly limited, but includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, and a heterocyclic structure (eg, imidazole ring or triazole ring).
• Compounds having active hydrogen and a tertiary amino group in the same molecule include, for example, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-dipropyl -1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1,4-butane diamines.
• Nitrogen-containing heterocycles when the tertiary amino group is a nitrogen-containing heterocyclic structure include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, Nitrogen-containing hetero 5-membered rings such as benzoxazole ring, benzothiazole ring and benzothiadiazole ring, and nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring. be done.
• an imidazole ring and a triazole ring are preferred.
• Examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole and 1-(2-aminoethyl)imidazole.
• Compounds having a triazole ring and an amino group include, for example, 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1,2,4-triazole , 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1,4-diphenyl-1 , 2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like.
• Compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl ) imidazole, 3-amino-1,2,4-triazole are preferred.
• a compound having an active hydrogen and a tertiary amino group in the same molecule may be used singly or in combination of two or more.
• the mixing ratio of the raw materials when producing the urethane-based polymer dispersant is 10 to 10 parts of a compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule, per 100 parts by mass of the polyisocyanate compound. 200 parts by mass is preferable, 20 to 190 parts by mass is more preferable, 30 to 180 parts by mass is more preferable, and 0.2 to 25 parts by mass of a compound having active hydrogen and a tertiary amino group in the same molecule is preferable, and 0 .3 to 24 parts by mass is more preferable.
• the urethane polymer dispersant is produced according to a known method for producing polyurethane resins.
• Solvents used for production include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; and benzene, toluene, xylene, hexane, and the like.
• Hydrocarbons some alcohols such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methylpyrrolidone, Aprotic polar solvents such as dimethylsulfoxide are preferably used.
• a solvent may be used individually by 1 type, and may use 2 or more types together.
• a urethanization reaction catalyst is preferably used in the production of the urethane polymer dispersant.
• catalysts include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannus octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; and tertiary catalysts such as triethylamine and triethylenediamine.
• An amine system is mentioned.
• a catalyst may be used individually by 1 type, and may use 2 or more types together.
• the introduction amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled within the range of 1 to 100 mgKOH/g, more preferably 5 to 95 mgKOH/g, based on the amine value after the reaction.
• the amine value is a value expressed in mg of KOH corresponding to the acid value obtained by neutralizing and titrating the basic amino group with an acid.
• the weight average molecular weight (Mw) of the urethane polymer dispersant is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, even more preferably 3,000 to 50,000.
• an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant), It is preferable to use random copolymers, graft copolymers and block copolymers with unsaturated group-containing monomers having no functional groups. These copolymers can be produced by known methods.
• unsaturated group-containing monomers having functional groups examples include (meth) acrylic acid, 2-(meth) acryloyloxyethyl succinic acid, 2-(meth) acryloyloxyethyl phthalate, 2-(meth) ) Acryloyloxyethyl hexahydrophthalic acid, unsaturated monomers having a carboxy group such as acrylic acid dimer, tertiary amino such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and quaternary products thereof groups, unsaturated monomers with a quaternary ammonium base.
• the unsaturated group-containing monomer having a functional group may be used alone or in combination of two or more.
• unsaturated group-containing monomers having no functional group examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl ( meth)acrylate, isobornyl (meth)acrylate, tricyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, ⁇ -methylstyrene, N-cycl
• the acrylic polymer dispersant is preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block having no functional group.
• the A block in addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, the A block contains a partial structure derived from the unsaturated group-containing monomer that does not contain the functional group. These may be contained in the A block in any form of random copolymerization or block copolymerization.
• the content of the partial structure containing no functional group in the A block is preferably 80% by mass or less, more preferably 50% by mass or less, and even 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. Partial structures derived from two or more types of monomers may be contained in one B block, and these may be contained in either form of random copolymerization or block copolymerization in the B block. .
• the AB or BAB block copolymer is prepared, for example, by the following living polymerization method.
• the living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method.
• the acrylic polymer dispersant may be an AB block copolymer or a BAB block copolymer, and the A block/B block ratio constituting the copolymer is 1/ It is preferably from 99 to 80/20, particularly from 5/95 to 60/40 (mass ratio), and within this range there is a tendency to ensure a balance between dispersibility and storage stability.
• the amount of the quaternary ammonium base in 1 g of the AB block copolymer or the BAB block copolymer is preferably 0.1 to 10 mmol, and good dispersibility is obtained within this range. tend to be able to secure
• the weight average molecular weight (Mw) of the block copolymer is preferably in the range of 1,000 to 100,000. Within the above range, there is a tendency to ensure good dispersibility.
• the specific structure of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, a repeating unit represented by the following general formula (e1) (hereinafter referred to as " It is preferable to have a repeating unit (e1)”.
• R 31 to R 33 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituted represents an aralkyl group which may be two or more of R 31 to R 33 may bond together to form a cyclic structure;
• R 34 is a hydrogen atom or a methyl group;
• X is a divalent linking group;
• Y ⁇ is a counter anion.
• the number of carbon atoms in the optionally substituted alkyl group in R 31 to R 33 of formula (e1) is not particularly limited, but is preferably 1 or more, preferably 10 or less, and 6 or less. It is more preferable to have The above upper and lower limits can be combined arbitrarily.
• the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-6.
• alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups, and methyl, ethyl, propyl, butyl, pentyl and hexyl groups.
• the alkyl group is preferred, and methyl group, ethyl group, propyl group and butyl group are more preferred.
• the alkyl group may be linear or branched, and may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
• the number of carbon atoms in the optionally substituted aryl group in R 31 to R 33 of formula (e1) is not particularly limited, but is preferably 6 or more, preferably 16 or less, and 12 or less. It is more preferable to have The above upper and lower limits can be combined arbitrarily.
• the aryl group preferably has 6 to 16 carbon atoms, more preferably 6 to 12 carbon atoms.
• aryl group examples include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group and anthracenyl group, and phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, A diethylphenyl group is preferred, and a phenyl group, a methylphenyl group and an ethylphenyl group are more preferred.
• the number of carbon atoms in the optionally substituted aralkyl group in R 31 to R 33 of formula (e1) is not particularly limited, but is preferably 7 or more, preferably 16 or less, and 12 or less. It is more preferable to have The above upper and lower limits can be combined arbitrarily.
• the aralkyl group preferably has 7 to 16 carbon atoms, more preferably 7 to 12 carbon atoms.
• the aralkyl group includes, for example, a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, a phenylisopropyl group, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, A phenylbutyl group is preferred, and a phenylmethyl group and a phenylethyl group are more preferred.
• each of R 31 to R 33 is preferably an alkyl group or an aralkyl group.
• R 31 and R 33 are each independently a methyl group or an ethyl group
• R 32 is preferably a phenylmethyl group or a phenylethyl group, more preferably R 31 and R 33 are methyl groups and R 32 is a phenylmethyl group.
• repeating unit (e2) a repeating unit represented by the following general formula (e2) (hereinafter sometimes referred to as “repeating unit (e2)"). It is preferred to have
• R 35 and R 36 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituted is an aralkyl group which may be R 35 and R 36 may be linked together to form a cyclic structure;
• R 37 is a hydrogen atom or a methyl group;
• Z is a divalent linking group.
• the alkyl groups exemplified as R 31 to R 33 in formula (e1) can be preferably employed.
• the optionally substituted aryl group for R 35 and R 36 in formula (e2) the aryl groups exemplified as R 31 to R 33 in formula (e1) above can be preferably employed.
• the optionally substituted aralkyl group for R 35 and R 36 in formula (e2) the aralkyl groups exemplified for R 31 to R 33 in formula (e1) above can be preferably employed.
• Each of R 35 and R 36 is preferably an optionally substituted alkyl group, more preferably a methyl group or an ethyl group.
• substituents that the alkyl group, aralkyl group or aryl group in R 31 to R 33 of formula (e1) and R 35 and R 36 of formula (e2) may have include a halogen atom, an alkoxy group, A benzoyl group and a hydroxyl group are mentioned.
• the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R 43 — group, —COO—R 44 — group (where R 43 and R 44 are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), --COO--R 44 -- group is preferred.
• examples of the counter anion Y ⁇ include Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , CH 3 COO ⁇ and PF 6 ⁇ .
• the content ratio of the repeating unit represented by the formula (e1) is not particularly limited, but from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (e1) and the repeating unit represented by the formula (e2)
• the total content is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, particularly preferably 35 mol% or less, and also preferably is 5 mol % or more, more preferably 10 mol % or more, still more preferably 20 mol % or more, and particularly preferably 30 mol % or more.
• the above upper and lower limits can be combined arbitrarily.
• the content ratio of the repeating unit represented by the formula (e1) to the sum of the content ratio of the repeating unit represented by the formula (e1) and the content ratio of the repeating unit represented by the formula (e2) is 5 to 60 mol. %, more preferably 10 to 50 mol %, even more preferably 20 to 40 mol %, particularly preferably 30 to 35 mol %.
• the content of the repeating unit represented by the formula (e1) in the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, and 5 mol% or more. more preferably 10 mol% or more, preferably 50 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less , 15 mol % or less.
• the above upper and lower limits can be combined arbitrarily.
• the content of the repeating unit represented by formula (e1) in the total repeating units of the polymeric dispersant is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, and further preferably 10 to 20 mol%. 10 to 15 mol % is particularly preferred.
• the content of the repeating unit represented by the formula (e2) in the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, and 10 mol% or more. more preferably 15 mol% or more, particularly preferably 20 mol% or more, and preferably 60 mol% or less, more preferably 40 mol% or less , is more preferably 30 mol % or less, and particularly preferably 25 mol % or less.
• the above upper and lower limits can be combined arbitrarily.
• the content of the repeating unit represented by the formula (e2) in the total repeating units of the polymeric dispersant is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, and further preferably 15 to 30 mol%. Preferably, 20 to 25 mol % is particularly preferred.
• the polymer dispersant is a repeating unit represented by the following general formula (e3) (hereinafter referred to as "repeating unit (e3)" It is preferable to have
• R40 is an ethylene group or a propylene group;
• R 41 is an optionally substituted alkyl group;
• R 42 is a hydrogen atom or a methyl group;
• n is an integer from 1 to 20;
• the number of carbon atoms in the optionally substituted alkyl group in R 41 of formula (e3) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 10 or less. is preferred, and 6 or less is more preferred.
• the above upper and lower limits can be combined arbitrarily.
• the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 2-6.
• alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups, and methyl, ethyl, propyl, butyl, pentyl and hexyl groups.
• methyl group is preferred, and methyl group, ethyl group, propyl group and butyl group are more preferred. Moreover, it may be linear or branched, and may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
• n in the formula (e3) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, and 5 or less, from the viewpoint of compatibility and dispersibility in a binder component such as a solvent. is more preferred.
• the above upper and lower limits can be combined arbitrarily.
• n is preferably 1-10, more preferably 2-5.
• the content ratio of the repeating unit represented by the formula (e3) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, It is more preferably 4 mol % or more, preferably 30 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less. Within the above range, it tends to be possible to achieve both compatibility with a binder component such as a solvent and dispersion stability. The above upper and lower limits can be combined arbitrarily.
• the content of the repeating unit represented by the formula (e3) in the total repeating units of the polymer dispersant is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and 4 to 10 mol%. More preferred.
• the polymer dispersant is a repeating unit represented by the following general formula (e4) (hereinafter referred to as "repeating unit (e4) ).
• R 38 is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group;
• R39 is a hydrogen atom or a methyl group.
• the number of carbon atoms in the optionally substituted alkyl group in R 38 of formula (e4) is not particularly limited, but is 1 or more, preferably 2 or more, more preferably 4 or more. It is preferably 10 or less, more preferably 8 or less.
• the above upper and lower limits can be combined arbitrarily.
• the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 2-8, even more preferably 4-8.
• Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups, and methyl, ethyl, propyl, butyl and pentyl groups.
• hexyl groups are preferred, and methyl, ethyl, propyl and butyl groups are more preferred. Moreover, it may be linear or branched, and may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
• the number of carbon atoms in the optionally substituted aryl group in R 38 of formula (e4) is not particularly limited, but is preferably 6 or more, preferably 16 or less, and preferably 12 or less. More preferably, it is 8 or less.
• the above upper and lower limits can be combined arbitrarily.
• the number of carbon atoms in the aryl group is preferably 6-16, more preferably 6-12, even more preferably 8-12.
• aryl group examples include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, A diethylphenyl group is preferred, and a phenyl group, a methylphenyl group and an ethylphenyl group are more preferred.
• the number of carbon atoms in the optionally substituted aralkyl group in R 38 of formula (e4) is not particularly limited, but is preferably 7 or more, preferably 16 or less, and preferably 12 or less. More preferably, it is 10 or less.
• the above upper and lower limits can be combined arbitrarily.
• the aralkyl group preferably has 7 to 16 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 7 to 10 carbon atoms.
• the aralkyl group includes, for example, a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, a phenylisopropyl group, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, A phenylbutyl group is preferable, and a phenylmethyl group and a phenylethyl group are more preferable.
• R 38 is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group or a phenylmethyl group.
• substituents that the alkyl group in R 38 may have include a halogen atom and an alkoxy group.
• substituents that the aryl group and aralkyl group may have include an alkyl group, a halogen atom, and an alkoxy group.
• the alkyl group represented by R 38 includes both straight-chain and branched-chain.
• the content of the repeating unit represented by the formula (e4) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more. It is preferably 50 mol % or more, more preferably 80 mol % or less, and more preferably 70 mol % or less.
• the above upper and lower limits can be combined arbitrarily.
• the content of the repeating unit represented by formula (e4) in the total repeating units of the polymeric dispersant is preferably 30 to 80 mol%, more preferably 40 to 70 mol%, and further 50 to 70 mol%. preferable.
• the polymeric dispersant may have repeating units other than the repeating unit (e1), the repeating unit (e2), the repeating unit (e3) and the repeating unit (e4).
• repeating units include, for example, styrene-based monomers such as styrene and ⁇ -methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide; Repeating units derived from monomers such as (meth)acrylamide-based monomers such as N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate; and N-methacryloylmorpholine.
• the polymer dispersant includes an A block having the repeating unit (e1) and the repeating unit (e2) and a B block having no repeating unit (e1) and the repeating unit (e2) and is preferably a block copolymer.
• the block copolymer is an AB block copolymer or a BAB block copolymer. Introducing not only a quaternary ammonium base but also a tertiary amino group into the A block tends to significantly improve the dispersing ability of the dispersant.
• the B block preferably has the repeating unit (e3), and more preferably has the repeating unit (e4).
• the repeating unit (e1) and the repeating unit (e2) may be contained in either random copolymerization or block copolymerization mode. Two or more types of repeating units (e1) and repeating units (e2) may be contained in one A block. It may be contained in any mode of block copolymerization.
• Repeating units other than the repeating unit (e1) and the repeating unit (e2) may be contained in the A block, and such repeating units include, for example, the above-mentioned (meth)acrylic ester monomer and repeating units derived from
• the content of the repeating units other than the repeating unit (e1) and the repeating unit (e2) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. It is preferably not contained in the block.
• Repeating units other than the repeating units (e3) and (e4) may be contained in the B block, and examples of such repeating units include styrene-based monomers such as styrene and ⁇ -methylstyrene; (Meth)acrylate-based monomers such as meth)acrylic acid chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate Examples include repeating units derived from monomers such as ether; N-methacryloylmorpholine.
• the content of the repeating units other than the repeating unit (e3) and the repeating unit (e4) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. It is preferably not contained in the block.
• the amine value of the dispersant is preferably 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, more preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, particularly preferably 50 mgKOH/g or more, and more preferably 90 mgKOH. /g or less, more preferably 80 mgKOH/g or less, particularly preferably 75 mgKOH/g or less.
• the above upper and lower limits can be combined arbitrarily.
• the amine value of the dispersant is preferably 1 to 100 mgKOH/g, more preferably 10 to 90 mgKOH/g, even more preferably 30 to 80 mgKOH/g, particularly preferably 50 to 75 mgKOH/g.
• the amine value of the dispersant is expressed by the mass of KOH equivalent to the amount of base per 1 g of the 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 a dispersant sample in a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized and titrated with a 0.1 mol/L HClO 4 acetic acid solution. The inflection point of the titration pH curve is defined as the end point of the titration, and the amine value is obtained by the following formula.
• Amine value [mgKOH / g] (561 ⁇ V) / (W ⁇ S) [W: dispersant sample weighed amount [g], V: titration amount at the end point of titration [mL], S: dispersant It represents the solid content concentration [mass %] of the sample. ]
• the acid value of the dispersant depends on the presence and type of acidic groups that are the source of the acid value, it is generally preferable that it is low, preferably 10 mgKOH/g or less.
• the dispersant may be used singly or in combination of two or more.
• the content is not particularly limited, relative to the total solid content of the photosensitive colored resin composition, preferably 1 wt% or more, 3 wt%
• the above is more preferable, 5% by mass or more is even more preferable, and 7% by mass or more is particularly preferable. Also, it is preferably 12% by mass or less, more preferably 10% by mass or less, even more preferably 9% by mass or less, and particularly preferably 8% by mass or less.
• the content is at least the lower limit, the generation of residue due to aggregates tends to be suppressed, and when the content is at most the upper limit, the developability tends to be improved.
• the above upper and lower limits can be combined arbitrarily.
• the content of the dispersant relative to the total solid content of the photosensitive colored resin composition is preferably 1 to 12% by mass, more preferably 3 to 10% by mass, 5 to 9 mass % is more preferred, and 7 to 8 mass % is particularly preferred.
• the photosensitive colored resin composition of the present invention may contain a pigment derivative as a dispersing aid in order to improve dispersibility and storage stability.
• pigment derivatives include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, and diketopyrrolopyrroles. and dioxazine-based derivatives, among which phthalocyanine-based and quinophthalone-based derivatives are preferred.
• Substituents of pigment derivatives include, for example, sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc., directly on the pigment skeleton or alkyl groups, aryl groups, etc. groups, heterocyclic groups, etc., preferably sulfonic acid groups.
• a single pigment skeleton may be substituted with a plurality of these substituents.
• pigment derivatives examples include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives.
• Pigment derivatives may be used alone or in combination of two or more.
• the photosensitive colored resin composition of the present invention may contain a surfactant in order to improve coating properties.
• surfactants examples include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.
• Nonionic surfactants are preferred because they are less likely to adversely affect various properties, and fluorine-based or silicone-based surfactants are effective in terms of coatability.
• commercially available products include "BM-1000” and “BM-1100” manufactured by BM Chemie, "Megafac F-142D”, “Megafac F-172”, and “Megafac F-173" manufactured by DIC.
• silicone surfactants examples include “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, and “SH8400” manufactured by Dow Corning Toray Co., Ltd. "BYK300”, “BYK323”, “BYK325", “BYK330” manufactured by Shin-Etsu Silicone Co., Ltd., and “KP340” manufactured by Shin-Etsu Silicone Co., Ltd. can be mentioned.
• Surfactants other than fluorine-based surfactants and silicone-based surfactants may be included, and other surfactants include, for example, nonionic surfactants, anionic surfactants, cationic surfactants, surfactants and amphoteric surfactants.
• One type of surfactant may be used alone, or two or more types may be used together in any combination and ratio. Among them, a combination of silicone surfactant/fluorosurfactant is preferable. In this combination of silicone surfactant / fluorine surfactant, for example, BYK-Chemie "BYK-300" or "BYK-330" / DIC "F-475""F-478""F-554" ” or “F-559”.
• the photosensitive colored resin composition of the present invention may contain a liquid repellent agent.
• a liquid repellent agent When the photosensitive colored resin composition of the present invention is used as a partition wall material to form partition walls and an organic electroluminescence element is produced by an inkjet method, it is preferable to contain a liquid-repellent agent. Since the liquid-repellent agent can impart liquid repellency to the surface of the partition wall, the resulting partition wall can prevent color mixture in each pixel of the organic layer.
• liquid repellent agents include silicone-containing compounds and fluorine-based compounds, and preferably liquid repellent agents having a cross-linking group (hereinafter sometimes referred to as "cross-linking group-containing liquid repellent agent").
• cross-linking group examples include an epoxy group and an ethylenically unsaturated group, preferably an ethylenically unsaturated group from the viewpoint of suppressing outflow of the liquid-repellent component of the developer.
• a cross-linking group-containing liquid-repellent agent is used, the cross-linking reaction on the surface of the formed coating film can be accelerated when exposed to light, and the liquid-repellent agent is less likely to flow out during the development process. can exhibit high liquid repellency.
• the fluorine-based compound When a fluorine-based compound is used as the liquid-repellent agent, the fluorine-based compound tends to be oriented on the surface of the partition wall and work to prevent ink bleeding and color mixing. More specifically, groups containing fluorine atoms tend to repel ink and prevent ink bleeding and color mixing due to ink crossing the partition walls and entering adjacent regions.
• Crosslinking group-containing liquid repellent agents particularly ethylenically unsaturated group-containing fluorine-based compounds, include, for example, perfluoroalkylsulfonic acid, perfluoroalkylcarboxylic acid, perfluoroalkylalkylene oxide adduct, perfluoroalkyltrialkylammonium salt, and perfluoroalkyltrialkylammonium salt.
• Oligomer containing fluoroalkyl group and hydrophilic group Oligomer containing perfluoroalkyl group and lipophilic group, oligomer containing perfluoroalkyl group, hydrophilic group and lipophilic group, urethane containing perfluoroalkyl and hydrophilic group, perfluoroalkyl Fluorine-containing organic compounds such as esters and perfluoroalkyl phosphates can be mentioned.
• fluorine-containing compounds include, for example, DIC's "DEFENSAMCF-300”, “DEFENSAMCF-310", “DEFENSAMCF-312”, “DEFENSAMCF-323”, “Megafac RS-72-K”, and 3M Japan. "Florado FC-431”, “Florado FC-4430”, “Florado FC-4432” manufactured by Asahi Glass Co., Ltd.
• the content of fluorine atoms in the liquid-repellent agent is not particularly limited. More preferably, it is 50% by mass or less, and more preferably 25% by mass or less. When it is equal to or higher than the lower limit, there is a tendency to exhibit a high contact angle, and when it is equal to or lower than the upper limit, there is a tendency that outflow to the pixel portion can be suppressed.
• the above upper and lower limits can be combined arbitrarily. For example, 1 to 50% by mass is preferable, and 5 to 25% by mass is more preferable.
• the molecular weight of the liquid-repellent agent is not particularly limited, and it may be a low-molecular-weight compound or a high-molecular-weight compound.
• a high-molecular-weight liquid-repellent agent is preferred because it suppresses the fluidity of the liquid-repellent agent due to baking, and tends to suppress the outflow of the liquid-repellent agent to the outside of the partition walls.
• the above upper and lower limits can be combined arbitrarily. For example, 100 to 100,000 is preferable, and 500 to 10,000 is more preferable.
• the content of the liquid-repellent agent in the photosensitive colored resin composition of the present invention is 0.00% relative to the total solid content of the photosensitive colored resin composition. 01% by mass or more is preferable, 0.05% by mass or more is more preferable, 0.1% by mass or more is further preferable, and 1% by mass or less is preferable, 0.5% by mass or less is more preferable, and 0.3% by mass % or less is more preferable.
• concentration is equal to or higher than the lower limit, high liquid repellency tends to be exhibited, and when the concentration is equal to or lower than the upper limit, the outflow of the liquid repellent agent to the pixel portion tends to be suppressed.
• the above upper and lower limits can be combined arbitrarily. For example, 0.01 to 1% by mass is preferable, 0.05 to 0.5% by mass is more preferable, and 0.1 to 0.3% by mass is even more preferable.
• the photosensitive colored resin composition of the present invention may contain an ultraviolet absorber.
• the ultraviolet absorber is added for the purpose of controlling the photocuring distribution by absorbing a specific wavelength of the light source used for exposure by the ultraviolet absorber. Addition of an ultraviolet absorber provides effects such as improving the verticality of the partition wall side surface after development and eliminating residues remaining in non-exposed areas after development.
• the ultraviolet absorber from the viewpoint of (b) inhibition of light absorption by the photopolymerization initiator, for example, a compound having an absorption maximum between wavelengths of 250 nm and 400 nm can be used.
• the UV absorber contains either one or both of a benzotriazole-based compound and a triazine-based compound.
• the benzotriazole-based compound and the triazine-based compound By including one or both of the benzotriazole-based compound and the triazine-based compound, the light absorptivity at the bottom of the film of the initiator decreases, and the line width at the bottom of the coating film becomes smaller, thereby reducing the verticality effect of the side walls of the barrier ribs. It is considered to be obtained.
• benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 3-[3-tert- Butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]octyl propionate, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2 -yl)-4-hydroxyphenyl]ethylhexyl propionate, 2-[2-hydroxy-3,5-bis( ⁇ , ⁇ -dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5 -methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octyl
• benzotriazole compounds include, for example, Sumisorb (registered trademark, hereinafter the same) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by Johoku Chemical Industry Co., Ltd.), TINUVIN (registered trademark, hereinafter the same.) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN326, TINUVIN900, "TINUVIN928", TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71 , EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (
• triazine compounds examples include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6- Bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl) -4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-ethylhexyl glycidyl ether reaction product, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6 -(2,4-dibutoxyphenyl)-1,3-5-triazine.
• a hydroxyphenyltriazine compound is preferable from the viewpoint of the verticality of the partition wall side surface and the resolution.
• examples of commercially available triazine compounds include TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (manufactured by BASF).
• ultraviolet absorbers include, for example, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes.
• SEESORB151 manufactured by Cipro Kasei Co., Ltd.
• other benzophenone compounds such as Cipro Kasei Co., Ltd.
• Sumisorb 400 manufactured by Sumitomo Chemical Co., Ltd.
• benzoate compounds such as phenyl salicylate
• cinnamic acid derivatives such as isoamyl mic acid
• naphthalene derivatives anthracene, anthracene such as 9,10-dihydroxyanthracene and derivatives thereof; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, p- dyes such as aminobenzoic acid dyes; From the viewpoint of resolution, it is preferable to use cinnamic acid derivatives and naphthalene derivatives, and it is particularly preferable to use cinnamic acid derivatives.
• a benzotriazole compound and a hydroxyphenyltriazine compound as the ultraviolet absorber, and a benzotriazole compound is particularly preferable.
• one type of compound may be used alone, or two or more types of compounds may be used in combination.
• the content is not particularly limited, relative to the total solid content of the photosensitive colored resin composition, preferably 0.01 wt% or more, 0.05% by mass or more is more preferable, 0.1% by mass or more is more preferable, 0.5% by mass or more is even more preferable, 1% by mass or more is particularly preferable, and 15% by mass or less is preferable, and 10% by mass % or less is more preferable, 5 mass % or less is still more preferable, and 3 mass % or less is particularly preferable.
• the content is at least the lower limit, the verticality of the side walls of the partition walls tends to be improved, and when the content is at most the upper limit, the curability tends to be high.
• the content of the ultraviolet absorbent relative to the total solid content of the photosensitive colored resin composition is preferably 0.01 to 15% by mass, and 0.05 to 10 % by mass is more preferred, 0.1 to 5% by mass is more preferred, 0.5 to 3% by mass is even more preferred, and 1 to 3% by mass is particularly preferred.
• the blending ratio for the photopolymerization initiator is as follows: 1 part by mass or more is preferred, 10 parts by mass or more is more preferred, 30 parts by mass or more is even more preferred, 50 parts by mass or more is even more preferred, 80 parts by mass or more is particularly preferred, and 500 parts by mass or less is preferred. It is more preferably 200 parts by mass or less, and particularly preferably 100 parts by mass or less.
• the amount of the ultraviolet absorber per 100 parts by weight of the photopolymerization initiator is preferably 1 to 500 parts by weight, and 10 to 300 parts by weight. 30 to 200 parts by weight is more preferred, 50 to 100 parts by weight is even more preferred, and 80 to 100 parts by weight is particularly preferred.
• the photosensitive colored resin composition of the present invention preferably contains a polymerization inhibitor.
• a polymerization inhibitor inhibits radical polymerization and tends to increase the taper angle of the obtained partition walls.
• Polymerization inhibitors include, for example, hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). From the viewpoint of the ability to inhibit polymerization, hydroquinone and methoxyphenol are preferred, and methylhydroquinone is more preferred.
• the polymerization inhibitor preferably contains one or two or more. Normally, (a) when producing an alkali-soluble resin, a polymerization inhibitor may be contained in the resin, and it may be used as it is, or in addition to the polymerization inhibitor contained in the resin, the same or A different polymerization inhibitor may be added during the production of the photosensitive colored resin composition.
• the content is not particularly limited, relative to the total solid content of the photosensitive colored resin composition, preferably 0.0005 wt% or more, 0.001% by mass or more is more preferable, 0.01% by mass or more is more preferable, 0.1% by mass or less is preferable, 0.08% by mass or less is more preferable, and 0.05% by mass or less is even more preferable.
• the content is at least the lower limit, the resolution tends to be improved, and when the content is at most the upper limit, the curability tends to be improved. The above upper and lower limits can be combined arbitrarily.
• the content of the polymerization inhibitor relative to the total solid content of the photosensitive colored resin composition is preferably 0.0005 to 0.1 wt%, 0.001 ⁇ 0.08% by mass is more preferred, and 0.01 to 0.05% by mass is even more preferred.
• Thermal polymerization initiator The photosensitive colored resin composition of the present invention may contain a thermal polymerization initiator. Inclusion of a thermal polymerization initiator tends to increase the degree of cross-linking of the coating film. Specific examples of thermal polymerization initiators include azo compounds, organic peroxides, and hydrogen peroxide. The thermal polymerization initiator may be used singly or in combination of two or more.
• the total content of the thermal polymerization initiator is in the photosensitive colored resin composition. It is preferable that the content of the photopolymerization initiator is the same, and the ratio of the photopolymerization initiator and the thermal polymerization initiator used together is, from the viewpoint of reducing the residue, to 100 parts by mass of the photopolymerization initiator. It is preferable that the amount of the thermal polymerization initiator is 5 to 300 parts by mass.
• the photosensitive colored resin composition of the present invention may contain an amino compound in order to accelerate thermosetting.
• the content of the amino compound, relative to the total solid content of the photosensitive colored resin composition preferably 40 wt% or less, 30 wt% or less is more preferable, 0.5% by mass or more is preferable, and 1% by mass or more is more preferable.
• the content is equal to or less than the upper limit, storage stability tends to be maintained, and when the content is equal to or greater than the lower limit, sufficient thermosetting property tends to be ensured.
• the above upper and lower limits can be combined arbitrarily.
• the content ratio with respect to the total solid content of the photosensitive colored resin composition is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass.
• amino compounds include amino compounds having a methylol group as a functional group and at least two alkoxymethyl groups obtained by subjecting the methylol group to condensation-denaturation with an alcohol having 1 to 8 carbon atoms.
• melamine resin obtained by polycondensation of melamine and formaldehyde
• benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde
• glycoluril resin obtained by polycondensation of glycoluril and formaldehyde
• Polycondensed urea resins resins obtained by co-polycondensing two or more of melamine, benzoguanamine, glycoluril, or urea with formaldehyde
• modified resins obtained by modifying methylol groups of the above resins by alcohol condensation.
• An amino compound may be used individually by 1 type, and may use 2 or more types together.
• melamine resins and modified resins thereof are preferred as amino compounds, modified resins having a modified ratio of methylol groups of 70% or more are more preferred, and modified resins having a modified ratio of methylol groups of 80% or more are particularly preferred.
• amino compounds include melamine resins and modified resins thereof, such as "Cymel” (registered trademark, hereinafter the same) 300, 301, 303, 350, 736, 738, 370, 771, 325 manufactured by Cytec Co., Ltd. , 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, Sanwa Chemical Co., Ltd. "Nikalac” (registered trademark, hereinafter the same) MW- 390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302.
• Examples of benzoguanamine resins and modified resins thereof include “Cymel” 1123, 1125 and 1128 manufactured by Cytec.
• Examples of glycoluril resins and modified resins thereof include “Cymel” 1170, 1171, 1174, 1172 manufactured by Cytech, and “Nikalac” MX-270 manufactured by Sanwa Chemical.
• Urea resins and modified resins thereof include, for example, “UFR” (registered trademark) 65, 300 manufactured by Cytec Co., Ltd., and “Nikalac” MX-290 manufactured by Sanwa Chemical Co., Ltd.
• silane coupling agent may be added to the photosensitive colored resin composition of the present invention in order to improve adhesion to the substrate.
• Various types of silane coupling agents such as epoxy, methacrylic, amino, and imidazole can be used. From the viewpoint of improving adhesion, epoxy and imidazole silane coupling agents are particularly preferred.
• the photosensitive colored resin composition of the present invention contains a silane coupling agent, the content of the silane coupling agent, from the viewpoint of adhesion, relative to the total solid content of the photosensitive colored resin composition, 20 mass % or less is preferable, and 15 mass % or less is more preferable.
• Inorganic filler The photosensitive colored resin composition of the present invention has an improved strength as a cured product and an excellent coating film due to moderate interaction (formation of a matrix structure) with an alkali-soluble resin.
• Inorganic fillers may be contained for the purpose of improving verticality and taper angle. Examples of inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, and those surface-treated with various silane coupling agents.
• the average particle size of the inorganic filler is preferably 0.005-2 ⁇ m, more preferably 0.01-1 ⁇ m.
• the average particle size is a value measured with a laser diffraction scattering particle size distribution analyzer manufactured by Beckman Coulter.
• silica sol and silica sol-modified materials tend to be excellent in the effect of improving the taper angle as well as the dispersion stability, and thus are preferred.
• the content of the inorganic filler from the viewpoint of resolution, relative to the total solid content of the photosensitive colored resin composition, 5 mass% 10% by mass or more is preferable, and 80% by mass or less is preferable, and 70% by mass or less is more preferable.
• the above upper and lower limits can be combined arbitrarily.
• the content ratio relative to the total solid content of the photosensitive colored resin composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.
• the photosensitive colored resin composition of the present invention may contain a phosphoric acid-based ethylenic monomer for the purpose of imparting adhesion to a substrate.
• a phosphoric acid-based ethylenic monomer (meth)acryloyloxy group-containing phosphates are preferable, and compounds represented by the following general formulas (g1), (g2) and (g3) are preferable.
• R 51 represents a hydrogen atom or a methyl group
• l and l' are integers of 1-10
• m is 1, 2 or 3.
• the phosphoric acid-based ethylenic monomers may be used singly or in combination of two or more.
• the content is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and 0.1 based on the total solid content of the photosensitive colored resin composition. It is more preferably at least 0.2% by mass, particularly preferably at least 0.2% by mass, preferably at most 4% by mass, more preferably at most 3% by mass, still more preferably at most 2% by mass, and particularly preferably at most 1% by mass.
• the photosensitive colored resin composition contains a phosphoric acid-based ethylenic monomer
• the content ratio relative to the total solid content of the photosensitive colored resin composition is preferably 0.02 to 4% by mass, and 0.05 to 3 % by mass is more preferable, 0.1 to 2% by mass is more preferable, and 0.2 to 1% by mass is particularly preferable.
• the photosensitive colored resin composition of the present invention preferably contains a solvent, and is used in a state in which each component described above is dissolved or dispersed in the solvent.
• the solvent is not particularly limited, and examples thereof include 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, 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 is capable of dissolving or dispersing each component in the photosensitive colored resin composition, and is selected according to the usage method of the photosensitive colored resin composition of the present invention. From the viewpoint of coatability, it is preferable to select a solvent having a boiling point in the range of 60 to 280° C. under atmospheric pressure. Solvents having a boiling point of 70° C. or more and 260° C. or less are more preferable, and for example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferable.
• a solvent can be used individually by 1 type or in mixture of 2 or more types.
• the proportion of the total solid content of the photosensitive colored resin composition of the solvent is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, particularly preferably 25% by mass or more, and It is preferably used in an amount of 90% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less.
• the solvent preferably has a proportion of the total solid content of the photosensitive colored resin composition of 10 to 90% by mass, more preferably 15 to 50% by mass, still more preferably 20 to 40% by mass, particularly preferably 25 to It is preferably used in an amount of 35% by weight.
• the photosensitive colored resin composition of the present invention can be prepared by mixing the above components with a stirrer.
• a stirrer for example, when the (d) colorant contains a solvent-insoluble component such as a pigment, it is preferable to previously disperse it using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. Since the (d) colorant is finely divided by the dispersion treatment, the application properties of the photosensitive colored resin composition are improved.
• Dispersion treatment is usually preferably carried out in a system in which (d) a colorant, a solvent, and a dispersant, a dispersing aid, and (a) a part or all of an alkali-soluble resin are used in combination (hereinafter referred to as dispersion
• the mixture subjected to the treatment and the composition obtained by the dispersion treatment are sometimes referred to as "ink” or "pigment dispersion”).
• a polymer dispersant as the dispersant because it suppresses the thickening of the obtained ink and photosensitive colored resin composition over time, in other words, provides excellent dispersion stability.
• the step of producing the photosensitive colored resin composition it is preferable to produce (d) a pigment dispersion containing at least a colorant, a solvent and a dispersant.
• a colorant, solvent, and dispersant that can be used in the pigment dispersion those described as those that can be used in the photosensitive colored resin composition can be preferably employed.
• the content ratio of each colorant in the (d) colorant in the pigment dispersion those described as the content ratio in the photosensitive colored resin composition can be preferably employed.
• 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 treatment apparatus, etc., and is therefore adjusted as appropriate.
• the index of dispersion is to control the gloss of the ink so that the 20 degree specular gloss (JIS Z8741) of the photosensitive colored resin composition is in the range of 50-300.
• the dispersed particle size of the pigment dispersed in the ink is preferably 0.03 to 0.3 ⁇ m.
• the dispersed particle size is measured, for example, by a dynamic light scattering method.
• Dispersed particle size measurement by dynamic light scattering (DLS) is a sufficiently diluted photosensitive colored resin composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, If there is a concentration recommended by the measuring instrument, follow that concentration.) and measure at 25°C.
• the ink obtained by the dispersion treatment is mixed with the above other components contained in the photosensitive colored resin composition to form a uniform solution or dispersion. In the manufacturing process of the photosensitive colored resin composition, since fine dust may be mixed in the liquid, it is desirable to filter the obtained photosensitive colored resin composition with a filter or the like.
• the cured product of the present invention can be obtained by curing the photosensitive colored resin composition of the present invention.
• the photosensitive colored resin composition of the present invention can be used to form partition walls by using itself as a partition wall material, and is particularly suitable for forming partition walls for partitioning the organic layers of an organic electroluminescence device. be able to.
• the method for forming partition walls using the photosensitive colored resin composition of the present invention is not particularly limited, and conventionally known methods can be employed.
• a method for forming the partition walls for example, a photosensitive colored resin composition is applied onto a substrate to form a photosensitive colored resin composition layer, and an exposure step of exposing the photosensitive colored resin composition layer. , and the like. Methods for forming such banks include, for example, an inkjet method and a photolithographic method.
• a photosensitive colored resin composition whose viscosity has been adjusted by dilution with a solvent or the like is used as an ink, and ink droplets are ejected onto a substrate along a predetermined partition pattern by an inkjet method to obtain a photosensitive colored resin.
• the composition is applied onto a substrate to form a pattern of uncured barrier ribs.
• the pattern of uncured barrier ribs is then exposed to form cured barrier ribs on the substrate.
• the exposure of the uncured barrier rib pattern is performed in the same manner as the exposure step in the photolithography method described later, except that no mask is used.
• a photosensitive colored resin composition is applied to the entire area of the substrate where the partition walls are to be formed to form a photosensitive colored resin composition layer. After the formed photosensitive colored resin composition layer is exposed according to a predetermined partition pattern, the exposed photosensitive colored resin composition layer is developed to form partitions on the substrate.
• a contact transfer type coating device such as a roll coater, reverse coater, bar coater, etc. or a spinner (rotating Coating device)
• a photosensitive colored resin composition is applied using a non-contact coating device such as a curtain flow coater, and if necessary, the solvent is removed by drying to form a photosensitive colored resin composition layer.
• a negative mask is used to irradiate the photosensitive colored resin composition with active energy rays such as ultraviolet rays and excimer laser beams, thereby partially exposing the photosensitive colored resin composition layer according to the bank pattern.
• active energy rays such as ultraviolet rays and excimer laser beams
• a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an extra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp, can be used.
• the amount of exposure varies depending on the composition of the photosensitive colored resin composition, it is preferably about 10 to 400 mJ/cm 2 , for example.
• the barrier ribs are formed by developing the exposed photosensitive colored resin composition layer according to the pattern of the barrier ribs with a developer.
• the developing method is not particularly limited, and for example, an immersion method or a spray method can be used.
• the developer include organic developers such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. mentioned. Antifoaming agents and surfactants can also be added to the developer.
• the barrier ribs are post-baked and cured by heating. Post-baking is preferably performed at 150 to 250° C. for 15 to 60 minutes.
• the substrate used for forming the partition is not particularly limited, and is appropriately selected, for example, according to the type of organic electroluminescence device manufactured using the substrate on which the partition is formed.
• Suitable substrate materials include glass and various resin materials.
• resin materials include polyester such as polyethylene terephthalate; polyolefin such as polyethylene and polypropylene; polycarbonate; poly(meth)methacrylic resin; polysulfone; and polyimide. Glass and polyimide are preferable because of their excellent heat resistance.
• a transparent electrode layer such as ITO or ZnO may be provided in advance on the surface of the substrate on which the barrier ribs are formed, depending on the type of organic electroluminescence element to be manufactured.
• the thickness of the barrier ribs of the present invention is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, still more preferably 1 ⁇ m or more, particularly preferably 1.5 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, 4 ⁇ m or less is more preferable, 3 ⁇ m or less is even more preferable, and 2 ⁇ m or less is particularly preferable.
• the light-shielding property tends to be improved, and when it is at most the upper limit, the adhesion tends to be improved.
• the film thickness of the partition wall is measured by a level difference/surface roughness/fine shape measuring device, a scanning white light interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, and an electron microscope.
• the above upper and lower limits can be combined arbitrarily. For example, 0.1 to 10 ⁇ m is preferable, 0.1 to 8 ⁇ m is more preferable, 0.5 to 4 ⁇ m is still more preferable, 1 to 3 ⁇ m is even more preferable, and 1.5 to 2 ⁇ m is particularly preferable.
• the image display device of the present invention includes the partition wall of the present invention.
• the image display device is not particularly limited as long as it displays an image or video, and examples thereof include a liquid crystal display device and an organic EL display device.
• the image display device of the present invention is formed, for example, by a method as described in "Organic EL Display” (Ohmsha, August 20, 2004, by Shizushi Tokito, Chihaya Adachi, and Hideyuki Murata). can do.
• An image may be displayed by combining an organic electroluminescent element that emits white light and a color filter, or an image may be displayed by combining organic electroluminescent elements emitting different colors such as RGB.
• the present invention will be described more specifically with reference to Synthesis Examples, Examples and Comparative Examples.
• the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
• the constituent components of the photosensitive colored resin composition used in the following examples and comparative examples are as follows.
• Alkali-soluble resin-I has a partial structure represented by general formula (a2-1).
• Alkali-soluble resin-II has a partial structure represented by general formula (a2-1).
• alkali-soluble resin-IV having a solid content acid value of 110 mgKOH/g and a polystyrene equivalent weight average molecular weight (Mw) of 5200 measured by GPC.
• Alkali-soluble resin-IV has a cardo skeleton.
• oxime ester An oxime derivative (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 ml of dichloromethane, cooled to 2°C with ice, and triethylamine (1.77 g, 17.5 mmol) was added dropwise. , was left to react for 1 hour. After confirming the disappearance of the raw materials by thin-layer chromatography, water was added to stop the reaction. The reaction solution was washed twice with 5 ml of a saturated sodium bicarbonate aqueous solution and twice with 5 ml of a saturated saline solution, and dried over anhydrous sodium sulfate.
• photoinitiator-I The structure of photoinitiator-I is as follows.
• the constituent components of the photosensitive colored resin compositions used in the following examples and comparative examples are as follows.
• Dispersant-I> An acrylic AB block copolymer comprising an A block having a quaternary ammonium base and a tertiary amino group in a side chain and a B block having no quaternary ammonium base and a tertiary amino group.
• Amine value is 70 mgKOH/g.
• Acid value is 1 mgKOH/g or less.
• the A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a).
• the content ratios of the repeating units of the following formulas (1a), (2a), and (3a) in the total repeating units of Dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. be.
• Alkali-soluble resin-I Resin described in Synthesis Example 1
• Alkali-soluble resin-II Resin described in Synthesis Example 2
• Alkali-soluble resin-IV resin described in Synthesis Example 3
• Photopolymerization initiator-I the photopolymerization initiator described in Synthesis Example 4
• Pigment Dispersions 1 to 4 The pigment, dispersant, alkali-soluble resin and solvent shown in Table 1 were mixed so as to have the mass ratio shown in Table 1 to obtain a mixture.
• the mixing ratio of the solvent in Table 1 also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin.
• This mixed liquid was subjected to dispersion treatment for 3 hours in the range of 25 to 45° C. using a paint shaker.
• As the beads 0.5 mm ⁇ zirconia beads were used, and 2.5 times the mass of the dispersion liquid was added. After completion of dispersion, the beads and the dispersion liquid were separated by a filter to prepare pigment dispersion liquids 1 to 4.
• ITO with a film thickness of 8 nm, silver with a film thickness of 120 nm, and ITO with a film thickness of 10 nm were deposited in this order on the electrode substrate, and the film thickness after heating and curing the photosensitive colored resin composition was It was applied with a spin coater so as to have a thickness of 1.5 ⁇ m, dried under reduced pressure for 1 minute, and then dried with a hot plate at 100° C. for 120 seconds.
• the coating film thus obtained was subjected to an overall exposure treatment without using a mask, using ultraviolet rays having a wavelength of 365 nm and an intensity of 45 mW/cm 2 to give an exposure amount of 40 mJ/cm 2 .
• a developer consisting of a 2.38% by mass aqueous solution of TMAH (tetramethylammonium hydroxide)
• shower development was performed at 24° C. with a water pressure of 0.05 MPa, development was stopped with pure water, and a washing spray was applied. was washed with The shower development time was twice the time required for dissolving and removing the unexposed portion of the coating film.
• the substrate was cured by heating in an oven at 230° C.
• the arithmetic mean surface roughness (Sa) of the coating film surface in the range of 10 ⁇ m ⁇ 10 ⁇ m of the obtained substrate was measured with a scanning white interference microscope VS1530 manufactured by Hitachi High Technology, and Sa was taken as the roughness of the coating film surface. .
• surface smoothness was evaluated according to the following criteria. Table 2 shows the measurement results and evaluation results.
• the measurement mode was the Focus mode, the magnification of the objective lens was 50, and the central wavelength of the measurement light was 520 nm. Sa is obtained by dividing the volume of the portion surrounded by the curved surface and the average surface by the measured area, and the smaller the value, the higher the surface smoothness of the coating film.
• ITO with a film thickness of 8 nm, silver with a film thickness of 120 nm, and ITO with a film thickness of 10 nm were deposited in this order on the electrode substrate, and the film thickness after heating and curing the photosensitive colored resin composition was It was applied with a spin coater so as to have a thickness of 1.5 ⁇ m, dried under reduced pressure for 1 minute, and then dried with a hot plate at 100° C. for 120 seconds. Subsequently, using a developer consisting of a 2.38% by mass aqueous solution of TMAH (tetramethylammonium hydroxide), shower development was performed at 24° C.
• TMAH tetramethylammonium hydroxide
• A The boundary between the wiped portion and the non-wiped portion is unknown. (ie, no residue is left on the ITO after development).
• B The boundary line between the wiped portion and the non-wiped portion can be visually recognized. (That is, there is a residue on the ITO after development.) The residue was evaluated for composition 1, and the evaluation was A.
• an alkali-soluble resin (a1) having a partial structure represented by general formula (a1-1) and general formula (a1-2) By using a photosensitive colored resin composition containing an alkali-soluble resin (a2) having a partial structure represented by, it is possible to form a cured product excellent in development form and roughness.
• the inclusion of the alkali-soluble resin (a1) having a cardo skeleton as the alkali-soluble resin improves the surface smoothness of the coating film. This is because the alkali-soluble resin (a1) has high hydrophobicity, so that it suppresses the penetration of the developer into the exposed portion of the coating film during development, and suppresses the decrease in surface smoothness due to surface roughness. Conceivable.
• the alkali-soluble resin (a2) has lower hydrophobicity than the alkali-soluble resin (a1), but has a sterically bulky partial structure, so aggregation of the resins in the coating film is suppressed, and aggregates This is probably because the surface smoothness does not deteriorate due to dissolution.
• the content of the alkali-soluble resin (a2) is 5 to 300 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (a1), the surface smoothness of the coating film It can be seen that the development form becomes good with In particular, when the content was 48 parts by mass, the surface smoothness was the best. This is because the hydrophobicity of the coating film is moderate, so that while suppressing excessive penetration of the developer into the exposed part of the coating film, aggregates that deteriorate the surface smoothness are appropriately dissolved. it is conceivable that.

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