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
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • G—PHYSICS
  • 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

Definitions

• the present invention relates to a photosensitive resin composition, a cured resin film, and an image display device.
• This application claims priority based on Japanese Patent Application No. 2022-197408 filed on December 9, 2022, the contents of which are incorporated herein by reference.
• color filters used as components of image display devices such as liquid crystal displays (LCDs), organic light-emitting displays (OLEDs), and quantum dot displays (QLEDs), as well as the overcoat layers and interlayer insulating films that are provided on these color filters.
• LCDs liquid crystal displays
• OLEDs organic light-emitting displays
• QLEDs quantum dot displays
• Photoresist is often used as a component of these devices, and patterning is performed using a photomechanical method.
• the photoresist is patterned through a process including an exposure step using a photomask, a development step using an alkaline solution, and a post-bake step. Therefore, photoresists are required to have various functions such as photocurability, developability, and dimensionality to suit each process.
• Patent Document 1 discloses a photosensitive resin composition using a fluorinated acrylate copolymer that includes (b1) a structural unit having an aromatic or non-aromatic hydrocarbon ring, (b2) a structural unit having a fluoroalkyl, (b3) a structural unit having an epoxy group, and (b4) a structural unit derived from an ethylenically unsaturated carboxylic acid.
• the resin used in the photoresist can be imparted with developability in the development step by using a structural unit derived from an ethylenically unsaturated carboxylic acid, or with thermosetting properties in the post-bake step by using a structural unit having an epoxy group.
• the present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide a photosensitive resin composition which gives a cured resin film having excellent hardness and transparency and has good developability. It is a further object of the present invention to provide a cured resin film having excellent hardness and transparency, and an image display device comprising the same.
• the present invention includes the following aspects.
• the photosensitive resin composition is characterized in that the modification is an addition of an ethylenically unsaturated group-containing compound (a-3) having a carboxy group to the epoxy group, and an addition of a ring-structure-containing polybasic acid or an anhydride thereof (a-4) to a hydroxy group generated by ring-opening of the epoxy group.
• the acid value of the resin (A) is 10 to 300 KOHmg/g,
• the epoxy equivalent of the resin (A) is 200 to 8,000 g/mol;
• the photosensitive resin composition according to [1] or [2], wherein the ring-containing polybasic acid or anhydride thereof (a-4) is a polybasic acid or anhydride thereof having a 6-membered ring structure.
• the epoxy group-containing (meth)acrylic resin is a copolymer of an ethylenically unsaturated group-containing compound (m-1) having an epoxy group and another ethylenically unsaturated group-containing compound (m-2),
• the epoxy group-containing ethylenically unsaturated group-containing compound (m-1) contains 30 to 99 mol % of structural units derived therefrom, Contains 1 to 70 mol % of structural units derived from the other ethylenically unsaturated group-containing compound (m-2),
• the resin (A) is With respect to 100 mol % of the structural units derived from the ethylenically unsaturated group-containing compound (m-1) having an epoxy group,
• the photosensitive resin composition according to any one of [1] to [4], containing 10 to 90 mol % of a structural unit derived from the ethylenically unsaturated group-containing compound (a-3) having a carboxy group.
• the weight average molecular weight of the resin (A) is 1,000 to 50,000
• the resin (A) is contained in an amount of 10 parts by mass to 85 parts by mass
• the reactive diluent (B) is contained in an amount of 10 parts by mass to 85 parts by mass
• the photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass
• a cured resin film comprising a cured product of the photosensitive resin composition according to any one of [1] to [8].
• An image display device comprising the cured resin film according to [9].
• the image display device according to [10] comprising an insulating film made of the cured resin film.
• the present invention can provide a photosensitive resin composition that gives a cured resin film with excellent hardness and transparency and has good developability. It can also provide a cured resin film with excellent hardness and transparency obtained by curing the resin composition, and an image display device equipped with the same.
• a photosensitive resin composition according to one embodiment of the present invention (sometimes referred to as the photosensitive resin composition of the present embodiment) contains a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D).
• the resin (A) contained in the photosensitive resin composition of this embodiment is a resin in which a part of the epoxy group of the epoxy group-containing (meth)acrylic resin is modified.
• the modification is the addition of an ethylenically unsaturated group-containing compound (a-3) having a carboxy group to the epoxy group, and the addition of a ring-structure-containing polybasic acid or its anhydride (a-4) to the hydroxy group generated by ring-opening of the epoxy group.
• an ethylenically unsaturated group is introduced into the resin (A) by the addition of the ethylenically unsaturated group-containing compound (a-3) having a carboxy group, and when used in a photosensitive resin composition, compatibility with a reactive diluent is good. Therefore, the transparency of the cured product is good.
• a carboxy group is introduced into the resin (A) by the addition of a ring-structure-containing polybasic acid or its anhydride (a-4), and the developability as a photosensitive resin composition is good.
• part of the epoxy groups of the epoxy group-containing (meth)acrylic resin does not mean all of the epoxy groups of the epoxy group-containing (meth)acrylic resin, but preferably means less than 90 mol%, more preferably 85 mol% or less, and even more preferably 80 mol% or less of the epoxy groups of the epoxy group-containing (meth)acrylic resin. It is also preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more.
• the proportion of modified epoxy groups among the epoxy groups of the epoxy group-containing (meth)acrylic resin is a value calculated from the amount of ethylenically unsaturated group-containing compound (a-3) having a carboxy group added to 100 mol% of the structural units derived from the ethylenically unsaturated group-containing compound (m-1) having an epoxy group, as described below.
• the acid value of the resin (A) is preferably 10 to 300 KOHmg/g, more preferably 15 to 200 KOHmg/g, and even more preferably 20 to 150 KOHmg/g.
• the acid value of the resin is the acid value of the curable polymer measured in accordance with JIS K6901 5.3. That is, the acid value means the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of the copolymer.
• the epoxy equivalent of the resin (A) is preferably 200 to 8,000 g/mol, more preferably 250 to 6,000 g/mol, and even more preferably 300 to 4,000 g/mol.
• the epoxy equivalent of the resin (A) is 200 g/mol or more, the stability as a photosensitive resin composition is good.
• it is 8,000 g/mol or less, the tackiness of the cured product is good.
• the epoxy equivalent is the mass of the polymer per mole of the epoxy group of the resin (A) and can be determined by dividing the mass of the polymer by the amount of epoxy groups (molar number) of the polymer (g/mol). In this specification, the epoxy equivalent is a theoretical value calculated from the amount of raw material used to introduce the epoxy group.
• the unsaturated group equivalent of the resin (A) is preferably from 200 to 6,000 g/mol, more preferably from 250 to 3,000 g/mol, and even more preferably from 300 to 1,500 g/mol.
• the unsaturated group equivalent of the resin (A) is 200 g/mol or more, the stability of the photosensitive resin composition is good.
• the unsaturated group equivalent is 8,000 g/mol or less, the compatibility with the reactive diluent (B) is good, and sufficient photocurability is obtained.
• the unsaturated group equivalent is the mass of resin (A) per mole of ethylenically unsaturated groups in resin (A).
• the unsaturated group equivalent can be determined by dividing the mass of resin (A) by the number of ethylenically unsaturated groups (moles) in the resin (g/mol).
• the unsaturated group equivalent of resin (A) is a theoretical value calculated from the amount of raw material used to introduce ethylenically unsaturated groups into the resin.
• Epoxy group-containing (meth)acrylic resin which is the raw material of the resin (A) according to the present embodiment, is not particularly limited as long as it is a (meth)acrylic resin having an epoxy group and no carboxy group.
• a copolymer of an ethylenically unsaturated group-containing compound (m-1) having an epoxy group and another ethylenically unsaturated group-containing compound (m-2) is preferred.
• the ethylenically unsaturated group-containing compound (m-1) having an epoxy group which is a raw material of the epoxy group-containing (meth)acrylic resin according to this embodiment (which may also be simply referred to as "compound (m-1)"), is not particularly limited as long as it is a compound having no carboxy group and an epoxy group and an ethylenically unsaturated group.
• (meth)acrylic acid ester derivatives containing an epoxy group such as glycidyl (meth)acrylate, 2-methyl glycidyl (meth)acrylate, 2-ethyl glycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, and glycidyloxyphenyl (meth)acrylate; (meth)acrylic acid ester derivatives containing an epoxy group-containing alicyclic carbon ring such as a 3,4-epoxycyclohexane ring such as 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)eth epoxy group
• epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, and glycidyloxyphenyl (meth)acrylate are preferred, with glycidyl (meth)acrylate being more preferred. These may be used alone or in combination of two or more.
• the content of the structural unit derived from the compound (m-1) in the epoxy group-containing (meth)acrylic resin is preferably 30 to 99 mol%, more preferably 40 to 90 mol%, and even more preferably 50 to 80 mol%.
• the content of the structural unit derived from the compound (m-1) is 30 mol% or more, the amount of the epoxy group introduced, the amount of the ethylenically unsaturated group introduced by the addition of the ethylenically unsaturated group-containing compound (a-3) having a carboxy group described later, and the amount of the carboxy group introduced by the addition of the ring-containing polybasic acid or its anhydride (a-4) can be sufficiently ensured.
• the content of the structural unit derived from the compound (m-1) is 99 mol% or less, the content of the other structural units of the structural unit (m-1) can be sufficiently ensured, and various properties such as adhesion, tackiness, and transparency can be further balanced.
• the other ethylenically unsaturated group-containing compound (m-2) (sometimes simply referred to as "compound (m-2)"), which is a raw material of the epoxy group-containing (meth)acrylic resin according to this embodiment, is not particularly limited as long as it is a compound that does not have a carboxy group or an epoxy group and has an ethylenically unsaturated group copolymerizable with compound (m-1).
• aromatic vinyl compounds include aromatic vinyl compounds, cyclic olefins having a norbornene structure, dienes, (meth)acrylic acid esters, (meth)acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, (meth)acrylic acid anilides, (meth)acrylonitrile, acrolein, and the like.
• aromatic vinyl compound examples include styrene, ⁇ -methylstyrene, o-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetylaminostyrene.
• cyclic olefins having a norbornene structure examples include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, dicyclopentadiene, and tricyclo[5.2.1.02,6]dec-8-ene.
• dienes include butadiene, isoprene, chloroprene, and the like.
• Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl acrylate, isobornyl (meth)acrylate, adam
• Examples of the (meth)acrylic acid amide include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diisopropylamide, and (meth)acrylic acid anthracenylamide.
• Examples of the vinyl compound include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene.
• Examples of the unsaturated dicarboxylic acid diester include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.
• monomaleimides examples include N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide. These may be used alone or in combination of two or more.
• a hydroxy group-containing ethylenically unsaturated group-containing compound is preferred.
• a monomer hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and 2,3-dihydroxypropyl 2-methylpropenoate are more preferred. This can further improve the developability of the photosensitive resin composition.
• (meth)acrylates having an alicyclic structure having 6 to 20 carbon atoms aromatic vinyl compounds, and alkyl (meth)acrylates having 1 to 20 carbon atoms.
• monomers dicyclopentanyl methacrylate, styrene, benzyl methacrylate, and 2-ethylhexyl (meth)acrylate are more preferred.
• the content of the structural unit derived from the compound (m-2) in the epoxy group-containing (meth)acrylic resin is preferably 1 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%.
• the structural unit derived from the compound (m-2) is 1 mol% or more, adhesion, tackiness, transparency, etc. can be further improved.
• the structural unit derived from the compound (m-2) is 70 mol% or less, the content of the structural unit derived from the compound (m-1) can be sufficiently ensured.
• the content thereof in the epoxy group-containing (meth)acrylic resin is preferably 1 to 30 mol %, more preferably 3 to 30 mol %, and still more preferably 5 to 20 mol %.
• the structural unit derived from the compound (m-2) contains a structural unit derived from a (meth)acrylate having an alicyclic structure having 6 to 20 carbon atoms, an aromatic vinyl compound, or an alkyl (meth)acrylate having 1 to 20 carbon atoms
• the content thereof in the epoxy group-containing (meth)acrylic resin is preferably 1 to 60 mol %, more preferably 5 to 50 mol %, and still more preferably 10 to 45 mol %.
• Compound (a-3) containing an ethylenically unsaturated group having a carboxy group The ethylenically unsaturated group-containing compound (a-3) having a carboxy group (sometimes simply referred to as "compound (a-3)"), which is a raw material for the resin (A) according to this embodiment, is a compound having one carboxy group and an ethylenically unsaturated group without having an epoxy group.
• (meth)acrylic acid examples include (meth)acrylic acid, ⁇ -bromo(meth)acrylic acid, ⁇ -furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, ⁇ -cyanocinnamic acid, monomethyl maleate, monoethyl maleate, and monoisopropyl maleate.
• (meth)acrylic acid is preferred from the viewpoint of reactivity with the epoxy group derived from compound (m-1). These may be used alone or in combination of two or more.
• the content of the structural units derived from the compound (a-3) is preferably 10 to 90 mol% relative to 100 mol% of the structural units derived from the ethylenically unsaturated group-containing compound (m-1) having an epoxy group, more preferably 10 mol% or more and less than 90 mol%, even more preferably 20 mol% or more and less than 90 mol%, and most preferably 30 to 80 mol%.
• the content of the structural units derived from the compound (a-3) may be 40 mol% or more, or 50 mol% or more, relative to 100 mol% of the structural units derived from the compound (m-1).
• It may be 73 mol% or less, or 68 mol% or less, relative to 100 mol% of the structural units derived from the compound (m-1).
• the content is 10 mol% or more relative to 100 mol% of the structural units derived from the compound (m-1)
• the compatibility with the reactive diluent used in the photosensitive resin composition is good.
• it is 90 mol% or less, the tackiness and curability of the cured product are good.
• the ring-containing polybasic acid or anhydride thereof (a-4) (sometimes simply referred to as "compound (a-4)"), which is a raw material for the resin (A) according to this embodiment, is a compound having a ring structure and two or more carboxy groups, or an anhydride thereof.
• the ring structure may be any of an alicyclic structure, an aromatic ring, and a heterocyclic ring.
• the ring structure may also have an ethylenically unsaturated group.
• a compound having a six-membered ring structure (cyclohexane ring, cyclohexene ring) and two or more carboxy groups is preferred from the viewpoints of a high addition rate to a hydroxy group and a slow reaction rate with an epoxy group.
• polybasic acids examples include phthalic acid, tetrahydrophthalic acid, cyclohexanedicarboxylic acid, trimellitic acid, and norbornane-5-ene-2,3-dicarboxylic acid.
• polybasic acid anhydrides include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, cyclohexanetricarboxylic anhydride, trimellitic anhydride, and himic anhydride.
• tetrahydrophthalic acid, cyclohexanedicarboxylic acid, trimellitic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexanedicarboxylic anhydride, trimellitic anhydride, and himic anhydride are preferred, and tetrahydrophthalic anhydride and himic anhydride are more preferred, in terms of their high addition rate to hydroxy groups and slow reaction rate with epoxy groups. These may be used alone or in combination of two or more.
• the content of the structural unit derived from the compound (a-4) is preferably 1 to 80 mol% relative to 100 mol% of the hydroxyl groups of the adduct of the ethylenically unsaturated group-containing compound (a-3) having a carboxyl group to the epoxy group-containing (meth)acrylic resin, more preferably 10 to 70 mol%, and even more preferably 15 to 60 mol%.
• the content of the structural unit derived from the compound (a-4) may be 20 mol% or more, or may be 30 mol% or more, relative to 100 mol% of the hydroxyl groups of the adduct of the compound (a-3) to the epoxy group-containing (meth)acrylic resin.
• the content of the structural unit derived from the compound (a-4) may be 50 mol% or less, or may be 40 mol% or less, relative to 100 mol% of the hydroxyl groups of the adduct of the compound (a-3) to the epoxy group-containing (meth)acrylic resin.
• the content of the structural unit derived from compound (a-4) is 1 mol% or more relative to 100 mol% of the hydroxyl groups of the adduct of compound (a-3) to the epoxy group-containing (meth)acrylic resin, the developability of the photosensitive resin composition is good.
• the content is 80 mol% or less, the acid value can be controlled within an appropriate range, and the storage stability of the photosensitive resin composition is good.
• the resin (A) contained in the photosensitive resin composition of this embodiment for example, it can be produced using the production method shown below. That is, the ethylenically unsaturated group-containing compound (m-1) having an epoxy group according to this embodiment and the other ethylenically unsaturated group-containing compound (m-2) according to this embodiment are copolymerized using a polymerization initiator according to a radical polymerization method known in the technical field to obtain an epoxy group-containing (meth)acrylic resin.
• a part of the epoxy group contained in the epoxy group-containing (meth)acrylic resin is subjected to an addition reaction with the ethylenically unsaturated group-containing compound (a-3) having a carboxy group according to this embodiment.
• the epoxy group is cleaved, and the hydroxy group generated by the cleavage is reacted with the ring structure-containing polybasic acid or its anhydride (a-4) according to this embodiment.
• the resin (A) is obtained.
• the compound (m-2) contains a hydroxy group-containing ethylenically unsaturated group-containing compound, the amount of the compound (a-4) added can be further increased.
• a method can be used in which a raw material monomer is dissolved in a polymerization solvent to prepare a raw material monomer solution, a polymerization initiator is added to the raw material monomer solution, and the copolymerization reaction is carried out, for example, at 50° C. to 130° C. for 1 hour to 20 hours while stirring.
• the polymerization initiator examples include t-butylperoxy-2-ethylhexanoate, azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis(methyl isobutyrate), benzoyl peroxide, etc.
• These polymerization initiators can be used alone or in combination of two or more kinds.
• the amount of the polymerization initiator used is generally 0.5 to 20 parts by mass, and preferably 1.0 to 10 parts by mass, per 100 parts by mass of the total amount of the raw material monomers charged.
• the first modification reaction can be carried out according to a conventional method.
• the reaction may be carried out at 50 to 150°C, preferably 80 to 130°C.
• the reaction time may be appropriately selected, but is usually 0.05 to 12 hours, preferably 0.1 to 8 hours.
• an acid group is introduced into the polymer by the second modification reaction in which the hydroxy group generated above is reacted with the compound (a-4).
• the second modification reaction can be carried out according to a conventional method.
• the reaction may be carried out at 40 to 100°C, preferably 50 to 80°C.
• the reaction time may be appropriately selected, but is usually 0.05 to 10 hours, preferably 0.1 to 8 hours.
• the reaction catalyst is not particularly limited, but examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chromium chelate compounds.
• the polymerization inhibitor is not particularly limited, but examples of the polymerization inhibitor that can be used include methylhydroquinone, butylhydroxytoluene, hydroquinone, methoquinone, and methylhydroquinone.
• a polybasic acid or anhydride thereof having no ring structure is used instead of the compound (a-4)
• the reaction rate between the epoxy group derived from the compound (m-1) and the carboxyl group derived from the polybasic acid or anhydride thereof having no ring structure is high, making it difficult to control the molecular weight and molecular weight distribution. Therefore, the coexistence of the remaining epoxy group derived from the compound (m-1) and the polybasic acid or anhydride thereof having no ring structure is not preferable.
• the curing characteristics and development characteristics tend to deteriorate.
• the content of the resin (A) in the photosensitive resin composition of this embodiment is preferably 10 parts by mass to 85 parts by mass, more preferably 20 parts by mass to 75 parts by mass, and most preferably 30 parts by mass to 65 parts by mass, when the total of the components excluding the solvent (D) contained in the photosensitive resin composition is 100 parts by mass.
• the total of the components excluding the solvent (D) contained in the photosensitive resin composition refers to the total components such as the resin (A), the reactive diluent (B), the photopolymerization initiator (C), and other additives described later.
• the reactive diluent (B) contained in the photosensitive resin composition of this embodiment is not particularly limited as long as it is a low molecular weight compound having an ethylenically unsaturated group such as a vinyl group, an allyl group, or a (meth)acryloyloxy group.
• a reactive diluent having a plurality of ethylenically unsaturated groups is preferred.
• reactive diluent (B) examples include aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; monofunctional (meth)acrylates; polyfunctional (meth)acrylates; triallyl cyanurate, etc.
• aromatic vinyl monomers include styrene, ⁇ -methylstyrene, ⁇ -chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate, and diallylbenzenephosphonate.
• monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ⁇ -hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.
• polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate.
• reactive diluent (B) polyfunctional (meth)acrylates are preferred in order to improve curability (reactivity), and dipentaerythritol penta(meth)acrylate and/or dipentaerythritol hexa(meth)acrylate are particularly preferred.
• These reactive diluents (B) may be used alone or in combination of two or more.
• the content of the reactive diluent (B) in the photosensitive resin composition of this embodiment is preferably 10 parts by mass to 85 parts by mass, more preferably 15 parts by mass to 70 parts by mass, and most preferably 25 parts by mass to 50 parts by mass, when the total of the components contained in the photosensitive resin composition excluding the solvent (D) is 100 parts by mass.
• the content of the reactive diluent (B) is within the above range, the viscosity and photocurability of the photosensitive resin composition become more appropriate.
• the photopolymerization initiator (C) contained in the photosensitive resin composition of the present embodiment is not particularly limited as long as it is a compound that generates radicals by irradiation with light.
• the photopolymerization initiator (C) include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; alkylphenones such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butyl an
• the content of the photopolymerization initiator (C) in the photosensitive resin composition of this embodiment is preferably 0.1 parts by mass to 30 parts by mass, more preferably 0.3 parts by mass to 20 parts by mass, and most preferably 0.5 parts by mass to 10 parts by mass, when the total of the components excluding the solvent (D) contained in the photosensitive resin composition is 100 parts by mass.
• the content of the photopolymerization initiator (C) is 0.1 parts by mass or more, the photosensitive resin composition has sufficient photocurability.
• the content of the photopolymerization initiator (C) is 30 parts by mass or less, the photopolymerization initiator (C) does not adversely affect the storage stability of the photosensitive resin composition and the performance of the resin cured film.
• the solvent (D) contained in the photosensitive resin composition of the present embodiment is not particularly limited as long as it is a solvent that is inactive to the resin (A) and the reactive diluent (B) and can dissolve the resin (A) and the reactive diluent (B).
• the solvent (D) may or may not contain the polymerization solvent used in producing the resin (A).
• the addition reaction for producing the resin (A) is carried out without removing the polymerization solvent from the reaction solution after the copolymerization reaction for producing the resin (A) is completed, and the polymerization solvent can be used as it is as part or all of the solvent (D) for the resin composition without separating and removing it from the reaction solution after the addition reaction is completed.
• the solvent (D) does not contain the polymerization solvent used in producing the resin (A), it refers to the case where the resin (A) used as the raw material of the photosensitive resin composition is one that has been separated and removed from the reaction solution in which the resin (A) was produced.
• the type and content of the solvent (D) can be appropriately selected according to the type of resin (A) and the use of the resin composition.
• the solvent (D) may be the same type as the polymerization solvent used in producing the resin (A), or a different type may be used.
• the solvent (D) is not particularly limited, but when the resin (A) is a (meth)acrylic acid-based polymer, a glycol ether solvent is preferred from the viewpoint of its solubility.
• a glycol ether solvent is preferred from the viewpoint of its solubility.
• Specific examples include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propy
• the solvent (D) may contain other solvents capable of dissolving the resin (A) and the reactive diluent (B).
• monoalcohols for example, monoalcohols, (poly)alkylene glycol monoalkyl ethers, and the like can be mentioned.
• monoalcohols include primary alcohols such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, and dodecyl alcohol; and secondary alcohols such as benzyl alcohol.
• solvents include tertiary alcohols such as tert-butyl alcohol and diacetone alcohol; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methoxypropionate, and the like.
• esters examples include methyl phosphate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate,
• the content of the solvent (D) in the photosensitive resin composition of this embodiment is preferably 30 parts by mass to 1000 parts by mass, more preferably 50 parts by mass to 800 parts by mass, and most preferably 100 parts by mass to 700 parts by mass, when the total amount of the components in the photosensitive resin composition excluding the solvent (D) is 100 parts by mass.
• the viscosity of the photosensitive resin composition can be adjusted to an appropriate range.
• the photosensitive resin composition of the present embodiment may contain one or more known additives such as a leveling agent, a thermal polymerization inhibitor, a sensitizer, etc., as necessary.
• the content of these additives is not particularly limited as long as it is within a range that does not impair the effects of the present invention.
• the photosensitive resin composition of this embodiment may contain an amine, hydrazide, aldehyde, or metal salt as a crosslinking agent to enhance curing properties.
• crosslinking agents include MXDA and 1,3-BAC manufactured by Mitsubishi Gas Chemical Co., Ltd., ADH and APA-280 manufactured by Otsuka Chemical Co., Ltd., SEQUAREZ 755 manufactured by OMNOVA Solutions, and ZIRCOZOL ZC-2 and 7 manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.
• the photosensitive resin composition of this embodiment may contain an acid generator or a base generator to enhance curing properties.
• an acid generator or a base generator to enhance curing properties.
• a photoacid generator, photobase generator, thermal acid generator, or thermal base generator it is preferable to use a photoacid generator, photobase generator, thermal acid generator, or thermal base generator, and from the viewpoint of storage stability, a photoacid generator or a photobase generator is even more preferable.
• photoacid generators include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S manufactured by San-Apro Chemical Co., Ltd., and iodonium salt compounds such as IK-1.
• photobase generators include WPBG-266, WPBG-300, and WPBG-345 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• the photosensitive resin composition of the present embodiment can be produced by mixing the resin (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), and additives used as necessary, using a known mixing device.
• the photosensitive resin composition of this embodiment can form a cured resin film with sufficient hardness and transparency. Moreover, since the photosensitive resin composition of this embodiment has excellent alkaline developability, fine patterns can be formed by developing with an alkaline aqueous solution. Therefore, the photosensitive resin composition of this embodiment is suitable for use as a resist.
• the cured resin film of this embodiment is made of a cured product of the photosensitive resin composition of this embodiment.
• the cured resin film of the present embodiment can be formed, for example, by a method including a coating step of coating the photosensitive resin composition of the present embodiment on a substrate to form a coating film, a pre-bake step of drying the coating film formed by the coating step, an exposure step of irradiating the dried coating film with light to photo-cure it, and a post-bake step of thermally curing the photo-cured coating film.
• the method shown below can be used. That is, the coating step and pre-baking step described above are performed. Then, in the exposure step, the dried coating film is irradiated with light through a photomask having a predetermined pattern, and the exposed parts are photo-cured. After the exposure step, a post-exposure heating treatment is performed as necessary. Then, a development step is performed in which the unexposed parts of the coating film are developed by dissolving them using a developer, and a post-baking step is performed in which the photo-cured coating film is thermally cured.
• the photosensitive resin composition of the present embodiment is coated on a substrate to form a coating film.
• a known substrate may be used as the substrate to which the photosensitive resin composition is coated, and the substrate may be appropriately selected depending on the application of the cured resin film.
• the method for applying the photosensitive resin composition is not particularly limited, and for example, a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, a slit coating method, or the like can be used.
• the coating film formed in the coating step is dried to reduce the amount of solvent remaining in the coating film.
• the substrate on which the coating film has been formed is heated, for example, at a temperature of 50° C. to 120° C., preferably 70° C. to 110° C., for 10 seconds to 600 seconds, preferably 120 seconds to 180 seconds.
• the substrate on which the coating film has been formed can be heated, for example, using a hot plate.
• the surface of the coating film dried in the pre-bake step is irradiated with light to photocure the coating film.
• the light source used for the light irradiation is not particularly limited, but for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. can be used.
• the exposure dose in the exposure step is not particularly limited, and can be appropriately set depending on the composition of the photosensitive resin composition and the thickness of the coating film.
• the surface of the coating film dried in the pre-bake step is irradiated with light through a photomask having a predetermined pattern, and the exposed portion is photo-cured.
• Post-exposure baking process When forming a resin cured film having a predetermined pattern, a post-exposure baking process is performed as necessary after the exposure process. By performing this process, the dissolution contrast between the exposed and unexposed parts of the coating film becomes more pronounced.
• the post-exposure baking process is different from the post-bake process described later, and does not completely cure the coating film.
• the post-exposure baking process is performed to leave only the exposed parts of the coating film on the substrate and more reliably remove the unexposed parts of the coating film by performing a development process. Therefore, it is not an essential process in the method for forming a resin cured film of this embodiment.
• the substrate after the exposure step is preferably heated, for example, at 40°C to 70°C, and more preferably at 50°C to 60°C.
• the heating temperature is 40°C or higher, the effect of improving the dissolution contrast between the exposed and unexposed parts of the coating film can be sufficiently obtained by performing the post-exposure heating step.
• the heating temperature is 70°C or lower, the epoxy groups in the unexposed parts do not react with the carboxylic acid groups, and good dissolution contrast can be obtained.
• the heating time in the post-exposure heating step is preferably 20 seconds to 600 seconds. When the heating time is 20 seconds or more, the temperature history of the entire coating film can be made uniform.
• the epoxy groups in the unexposed parts do not react with the carboxylic acid groups, and good dissolution contrast can be obtained.
• a hot plate, an oven, or a furnace can be used as a method for heating the substrate after the exposure step in the post-exposure heating step.
• the alkaline aqueous solution is not particularly limited, but examples thereof include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine, etc.; aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide; aqueous solutions of p-phenylenediamine compounds such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, and sulfates, hydrochlorides, or p
• one or more additives such as an antifoaming agent and a surfactant may be added to the aqueous alkaline solution.
• the development conditions in the development step can be appropriately determined depending on the composition of the photosensitive resin composition, the composition of the developer, the thickness of the coating film, and the like.
• it is preferable to develop the unexposed portion of the coating film by dissolving it with the above-mentioned aqueous alkaline solution, followed by rinsing with water and drying.
• post-bake process In this embodiment, after the development process, a post-bake process is performed in which the photocured coating film is thermally cured to form a resin cured film.
• the heating temperature and heating time in the post-bake process are not particularly limited, and can be appropriately set depending on the composition of the photosensitive resin composition, the thickness of the coating film, the material of the substrate, etc.
• the heating temperature in the post-bake process can be, for example, 50°C to 230°C. If the heating temperature is 230°C or less, a material with low heat resistance, such as a protective film provided on the top of a color filter, can be used.
• the heating temperature may be 150°C or less, 120°C or less, or 100°C or less. In addition, if the heating temperature is 150°C or less, the amount of energy required to harden the coating film is small, which is preferable.
• the heating temperature in the post-baking step is 50° C. or higher, the resin (A) and the reactive diluent (B) are sufficiently crosslinked, so that a resin cured film having sufficient hardness and solvent resistance can be obtained. Also, when the heating temperature is 50° C. or higher, the heating time in the post-baking step can be shortened, and the resin cured film can be efficiently formed.
• the heating temperature in the post-baking step is more preferably 60° C. or higher, and even more preferably 70° C. or higher.
• the crosslinking reaction between the epoxy group and the carboxylic acid group in the resin (A) is also thought to contribute to the hardness of the cured resin film.
• the heating time in the post-bake process can be appropriately selected depending on the heating temperature, the thickness of the coating film, the composition of the photosensitive resin composition, etc., and can be, for example, 10 minutes to 4 hours, and preferably 20 minutes to 2 hours.
• the cured resin film of this embodiment is made of a cured product of the photosensitive resin composition of this embodiment, and therefore has sufficient hardness and solvent resistance.
• the cured resin film of the present embodiment can be suitably used as a material for various insulating films, such as a protective film provided on the top of a color filter, an insulating film provided between electrodes of a touch panel, and an interlayer insulating film of a thin film transistor (TFT).
• TFT thin film transistor
• the image display device according to one embodiment of the present invention (sometimes referred to as the image display device according to the present embodiment) is not particularly limited as long as it is provided with the resin cured film according to the present embodiment.
• Examples of the image display device according to the present embodiment include an image display device containing at least one configuration selected from the group consisting of a color filter, a touch panel, and a thin film transistor (TFT).
• TFT thin film transistor
• at least one film selected from the group consisting of various insulating films, such as a protective film provided on the top of the color filter, an insulating film provided between the electrodes of the touch panel, and an interlayer insulating film of the thin film transistor (TFT) preferably contains the resin cured film according to the present embodiment.
• a monomer mixture consisting of 40.6 g (0.1 mol) of dicyclopentanyl methacrylate, 19.2 g (0.1 mol) of styrene, 24.0 g (0.1 mol) of hydroxyethyl methacrylate, and 183.2 g (0.7 mol) of glycidyl methacrylate was mixed with 21.4 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl (registered trademark) O), and the mixture was dropped into the flask from the dropping funnel over 1 hour. After the dropwise addition, the mixture was stirred at 120° C.
• a hydroxy group was generated by the cleavage of the epoxy group.
• 56.0 g (0.2 mol) of tetrahydrophthalic anhydride was added to the reaction system, and the reaction was continued for 8 hours at 60° C.
• the hydroxy group was reacted with the anhydride group of tetrahydrophthalic anhydride to introduce a carboxy group into the side chain.
• the hydroxy group includes the hydroxy group generated by the cleavage of the epoxy group and the hydroxy group derived from hydroxyethyl methacrylate.
• the amount of resin (A) in the photosensitive resin composition in Table 3 does not include the solvent used when synthesizing resin (A). Also, the amount of (D) solvent in Table 3 is the total amount of the solvent used when synthesizing resin (A) in the photosensitive resin composition and the additional solvent added when preparing the photosensitive resin composition.
• Evaluation criteria ⁇ : 4 hours or more. ⁇ : Less than 4H.
• a photosensitive resin composition was applied onto a glass substrate, spin-coated so that the average thickness of the final resin cured film was 2.0 ⁇ m, and then heated (pre-baked) at 100 ° C. for 3 minutes to volatilize the solvent.
• the coating film immediately after the solvent was evaporated was evaluated for dryness (tackiness) when touched with a finger.
• 200 mJ/cm 2 light was irradiated onto the surface of the dried coating film through a photomask using an ultra-high pressure mercury lamp (exposure process). The exposure process was performed by placing a photomask at a position 100 ⁇ m away from the coating film.
• the photomask one having a line and space pattern with a width of 3 to 100 ⁇ m was used.
• the degree of peel resistance between the coating film and the mask and the state of the coating film after removing the mask were confirmed, and the results were evaluated according to the following criteria. The results are shown in Table 4 or Table 5.
• Evaluation criteria ⁇ : The coating film after pre-baking felt no tackiness when touched with a finger, and no trace of the mask was observed on the coating film after removal of the mask after exposure. ⁇ : The coating film after prebaking felt slightly sticky when touched with a finger, and a mask mark was found on the coating film after removing the mask after exposure. ⁇ : The coating film after pre-baking felt significantly sticky when touched with a finger, and the coating film was damaged when the mask was removed after exposure.
• a glass substrate having a cured resin film produced in the same manner as in (1) above was prepared as a test specimen.
• resin cured films were prepared as in (1) above and used as test specimens, except that a substrate having an indium tin oxide (ITO) film formed on a glass substrate, a substrate having a metal mesh (Cu, Ag) formed on a glass substrate, and a substrate having a molybdenum (Mo) film formed on a glass substrate were used instead of the glass substrate.
• the adhesiveness of the cured resin film of each test specimen thus prepared was evaluated by the cross-cut method of JIS K5600-5-6. Specifically, the number of peeled pieces out of 100 grids was counted and evaluated according to the following criteria. The results are shown in Tables 4 and 5.
• the weight average molecular weight means a weight average molecular weight measured by gel permeation chromatography (GPC) under the following conditions in terms of standard polystyrene.
• GPC gel permeation chromatography
• the viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) at a liquid temperature of 25° C., a rotation speed of 10 rpm, and a rotor of 1°34′ ⁇ R24. 10 g of each test specimen was weighed out into a 20 ml glass container, sealed, and stored in a thermostatic chamber maintained at 12° C. for 3 months to carry out a storage test. After the storage test, the weight average molecular weight (Mw) and the viscosity at 25° C. of each test specimen were measured again by the above-mentioned method.
• Mw weight average molecular weight
• Viscosity increase rate (%) ((viscosity before storage test - viscosity after storage test) / viscosity before storage test) x 100 (II)
• the photomask used had a line and space pattern with a width of 3 to 100 ⁇ m.
• Semiclean DL-A10 developer manufactured by Yokohama Yushi Kogyo Co., Ltd.
• diluted 5 times was sprayed on the surface of the coating film for 60 seconds under conditions of a temperature of 23°C and a pressure of 0.1 MPa to remove the unexposed portion (development process).
• the glass substrate having the coating film after the development process was left in a dryer at 100°C for 30 minutes to thermally cure the coating film (post-bake process) to obtain a pattern.
• the patterns thus obtained were observed using an S-3400 electron microscope manufactured by Hitachi High-Technologies Corporation, and the minimum line width (minimum development dimension) that could be developed and the presence or absence of residues in unexposed areas between the developed patterns were evaluated.
• the presence or absence of residues was evaluated according to the following criteria. The results are shown in Table 4 or Table 5.
• Evaluation criteria ⁇ : Meets all of the following requirements. (1) Pencil hardness of 4H or higher. (2) Transmittance is 98% or more. (3) The number of peeled pieces in adhesion was 0. (4) The minimum development dimension in developability is 30 ⁇ m or less, and no residue remains in the unexposed areas. ⁇ : One or more of the above ⁇ items is not met, and there is an ⁇ in one place.
• the resin cured films formed by photocuring the coating films formed from the photosensitive resin compositions of Examples 1 to 9 and then thermally curing them at 230° C. had excellent hardness, with a pencil hardness of 5H or more. Moreover, it was confirmed that the above-mentioned resin cured films had no tackiness after prebaking and had excellent adhesion, transmittance, and stability. In contrast, as shown in Table 5, the photosensitive resin compositions of Comparative Examples 1 to 3 had tackiness after prebaking and were insufficient in alkali developability, pencil hardness or transmittance.
• the resin (A) of sample number cP1 contained in the photosensitive resin composition of Comparative Example 1 has an epoxy group equivalent of 0, as shown in Comparative Synthesis Example 1 in Table 2. Therefore, as shown in Table 5, the result of strong tackiness after pre-baking was obtained (evaluation result: ⁇ ).
• the resin (A) of sample number cP2 contained in the photosensitive resin composition of Comparative Example 2 used succinic anhydride (SA) that does not contain a ring structure as compound (a-4).
• the present invention provides a photosensitive resin composition that gives a resin cured film having excellent hardness and transparency and has good developability. It also provides a resin cured film having excellent hardness and transparency, and an image display device having the same.
• the photosensitive resin composition can be preferably used as a transparent film, a protective film, an insulating film, an overcoat, a photospacer, a black matrix, a black column spacer, and a resist for a color filter.

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