Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
  • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
  • C09D163/10—Epoxy resins modified by unsaturated compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
  • B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
• • 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
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—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 end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/14—Polycondensates modified by chemical after-treatment
  • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
  • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
  • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
  • C08G59/1461—Unsaturated monoacids
  • C08G59/1466—Acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/66—Mercaptans
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—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
  • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
  • H10D86/00—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates
  • H10D86/40—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates characterised by multiple TFTs
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
  • H10D86/00—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates
  • H10D86/40—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates characterised by multiple TFTs
  • H10D86/60—Integrated devices formed in or on insulating or conducting substrates, e.g. formed in silicon-on-insulator [SOI] substrates or on stainless steel or glass substrates characterised by multiple TFTs wherein the TFTs are in active matrices
• • 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

Definitions

• the present invention relates to a curable resin composition, a cured resin film, partition walls and an optical element.
• a pattern printing method using an inkjet (IJ) method may be used, using organic layers such as a light-emitting layer as dots.
• IJ inkjet
• partition walls are provided along the outline of dots to be formed, and ink containing the material of the organic layer is injected into the partitions (hereinafter also referred to as "openings") surrounded by the partition walls. , to form a desired pattern of dots by drying and/or heating.
• the upper surface of the partition wall has ink repellency, while the opening for dot formation surrounded by the partition wall including the side surface of the partition wall.
• the part must have ink affinity.
• barrier ribs having ink repellency on the upper surface a method is known in which a curable resin composition containing an ink repellent agent is used to form barrier ribs corresponding to a dot pattern, for example, by photolithography. ing.
• Patent Document 1 a resin or monomer having an ethylenic double bond and a thiol compound having 3 or more mercapto groups in one molecule for the purpose of enhancing crosslinkability, a negative photosensitive resin containing A resin composition is disclosed.
• Patent Document 2 discloses a positive photosensitive agent solution containing a quinonediazide-based photosensitive agent and a thiol compound for the purpose of preventing precipitation of the quinonediazide-based photosensitive agent.
• an organic EL element when an organic EL element is manufactured by an inkjet method, there is a step of thermally drying at about 200°C under reduced pressure after inkjet-printing an ink containing a light-emitting material and the like in the openings of the partition walls. It is known that the outgassing that can occur at this time can deteriorate the organic EL element.
• the present invention provides a curable resin composition that reduces outgassing after curing and provides a cured resin film with excellent heat resistance, a cured resin film and partition walls with excellent heat resistance obtained from the composition, and the partition walls.
• An object of the present invention is to provide an optical element having
• the present inventors have found that outgassing can be reduced when a thiol compound satisfies specific conditions.
• the present invention relates to the following [1] to [14].
• the hydrogen atom has a charge of 0.265 or less obtained by natural electron density analysis after structural optimization based on density functional theory
• the SH group of the polyfunctional thiol compound is a secondary SH group and a tertiary SH group.
• the curable resin composition according to [1] or [2], wherein the polyfunctional thiol compound has a structure represented by the following formula (1).
• the polyfunctional thiol compound has a 2-mercaptoalkyl ester structure represented by the following formula (1-11a) or a 4-mercaptoalkyl ester structure represented by the following formula (1-11b), [1] to [3 ]
• the curable resin composition according to any one of the above.
• the polyfunctional thiol compound has a 2-mercaptopropionate structure represented by the following formula (1-11a-i) or a 4-mercaptopentanoate structure represented by the following formula (1-11b-i), [1]
• the curable resin composition according to any one of [4].
• the polyfunctional thiol compound is one or more compounds selected from compounds represented by the following formula (2-2), formula (2-4), formula (2-5), or formula (2-6)
• the curable resin composition according to any one of [1] to [5].
• a curable resin composition that reduces outgassing after curing and provides a cured resin film with excellent heat resistance, a cured resin film and partition walls with excellent heat resistance obtained from the composition, An optical element with partitions can be provided.
• (meth)acryloyl group is a generic term for "methacryloyl group” and "acryloyl group”.
• (Meth)acryloyloxy group, (meth)acrylic acid, (meth)acrylate, (meth)allyl, (meth)acrylamide, and (meth)acrylic resin also conform to this.
• side chain refers to a group other than a hydrogen atom or a halogen atom that bonds to a carbon atom that constitutes the main chain in a polymer whose main chain is composed of repeating units.
• total solid content of the curable resin composition refers to, among the components contained in the curable resin composition, a component that forms a cured resin film described later, and the curable resin composition is determined from the residue after heating at 60° C. for 24 hours to remove the solvent. The total solid content can also be calculated from the charged amount.
• cured resin film a film made of a cured product of a composition containing a resin as a main component
• a film coated with a curable resin composition is referred to as a “coated film”
• a film obtained by drying it is referred to as a “dried film”.
• a film obtained by curing the “dry film” is a “cured resin film”.
• the "cured resin film” may be simply referred to as "cured film”.
• the cured resin film may be in the form of partitions formed to divide a predetermined area into a plurality of compartments. For example, the following “ink” is injected into the partitions partitioned by the partitions, that is, the openings surrounded by the partitions to form "dots".
• Ink repellency as used herein means the property of repelling the above ink, and has both water repellency and oil repellency. Ink repellency can be evaluated, for example, by the contact angle when ink is dropped. "Ink affinity" is a property opposite to ink repellency, and can be evaluated by the contact angle when ink is dropped, like ink repellency. Alternatively, the ink affinity can be evaluated by evaluating the degree of wetting and spreading of the ink when the ink is dropped (wetting and spreading property of the ink) according to a predetermined standard.
• Dot in this specification indicates the minimum area in which the light can be modulated in the optical element.
• optical elements such as organic EL elements, color filters of liquid crystal elements, and organic TFT arrays
• 1 dot 1 pixel in the case of black-and-white display
• 3 dots R (red), G (green), etc.) in the case of color display.
• B (blue), etc.) 1 pixel.
• the curable resin composition of the present invention contains a polyfunctional thiol compound that satisfies the following property (1) or property (2).
• (1) Does not have a CH structure 2 atoms adjacent to the S atom (2)
• the compound obtained by adding ethylene to all SH groups of the polyfunctional thiol compound it binds to the carbon atom 2 atoms adjacent to the S atom
• the charge obtained by natural electron density analysis after structural optimization based on the density functional theory of hydrogen atoms is 0.265 or less
• the curable resin composition of the invention contains a polyfunctional thiol compound.
• the curable resin composition of the present invention is, for example, a negative photosensitive resin composition
• radicals of the polyfunctional thiol compound (C) are generated by radicals generated from the photopolymerization initiator (B) described later during exposure.
• ene-thiol reaction occurs, which acts on the ethylenic double bonds of the alkali-soluble resin or alkali-soluble monomer (A) and the cross-linking agent (E), which will be described later.
• This ene-thiol reaction unlike the radical polymerization of normal ethylenic double bonds, is not inhibited by oxygen, so it has high chain transferability and also crosslinks at the same time as polymerization, resulting in cured products.
• There are advantages such as a low shrinkage rate when it becomes, and a uniform network can be easily obtained.
• a cured film having liquid repellency is formed from a curable resin composition, sufficient curing is performed even in the upper layer including the upper surface of the cured film, which is particularly susceptible to reaction inhibition by oxygen. It is possible to impart good ink repellency to the upper surface.
• the polyfunctional thiol compound in the present invention satisfies the property (1) or property (2).
• (1) Does not have a CH structure 2 atoms adjacent to the S atom (2)
• the compound obtained by adding ethylene to all SH groups of the polyfunctional thiol compound it binds to the carbon atom 2 atoms adjacent to the S atom
• the charge obtained by natural electron density analysis after structural optimization based on the density functional theory of hydrogen atoms is 0.265 or less
• the polyfunctional thiol compound can form a crosslinked structure through an addition reaction with an ethylenic double bond during exposure, as described above. .
• the polyfunctional thiol compound can form a crosslinked structure through an addition reaction with an ethylenic double bond in a thermosetting step during photolithography, for example.
• the reactant after the addition reaction if a highly reactive hydrogen atom is bonded to the carbon atom two atoms adjacent to the S atom, it is likely to be desorbed at high temperatures, resulting in outgassing and heat resistance of the reactant. may decrease.
• the polyfunctional thiol compound satisfies the property (1) or property (2), it does not contain highly reactive hydrogen atoms in the reaction product after the addition reaction, so the cured product with high heat resistance and reduced outgassing is obtained. can get.
• the charge is an index of the reactivity of the hydrogen atom, and the larger the charge, the higher the reactivity.
• Natural electron density analysis uses quantum chemical calculation software Gaussian 16, structure optimization with DFT (B3LYP / 6-31G (d)), NBO version 3.1 (NBO Version 3.1, E. D. Glendening, A E. Reed, J. E. Carpenter, and F. Weinhold.).
• the polyfunctional thiol compound In order for the polyfunctional thiol compound to satisfy property (1) or property (2), for example, it has a partial structure represented by formula (1-11a) or a partial structure represented by formula (1-11b) described later, that is, ,
• the SH group is bound to a carbon atom other than the ⁇ -position from the carbon atom forming the ester bond, preferably to the ⁇ - or ⁇ -position carbon atom. .
• the polyfunctional thiol compound preferably has a partial structure represented by the following formula (1).
• Formula (1) represents that a 5- to 7-membered cyclic structure is formed by forming a hydrogen bond between a hydrogen atom of an SH group and an oxygen atom or a nitrogen atom of a divalent organic group X.
• the SH group in such a cyclic structure has high chain transferability and is highly effective in suppressing curing inhibition due to oxygen. As a result, the surface curability of the resulting cured product can be improved.
• a structure represented by the following formula (1-1) or a structure represented by the following formula (1-2) is more preferable.
• the structure represented by formula (1-1) is more preferably a structure represented by formula (1-11) below.
• R 1 a single bond, —CR 11 R 12 —, or —CR 13 R 14 —CR 15 R 16 — R 11 to R 16 each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• R 2 a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• R 3 a hydrogen atom or an alkyl group having 1 to 4 carbon atoms dashed line : Hydrogen bond A: 5- to 7-membered cyclic structure]
• R 11 to R 16 , R 2 and R 3 are alkyl groups
• the alkyl groups may be linear or branched.
• R 1 is preferably a single bond or -CR 13 R 14 -CR 15 R 16 -.
• the polyfunctional thiol compound easily satisfies the characteristic (1) or the characteristic (2) as described later.
• —CH 2 CH 2 — is particularly preferred as —CR 13 R 14 —CR 15 R 16 —.
• R 2 and R 3 each independently include a hydrogen atom, a methyl group, or an ethyl group. Among them, a hydrogen atom or a methyl group is preferable from the viewpoint of less steric hindrance and increased chain transferability of the SH group.
• ring A is more preferably a 5- or 7-membered cyclic structure.
• the structure of formula (1-11) becomes an ⁇ -thiol structure because R 1 is a single bond.
• the structure of formula (1-11) is a ⁇ thiol structure because R 1 is an ethylene skeleton. Since the ⁇ -thiol structure and the ⁇ -thiol structure easily satisfy the property (1) or property (2) described above, outgassing can be reduced by using a polyfunctional thiol having such a structure.
• the structure represented by formula (1-2) is more preferably a structure represented by formula (1-21) below.
• R 4 single bond, —CR 41 R 42 —, or —CR 43 R 44 —CR 45 R 46 —
• R 41 to R 46 each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms dashed line: hydrogen bond A: cyclic structure having 5 to 7 members]
• R 4 when R 4 is —CR 41 R 42 —, one of R 41 and R 42 is a hydrogen atom, and the other is an alkyl group having 1 to 4 carbon atoms, SH group is Since it becomes the 2nd grade, it is preferable.
• R 4 is —CR 43 R 44 —CR 45 R 46 — and SH is bound to CR 45 R 46 , one of R 45 and R 46 is a hydrogen atom and the other has 1 to 4 carbon atoms. is preferable because the SH group is secondary.
• the SH group of the polyfunctional thiol compound in the present invention is preferably at least one of a secondary SH group and a tertiary SH group from the viewpoint of obtaining a curable resin composition with high storage stability.
• the SH group is preferably at least one of a primary SH group and a secondary SH group in terms of obtaining a curable resin composition having high cross-linking reactivity. It is particularly preferable that all SH groups are secondary in that a curable resin composition excellent in both storage stability and cross-linking reactivity can be obtained.
• the partial structure preferably possessed by the polyfunctional thiol compound include a 2-mercaptoalkyl ester structure represented by the following formula (1-11a) and a 4-mercaptoalkyl ester structure represented by the following formula (1-11b). be done.
• the SH group in the polyfunctional thiol compound binds to the carbon atom at the ⁇ -position or ⁇ -position from the carbon atom forming the ester bond, so that the reaction after the addition reaction between the thiol and the ethylenic double bond
• a highly reactive hydrogen atom does not bond to the carbon atom two atoms adjacent to the S atom, so the polyfunctional thiol compound easily satisfies the property (1) or property (2) described above.
• a 2-mercaptopropionate structure represented by the following formula (1-11a-i) and a 4-mercaptopentanoate structure represented by the following formula (1-11b-i) are particularly preferable.
• the number of SH groups in the polyfunctional thiol compound is preferably 2 to 10, more preferably 3 to 6, in one molecule from the viewpoint of storage stability of the curable resin composition.
• the molecular weight of the polyfunctional thiol compound is not particularly limited.
• the mercapto group equivalent represented by [molecular weight / number of mercapto groups] (hereinafter also referred to as "SH equivalent") is a low exposure amount when the curable resin composition of the present invention is photocurable. 40 to 1,000 is preferable, 40 to 500 is more preferable, and 40 to 250 is particularly preferable, from the viewpoint of curability at .
• polyfunctional thiol compounds mercaptocarboxylic acid and polyhydric alcohol esters and glycoluril derivatives are preferable.
• the polyfunctional thiol compound may be an aliphatic compound or an aromatic compound.
• Mercaptocarboxylic acids include thioglycolic acid, 2-mercaptopropionic acid, 2-mercapto-2-methylpropionic acid, 3-mercaptopropionic acid, 3-mercapto-2-methylpropionic acid, 2-mercaptobutanoic acid, 2- Mercapto-2-methylbutanoic acid, 2-mercapto-3-methylbutanoic acid, 3-mercaptobutanoic acid, 3-mercapto-2-methylbutanoic acid, 3-mercapto-3-methylbutanoic acid, 4-mercaptobutanoic acid, 4-mercapto- 2-methylbutanoic acid, 4-mercapto-3-methylbutanoic acid, 2-mercaptopentanoic acid, 2-mercapto-2-methylpentanoic acid, 2-mercapto-3-methylpentanoic acid, 2-mercapto-4-methylpentanoic acid, 3-mercaptopentanoic acid, 3-mercapto-2-methylpentanoic acid, 3-mercapto-3-methylpenta
• Polyhydric alcohols include alcohols having 3 or more hydroxyl groups, such as glycerin, diglycerin, trimethylolethane, trimethylolpropane, triethylolethane, triethylolpropane, ditrimethylolpropane, tris(2-hydroxyethyl)isocyanate. Nurate, hexanetriol, sorbitol, pentaerythritol, dipentaerythritol, sucrose and the like.
• the polyfunctional thiol compound includes compounds represented by the following formulas (2-1) to (2-7).
• a polyfunctional thiol compound may be used individually by 1 type, or may use 2 or more types together.
• Rs is a thiol group-containing group, a monovalent represented by any of the following formulas (Rs-1) to (Rs-3) is the base.
• a plurality of Rs in formula (2-1) may be the same or different. The same applies to multiple Rs in formulas (2-2) to (2-7).
• Rs is preferably a monovalent group represented by formula (Rs-2) or formula (Rs-3).
• Polyfunctional thiol compound in the present invention JP 2011-84479, JP 2019-85403, JP 2019-85403 with reference to known methods described in JP 2019-85403, etc. can be manufactured.
• the curable resin composition of the present invention is preferably It is contained in an amount of 0.0001 to 1 mol, more preferably 0.0005 to 0.5 mol, particularly preferably 0.001 to 0.5 mol. When the content is within the above range, when the curable resin composition is photocurable, photocurability and developability are good even at a low exposure dose.
• the curable resin composition of the present invention may be a photocurable resin composition or a thermosetting resin composition.
• the curable resin composition of the present invention may be either a negative photosensitive resin composition or a positive photosensitive resin composition.
• the curable resin composition of the present invention is a negative photosensitive resin composition
• the curable resin composition of the present invention further contains an ethylenic double bond-containing alkali-soluble resin (AP) or an ethylenic double bond-containing alkali-soluble monomer (AM ) is preferably included.
• AP ethylenic double bond-containing alkali-soluble resin
• AM ethylenic double bond-containing alkali-soluble monomer
• a curable resin having an acidic group and an ethylenic double bond in one molecule is preferable as the alkali-soluble resin (AP) having an ethylenic double bond. Since the alkali-soluble resin (AP) has an ethylenic double bond in the molecule, the exposed portion of the photocurable resin composition is polymerized and cured by radicals generated from the photopolymerization initiator (B) described later. . At this time, the polyfunctional thiol compound (C) generates radicals, and due to its high chain transferability, acts well on the ethylenic double bonds to contribute to polymerization and cross-linking, thereby ensuring sufficient curing.
• the exposed areas that have been sufficiently cured in this way are not removed with an alkaline developer.
• the alkali-soluble resin (AP) since the alkali-soluble resin (AP) has an acidic group in the molecule, it is possible to selectively remove the non-exposed areas of the uncured photocurable resin composition with an alkaline developer.
• the cured resin film can be in the form of partition walls that partition a predetermined region into a plurality of sections.
• the acidic group includes a carboxy group, a phenolic hydroxyl group, a sulfo group, a phosphoric acid group, and the like, and these may be used alone or in combination of two or more.
• ethylenic double bonds include double bonds having addition polymerizability such as (meth)acryloyl groups, allyl groups, vinyl groups, vinyloxy groups, and vinyloxyalkyl groups. These may be used individually by 1 type, or may use 2 or more types together.
• some or all of the hydrogen atoms of the ethylenic double bond may be substituted with an alkyl group such as a methyl group.
• the alkali-soluble resin (AP) having an ethylenic double bond includes a resin (A-1) having a side chain having an acidic group and a side chain having an ethylenic double bond (A-1), an epoxy resin having an acidic group and an ethylenic Resin (A-2) into which a double bond is introduced, and the like. These may be used individually by 1 type, or may use 2 or more types together.
• Resin (A-1) can be synthesized, for example, by the following method (i) or (ii). (i) Copolymerizing a monomer having a side chain with a reactive group other than an acidic group, for example, a reactive group such as a hydroxyl group or an epoxy group, and a monomer having an acidic group in the side chain to obtain a reactive A copolymer having a side chain having a group and a side chain having an acidic group is obtained. Then, this copolymer is reacted with a compound having a functional group and an ethylenic double bond capable of bonding to the reactive group.
• a reactive group other than an acidic group for example, a reactive group such as a hydroxyl group or an epoxy group
• a compound having a functional group capable of binding to the acidic group and an ethylenic double bond is added to the monomer so that the acidic group remains after the reaction. amount, react.
• (i) and (ii) are preferably carried out in a solvent.
• method (i) is preferably used.
• the method (i) will be specifically described below.
• Examples of monomers having a hydroxyl group as a reactive group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxy ethyl vinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl(meth)acrylamide, N,N-bis(hydroxymethyl)(meth)acrylamide and the like.
• the monomer having an acidic group to be copolymerized includes, in addition to the monomer having a carboxyl group described below, a monomer having a phosphate group. -(meth)acryloyloxyethyl phosphate and the like. Copolymerization of a monomer having a hydroxyl group as a reactive group and a monomer having an acidic group can be carried out by a conventionally known method.
• the compound having an ethylenic double bond and a functional group capable of bonding to a hydroxyl group to be reacted with the obtained copolymer includes an acid anhydride having an ethylenic double bond, an isocyanate group and an ethylenic double bond.
• Acid anhydrides having an ethylenic double bond include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, and 3,4,5,6-tetrahydrophthalic anhydride.
• Compounds having an isocyanate group and an ethylenic double bond include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate.
• Compounds having an acyl chloride group and an ethylenic double bond include (meth)acryloyl chloride and the like.
• Monomers having an epoxy group as a reactive group include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and the like.
• the monomer having an acidic group to be copolymerized with the monomer having an epoxy group as a reactive group the same monomer as described in the monomer having a hydroxyl group as a reactive group can be used, Copolymerization of a monomer having an epoxy group as a reactive group and a monomer having an acidic group can also be carried out by a conventionally known method.
• Examples of the compound having an ethylenic double bond and a functional group capable of bonding to an epoxy group to be reacted with the obtained copolymer include compounds having a carboxyl group and an ethylenic double bond. Specific examples of such compounds include (meth)acrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, salts thereof, and monoesters in the case of dibasic acids.
• a carboxyl group may be introduced into the resin (A-1) by reacting the resulting hydroxyl group with an acid anhydride in which the dehydration-condensation portion of the carboxylic acid forms a part of the cyclic structure.
• Monomers having a carboxyl group as a reactive group include (meth)acrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, salts thereof, mono Ester etc. are mentioned. These monomers are also used as the above-mentioned monomers having acidic groups.
• a compound having an ethylenic double bond and a functional group capable of bonding to a carboxyl group to be reacted with the obtained polymer includes a compound having an epoxy group and an ethylenic double bond.
• Such compounds include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate and the like.
• the amount of the compound having a functional group capable of bonding to the carboxyl group and the ethylenic double bond to be reacted with the polymer having the carboxyl group is determined so that the carboxyl group is present as an acidic group in the polymer after the reaction. The amount that remains on the chain.
• the resin (A-2) can be synthesized by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond, which will be described later, and then reacting with a polyvalent carboxylic acid or its anhydride.
• an ethylenic double bond is introduced into the epoxy resin by reacting the epoxy resin with a compound having a carboxyl group and an ethylenic double bond.
• a carboxyl group can be introduced by reacting the epoxy resin into which the ethylenic double bond has been introduced with a polyvalent carboxylic acid or its anhydride.
• the epoxy resin is not particularly limited, and may be bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, trisphenolmethane type epoxy resin, epoxy resin having a naphthalene skeleton, the following formula ( An epoxy resin having a biphenyl skeleton represented by A-2a), a fluorenyl-substituted bisphenol A-type epoxy resin represented by the following formula (A-2b), and an epoxy having a biphenyl skeleton represented by the following formula (A-2c) Resin etc. are mentioned.
• the hydrogen atoms of the benzene ring are each independently an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a partial hydrogen atom may be substituted with a phenyl group which may be substituted with a substituent.
• R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and w is 0 or an integer of 1 to 10.
• the hydrogen atoms of the benzene ring may be independently substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group in which some of the hydrogen atoms may be substituted with a substituent.
• z is 0 or an integer from 1 to 10.
• Compounds having a carboxyl group and an ethylenic double bond include (meth)acrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid or salts thereof, dibasic acids Monoesters are preferred, and (meth)acrylic acid is particularly preferred.
• the alkali-soluble resin (AP) having an ethylenic double bond peeling of the cured film during development can be suppressed, and a high-resolution dot pattern can be obtained. It is preferable to use the resin (A-2) in terms of good linearity and easy to obtain a smooth cured film surface.
• the resin (A-2) include a resin obtained by introducing an acidic group and an ethylenic double bond into a bisphenol A type epoxy resin, a resin obtained by introducing an acidic group and an ethylenic double bond into a bisphenol F type epoxy resin, and phenol.
• a resin obtained by introducing an acidic group and an ethylenic double bond into a novolac-type epoxy resin a resin obtained by introducing an acidic group and an ethylenic double bond into a cresol novolac-type epoxy resin, an acidic group and ethylene into a trisphenolmethane-type epoxy resin
• resins into which an acidic group and an ethylenic double bond have been introduced or resins into which an acidic group and an ethylenic double bond have been introduced into epoxy resins represented by formulas (A-2a) to (A-2c).
• alkali-soluble monomer (AP) having an ethylenic double bond for example, a monomer (A-3) having a side chain having an acidic group and a side chain having an ethylenic double bond is preferably used. be done. Acidic groups and ethylenic double bonds are similar to alkali-soluble resins (AP) with ethylenic double bonds. Examples of the monomer (A-3) include 2,2,2-triacryloyloxymethylethylphthalic acid.
• the alkali-soluble resin or alkali-soluble monomer (A) having an ethylenic double bond contained in the photocurable resin composition may be used singly or in combination of two or more.
• the content of the alkali-soluble resin or alkali-soluble monomer (A) having an ethylenic double bond in the total solid content of the photocurable resin composition is preferably 5 to 80% by mass, and 10 to 60% by mass. Especially preferred. When the content is within the above range, the photocurable resin composition has good photocurability and developability.
• photopolymerization initiator (B) When the curable resin composition of the present invention is photocurable, it preferably further contains a photopolymerization initiator (B).
• the photopolymerization initiator (B) is not particularly limited as long as it is a compound having a function as a photopolymerization initiator, and is preferably a compound that generates radicals upon exposure to light.
• the photopolymerization initiator (B) includes ⁇ -diketones such as methylphenyl glyoxylate and 9,10-phenanthrenequinone; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like.
• thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, and 2,4-diethylthioxanthone
• benzophenone 4,4'-bis(dimethylamino) benzophenones such as benzophenone and 4,4'-bis(diethylamino)benzophenone
• photopolymerization initiators (B) benzophenones, aminobenzoic acids and aliphatic amines are preferred because they exhibit a sensitizing effect when used together with other radical initiators.
• photopolymerization initiator (B) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpho linophenyl)-butan-1-one, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime), ethanone 1-[9-ethyl-6-(2-methyl Benzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) or 2,4-diethylthioxanthone are preferred.
• combinations of these with benzophenones, such as 4,4'-bis(diethylamino)benzophenone are particularly
• the content of the photopolymerization initiator (B) in the total solid content of the curable resin composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and 5 to 20% by mass. Especially preferred. When the content is within the above range, the photocurability and developability of the curable resin composition are good.
• the curable resin composition of the present invention preferably further contains an ink repellent agent (D).
• the ink repellent agent (D) has a property of migrating to the upper surface (upper surface migration property) and ink repellency in the process of forming a cured film using the curable resin composition.
• the ink repellent agent (D) By using the ink repellent agent (D), the upper layer portion including the upper surface of the resulting cured film becomes a layer in which the ink repellent agent (D) is densely present (hereinafter sometimes referred to as "ink repellent layer"). , ink repellency is imparted to the upper surface of the cured film.
• the ink repellent agent (D) having the properties described above preferably has a fluorine atom from the viewpoint of migration to the upper surface and ink repellency.
• the fluorine atom content in the ink repellent agent (D) is preferably 1 to 40% by mass, more preferably 5 to 35% by mass, and particularly preferably 10 to 30% by mass.
• the fluorine atom content of the ink repellent agent (D) is at least the lower limit of the above range, good ink repellency can be imparted to the upper surface of the cured film. Good compatibility with other components.
• the ink repellent agent (D) is preferably a compound having an ethylenic double bond. Since the ink repellent agent (D) has an ethylenic double bond, the radical of the polyfunctional thiol compound (C) acts on the ethylenic double bond of the ink repellent agent (D) that has migrated to the upper surface, resulting in ink repellent. agent (D) with each other or ink repellent agent (D) and another component having an ethylenic double bond contained in the curable resin composition and (co)polymerization and/or via polyfunctional thiol compound (C) Cross-linking becomes possible.
• the fixability of the upper layer portion of the cured film of the ink repellent agent (D), that is, the ink repellent layer can be improved.
• the ink repellent agent (D) is sufficiently applied to the ink repellent layer even when the exposure dose during exposure is low. can be settled in The case where the ink repellent agent (D) has an ethylenic double bond is as described above.
• the alkali-soluble resin or the photocurable component mainly composed of the alkali-soluble monomer (A) present around the ink repellent agent (D) Sufficient curing allows the ink repellent agent (D) to be sufficiently fixed.
• the surface of the cured film or partition wall that is in contact with the atmosphere is more likely to be inhibited by oxygen, but the radical reaction by the polyfunctional thiol compound (C) is hardly inhibited by oxygen. Therefore, it is particularly advantageous for fixing the ink repellent agent (D) at a low exposure amount. Furthermore, in the production of partition walls, it is possible to sufficiently prevent the ink-repellent agent (D) from detaching from the ink-repellent layer and the upper surface of the ink-repellent layer from peeling off during development.
• the ink repellent agent (D) examples include, for example, an ink repellent agent (D1) composed of a partially hydrolyzed condensate of a hydrolyzable silane compound and having a fluorine atom, or an ink repellent agent (D1) having a hydrocarbon chain as a main chain and An ink repellent agent (D2) made of a compound containing a fluorine atom and the like are included.
• the ink repellent agent (D1) and the ink repellent agent (D2) are used alone or in combination.
• the ink repellent agent (D1) and the ink repellent agent (D2) specifically, the ink repellent agents described in International Publication No. 2014/084279, International Publication No. 2015/093415, etc. can be used.
• the content of the ink repellent agent (D) in the total solid content of the curable resin composition is preferably 0.01 to 15% by mass, more preferably 0.01 to 5% by mass, and 0.03 to 1.5% by mass. % by weight is particularly preferred.
• the content is at least the lower limit of the above range, the upper surface of the cured film formed from the curable resin composition has excellent ink repellency. If it is at most the upper limit of the above range, the adhesion between the cured film and the substrate will be good.
• the curable resin composition of the present invention may further contain a cross-linking agent (E).
• the cross-linking agent (E) is a compound having two or more ethylenic double bonds in one molecule and no acidic groups.
• the compound (E1) having two or more allyl groups in one molecule is preferable from the viewpoint of good reactivity with the polyfunctional thiol compound.
• the number of allyl groups in compound (E1) is preferably 2-10, more preferably 2-6.
• Examples of the compound (E1) include trimeth(allyl)cyclohexane, tri(meth)allyl(iso)cyanurate, di(meth)allylmonoglycidyl(iso)cyanurate, 3,9-di(meth)allyl-2,4 , 8,10-tetraoxaspiro[5.5]undecane, di(meth)allyl phthalate, di(meth)allyl isophthalate, di(meth)allyl terephthalate, di(meth)allyl maleate, di(meth)allyl fumarate, di(meth)allyl endomethylenetetrahydrophthalate anhydride, tri(meth)allyl trimellitate, pentaerythritol tetra(meth)allyl ether, pentaerythritol tri(meth)allyl ether, tetra(meth)allyl glycoluril, etc. mentioned. Triallyl isocyanurate is
• cross-linking agent (E) other than the compound (E1) examples include diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra (Meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, tris-(2-acryloxyethyl)isocyanurate, ⁇ -caprolactone-modified tris -(2-acryloxyethyl) isocyanurate, urethane acrylate, and the like.
• ethylenic double bonds For example, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate or urethane acrylate. preferable.
• the cross-linking agent (E) may be used alone or in combination of two or more.
• the content of the cross-linking agent (E) in the total solid content of the curable resin composition is preferably 10 to 70% by mass, particularly preferably 20 to 60% by mass.
• the content of the compound (E1) in the total solid content is preferably 1 to 50% by mass, and 5 to 40% by mass. % by weight is particularly preferred.
• trimeta(allyl)cyclohexane tri(meth)allyl(iso)cyanurate, 3,9-di(meth)allyl-2,4,8,10-tetraoxaspiro[5.5] Undecane is preferred, and trimeta(allyl)cyclohexane and 3,9-di(meth)allyl-2,4,8,10-tetraoxaspiro[5.5]undecane are particularly preferred.
• the curable resin composition obtained in the above range or the above compound has good photocurability and developability, and the partition walls to be formed have sufficiently reduced residue in the openings. Furthermore, when used together with an ink repellent agent, the liquid repellency tends to increase.
• the curable resin composition of the present invention preferably further contains a solvent (F). This reduces the viscosity of the composition, making it easier to apply the curable resin composition to the substrate surface. As a result, a coating film of the curable resin composition having a uniform thickness can be formed.
• a known solvent is used as the solvent (F).
• the solvent (F) may be used alone or in combination of two or more.
• Examples of the solvent (F) include alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, alcohols, solvent naphthas, and the like. Among them, at least one solvent selected from the group consisting of alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, and alcohols is preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, and At least one solvent selected from the group consisting of 2-propanol is more preferred.
• the content of the solvent (F) in the curable resin composition is preferably 50-99% by mass, more preferably 60-95% by mass, and particularly preferably 65-90% by mass, relative to the total amount of the composition.
• the curable resin composition of the present invention contains a coloring agent (G) in the case of imparting a light-shielding property to the cured film, particularly to partition walls, depending on the application.
• a coloring agent (G) include carbon black, aniline black, and organic black pigments.
• organic black pigments include black pigments described in International Publication No. 2018/101314, anthraquinone black pigments, perylene black pigments, and the like. Specifically, C.I. I. Pigment Black 1, 6, 7, 12, 20, 31 and the like. Further, Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) can be mentioned as a trade name. Mixtures of organic and/or inorganic pigments such as red, blue and green pigments can also be used.
• the colorant (G) may be used alone or in combination of two or more.
• the content of the coloring agent (G) in the total solid content is preferably 15 to 65% by mass, more preferably 20 to 50% by mass. is particularly preferred.
• the curable resin composition obtained within the above range has good sensitivity, and the barrier ribs formed have excellent light-shielding properties.
• the curable resin composition in the invention may further contain an acidic component (H).
• the acidic component (H) include sulfuric acid, nitric acid, phosphoric acid, phosphoric acid compound (H1), acetic acid, oxalic acid and maleic acid. Among them, nitric acid and phosphoric acid compound (H1) are preferable.
• the acidic component (H) may be used alone or in combination of two or more.
• Phosphate compound (H1) When the curable resin composition of the present invention contains the phosphoric acid compound (H1), the adhesiveness to the substrate can be improved in addition to the effects of the acidic component described below.
• Phosphate compounds include mono (meth) acryloyloxyethyl phosphate, di (meth) acryloyloxyethyl phosphate, mono (2- (meth) acryloyloxyethylcaproate acid) phosphate, bis (2-( meth) acryloyloxyethyl caproate acid) phosphate and the like.
• mono(2-(meth)acryloyloxyethylcaproate acid) phosphate and bis(2-(meth)acryloyloxyethylcaproate acid) phosphate are preferred, and mono(2-(meth)acryloyloxyethyl Caproate acid) phosphate is particularly preferred.
• the content of the acidic component (H) in the total solid content is preferably 0.01 to 1% by mass, and 0.01% by mass. ⁇ 0.5% by weight is particularly preferred. Within the above range, the resulting curable resin composition has good storage stability and good coating film flatness.
• the curable resin composition in the present invention further optionally contains a thermal cross-linking agent, a polymer dispersant, a dispersing aid, a silane coupling agent, fine particles, a curing accelerator, a thickener, a plasticizer, and an antifoaming agent. , a leveling agent, an anti-cratering agent, an ultraviolet absorber, or other additives such as one or more.
• the curable resin composition of the present invention may be a positive photosensitive resin composition other than the negative photosensitive resin composition described above.
• the curable resin composition of the present invention is obtained by mixing predetermined amounts of the above components. Since the curable resin composition of the present invention reduces outgassing after curing, the use of the curable resin composition of the present invention makes it possible to produce cured resin films with excellent heat resistance, particularly partition walls. .
• the curable resin composition of the present invention is photocurable, for example, the curable resin composition of the present invention is applied to the surface of a substrate such as a substrate. It is obtained by applying a resin composition, drying it if necessary to remove the solvent and the like, and then curing it by exposing it to light.
• the cured resin film obtained exhibits remarkable effects when used for optical elements, particularly organic EL displays, quantum dot displays, TFT arrays, thin film solar cells, hard coats, and the like.
• the curable resin composition of the present invention is thermosetting, for example, it is cured by heating to a predetermined temperature to obtain a cured resin film.
• the cured resin film obtained is useful for hard coating and the like.
• partition walls made of a cured resin film using the composition are provided on the substrate surface for dot formation. It is formed in a shape that partitions into a plurality of compartments.
• the partition wall is formed by masking the portion of the coating film made of the curable resin composition before exposure, and then developing the mask after exposure. is obtained by
• the unexposed portions are removed by masking during development, and openings corresponding to the divisions for dot formation are formed together with partition walls.
• the exposed portions are removed by masking and openings corresponding to the partitions for dot formation are formed together with the partition walls by development.
• the barrier ribs of the embodiments of the present invention exhibit particularly remarkable effects when used in optical elements, particularly quantum dot displays, TFT arrays, and thin-film solar cells.
• Drying methods include drying by heating, drying under reduced pressure, drying by heating under reduced pressure, and the like. Although depending on the type of solvent, in the case of heat drying, the heating temperature is preferably 50 to 120°C.
• the curable resin composition contains an ink-repellent agent, the ink-repellent agent migrates to the upper layer of the dry film during the drying process.
• Examples of light to be irradiated during exposure include visible light; ultraviolet light; far ultraviolet light ; excimer laser light; X-rays; electron beams, and the like.
• Light with a wavelength of 100 to 600 nm is preferable, light with a wavelength of 300 to 500 nm is more preferable, and light including i-line (365 nm), h-line (405 nm) or g-line (436 nm) is particularly preferable as the light for irradiation.
• light of 330 nm or less may be cut as needed.
• Examples of the exposure method include full-surface exposure, scanning exposure, and the like.
• the same portion may be exposed to light in a plurality of times. At this time, the exposure conditions for multiple times may or may not be the same.
• the exposure amount is preferably 5 to 1,000 mJ/cm 2 , more preferably 5 to 500 mJ/cm 2 , still more preferably 5 to 300 mJ/cm 2 , and 5 to 200 mJ/cm 2 in any of the above exposure methods. 2 is particularly preferred, and 5-50 mJ/cm 2 is most preferred.
• the amount of exposure is appropriately optimized according to the wavelength of the light to be irradiated, the composition of the curable resin composition, the thickness of the coating film, and the like.
• the exposure time per unit area is not particularly limited, and is designed based on the exposure power of the exposure device used and the required exposure amount. In the case of scanning exposure, the exposure time is obtained from the light scanning speed.
• the exposure time per unit area is usually about 0.01 to 60 seconds.
• the curable resin composition is a negative photosensitive resin composition and contains an alkali-soluble resin having an ethylenic double bond or an alkali-soluble monomer (A) having an ethylenic double bond
• the exposure In part, the alkali-soluble resin or monomer (A) is radically polymerized during exposure, and the alkali-soluble resin or monomer (A) is crosslinked by the polyfunctional thiol compound (C).
• Development is performed using an alkaline developer, which forms partition walls and openings.
• the curable resin composition contains an ink-repellent agent
• an ink-repellent layer is formed on the uppermost layer including the upper surface of the partition walls, and an alkali-soluble resin and a polyfunctional thiol are mainly formed on the lower side of the ink-repellent layer.
• Photocuring components such as compounds and cross-linking agents are photocured to form a layer containing almost no ink repellent agent.
• the partition walls may be further heated.
• the heating temperature is preferably 130-250°C.
• the partition walls are hardened more firmly by heating.
• the ink-repellent agent is firmly fixed by the ink-repellent layer.
• a substrate with a partition was attached to remove the development residue of the curable resin composition that may exist in the opening. It may be subjected to UV/ozone treatment.
• the partition walls formed from the curable resin composition of the present invention preferably have a width of, for example, 100 ⁇ m or less, and particularly preferably 20 ⁇ m or less. Also, the distance (pattern width) between adjacent partition walls is preferably 300 ⁇ m or less, particularly preferably 100 ⁇ m or less. The height of the partition wall is preferably 0.05 to 50 ⁇ m, particularly preferably 0.2 to 10 ⁇ m.
• the partition walls formed from the curable resin composition of the present invention have less unevenness at the edges when formed with the above width and have excellent linearity. As a result, even a fine pattern can be formed with high accuracy. If such highly accurate pattern formation can be performed, it is particularly useful as partition walls for organic EL displays, quantum dot displays, TFT arrays, and thin film solar cells.
• the partition according to the present invention can be used as a partition whose opening is used as an ink injection region when pattern printing is performed by the IJ method.
• the partition wall has ink repellency
• the partition wall is formed so that the opening of the partition matches the desired ink injection region, the upper surface of the partition wall has good ink repellency. Injection of ink into an undesired opening, ie, an ink injection region (contamination) can be suppressed.
• the opening surrounded by the partition wall has good wetting and spreading properties of the ink, it is possible to uniformly print the ink in a desired area without causing repelling or the like.
• baking treatment is usually performed by heating at a temperature of about 150 to 300° C. for about 1 hour under a pressure of about 133 to 66500 Pa, for example.
• the polyfunctional thiol compound satisfies the specific conditions, less outgassing is generated during the baking process, so that the ink layer is less contaminated and an optical element with good properties can be manufactured.
• the cured resin film obtained using the curable resin composition of the present invention preferably has a water contact angle of 60 degrees or more, more preferably 80 degrees or more, on the surface.
• the water contact angle is easily within the above range, particularly 80 degrees or more.
• the contact angle of propylene glycol monomethyl ether acetate (PGMEA) on the surface of the cured resin film is preferably 30 degrees or more, more preferably 40 degrees or more.
• the curable resin composition preferably contains an ink repellent agent.
• the curable resin composition preferably contains an ink repellent agent. preferable.
• the cured resin film is formed on the substrate and used as it is.
• the surface of the cured resin film means the upper surface of the cured resin film.
• the ink-repellent property on the surface of the cured resin film is similarly exhibited on the upper surface of the partition wall. That is, regardless of whether the ink used in the IJ method is water-based or oil-based, the upper surface of the partition wall has a property of repelling the ink sufficiently, and contamination and repelling of the ink can be sufficiently suppressed in the openings.
• the contact angle is measured by placing water droplets or PGMEA droplets on the surface of the cured film at three locations according to JIS R3257 "Wettability test method for substrate glass surface" by the sessile drop method, and measuring each water droplet or PGMEA droplet. .
• the droplet size is 2 ⁇ L/drop, and the measurement is performed at 20°C.
• the contact angle is determined from the average value of 3 measured values.
• the partition according to the present invention is an optical element, particularly an organic EL display, a quantum dot display, a TFT array, a thin film, having a plurality of dots and partitions positioned between adjacent dots on the substrate surface on which dots are formed by the IJ method. It is useful as a partition wall for solar cells.
• optical element In the optical element having partition walls formed using the curable resin composition of the present invention, since the residue is reduced in the openings partitioned by the partition walls as described above, the ink spreads evenly and uniformly. is possible. Furthermore, the partition has excellent adhesion to the substrate. If the adhesion between the partition wall and the substrate is insufficient, for example, the ink may spread outside the opening, causing a problem. In the optical element having partition walls formed using the curable resin composition of the present invention, since the polyfunctional thiol compound in the composition satisfies the specific conditions as described above, less outgassing is generated during baking. , and has good characteristics with less contamination in the ink layer.
• the partition walls are made of, for example, inorganic oxides such as glass, aluminum oxide, tantalum oxide, and titanium oxide, inorganic nitrides such as silicon nitride and aluminum nitride, polyimide, polyamide, polyester, polyacrylate, photoradical polymerization, and photocationic polymerization.
• organic conductors such as carbon nanotubes, tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO ) is also excellent in adhesion to a substrate made of a conductive material.
• the optical element having the partition according to the present invention has dots formed with high accuracy by improving the adhesion of the partition to the base material and reducing the residue in the opening.
• Quantum dot displays, TFT arrays or thin film solar cells are examples of Quantum dot displays, TFT arrays or thin film solar cells.
• An organic EL display can be manufactured, for example, as follows, but is not limited to this.
• a light-transmitting electrode such as ITO is formed on a light-transmitting substrate such as glass by a sputtering method or the like. This translucent electrode is patterned as required.
• partition walls are formed in a grid pattern in plan view along the outline of each dot by a photolithography method including coating, exposure and development.
• the dots are coated with a charge injection material solution and/or a charge transport material solution as required by the IJ method, dried, and then a light emitting material solution that emits light electrically is coated and dried to fabricate a module. .
• an organic EL display with excellent color reproducibility can be obtained.
• a TFT array element has a plurality of dots arranged in a matrix in a plan view, each dot is provided with a pixel electrode and a TFT as a switching element for driving the pixel electrode, and an inorganic semiconductor layer as a semiconductor layer including a channel layer of the TFT. Alternatively, it is an element using an organic semiconductor layer.
• the organic TFT array element is provided, for example, as a TFT array substrate in a liquid crystal element.
• a TFT array can be manufactured, for example, as follows, but is not limited to this.
• a gate electrode made of aluminum or an alloy thereof is formed on a translucent substrate such as glass by a sputtering method or the like. This gate electrode is patterned as required.
• a gate insulating film such as silicon nitride is formed by plasma CVD or the like.
• a source electrode and a drain electrode may be formed on the gate insulating film.
• the source electrode and the drain electrode can be produced by forming a thin film of metal such as aluminum, gold, silver, copper, or alloys thereof by vacuum deposition or sputtering, for example.
• the source and drain electrodes As a method for patterning the source and drain electrodes, after forming a metal thin film, a resist is applied, exposed and developed to leave the resist in the area where the electrode is to be formed, and then exposed with phosphoric acid or aqua regia. There is a method of removing the metal and finally removing the resist. In addition, when a metal thin film such as gold is formed, a resist is applied in advance, exposed and developed to leave the resist in the areas where the electrodes are not to be formed. There are methods to remove it. Also, the source electrode and the drain electrode may be formed by a technique such as inkjet using a metal nanocolloid such as silver or copper.
• interlayer insulating film When forming an interlayer insulating film using the curable resin composition of the present invention, the tensile strength at break is high due to the crosslinked structure resulting from the enethiol reaction of the polyfunctional thiol compound and the crosslinking agent, and the stress stress of the film is reduced. It is possible to suppress the occurrence of cracks when forming an interlayer insulating film. Furthermore, even when heat treatment is performed in a post-process after the formation of the interlayer insulating film, outgassing is small and a low dielectric constant can be maintained.
• [charge] A compound obtained by substituting all —SH groups of a polyfunctional thiol compound with —S—C 2 H 5 , that is, a reaction product of a polyfunctional thiol compound and ethylene was subjected to spontaneous electron density analysis to obtain a charge density.
• Natural electron density analysis uses quantum chemical calculation software Gaussian 16, structure optimization with DFT (B3LYP / 6-31G (d)), NBO version 3.1 (NBO Version 3.1, ED Glendening, A .E. Reed, JE Carpenter, and F. Weinhold.).
• the column was held at 37 ° C., tetrahydrofuran was used as the eluent, the flow rate was 0.2 mL / min, and a 0.5% tetrahydrofuran solution of the measurement sample was used. 40 ⁇ L was injected.
• fluorine atom content was calculated by 19 F NMR measurement using 1,4-ditrifluoromethylbenzene as a standard substance.
• a resin alkali-soluble resin (A2), acid value 50 mg KOH/g).
• the composition of the alkali-soluble resin (A2) (solid content: 70% by mass, PGMEA: 30% by mass) was used.
• Polyfunctional thiol compounds C1 to C3 and CR1 to CR3 were synthesized with reference to the method described in Japanese Patent Application Laid-Open No. 2011-84479.
• ink repellent agent (D) An ink repellent agent (D2-1) synthesized by the following method using the following raw material compounds was used.
• raw material compound Compound (s1-1); F(CF 2 ) 6 CH 2 CH 2 Si(OCH 3 ) 3 (produced by a known method) Compound (s2-1); Si(OC 2 H 5 ) 4 Compound (s3-1); CH 2 ⁇ CHCOO(CH 2 ) 3 Si(OCH 3 ) 3
• the obtained ink repellent agent (D2-1) had a number average molecular weight (Mn) of 1200, a mass average molecular weight (Mw) of 1310, and a measured fluorine atom content of 21.0% by mass. rice field.
• each curable resin composition obtained above using a spinner After applying each curable resin composition obtained above using a spinner to the surface of the glass substrate after the washing, it is dried on a hot plate at 100 ° C. for 2 minutes to dry to a film thickness of 2.4 ⁇ m. A film was formed. The entire surface of the resulting dry film was irradiated with UV light from an ultra-high pressure mercury lamp having an exposure power (exposure output) of 300 mW/cm 2 in terms of 365 nm. By this method, two types of cured films were produced by adjusting the irradiation time so that the exposure amount was 50 mJ/cm 2 . In each case, light of 330 nm or less was cut during exposure.
• the exposed glass substrate was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution for 60 seconds, rinsed with water, and then dried. Then, this was heated on a hot plate at 230° C. for 60 minutes to obtain a cured film without openings.
• a primary trap tube containing 8 glass substrates with a cured film cut to 1 ⁇ 4 cm was cut to 230 using a P&T-GCMS apparatus consisting of Shimadzu's "HS-20TRAP” and Shimadzu's "GCMS-QP2020". C. for 60 minutes, and the evolved gas was collected in a secondary trap tube cooled to -10.degree. The secondary trap tube was then heated to 250° C. and the released gas was chromatographed. As a standard sample, triallyl isocyanurate was placed in the primary trap tube, and the chromatogram was measured in the same manner as above.
• outgassing amount is less than 0.1 ⁇ g
• outgassing amount is 0.1 ⁇ g or more
• Water droplets or PGMEA droplets were placed on the upper surface of the cured film at three locations according to JIS R3257 "Testing method for wettability of substrate glass surface" by the sessile drop method, and each water droplet or PGMEA droplet was measured.
• the droplet size was 2 ⁇ L/drop, and the measurement was performed at 20°C.
• the contact angle was calculated from the average value of 3 measured values. ⁇ : The average value of the contact angle is 40 ° or more ⁇ : The average value of the contact angle is less than 40 °
• Examples 1 to 4 are working examples, and examples 5 to 8 are comparative examples.
• the curable resin compositions of Examples 1 to 4 containing polyfunctional thiol compounds satisfying the specific conditions produced cured films with a small amount of outgassing and excellent ink repellency.
• Examples 3 and 4 in which the SH group of the polyfunctional thiol compound is secondary have higher storage stability than Examples 1 and 2, in which the SH group is primary.
• a large amount of outgas was generated in the curable resin compositions of Examples 5 to 7, in which the polyfunctional thiol compound did not satisfy the specific conditions.
• the curable resin composition of the present invention is suitable as a composition for forming barrier ribs when performing pattern printing by the IJ method in optical elements such as organic EL displays, quantum dot displays, TFT arrays or thin-film solar cells. can be used for
• the curable resin composition of the present invention can also be suitably used as a composition for forming hard coats in optical parts and the like.
• the curable resin composition of the present invention can also be suitably used as a composition for forming interlayer insulating films in semiconductor members and the like.

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