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
• • 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
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
• • 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
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • 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
  • G03F7/075—Silicon-containing compounds
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
  • H05B33/22—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
• • 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

Definitions

• the present invention relates to a photosensitive resin composition, a cured product, a display device, and a method for manufacturing a display device.
• organic EL display devices Many products using organic electroluminescence (hereinafter referred to as "organic EL") display devices have been developed in display devices with flat displays, such as smartphones, tablet PCs, and televisions.
• an organic EL display device has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode on a substrate, and between the opposing first and second electrodes, It can emit light by applying voltage.
• photosensitive resin compositions that can be patterned by ultraviolet irradiation are generally used as materials for the flattening layer and materials for the insulating layer.
• photosensitive resin compositions using polyimide-based or polybenzoxazole-based resins have high heat resistance and generate little gas components from the cured product, so they can provide highly durable organic EL display devices. It is suitably used because it can be used (Patent Document 1).
• a solution of a functional material such as a luminescent material, a hole transport material, an electron transport material, etc. is dropped into the openings between the barrier ribs using an inkjet method.
• a method of forming an organic EL display device having a functional layer is known.
• Patent Document 2 a method is being considered in which the upper surface of the partition pattern on the substrate is subjected to fluorination treatment by plasma irradiation to develop liquid repellency.
• a method of forming partition walls using a photosensitive resin composition to which a liquid-repellent compound is added is also being considered.
• a resist composition containing a polymer having a specific fluorinated alkyl group Patent Document 3
• a photosensitive resin composition containing a polysiloxane having a perfluoroalkylene group Patent Document 4
• Patent Document 1 Since the technology of Patent Document 1 does not have liquid repellency on the upper surface of the formed partition wall, there is a problem in that the functional material solution dropped by the inkjet method crosses the partition wall and mixes into neighboring pixels, causing poor light emission. .
• Patent Document 2 has a problem in that the liquid-repellent component also adheres to the openings between the partition walls due to the fluorination treatment, resulting in insufficient ink wettability at the openings.
• Patent Document 3 and Patent Document 4 have sufficient liquid repellency and can form a pattern as a photosensitive resin composition, but the wettability of the openings to ink is insufficient.
• the polymer having a fluorinated alkyl group disclosed in Patent Document 3 has poor UV ozone resistance, and the liquid repellency of the upper surface of the partition wall is insufficient after UV ozone treatment. Furthermore, it has poor heat resistance and has problems with ink wettability due to contamination of the openings during curing.
• the polysiloxane having a perfluoroalkylene group described in Patent Document 4 has excellent heat resistance, but has insufficient alkali solubility, so there is a problem with ink wettability due to opening residue after development. Further, there is a problem that the polysiloxane having a fluorine atom and the alkali-soluble resin are not sufficiently compatible with each other, resulting in defects in the cured product.
• the present invention aims to solve the problems associated with the prior art as described above, and to obtain a partition wall pattern that has few defects, has high liquid repellency on the top surface of the partition wall, and has excellent ink wettability at the openings. do.
• Component (A-1) polysiloxane containing perfluoroalkyl group or/and perfluoroalkylene ether group
• Component (A-2) Acrylic polymer containing perfluoroalkyl group or/and perfluoroalkylene ether group.
• the photosensitive resin composition according to (1) wherein the content of the liquid repellent material (A) is 0.1 to 5 parts by mass based on 100 parts by mass of total solids.
• the mass ratio (A-1)/(A-2) of the content of the component (A-2) to the content of the component (A-1) is 1/100 to 100 (1) or The photosensitive resin composition described in (2).
• the mass ratio (A-1)/(A-2) of the content of the component (A-2) to the content of the component (A-1) is 1 to 10 (1) to (3)
• R f is a perfluoroalkyl group having 3 to 10 carbon atoms and/or a perfluoroalkylene ether group having 3 to 30 carbon atoms
• R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a perfluoroalkyl group having 1 to 6 carbon atoms.
• R 2 is an aryl group having 6 to 15 carbon atoms
• R 3 is a single bond or an alkylene group having 1 to 4 carbon atoms
• z is an aryl group having 6 to 15 carbon atoms. 1 or 2.
• R 4 is a monovalent organic group containing an acidic group and having 2 to 20 carbon atoms. * indicates a covalent bond.
• R 2 is a 1-naphthyl group, a 2-naphthyl group, or a structure represented by formula (11).
• R 8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• R 9 represents a divalent aliphatic group having 1 to 6 carbon atoms
• R 10 represents formula (24) (* indicates a covalent bond.)
• X is selected from structural formulas (a) to (e), and all Xs may have the same structure, or multiple structures may exist randomly or in a block form.
• m is a repeating An integer from 1 to 30 representing the number of units. * indicates a covalent bond.
• the photosensitive resin composition of the present invention By using the photosensitive resin composition of the present invention, it is possible to obtain a partition wall pattern with few defects, high liquid repellency on the upper surface of the partition wall, and excellent ink wettability at the openings.
• FIG. 2 is a schematic diagram of a substrate used for evaluation in Examples.
• FIG. 2 is a schematic cross-sectional view of an example of a substrate with partition walls.
• FIG. 7 is a schematic cross-sectional view of another example of a substrate with partition walls.
• the photosensitive resin composition of the present invention is a photosensitive resin composition containing a liquid repellent material (A), an alkali-soluble resin (B), and a photosensitizer (C), in which the liquid repellent material (A) is
• This is a photosensitive resin composition containing component (A-1) and component (A-2).
• Component (A-1) Polysiloxane containing perfluoroalkyl group or/and perfluoroalkylene ether group
• Component (A-2) Acrylic polymer containing perfluoroalkyl group or/and perfluoroalkylene ether group ⁇ Liquid repellent material (A)>
• the liquid repellent material (A) contains the following components (A-1) and (A-2).
• component (A-1) By containing component (A-1) and component (A-2), it is possible to achieve both liquid repellency on the upper surface of the cured film and compatibility with the alkali-soluble resin (B).
• Component (A-1) Polysiloxane containing perfluoroalkyl group or/and perfluoroalkylene ether group
• Component (A-2) Acrylic polymer containing perfluoroalkyl group or/and perfluoroalkylene ether group
• the component (A-1) is , (i), (ii) and (iii).
• the main chain polysiloxane since the main chain polysiloxane has excellent heat resistance, it does not decompose during the curing process, prevents the liquid repellent component from scattering to the openings, and improves the wettability of the functional ink applied to the openings. can.
• R f is a perfluoroalkyl group having 3 to 10 carbon atoms and/or a perfluoroalkylene ether group having 3 to 30 carbon atoms
• R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a perfluoroalkylene ether group having 1 to 6 carbon atoms.
• R 2 is an aryl group having 6 to 15 carbon atoms
• R 3 is a single bond or an alkylene group having 1 to 4 carbon atoms
• z is 1 or 2.
• R 4 is a monovalent organic group containing an acidic group and having 2 to 20 carbon atoms. * indicates a covalent bond.
• Component (A-1) preferably has a repeating structural unit represented by formula (1) and/or formula (2) of (i).
• R f in the repeating structural unit represented by formula (1) and/or formula (2) is a perfluoroalkyl group having 3 to 10 carbon atoms and/or a perfluoroalkylene ether group having 3 to 30 carbon atoms.
• perfluoroalkyl group having 10 or less carbon atoms and/or a perfluoroalkylene ether group having 30 or less carbon atoms good compatibility with the alkali-soluble resin to be used later can be obtained. More preferred are perfluoroalkyl groups having 4 to 8 carbon atoms and/or perfluoroalkylene ether groups having 6 to 25 carbon atoms. More preferred is a perfluoroalkylene ether group having 6 to 25 carbon atoms from the viewpoint of reducing the burden on the environment.
• perfluoroalkyl group for R f examples include heptafluoropentyl group, nonafluorohexyl group, undecafluoroheptyl group, tridecafluorooctyl group, pentadecafluorononatyl group, heptadecafluorodecyl group, 5, Examples include 5,6,6,7,7,7-heptafluoro-4,4-bis(trifluoromethyl)heptyl group. From the viewpoint of liquid repellency and environmental impact, nonafluorohexyl, undecafluoroheptyl, and tridecafluorooctyl groups having 6 to 8 carbon atoms are preferred.
• the perfluoroalkylene ether group of R f has at least one -O-CF 2 - group or -CF 2 -O- group and is represented by formula (7) or formula (8), for example. preferable.
• M is an alkylene group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms.
• Y is a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and at least one Y in each repeating unit bounded by n1, n2, n3, n4, and n5 is a fluorine atom or a trifluoromethyl group.
• n1, n2, n3, and n4 are each independently an integer of 0 to 20, and n1+n2+n3+n4 is 1 or more.
• n5 is an integer from 1 to 4.
• the order of each repeating unit grouped by n1, n2, n3, and n4 in formula (7) and formula (8) is not limited.
• Z is a divalent organic group having 1 to 6 carbon atoms. * indicates a covalent bond.
• Examples of the alkylene group having 1 to 4 carbon atoms represented by M include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, etc.
• Examples of the fluorinated alkyl group of ⁇ 4 include linear perfluoroalkyl groups.
• divalent organic group having 1 to 6 carbon atoms represented by Z include the following.
• n is an integer of 1 to 5 independently for each group. * indicates a covalent bond.
• Preferred specific examples of the perfluoroalkylene ether group represented by R f include the following. * indicates a covalent bond.
• the component (A-1) is a perfluoroalkylene ether group-containing polysiloxane. That is, it is preferable that the above-mentioned R f is a perfluoroalkylene ether group.
• component (A-1) is a perfluoroalkylene ether group-containing polysiloxane, it is possible to achieve both good liquid repellency on the surface of the cured film and good wettability of the functional ink applied to the openings.
• the total amount of repeating structural units represented by formula (1) and/or formula (2) be 5 to 30 mol% in 100 mol% of all repeating structural units of component (A-1). More preferably, it is 10 to 25 mol%.
• Good liquid repellency can be exhibited by containing 5 mol % or more of the repeating structural unit represented by formula (1) and/or formula (2). Further, by containing 30 mol% or less, aggregation of R f can be reduced.
• Component (A-1) has a repeating structural unit represented by formula (3) and/or formula (4) of (ii). Since the repeating structural unit represented by formula (3) and/or formula (4) has an aryl group, aggregation of R f can be suppressed due to steric hindrance of the aryl group, and a cured product with few defects can be obtained.
• R 2 is an aryl group having 6 to 15 carbon atoms.
• R 6 is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, A hydroxyalkyl group having 1 to 5 carbon atoms or a halogenated hydroxyalkyl group having 1 to 5 carbon atoms.
• b represents an integer from 0 to 3. * indicates a covalent bond.
• alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and the like.
• alkoxy group having 1 to 5 carbon atoms include methoxy group and ethoxy group.
• halogenated alkyl group having 1 to 5 carbon atoms include trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, trichloromethyl group, pentachloroethyl group, heptachloropropyl group, and the like.
• hydroxyalkyl group having 1 to 5 carbon atoms include hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, and 3-hydroxypropyl group.
• halogenated hydroxyalkyl group having 1 to 5 carbon atoms include the following structures. In the structural formula, * indicates a covalent bond.
• R 6 may be bonded to either of the two rings of the naphthalene ring.
• b is an integer from 0 to 3. From the viewpoint of polymerizability, b is preferably 0 to 2, more preferably 0 to 1.
• formula (9) examples include phenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 3-t-butylphenyl group, 4-t-butyl group.
• * represents a covalent bond directly connected to R 3 in formula (3) or formula (4).
• R 3 in the formula (3) or formula (4) is a single bond, it represents a covalent bond directly connected to a silicon atom.
• a represents an integer from 1 to 3. From the viewpoint of polymerizability, a is preferably 1 to 2, and more preferably 1.
• Specific examples of the structure represented by formula (11) include the following structures.
• formula (10) include 1-naphthyl group, 2-naphthyl group, 4-methyl-1-naphthyl group, 4-hydroxy-1-naphthyl group, 4-hydroxymethyl-1-naphthyl group, etc. It will be done.
• the photosensitive resin composition in which component (A-1) has a repeating structural unit represented by formula (1) and/or formula (2) of (i) has the effect of inhibiting aggregation of R f and the polymerizability.
• component (A-1) has a repeating structural unit represented by formula (1) and/or formula (2) of (i) has the effect of inhibiting aggregation of R f and the polymerizability.
• at least one of the R 2 groups is a 1-naphthyl group, a 2-naphthyl group, or a structure represented by formula (11).
• z in the repeating structural unit represented by formula (4) is more preferably 1.
• R 3 is a single bond or an alkylene group having 1 to 4 carbon atoms.
• alkylene group having 1 to 4 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, and t-butylene group.
• a total of 20 to 70 mol% of repeating structural units represented by formula (3) and/or formula (4) be contained in 100 mol% of all repeating structural units of component (A-1). More preferably, it is 30 to 60 mol%.
• a total of 20 mol % or more of repeating structural units represented by formula (3) and formula (4) a good effect of suppressing aggregation of R f can be obtained. Further, from the viewpoint of controlling polymerizability, it is preferably 70 mol% or less.
• Component (A-1) has a repeating structural unit represented by formula (5) and/or formula (6) of (iii). Since the repeating structural unit represented by formula (5) and/or formula (6) has a monovalent organic group having 2 to 20 carbon atoms including an acidic group, it has improved solubility in an alkaline developer and has good properties. Ink wettability of the opening can be obtained.
• the monovalent organic group having 2 to 20 carbon atoms containing an acidic group may contain at least one acidic group selected from the group consisting of a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, and a sulfonic acid group.
• a structure represented by formula (12) or formula (13) is more preferable.
• R 7 is a single bond or an alkylene group having 1 to 10 carbon atoms. * indicates a covalent bond.
• R 4 more preferably has a carboxyl group. That is, in the photosensitive resin composition of the present invention, R 4 is preferably a monovalent organic group having 2 to 20 carbon atoms and containing a carboxyl group. When R 4 is a monovalent organic group having 2 to 20 carbon atoms and containing a carboxyl group, it is possible to obtain both good opening ink wettability and a cured product with few defects. Furthermore, a dicarboxy group obtained by hydrolyzing a carboxylic anhydride group is more preferable.
• monovalent organic groups having 2 to 20 carbon atoms containing acidic groups include 2-hydroxyethyl group, 3-hydroxypropyl group, bis(2-hydroxyethyl)-3-aminopropyl group, and carboxymethyl group.
• As the structure having a carboxyl group, a carboxymethyl group, a 2-carboxyethyl group, a 3-carboxypropyl group, a structure ( ⁇ ), and a structure ( ⁇ ) are preferable, and a structure ( ⁇ ) and a structure ( ⁇ ) are more preferable.
• * indicates a covalent bond directly connected to the silicon atom.
• a total of 1 to 40 mol% of repeating structural units represented by formula (5) and/or formula (6) be contained in 100 mol% of all repeating structural units of component (A-1). More preferably, it is 5 to 30 mol%.
• a total of 1 mol % or more of the repeating structural units represented by formula (5) and/or formula (6) good ink wettability and compatibility at the opening can be exhibited. Further, by containing 40 mol% or less, good liquid repellency can be exhibited.
• component (A-1) further has a repeating structural unit represented by formula (14).
• Having the repeating structural unit represented by formula (14) increases the degree of polymerization of component (A-1), makes component (A-1) difficult to decompose in the curing process, and prevents the liquid-repellent component from entering the opening. It is possible to prevent scattering and further improve the wettability of the functional ink applied to the opening.
• Component (A-1) preferably contains 30 to 300 parts by mole of the repeating structural unit represented by formula (14) per 100 parts by mole of the repeating structural unit of (iii). Since the acidic group contained in the repeating structural unit (iii) acts as an acid catalyst, it is possible to increase the degree of polymerization of the repeating structural unit represented by formula (14). The heat resistance of component (A-1) is improved by containing 30 mole parts or more of the repeating structural unit represented by formula (14) with respect to 100 mole parts of the repeating structural unit of (iii).
• component (A-1) contains 300 mole parts or less of the repeating structural unit represented by formula (14) with respect to 100 mole parts of the repeating structural unit of (iii), thereby forming the alkali-soluble resin (B) described below. It becomes easier to improve the compatibility with.
• Component (A-1) may have a repeating structural unit represented by formula (15) and/or formula (16).
• R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms
• R 5 is R f , R 2 -R 3 -, and R 4 represents a monovalent organic group having 1 to 10 carbon atoms. * indicates a covalent bond.
• R 5 is not particularly limited as long as it is an organic group having 1 to 10 carbon atoms that does not fall under any of R f , R 2 -R 3 -, and R 4 .
• R5 include hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, and cyclohexyl group; 3-amino Amino group-containing groups such as propyl group, N-(2-aminoethyl)-3-aminopropyl group, N- ⁇ -(aminoethyl)- ⁇ -aminopropyl group; cyano group-containing groups such as ⁇ -cyanoethyl group ; glycidoxymethyl group, ⁇ -glycidoxyethyl group, ⁇ -glycidoxypropyl group, ⁇ -glycidoxyprop
• fluoro group-containing groups ⁇ , ⁇ -unsaturated ester group-containing groups such as ⁇ -acryloylpropyl group and ⁇ -methacryloylpropyl group
• vinyl group-containing groups such as vinyl group and styryl group; and the like.
• R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. It is. From the viewpoint of controlling polymerizability, R 1 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. Among these, from the viewpoint of controlling polymerizability, a hydrogen atom, a methyl group, and an ethyl group are more preferable.
• Component (A-1) is, for example, an alkoxysilane represented by the following formulas (17), (18), and (19), and optionally the following formulas (20) and (21), in a solvent. , can be obtained by hydrolysis and polycondensation.
• Component (A-1) is preferably a polysiloxane obtained in this manner.
• R f is a perfluoroalkyl group having 3 to 10 carbon atoms and/or a perfluoroalkylene ether group having 3 to 30 carbon atoms
• R 1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a perfluoroalkylene ether group having 1 to 6 carbon atoms.
• R 2 is an aryl group having 6 to 15 carbon atoms
• R 3 is a single bond or an alkylene group having 1 to 4 carbon atoms
• z is 1 or 2.
• R 4 is a monovalent organic group containing an acidic group and having 2 to 20 carbon atoms.
• R 5 is an organic group having 1 to 10 carbon atoms.
• the hydrolysis reaction is carried out after adding an acid catalyst and water to the alkoxysilanes represented by formulas (17), (18) and (19), and optionally formulas (20) and (21) in a solvent.
• the reaction is preferably carried out at room temperature to 110°C for 1 to 180 minutes. By carrying out the hydrolysis reaction under such conditions, rapid reaction can be suppressed.
• the reaction temperature is more preferably 40 to 105°C.
• the reaction solution After obtaining a silanol compound through a hydrolysis reaction, it is preferable to heat the reaction solution at a temperature of 50° C. or higher and below the boiling point of the solvent for 1 to 100 hours to perform a condensation reaction. Furthermore, in order to increase the degree of polymerization of the siloxane compound obtained by the condensation reaction, it is also possible to add an acid or base catalyst or to perform reheating.
• Various conditions in the hydrolysis reaction can be appropriately set in consideration of the reaction scale, the size and shape of the reaction container, etc. For example, by setting the acid concentration, reaction temperature, reaction time, etc., a polysiloxane having a desired degree of polymerization can be obtained.
• Ion-exchanged water is preferably used as the water for the hydrolysis reaction.
• the amount of water can be arbitrarily selected, it is preferably used in a range of 1.0 to 4.0 mol per 1 mol of the alkoxysilane compound.
• Solvents used in the hydrolysis reaction include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 3-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene Glycol mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, ethylene glycol, propylene glycol, benzyl alcohol, 2-methylbenzy
• acid catalysts used in the hydrolysis reaction include acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids or their anhydrides, and ion exchange resins.
• acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polycarboxylic acids or their anhydrides, and ion exchange resins.
• an acidic aqueous solution using formic acid, acetic acid or phosphoric acid is preferred.
• the content of the acid catalyst is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of all the alkoxysilane compounds used during the hydrolysis reaction. Further, the content of the acid catalyst is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
• the total amount of alkoxysilane compounds refers to an amount that includes all alkoxysilane compounds, their hydrolysates, and their condensates, and the same shall apply hereinafter.
• the polysiloxane solution after hydrolysis and partial condensation does not contain the above catalyst, and the catalyst can be removed if necessary.
• washing with water and/or treatment with an ion exchange resin are preferred from the viewpoint of ease of operation and removability.
• Water washing is a method in which a polysiloxane solution is diluted with a suitable hydrophobic solvent, washed several times with water, and the resulting organic layer is concentrated using an evaporator or the like.
• Treatment with an ion exchange resin is a method in which a polysiloxane solution is brought into contact with a suitable ion exchange resin.
• Component (A-2) preferably has a structural unit represented by formula (22) or formula (23).
• component (A-2) has a structural unit represented by formula (22) or formula (23)
• the cured film surface can exhibit good liquid repellency.
• R 8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• R 9 represents a divalent aliphatic group having 1 to 6 carbon atoms
• R 10 represents a group represented by formula (24). It has a structure that is In formula (23), R 14 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 15 represents a divalent aliphatic group having 1 to 6 carbon atoms, and R 16 represents an aliphatic group having 3 to 10 carbon atoms.
• R 10 and R 16 preferably have 3 or more carbon atoms, and from the viewpoint of compatibility with the alkali-soluble resin (B) described later, preferably have 30 or less carbon atoms.
• X is selected from structural formulas (a) to (e), and all Xs may have the same structure, or a plurality of structures may exist randomly or in a block shape.
• m is an integer from 1 to 30 representing the number of repeating units. * indicates a covalent bond.
• the alkyl group having 1 to 4 carbon atoms in R 8 in formula (22) and R 14 in formula (23) is a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, Examples include isobutyl group and tert-butyl group, and examples of the divalent aliphatic group having 1 to 6 carbon atoms in R 9 and R 15 include groups represented by the following structure. In the structural formula, * indicates a covalent bond.
• perfluoroalkyl group having 3 to 10 carbon atoms represented by R 16 include heptafluoropropyl group, nonafluorobutyl group, undecafluoropentyl group, and tridecafluorohexyl group. , a pentadecafluoroheptyl group, a heptadecafluorooctyl group, and the like. From the viewpoint of liquid repellency and environmental impact, tridecafluorohexyl, pentadecafluoroheptyl, and heptadecafluorooctyl groups each having 6 to 8 carbon atoms are preferred.
• component (A-2) is an acrylic polymer containing a perfluoroalkylene ether group. Since component (A-2) is an acrylic polymer containing a perfluoroalkylene ether group, the cured film surface maintains good liquid repellency, and the functional ink applied to the openings has good wettability, which will be described later. The compatibility with the alkali-soluble resin (B) can be improved.
• a preferred example of the perfluoroalkylene ether group-containing acrylic polymer is an acrylic polymer having a structural unit represented by formula (22). That is, it is preferable that the component (A-2) has a structural unit represented by formula (22). When component (A-2) has the structural unit represented by formula (22), it is possible to further improve the good wettability of the functional ink applied to the opening.
• component (A-2) has a structural unit represented by formula (22), it is preferable that it further has a structural unit represented by formula (25).
• component (A-2) has a structural unit represented by formula (25)
• its compatibility with the alkali-soluble resin (B) described later is improved, and a cured product with fewer defects can be obtained.
• R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• R 12 represents a divalent aliphatic group having 1 to 6 carbon atoms
• R 13 represents a urethane group of formula (26) or formula (27). * indicates a covalent bond.
• the alkyl group having 1 to 4 carbon atoms in R 11 includes a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, etc.
• the divalent aliphatic group having 1 to 6 carbon atoms in R 12 is a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an oxymethylene group.
• (A-2) has a structural unit represented by formula (23), it is preferable that it further has a structural unit represented by formula (28). Since (A-2) has the structural unit represented by formula (28), the compatibility with the alkali-soluble resin (B) described later is improved, and a cured product with fewer defects can be obtained.
• R 17 , R 18 and R 19 represent a monovalent organic group having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be the same or different. * indicates a covalent bond.
• the alkyl group having 1 to 4 carbon atoms in R 17 , R 18 and R 19 is a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, Examples include tert-butyl group.
• Preferred examples of the structural unit represented by formula (28) include N,N-dimethylacrylamide and N,N-diethylacrylamide.
• Component (A-2) preferably contains a compound having a structural unit represented by formula (22) and a structure represented by formula (25). By including such a compound, the compatibility of the liquid repellent material (A) with the alkali-soluble resin (B) can be further improved.
• liquid repellent material containing a compound having a structural unit represented by formula (22) and a structure represented by formula (25), "Megafac” (registered trademark) RS-72-K, RS-72 -A, RS-75, RS-76-E, RS-76-NS, RS-78, and RS-90 (all trade names, manufactured by DIC Corporation).
• Component (A-2) is usually a (co)polymer.
• the (co)polymer as a compound contained in component (A-2) can be obtained by a known polymerization method.
• the (co)polymer may be obtained by, for example, ionic polymerization such as radical polymerization or anionic polymerization. Further, it may be a random copolymer, a block copolymer, a graft (co)polymer, or an alternating copolymer.
• Component (A-2) can be obtained, for example, by (co)polymerizing a (meth)acrylate monomer represented by formula (29) and a (meth)acrylate monomer represented by formula (30).
• R 8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• R 9 represents a divalent aliphatic group having 1 to 6 carbon atoms
• R 10 represents the above-mentioned formula (24). It has the structure represented by * indicates a covalent bond.
• R 10 preferably has 3 or more carbon atoms, and from the viewpoint of compatibility with the alkali-soluble resin (B) described below, R 10 preferably has 30 or less carbon atoms.
• the alkyl group having 1 to 4 carbon atoms in R 8 is the same as the alkyl group having 1 to 4 carbon atoms in R 8 in the above-mentioned formula (22), and the alkyl group having 1 to 4 carbon atoms in R 9
• the aliphatic group 6 is the same as the aliphatic group having 1 to 6 carbon atoms in R 9 in the above-mentioned formula (22).
• R 11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• R 12 represents a divalent aliphatic group having 1 to 6 carbon atoms
• R 13 represents a urethane group represented by the above-mentioned formula (26) or formula (27).
• the alkyl group having 1 to 4 carbon atoms in R 11 is the same as the alkyl group having 1 to 4 carbon atoms in R 11 in the above-mentioned formula (25), and the alkyl group having 1 to 4 carbon atoms in R 12 is the same as the alkyl group having 1 to 4 carbon atoms in R 12 .
• the divalent aliphatic group 6 is the same as the divalent aliphatic group having 1 to 6 carbon atoms in R 12 in the above-mentioned formula (25).
• Preferred examples of the (meth)acrylate monomer represented by formula (29) include 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, and the like. More preferable examples include the following structures.
• k is an integer from 1 to 30 representing the number of repeating units
• l is an integer from 1 to 30 representing the number of repeating units.
• Preferred examples of the (meth)acrylate monomer represented by formula (30) include the following structures.
• x is an integer from 1 to 30 representing the number of repeating units
• y is an integer from 1 to 30 representing the number of repeating units.
• component (A-2) has a structural unit represented by formula (22), from the viewpoint of achieving both liquid repellency on the upper surface of the cured film and compatibility with alkali-soluble resin (B), formula (22)
• the total number of fluorine atoms contained in the structural unit represented by is preferably in the range of 18 to 200, more preferably in the range of 25 to 150.
• the structural unit represented by formula (25) tends to improve its compatibility with the alkali-soluble resin (B), it may be contained in an amount of 15 mol% or more of the total structural units constituting component (A-2). It is preferably 30 mol% or more, and more preferably 30 mol% or more. Further, in order to facilitate the development of liquid repellency on the surface of the cured film, the amount is preferably 98 mol% or less, and more preferably 95 mol% or less.
• component (A-2) has a structural unit represented by formula (23), from the viewpoint of achieving both liquid repellency on the upper surface of the cured film and compatibility with alkali-soluble resin (B), formula (23)
• the structural unit represented by is preferably contained in an amount of 1 to 40 mol% of the total structural units constituting component (A-2). More preferably, it is 5 to 30 mol%.
• the structural unit represented by formula (28) tends to improve compatibility with the alkali-soluble resin (B), it may be contained in an amount of 15 mol% or more of the total structural units constituting component (A-2). It is preferably 30 mol% or more, and more preferably 30 mol% or more. Further, in order to facilitate the development of liquid repellency on the surface of the cured film, the amount is preferably 85 mol% or less, and more preferably 70 mol% or less.
• Component (A-2) may also be a copolymer obtained by copolymerizing a (meth)acrylate monomer having a cyclic ether structure.
• a cyclic ether structure By having a cyclic ether structure, it is polycondensed with the alkali-soluble resin (B), reducing the scattering of the liquid-repellent component to the openings, making it easier to further improve the wettability of the functional ink applied to the openings.
• An example of the cyclic ether structure is preferably an epoxy group or an oxetanyl group.
• Preferred examples of (meth)acrylate monomers having a cyclic ether structure include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether (hereinafter referred to as 4-HBAGE), 4-hydroxybutyl methacrylate glycidyl ether, (3-ethyl Examples include methyl acrylate (oxetan-3-yl), methyl methacrylate (3-ethyloxetan-3-yl), acrylate having an alicyclic epoxy group or oxetanyl group, and metharylate having an alicyclic epoxy group or oxetanyl group.
• Component (A-2) may also be a copolymer obtained by copolymerizing different functional group-substituted (meth)acrylic monomers. Furthermore, by copolymerizing different functional group-substituted (meth)acrylic monomers, it is possible to easily balance liquid repellency and alkali solubility. For example, hydroxyl group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylamides, alkoxy group-containing (meth)acrylates, blocked isocyanate group-containing (meth)acrylates, phenoxy group-containing (meth)acrylates, alkyl (meth)acrylates. Examples include acrylates and vinyl group-containing compounds.
• hydroxyl group-containing (meth)acrylates examples include 2-hydroxyethyl (meth)acrylate.
• hydroxyl group-containing (meth)acrylamides examples include N-hydroxymethylacrylamide.
• Examples of (meth)acrylates having an alkoxy group include 3-methacryloxypropylmethyldimethoxysilane.
• Blocked isocyanate group-containing (meth)acrylates include, for example, 2-(0-[1′-methylpropylideneamino]carboxyamino)ethyl methacrylate (“Karens” (registered trademark) MOI-BM; manufactured by Showa Denko K.K. (manufactured by), etc.
• phenoxy group-containing (meth)acrylates examples include 2-phenoxybenzyl acrylate and 3-phenoxybenzyl acrylate.
• Alkyl (meth)acrylates are unsubstituted, substituted with at least one of an amino group, a monoalkylamino group, a dialkylamino group, a hydrocarbon aromatic ring, or a heterocycle, or have an acid anhydride cleaved and added to a hydroxy group.
• Examples include diluent monomers that are unsubstituted or substituted alkyl (meth)acrylates having a linear, branched, and/or cyclic alkyl group having 1 to 12 carbon atoms, such as alkyl acrylates.
• vinyl group-containing compounds examples include n-butyl vinyl ether.
• the weight average molecular weight (Mw) of the liquid repellent material (A) is not particularly limited, but is preferably 500 or more, more preferably 1,500 or more in terms of polystyrene measured by GPC (gel permeation chromatography). . Further, it is preferably 20,000 or less, more preferably 10,000 or less. By setting the weight average molecular weight within this range, the compatibility with the alkali-soluble resin (B) tends to improve, and the antifoaming property of the photosensitive resin composition solution tends to increase.
• the content of the liquid repellent material (A) is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total solid content.
• the total solid content refers to other components excluding the organic solvent described below.
• the content of the liquid repellent material (A) is within the above-mentioned preferred range, the upper surface of the obtained cured film will easily exhibit sufficient liquid repellency, and it will also be difficult to cause liquid repellency within the pixel, and the openings will It is possible to improve the wettability of the functional ink applied to the surface.
• the content of the liquid repellent material (A) is more preferably 0.3 parts by mass or more, and more preferably 3 parts by mass or less.
• the mass ratio (A-1)/(A-2) of the content of component (A-2) to the content of component (A-1) is preferably 1/100 to 100, and 1 to 10 It is more preferable that By setting the above mass ratio (A-1)/(A-2) in the range of 1/100 to 100, it is possible to achieve both liquid repellency on the upper surface of the cured film and compatibility with the alkali-soluble resin (B). can. Furthermore, by setting the mass ratio (A-1)/(A-2) in the range of 1 to 10, the effect of suppressing the aggregation of component (A-1) becomes greater, and the alkali-soluble resin (B ) can be improved.
• the appropriate amount of the liquid repellent material (A) to be added is determined by dropping propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as "PGMEA") onto the surface of the cured film of the photosensitive resin composition of the present invention.
• PPGMEA propylene glycol monomethyl ether acetate
• the contact angle when measured by the sessile drop method is preferably 35° or more, and preferably 45° or more. It is more preferable.
• the contact angle on the surface of the cured film increases as the content of the liquid repellent material (A) increases, and decreases as the content of the liquid repellent material (A) decreases. Therefore, for example, by adjusting the content of the liquid repellent material (A), the above range can be achieved.
• the photosensitive resin composition of the present invention contains an alkali-soluble resin (B).
• the alkali-soluble resin in the present invention refers to a resin whose dissolution rate as defined below is 50 nm/min or more. Specifically, a solution of a resin dissolved in ⁇ -butyrolactone is applied onto a silicon wafer, and prebaked at 120°C for 4 minutes to form a prebaked film with a thickness of 10 ⁇ m ⁇ 0.5 ⁇ m. The dissolution rate determined from the thickness reduction when immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) at 1°C for 1 minute and rinsed with pure water is 50 nm/min or more. Refers to resin.
• TMAH tetramethylammonium hydroxide
• the alkali-soluble resin (B) preferably has an alkali-soluble group in the structural unit of the resin and/or at the end of its main chain in order to impart alkali solubility.
• the alkali-soluble group refers to a functional group that increases solubility in an alkaline solution by interacting or reacting with an alkali.
• Preferred alkali-soluble groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and thiol groups.
• the alkali-soluble resin (B) has a structure having the alkali-soluble group described above, the main chain skeleton of the polymer constituting the resin and the types of side chains are not limited.
• examples include, but are not limited to, polyimide resins, polybenzoxazole resins, polyamideimide resins, cardo resins, acrylic resins, novolak resins, polyhydroxystyrene resins, phenolic resins, and polysiloxane resins.
• the alkali-soluble resin (B) has a trifluoromethyl group.
• the trifluoromethyl group can reduce the water absorption of the cured product of the photosensitive resin composition and improve the durability of the display device. Further, since the trifluoromethyl group does not impart liquid repellency, a cured product with a lyophilic surface can be formed by "half exposure" described below.
• the alkali-soluble resin (B) is one or more types selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, precursors of any of these, and copolymers thereof. It is preferable to include. These alkali-soluble resins may be contained alone or in combination of a plurality of alkali-soluble resins. Since these alkali-soluble resins have high heat resistance, when used in a display device, the amount of outgassing at high temperatures of 200° C. or higher after heat treatment is reduced, and the durability of the display device can be increased.
• Polyimide can be obtained, for example, by reacting tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride, etc. with diamine, diisocyanate compound, trimethylsilylated diamine, etc. Polyimide has tetracarboxylic acid residues and diamine residues. Moreover, polyimide can be obtained by, for example, dehydrating and ring-closing polyamic acid, which is one of the polyimide precursors obtained by reacting a tetracarboxylic dianhydride and a diamine, by heat treatment.
• a solvent that is azeotropic with water such as m-xylene
• a solvent that is azeotropic with water such as m-xylene
• a dehydration condensing agent such as a carboxylic acid anhydride or dicyclohexylcarbodiimide, or a base such as triethylamine as a ring-closing catalyst
• dehydrating and ring-closing it by chemical heat treatment.
• it can also be obtained by adding a weakly acidic carboxylic acid compound and performing dehydration ring closure by heat treatment at a low temperature of 100° C. or lower.
• Polybenzoxazole can be obtained, for example, by reacting a bisaminophenol compound with a dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid active ester, or the like. Polybenzoxazole has dicarboxylic acid residues and bisaminophenol residues. Further, polybenzoxazole can be obtained, for example, by dehydrating and ring-closing polyhydroxyamide, which is one of the polybenzoxazole precursors obtained by reacting a bisaminophenol compound and a dicarboxylic acid, by heat treatment. Alternatively, it can be obtained by adding phosphoric anhydride, a base, a carbodiimide compound, etc., and dehydrating and ring-closing it by chemical treatment.
• polyimide precursor examples include polyamic acid, polyamic acid ester, polyamic acid amide, polyisoimide, and the like.
• polyamic acid can be obtained by reacting tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic diester dichloride, or the like with a diamine, a diisocyanate compound, or a trimethylsilylated diamine.
• Polyimide can be obtained, for example, by dehydrating and ring-closing the polyamic acid obtained by the above method by heating or chemical treatment with an acid or a base.
• polybenzoxazole precursor examples include polyhydroxyamide.
• polyhydroxyamide can be obtained by reacting bisaminophenol with dicarboxylic acid, dicarboxylic acid chloride, dicarboxylic acid active ester, or the like.
• Polybenzoxazole can be obtained, for example, by dehydrating and ring-closing polyhydroxyamide obtained by the above method by heating or chemical treatment with phosphoric anhydride, a base, a carbodiimide compound, or the like.
• the polyamide-imide precursor can be obtained, for example, by reacting tricarboxylic acid, the corresponding tricarboxylic anhydride, tricarboxylic anhydride halide, etc. with diamine or diisocyanate.
• Polyamideimide can be obtained, for example, by dehydrating and ring-closing the precursor obtained by the above method by heating or by chemical treatment with an acid or a base.
• the copolymer of polyimide, polybenzoxazole, polyamideimide, or a precursor of any of these may be a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, or a combination thereof.
• a block copolymer can be obtained by reacting polyhydroxyamide with a tetracarboxylic acid, the corresponding tetracarboxylic dianhydride, tetracarboxylic diester dichloride, or the like.
• dehydration and ring closure can also be carried out by heating or chemical treatment with acids or bases.
• polyimide, polybenzoxazole, polyamideimide, a precursor of any of these, and a copolymer thereof has the formula ( It is preferable to have the structure shown in 31). Since the structure represented by formula (31) has excellent compatibility with the liquid repellent (A), it is possible to suppress aggregation of the liquid repellent (A) and obtain a cured product with fewer defects. Furthermore, the trifluoromethyl group included in the structure represented by formula (31) can reduce the water absorption of the cured product of the photosensitive resin composition and improve the durability of the display device. Further, since the trifluoromethyl group does not impart liquid repellency, a cured product with a lyophilic surface can be formed by "half exposure" performed later. In formula (31), * indicates a covalent bond.
• the copolymer has a structure represented by formula (31) in the residue of the carboxylic acid component and the residue of the diamine component.
• the alkali-soluble resin (B) preferably has a structural unit represented by any one of formulas (32) to (35), and more preferably has a structural unit represented by formula (35). Two or more types of resins having these structural units may be contained, or two or more types of structural units may be copolymerized.
• the alkali-soluble resin (B) preferably contains 3 to 1,000 structural units represented by formulas (32) to (35) in its molecule, more preferably 20 to 200.
• R 20 and R 25 are a tetravalent organic group
• R 21 , R 23 and R 24 are a divalent organic group
• R 22 is a trivalent organic group
• R 26 is a divalent organic group.
• R 27 represents a 2-12-valent organic group.
• R 28 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• p represents an integer of 0 to 2
• q represents an integer of 0 to 10.
• r represents an integer from 0 to 2. * indicates a covalent bond.
• All of R 20 to R 27 preferably have an aromatic ring and/or an aliphatic ring.
• R 20 , R 22 , R 24 , R 26 (COOR 28 ) r (OH) p in formulas (32) to (35) can be obtained, for example, by using the respective corresponding carboxylic acid components. be able to. That is, for example, R 20 can be obtained by using a tetracarboxylic acid, R 24 a dicarboxylic acid, R 22 a tricarboxylic acid, and R 26 a di-, tri- or tetra-carboxylic acid.
• Examples of carboxylic acid components used to obtain R 20 , R22, R24, R 26 (COOR 28 ) r (OH) p include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis( Examples of tricarboxylic acids include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc.
• Examples include tetracarboxylic acid and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid.
• tetracarboxylic acid and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid.
• one or two carboxyl groups of tricarboxylic acid and tetracarboxylic acid correspond to 28 COOR groups.
• These acid components can be used as they are, or as acid anhydrides, active esters, and the like. Moreover, you may use these two or more types of acid components in combination.
• the alkali-soluble resin (B) preferably has a structure represented by formula (31) in the residue of the carboxylic acid component.
• Preferred are (carboxyphenyl)hexafluoropropane, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane.
• the partial structures containing R 21 , R 23 , R 25 , and R 27 (OH) q in formulas (32) to (35) can be obtained, for example, by using the corresponding diamine components.
• diamine components used to obtain R 21 , R 23 , R 25 , R 27 (OH) q include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4 -hydroxyphenyl) sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino Hydroxyl group-containing diamines such as -4-hydroxy)biphenyl and bis(3-amino-4-hydroxyphenyl)fluorene, sulfonic acid-containing diamines such as 3-sulfonic acid-4,4'-diaminodiphenyl
• diamines can be used as they are or as corresponding diisocyanate compounds or trimethylsilylated diamines. Moreover, you may use these two or more types of diamine components in combination. In applications where heat resistance is required, it is preferable to use aromatic diamine in an amount of 50 mol% or more of the total diamine.
• R 20 to R 27 in formulas (32) to (35) can contain a phenolic hydroxyl group, a sulfonic acid group, a thiol group, etc. in their skeletons.
• a resin having an appropriate amount of phenolic hydroxyl group, sulfonic acid group, or thiol group a positive photosensitive resin composition having appropriate alkali solubility can be obtained.
• the main chain end of the alkali-soluble resin (B) is treated with a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, etc. It is preferable to seal with an end capping agent.
• the amount of monoamine used as a terminal capping agent to be introduced is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, based on the total amine component. Further, the amount introduced is preferably 60 mol% or less, particularly preferably 50 mol% or less, based on the total amine component.
• the amount of acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound used as a terminal capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol%, based on the diamine component. That's all. Further, the amount introduced is preferably 100 mol% or less, particularly preferably 90 mol% or less, based on the diamine component.
• a plurality of different terminal groups may be introduced by reacting a plurality of terminal capping agents.
• the number of repeats of the structural unit is preferably 3 or more and 200 or less. Further, in the resin having the structural unit represented by formula (35), the number of repeats of the structural unit is preferably 10 or more and 1,000 or less. Within this range, a thick film can be easily formed.
• the alkali-soluble resin (B) may consist only of structural units represented by any of formulas (32) to (35), or may be a copolymer or a mixture with other structural units. You can. In this case, it is preferable that the structural unit represented by any one of formulas (32) to (35) be contained in an amount of 10% by mass or more, more preferably 30% by mass or more based on the entire resin.
• the type and amount of structural units used for copolymerization or mixing can be selected within a range that does not impair the mechanical properties of the thin film obtained by the final heat treatment.
• the alkali-soluble resin (B) preferably contains a phenol resin and/or a polyhydroxystyrene resin. Furthermore, two or more of these phenol resins and/or polyhydroxystyrene resins may be used in combination.
• a positive type photosensitive agent (C) as described below, the amount of film loss in the developing process can be reduced by the alkali-soluble resin (B) containing a phenol resin and/or a polyhydroxystyrene resin. This has the effect of making it easier to retain the liquid repellent material (A) on the film surface after development, and better liquid repellency can be obtained.
• Phenol resins include novolak phenol resins and resol phenol resins, and are obtained by polycondensing various phenol compounds alone or in mixtures of multiple types thereof using an aldehyde compound such as formalin by a known method.
• phenol compounds constituting the novolak phenol resin and resol phenol resin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethyl Phenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol, methylenebis p-cresol, resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3- Dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethyl
• aldehyde compound examples include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, and the like, and these can be used alone or as a mixture of a plurality of them.
• polyhydroxystyrene resin it is also possible to use a homopolymer of vinylphenol or a copolymer with styrene.
• the preferable weight average molecular weight of the phenol resin and polyhydroxystyrene resin is 2,000 to 20,000, preferably 3,000 to 10,000 in terms of polystyrene by GPC (gel permeation chromatography). Within this range, a resin composition with high concentration and low viscosity can be obtained.
• the content of the liquid repellent material (A) relative to 100 parts by mass of the alkali-soluble resin (B) is preferably 0.1 parts by mass or more, and 0.3 parts by mass or more. More preferred. When the content of the liquid repellent material (A) is 0.1 part by mass or more, the obtained cured product will easily exhibit sufficient liquid repellency. Further, the content of the liquid repellent material (A) relative to 100 parts by mass of the alkali-soluble resin (B) is preferably 5 parts by mass or less, more preferably 3 parts by mass or less. When the content of the liquid repellent material (A) is 5 parts by mass or less, it is difficult to produce liquid repellency within the pixel, and high durability is easily obtained.
• the photosensitive resin composition of the present invention contains a photosensitizer (C).
• the content of the photosensitive component of the photosensitizer (C) is preferably 10 parts by mass or more, and preferably 50 parts by mass or less.
• the content of the photosensitive component of the photosensitizer (C) refers to the content of (C-1) described later (however, if (C-1) is a polymerizable unsaturated compound, it is excluded from the content). It means the total value including the content of (C-2). That is, for (C-1), only the content of the photopolymerization initiator is added to the content of (C-2).
• the photosensitizer (C) may be a negative type that is cured by light or a positive type that is solubilized by light.
• the photosensitizer (C) (C-1) a polymerizable unsaturated compound and a photopolymerization initiator, or (C-2) a quinonediazide compound, etc. can be preferably contained.
• C-2) By containing the quinone diazide compound, a positive type photosensitive resin composition can be obtained, and a step-shaped cured product can be formed in a single photolithography process using "half exposure". Therefore, in the photosensitive resin composition of the present invention, it is preferable that the photosensitizer (C) contains a quinonediazide compound.
• Examples of the polymerizable unsaturated compound in (C-1) include unsaturated double bond functional groups such as a vinyl group, allyl group, acryloyl group, and methacryloyl group, and/or unsaturated triple bond functional groups such as a propargyl group.
• unsaturated double bond functional groups such as a vinyl group, allyl group, acryloyl group, and methacryloyl group
• unsaturated triple bond functional groups such as a propargyl group.
• conjugated vinyl groups, acryloyl groups, and methacryloyl groups are preferred from the viewpoint of polymerizability.
• the number of functional groups contained is preferably 1 to 4 from the viewpoint of stability, and they do not have to be the same group.
• the compound referred to herein preferably has a molecular weight of 30 to 800.
• the polymer has good compatibility with the polymer and the reactive diluent. Specifically, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, isobornyl acrylate, isobornyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate.
• the content of the polymerizable unsaturated compound in (C-1) is not particularly limited, but is preferably 10 parts by mass or more based on 100 parts by mass of the alkali-soluble resin (B) from the viewpoint of improving alkali solubility. From the viewpoint of good pattern formation, the amount is preferably 70 parts by mass or less.
• the photopolymerization initiator in (C-1) means one that initiates polymerization mainly by generating radicals when irradiated with light in the ultraviolet to visible light range.
• Examples of the photopolymerization initiator in (C-1) include benzophenone, Michler's ketone, 4,4-bis(diethylamino)benzophenone, and 3,3,4,4-tetra(t-butylperoxycarbonyl)benzophenone.
• Benzophenones such as 3,5-bis(diethylaminobenzylidene)-N-methyl-4-piperidone, 3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidone, 7-diethylamino-3-tetra Nonylcoumarin, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis(7-diethylaminocoumarin), 7-diethylamino-3-(1-methylmethylbenzimidazolyl)coumarin, 3-(2-benzothiazolyl) Coumarins such as -7-diethylaminocoumarin, anthraquinones such as 2-t-butylanthraquinone, 2-ethylanthraquinone, and 1,2-benzanthraquinone, benzoins such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropy
• the content of the photopolymerization initiator in (C-1) is not particularly limited, but is preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the alkali-soluble resin (B). Within this range, it becomes possible to form a good pattern, and it becomes easy to ensure transmittance for obtaining appropriate sensitivity.
• the quinonediazide compound (C-2) is one in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy compound through an ester bond, a compound in which the sulfonic acid of quinonediazide is bonded to a polyamino compound through a sulfonamide bond, and a compound in which the sulfonic acid of quinonediazide is bonded to a polyhydroxy polyamino compound through an ester bond.
• Examples include those with a bond and/or a sulfonamide bond.
• the esterification rate the mol% of the functional groups substituted with sulfonic acid in quinonediazide.
• the polyhydroxy compound used here has two or more, preferably three or more, phenolic hydroxyl groups in the molecule.
• Polyhydroxy compounds include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ.
• BisOCP-IPZ BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML- PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML- HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all product names manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A,
• polyamino compound examples include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'- Examples include, but are not limited to, diaminodiphenyl sulfide.
• polyhydroxypolyamino compound examples include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.
• examples of the sulfonic acid of quinonediazide include, but are not limited to, 1,2-naphthoquinonediazide-4-sulfonic acid and 1,2-naphthoquinonediazide-5-sulfonic acid.
• the (C-2) quinonediazide compound a compound in which quinonediazide sulfonic acid is bonded to a polyhydroxy compound is preferably used.
• a quinonediazide compound By using such a quinonediazide compound, it is sensitive to the I-line (wavelength 365 nm), H-line (wavelength 405 nm), and G-line (wavelength 436 nm) of a mercury lamp, which are common ultraviolet rays, resulting in high sensitivity and higher resolution. Obtainable.
• C-2) quinonediazide compounds include compounds represented by formula (36) or formula (37).
• Q each independently represents a hydrogen atom, a group represented by structural formula (38), or a group represented by structural formula (39).
• * indicates a covalent bond.
• Q in formula (36) or formula (37) is each independently represented by a hydrogen atom or a group represented by structural formula (38).
• the esterification rate is calculated as "(number of moles of quinonediazide sulfonic acid ester group)/(number of moles of hydroxyl group before esterification of polyhydroxy compound)" for polyhydroxy compounds, and as "(number of moles of quinone diazide sulfonic acid ester groups)/(number of moles of hydroxyl groups before esterification of polyhydroxy compound) x 100" for polyamino compounds.
• the esterification rate is determined as the average esterification rate by summing the esterification rate of each quinonediazide compound multiplied by the ratio to all quinonediazide compounds, as shown in the following formula.
• the esterification rate of the quinone diazide compound in the photosensitive resin composition can be determined by removing the resin component of the photosensitive resin composition by reprecipitation method, separating the contained components by column fractionation method, etc., and then chemically analyzing it by NMR or IR. It can be determined by identifying the structure.
• the method for producing the quinonediazide compound is not particularly limited, but according to a conventional method, quinonediazide sulfonic acid halide (preferably quinonediazide sulfonic acid chloride) is mixed with sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, or water in a solvent such as acetone, dioxane, or tetrahydrofuran.
• quinonediazide sulfonic acid halide preferably quinonediazide sulfonic acid chloride
• the content of the quinonediazide compound (C-2) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, based on 100 parts by mass of the total content of the alkali-soluble resin (B). Moreover, 50 parts by mass or less is preferable, and 40 parts by weight or less is more preferable.
• the photosensitive resin composition of the present invention further contains a crosslinking agent.
• a crosslinking agent refers to a compound containing at least two thermally reactive functional groups such as a methylol group, an alkoxymethyl group, an epoxy group, and an oxetanyl group in its molecule.
• the liquid repellent material (A), the alkali-soluble resin (B), or other additive components can be crosslinked, thereby increasing the durability of the cured film.
• Preferred examples of compounds containing at least two methylol groups or alkoxymethyl groups include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML -OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM -PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM -BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP
• Examples of compounds containing epoxy groups include “Epicoat” (registered trademark) 807, “Epicoat” (registered trademark) 828, “Epicoat” (registered trademark) 1002, “ “Epicort” (registered trademark) 1750, “Epicort” (registered trademark) 1007, YX8100-BH30, E1256, E4250, E4275 (all product names, manufactured by Japan Epoxy Co., Ltd.), “Epiclon” (registered trademark) EXA-4880, “Epicron” (registered trademark) EXA-4822, “Epiclon” (registered trademark) EXA-9583, HP4032 (all product names, manufactured by Dainippon Ink and Chemicals Co., Ltd.), “Epolite” (registered trademark) 40E, “Epolite” ” (registered trademark) 100E, “Epolite” (registered trademark) 200E, “Epolite” (
• Examples include VG3101L (trade name, manufactured by Printec Co., Ltd.), "Tepic” (registered trademark) S, “Tepic” (registered trademark) G, “Tepic” (registered trademark) P (trade name, manufactured by Nissan Chemical Co., Ltd.).
• Compounds containing at least two oxetanyl groups include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (all trade names, manufactured by Toagosei Co., Ltd.), "Ethanachol” ” (registered trademark) OXBP, “Ethanachol” (registered trademark) OXTP (all trade names, manufactured by Ube Industries, Ltd.), etc., which are available from various companies.
• the crosslinking agent preferably has a phenolic hydroxyl group in one molecule and a methylol group and/or alkoxymethyl group at both ortho positions of the phenolic hydroxyl group.
• the durability of the cured film can be further improved.
• the alkoxymethyl group include, but are not limited to, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.
• the content of the crosslinking agent is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the alkali-soluble resin (B). Moreover, 50 parts by mass or less is preferable, and 40 parts by weight or less is more preferable.
• the total content of the liquid repellent material (A), the alkali-soluble resin (B), the photosensitizer (C), and the crosslinking agent is 5% by mass or more and 80% by mass in the photosensitive resin composition. It is preferably at most 8% by mass and at most 50% by mass.
• the content is 5% by mass or more, better pattern formation becomes possible and sufficient liquid repellency can be easily imparted to the surface of the cured product.
• the content is 80% by mass or less, better workability can be obtained when applying the photosensitive resin composition onto a substrate.
• the photosensitive resin composition of the present invention preferably contains an organic solvent.
• the organic solvent include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, and alcohols.
• ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n- Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether , dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether,
• the amount of the organic solvent to be used is not particularly limited as it varies depending on the required film thickness and the coating method employed, but it is from 100 to 100 parts by mass of the total solid content (other components excluding the organic solvent). 2,000 parts by weight is preferred, particularly 150 to 900 parts by weight.
• the photosensitive resin composition of the present invention can further contain a colorant.
• a colorant include known organic pigments, inorganic pigments, and dyes commonly used in the field of electronic information materials.
• the colorant is preferably an organic pigment and/or an inorganic pigment.
• organic pigments examples include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, or metal-free phthalocyanine, aminoanthraquinone, diaminodianthraquinone, and anthraquinone.
• Anthraquinone pigments such as pyrimidine, flavanthrone, anthrone, indanthrone, pyrantrone or violanthrone, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments , quinophthalone pigments, threne pigments, benzofuranone pigments, and metal complex pigments.
• inorganic pigments include black iron oxide, cadmium red, red iron, molybdenum red, molybdate orange, chromium vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, and cobalt.
• examples include green, cobalt chrome green, Victoria green, ultramarine, navy blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.
• dyes examples include azo dyes, anthraquinone dyes, fused polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine or polymethine dyes, and the like.
• the colorant is preferably black, which can block visible light over the entire wavelength range, and contains at least one selected from organic pigments, inorganic pigments, and dyes.
• a colorant that exhibits a black color when cured is used.
• the above-mentioned black organic pigment and black inorganic pigment may be used, or two or more types of organic pigments and dyes may be mixed to create a pseudo-black color.
• pseudo-blackening it can be obtained by mixing two or more of the above-mentioned red, orange, yellow, purple, blue, green, and other organic pigments and dyes.
• the photosensitive resin composition itself in the present invention does not necessarily have to be black, and a coloring agent that changes color during heat curing so that the cured product exhibits a black color may be used.
• a coloring agent that contains an organic pigment and/or an inorganic pigment and exhibits a black color when cured.
• a coloring agent that contains an organic pigment and/or dye and exhibits a black color when cured it is preferable to use a coloring agent that contains an organic pigment and exhibits a black color when cured.
• the content of the colorant is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, even more preferably 30 parts by weight or more, and preferably 300 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B).
• the amount is more preferably 200 parts by mass or less, still more preferably 150 parts by mass or less.
• the colorant When using a pigment as a colorant, it is preferable to include a dispersant.
• a dispersant By containing the dispersant, the colorant can be uniformly and stably dispersed in the resin composition.
• the dispersant is not particularly limited, but a polymer dispersant is preferred.
• the polymer dispersant include polyester polymer dispersants, acrylic polymer dispersants, polyurethane polymer dispersants, polyallylamine polymer dispersants, and carbodiimide polymer dispersants.
• a polymeric dispersant has a main chain consisting of polyamino, polyether, polyester, polyurethane, polyacrylate, etc., and has an amine, carboxylic acid, phosphoric acid, amine salt, or carboxylic acid at the side chain or main chain terminal.
• polar groups such as acid salts and phosphates. The polar group is adsorbed onto the pigment, and the steric hindrance of the main chain polymer plays a role in stabilizing the dispersion of the pigment.
• the dispersant may be a (polymer) dispersant that has only an amine value, a (polymer) dispersant that has only an acid value, a (polymer) dispersant that has an amine value and an acid value, or a (polymer) dispersant that has both an amine value and an acid value. Although it is classified as a (polymer) dispersant that does not have an amine value, a (polymer) dispersant that has an amine value and an acid value, and a (polymer) dispersant that has only an amine value are preferable. Molecular) dispersants are more preferred.
• polymeric dispersants having only an amine value include “DISPERBYK” (registered trademark) 102, 160, 161, 162, 2163, 164, 2164, 166, 167, 168, 2000, 2050, 2150, 2155, 9075, 9077, BYK-LP N6919, BYK-LP N21116 or BYK-LP N21234 (all manufactured by BYK Chemie Japan Co., Ltd.), “EFKA” (registered trademark) 4015, 4020, 4046, 4047, 4050 , 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403 or 4800 (all manufactured by BASF), "Ajisper” (registered trademark) PB711 (manufactured by Ajinomoto Fine Techno Co., Ltd.), Examples include “SOLSPERSE” (registered trademark) 13240, 13940, 20000, 71000, or 76500 (all manufactured by Japan Lubrizol Co
• the ratio of the dispersant to the colorant is preferably 1% by mass or more, more preferably 3% by mass or more, in order to improve dispersion stability while maintaining heat resistance. Further, it is preferably 100% by mass or less, more preferably 50% by mass or less.
• an acetate compound as an organic solvent in order to stabilize the dispersion of the pigment.
• the proportion of acetate compounds in all organic solvents contained in the photosensitive resin composition is preferably 50% by mass or more, more preferably 70% by mass or more. Further, it is preferably 100% by mass or less, more preferably 90% by mass or less.
• the photosensitive resin composition of the present invention can further contain an adhesion improver.
• adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, Silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds and alkoxy group containing Examples include compounds obtained by reacting silicon compounds.
• the content of the adhesion improver is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, based on 100 parts by mass of the alkali-soluble resin (B). Further, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
• the photosensitive resin composition of the present invention may optionally contain a surfactant, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, tetrahydrofuran, and dioxane. It may also contain ethers such as. By containing such a component, wettability with the substrate can be improved.
• esters such as ethyl lactate and propylene glycol monomethyl ether acetate
• alcohols such as ethanol
• ketones such as cyclohexanone and methyl isobutyl ketone
• tetrahydrofuran and dioxane.
• dioxane dioxane
• silicone surfactants include SH series, SD series, and ST series from DuPont Toray Specialty Materials, BYK series from BYK Chemie Japan, and Shin-Etsu Chemical Co., Ltd. KP series, Momentive Performance Materials Japan LLC's TSF series, etc.
• Fluorinated surfactants include DIC Corporation's "Megafac” (registered trademark) series, 3M Japan Ltd.'s Examples include the Florado series, AGC Corporation's "Surflon” (registered trademark) series, "Asahi Guard” (registered trademark) series, Mitsubishi Materials Electronic Chemicals Co., Ltd.'s EF series, and Omnova Solutions' Polyfox series.
• surfactants made of acrylic and/or methacrylic polymers include the Polyflow series from Kyoeisha Kagaku Co., Ltd. and the "Disparon” (registered trademark) series from Kusumoto Kasei Co., Ltd. Not limited to these.
• the content of the surfactant is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, based on 100 parts by mass of the alkali-soluble resin (B). Further, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less.
• the cured product of the present invention is a cured product obtained by curing the above photosensitive resin composition.
• the cured product of the present invention can be used for electronic components such as organic EL display devices, liquid crystal display devices, semiconductor devices, and multilayer wiring boards. Specifically, partition walls of organic EL elements, flattening layers of substrates with drive circuits of display devices using organic EL elements, color filters of liquid crystal devices, black matrices of liquid crystal devices, and rewiring spaces of semiconductor devices or semiconductor components.
• interlayer insulating film for semiconductors passivation film for semiconductors, surface protection film for semiconductor elements, interlayer insulating film for multilayer wiring for high-density packaging, wiring protection insulating layer for circuit boards, on-chip microlenses for solid-state imaging devices, and various displays and solid-state imaging devices. It is suitably used for applications such as a flattening layer for devices.
• electronic devices having a surface protective film, interlayer insulating film, etc. on which the cured product of the present invention is disposed include MRAMs with low heat resistance.
• it can be preferably used for partition walls and insulating layers of display devices such as LCDs (liquid crystal displays), ECDs (electrochromic displays), and OLEDs (organic EL displays).
• the functional layer contains an organic EL material containing at least one selected from the group consisting of an organic EL luminescent material, a hole injection material, and a hole transport material. It can be suitably used for EL display devices.
• the display device of the present invention includes a cured product obtained by curing the photosensitive resin composition.
• a display device including a first electrode formed on a substrate and a second electrode provided opposite to the first electrode such as a display device such as an LCD, ECD, ELD, or organic EL. can be mentioned.
• the display device of the present invention is a display device having a grid-like partition wall formed on a substrate, and it is preferable that the partition wall contains the cured product of the present invention.
• the upper surface of the partition wall has high liquid repellency, which prevents ink used in the inkjet method from penetrating into adjacent pixels, and furthermore, the openings between the partition walls have a good resistance to ink.
• By having good wettability it is possible to obtain an organic EL display device with less occurrence of display defects and excellent durability.
• the thickness of the partition wall is preferably 0.5 to 10 ⁇ m. If it is 0.5 ⁇ m or more, the functional ink can be easily retained within the pixel. From the viewpoint of making it easier to process the photosensitive resin composition by photolithography, it is preferable that the thickness of the partition wall is 10 ⁇ m or less.
• a functional layer is formed in a region surrounded by partition walls of the display device.
• a functional layer is formed in a region surrounded by partition walls of the display device.
• a colored layer that colors transmitted light and arranging a plurality of colored layers having different colors for each pixel, it can be used as a color filter.
• an organic EL light emitting layer containing at least one selected from organic EL light emitting materials, hole injection materials, and hole transport materials, it can be used as an organic EL display device.
• the organic EL display device of the present invention has a drive circuit, a planarization layer, a first electrode, a partition wall, an organic EL light emitting layer, and a second electrode on a substrate, and the partition wall is made of the cured product of the present invention.
• the partition wall is made of the cured product of the present invention.
• an active matrix display device it has a TFT on a substrate such as glass or a resin film, and wiring located on the side of the TFT and connected to the TFT, and covering unevenness on top of the TFT. In this manner, a flattening layer is provided, and a display element is further provided on the flattening layer.
• the display element and the wiring are connected through contact holes formed in the planarization layer.
• An organic EL display device comprising a cured product of the photosensitive resin composition of the present invention is preferably used when using a manufacturing method in which at least a part of a pixel surrounded by the cured product is formed by an inkjet method. be done.
• the cured product obtained by curing the photosensitive resin composition or photosensitive resin sheet of the present invention it has liquid repellency and prevents the ejected liquid used in the inkjet method from entering into adjacent pixels. Therefore, an organic EL display device with less occurrence of display defects and excellent durability can be obtained.
• the photosensitive resin composition of the present invention can be obtained by dissolving the liquid repellent material (A), the alkali-soluble resin (B), the photosensitizer (C), and the crosslinking agent in an organic solvent.
• the dissolution method include stirring and heating.
• the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually 20°C to 80°C.
• the order of dissolving each component is not particularly limited, and for example, there is a method of dissolving compounds in order starting from the one with the lowest solubility.
• the obtained photosensitive resin composition is preferably filtered using a filtration filter to remove dust and particles.
• filter pore diameters include, but are not limited to, 1 ⁇ m, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, and 0.05 ⁇ m.
• Materials for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), and it is preferable to use polyethylene or nylon for filtration.
• a photosensitive resin film is obtained by applying the photosensitive resin composition of the present invention onto a substrate and drying it. This is achieved by forming a cured product by following the steps of exposing the photosensitive resin film, developing the exposed photosensitive resin film, and heat-treating the developed photosensitive resin film, which will be described later.
• a cured product can be obtained by curing the composition.
• the liquid-repellent bank is formed in a lattice shape or stripe shape on the substrate, and separates light emitting materials and the like.
• the upper surface of the liquid-repellent bank has liquid repellency, while the side surface of the liquid-repellent bank and the portion (opening) where there is no liquid-repellent bank do not have liquid repellency.
• the liquid-repellent bank can be suitably used in an organic EL display device manufactured by an inkjet method. Although the method for forming the liquid-repellent bank is not particularly limited, it can be obtained, for example, by following the method for manufacturing a substrate with partition walls, which will be described later.
• a patterned first electrode and a cured product of the present invention are laminated in this order on the substrate, and at least a part of the cured product on the first electrode is open.
• Examples include substrates. Because the surface of the cured product has good liquid repellency, a display device in which a functional layer is formed by applying a functional ink using an inkjet to an area where at least a part of the cured product is open on the first electrode. It can be suitably used.
• the organic EL display device includes at least one type selected from the group consisting of an organic EL light emitting material, a hole injection material, and a hole transport material in the functional layer. It can be suitably used for.
• the substrate with partition walls having partition walls containing the cured product of the present invention satisfies characteristics (iv) and (v) when analyzed by X-ray photoelectron spectroscopy (XPS).
• XPS X-ray photoelectron spectroscopy
• FIG. 2 shows a schematic cross-sectional view of an example of a substrate with partition walls having partition walls containing the cured product of the present invention.
• a flattening layer 9, a patterned first electrode 10, and a cured product 11 of the present invention are laminated in this order on a substrate 8, and at least a part of the cured product 11 on the patterned first electrode 10 is open.
• Characteristics (iv) of the cured product analyzed by X-ray photoelectron spectroscopy (XPS) are measured from the surface 12 opposite to the surface where the first electrode and the cured product are in contact. It is preferable to measure within a range of 100 ⁇ m from the end of the opening of the cured product 11.
• characteristic (v) is perpendicular to the interface 13 where the first electrode and the cured product are in contact, and in a direction from the substrate to the cured product, and starting from the interface where the first electrode and the cured product are in contact.
• 100 nm to 15 to further 100 nm that is, perpendicular to the interface 13 where the first electrode and the cured product are in contact, and in the direction from the substrate to the cured product, and the first electrode and the cured product are It is measured in any one of the ranges 14 from 100 nm to 200 nm starting from the contacting interface.
• the opening is perpendicular to the interface between the first electrode and the cured material shown in FIG.
• a first electrode is present in the range 14 of 100 to 200 nm starting from the interface of the cured product, measurement is performed in any range of 100 to 200 nm from the height of the first electrode. Note that when there is variation in the thickness of the first electrode, it is assumed that in the opening of the patterned first electrode, there is a first electrode having an average thickness at the end of the opening.
• a method for the partition wall containing the cured product of the present invention to satisfy property (iv) for example, a method of forming a cured product with a photosensitive resin composition containing the component (A-1) and the component (A-2). can be mentioned.
• Polysiloxane is a compound having a structure in which silicon (Si) and oxygen (O) are alternately bonded.
• polyether-modified silicone or alkyl-modified silicone may be further contained. From the viewpoint of uneven distribution on the surface of the cured product, polyether-modified silicone and the component (A-1) are preferred.
• Products commercially available as polyether-modified silicones include, for example, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-642 (manufactured by Shin-Etsu Chemical Co., Ltd.), SH8400, Examples include SH8700, SF8410 (manufactured by Dow Corning Toray Industries, Inc.), BYK-300, BYK-306, BYK-307, BYK-320, BYK-325, BYK-330 (manufactured by BYK Chemie Corporation).
• a method for setting the concentration of F atoms of characteristic (iv) within the above range for example, adjusting the content of component (A-1) and/or component (A-2) in the photosensitive resin composition.
• Increasing the content can increase the concentration of F atoms with characteristic (iv)
• decreasing the content can decrease the concentration of F atoms with characteristic (iv).
• Increasing the concentration of the perfluoroalkyl group or/and perfluoroalkylene ether group can increase the concentration of F atoms of property (iv), and decreasing the concentration of the perfluoroalkyl group or/and perfluoroalkylene ether group, The concentration of F atoms in characteristic (iv) can be reduced.
• the concentration of Si atoms of characteristic (iv) within the above range, for example, there is a method of adjusting the content of component (A-1) in the photosensitive resin composition. Increasing the content can increase the concentration of Si atoms with characteristic (iv), and decreasing the content can decrease the concentration of Si atoms with characteristic (iv).
• a method for the partition wall containing the cured product of the present invention to satisfy characteristic (v) for example, a method of forming a cured product with a photosensitive resin composition containing the alkali-soluble resin (b-1) having a trifluoromethyl group can be mentioned.
• the trifluoromethyl group is less likely to be unevenly distributed on the surface of the cured product, and can retain F atoms inside the cured product.
• a method for setting the concentration of F atoms of characteristic (v) within the above range for example, a method of adjusting the content of the alkali-soluble resin (b-1) having a trifluoromethyl group in the photosensitive resin composition.
• Increasing the content can increase the concentration of F atoms with characteristic (v), and decreasing the content can decrease the concentration of F atoms with characteristic (v).
• Another method is to adjust the concentration of trifluoromethyl groups contained in the alkali-soluble resin (b-1). Increasing the concentration of trifluoromethyl groups can increase the concentration of F atoms of characteristic (v), and decreasing the concentration of trifluoromethyl groups can decrease the concentration of F atoms of characteristic (v).
• the alkali-soluble resin (b-1) having a trifluoromethyl group is not limited in the main chain skeleton and side chains of the polymer constituting the resin. Examples include, but are not limited to, polyimide resins, polybenzoxazole resins, polyamideimide resins, acrylic resins, novolak resins, polyhydroxystyrene resins, phenolic resins, and polysiloxane resins. From the viewpoint of heat resistance, the alkali-soluble resin (b-1) having a trifluoromethyl group is selected from the group consisting of polyimide, polybenzoxazole, polyamideimide, a precursor of any of these, and a copolymer thereof. It is preferable to include one or more types. Since these alkali-soluble resins have high heat resistance, when used in a display device, the amount of outgassing at high temperatures of 200° C. or higher after heat treatment is reduced, and the durability of the display device can be increased.
• Characteristic (iv) is measured from the surface of the cured product opposite to the surface where the first electrode and the cured product contact. Further, it is preferable to measure within a range of 100 ⁇ m from the end of the opening of the cured product. By measuring this range, the liquid repellency of the surface of the cured product against the functional ink can be analyzed.
• the partition wall containing the cured product of the present invention preferably has a concentration of F atoms of 8.1 atom% or more and 30.0 atom% or less. More preferably, it is 15.0 atom% or more and 26 atom% or less.
• concentration of F atoms is 8.1 atom% or more, liquid repellency can be imparted to the surface of the cured product.
• concentration of F atoms is 30 atom % or less, aggregation of F atoms can be suppressed and a cured product with few defects can be obtained.
• the partition wall containing the cured product of the present invention preferably has a concentration of Si atoms of 1.0 atom % or more and 6.0 atom % or less. More preferably, it is 1.5 atom% or more and 4.5 atom% or less.
• concentration of Si atoms is 1.0 atom% or more
• the UV ozone resistance of the cured product improves, and good liquid repellency can be obtained even after UV ozone treatment.
• the polysiloxane skeleton exhibits good heat resistance, it does not decompose during the curing process, prevents liquid-repellent components from scattering to the openings, and improves the wettability of the functional ink applied to the openings. I can do it.
• concentration of Si atoms is 6.0 atom% or less, agglomeration of Si atoms can be suppressed and a cured product with few defects can be obtained.
• Characteristic (iv) is preferably analyzed using an XPS device with a detector tilted at 45° with respect to the sample surface. Since the detector is tilted at 45°, it is possible to accurately analyze a region near the surface where the polysiloxane concentration of component (A-1) is high.
• Characteristic (v) is perpendicular to the interface where the first electrode and the cured product are in contact, and in the direction from the substrate to the cured product, and within a range of 100 to 200 nm starting from the interface where the first electrode and the cured product are in contact. It is measured either. When the thickness of the cured product is 200 nm or less, the median thickness of the cured product is measured. When the F component is contained in the cured product, the water absorbency of the cured product is reduced, so corrosion of the electrodes can be suppressed and the durability of the display device can be improved.
• the partition wall containing the cured product of the present invention preferably has a concentration of F atoms of 0.1 atom% or more and 8.0 atom% or less. More preferably, it is 4.0 atom% or more and 7.5 atom% or less.
• concentration of F atoms is 0.1 atom% or more, the water absorption of the cured product is reduced, so that the durability of the display device can be improved.
• concentration of F atoms is 8.0 atom % or less, it is possible to achieve both durability of the display device and good mechanical properties of the cured product.
• Characteristic (v) is that the cured product is excavated with Ar gas cluster ions (Ar-GCIB), and the area is perpendicular to the interface where the first electrode and the cured product are in contact, and within a range of 100 to 200 nm from the substrate in the direction of the cured product. After either is exposed, it is preferable to measure by X-ray photoelectron spectroscopy (XPS).
• XPS X-ray photoelectron spectroscopy
• the partition-equipped substrate includes partition walls containing a cured product of a photosensitive resin composition.
• a method for manufacturing a substrate with partition walls includes, for example, the following steps (1) to (4) in this order.
• Step of exposing the photosensitive resin film (3) Developing the exposed photosensitive resin film
• Examples of methods for applying the photosensitive resin composition onto the substrate having the first electrode include spin coating, slit coating, dip coating, spray coating, and printing.
• the substrate to which the photosensitive resin composition is applied may be pretreated with the adhesion improver described above.
• a solution in which 0.5 to 20% by mass of the adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. is used.
• Examples include methods of treating the surface of the base material.
• Examples of methods for treating the surface of the substrate include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.
• the applied photosensitive resin film is subjected to a vacuum drying treatment as necessary, and then heat treated at a temperature of 50°C to 180°C for 1 minute to several hours using a hot plate, oven, infrared rays, etc. By applying this, a dry photosensitive resin film can be obtained.
• Actinic radiation is irradiated onto the photosensitive resin film through a photomask having a desired pattern.
• Actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays, but in the present invention, it is preferable to use I-lines (365 nm), H-lines (405 nm), and G-lines (436 nm) from a mercury lamp. .
• a post-exposure bake may be performed. By performing post-exposure baking, effects such as improved resolution after development or increased allowable range of development conditions can be expected.
• the post-exposure bake temperature is preferably 50 to 180°C, more preferably 60 to 150°C.
• the post-exposure bake time is preferably 10 seconds to several hours. When the post-exposure bake time is within the above range, the reaction proceeds favorably and the development time may be shortened. At this time, a lattice-shaped cured product can be obtained by using a lattice-shaped photomask.
• half exposure refers to a process in which a certain amount of the base of the dried photosensitive resin remains in the exposed area when development is completed. In other words, it refers to a process in which exposure is performed so that the lower layer of the dried photosensitive resin is not exposed to light.
• the cured product shown in FIG. 3 from a positive type photosensitive resin dry product
• the part that becomes the first stage 16 of the thick cured product is left unexposed, and the part that becomes the second stage 17 of the thin cured product
• the areas can be formed by performing "half exposure” in which the lower layer of the dried photosensitive resin is exposed to an actinic radiation dose to which it is not sensitive, followed by development and heat treatment.
• the thickness of the dried photosensitive resin material that remains after completion of development can be adjusted. Specifically, when the dried photosensitive resin material is a positive type, increasing the amount of actinic radiation reduces the thickness of the dried photosensitive resin material that remains after development is completed. On the other hand, when the dried photosensitive resin is of a negative type, increasing the amount of actinic radiation increases the thickness of the dried photosensitive resin that remains after development is completed.
• the actinic radiation dose may be adjusted by irradiating actinic radiation through a photomask having two or more types of areas with different transmittances.
• the surface of the cured product formed by half exposure has no liquid repellency and can have good ink applicability. That is, a cured product with a liquid-repellent surface and a cured product with a lyophilic surface can be formed by one photolithography.
• the exposed photosensitive resin film is developed using a developer to remove areas other than the exposed areas.
• a developer TMAH, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate,
• alkaline compounds such as cyclohexylamine, ethylenediamine, and hexamethylenediamine are preferred.
• polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone, and dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination. good.
• methods such as spray, paddle, immersion, and ultrasonic waves are possible.
• alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, etc. may be added to distilled water for rinsing.
• a cured product is obtained by heat-treating the developed photosensitive resin film.
• a cured product of the photosensitive resin composition can be suitably used for partition walls of an organic EL display device. Since residual solvent and components with low heat resistance can be removed by heat treatment, heat resistance and chemical resistance can be improved. Moreover, by containing a crosslinking agent, a thermal crosslinking reaction can be advanced by heat treatment, and heat resistance and chemical resistance can be improved. This heat treatment is carried out by selecting a temperature and increasing the temperature stepwise, or by selecting a certain temperature range and increasing the temperature continuously for 5 minutes to 5 hours. An example is a method of heat treatment at 150° C. and 250° C. for 30 minutes each.
• the heat treatment conditions in the present invention are preferably 180°C or higher, more preferably 200°C or higher, and even more preferably 230°C or higher.
• the heat treatment conditions are preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 300°C or lower.
• the method for manufacturing a display device of the present invention includes the following steps (I) to (II) in this order.
• (I) In a partition-equipped substrate having partition walls containing a cured product obtained by curing the photosensitive resin composition, forming a functional layer by applying a functional ink to an area surrounded by the partition walls using an inkjet method.
• (II) A step of forming a second electrode on the functional layer.
• a functional layer is formed by applying functional ink using an inkjet method within the region (pixel) surrounded by the partition walls of the partition wall-equipped substrate produced by the above-described method for producing a partition wall-equipped substrate.
• a composition containing at least one selected from the group consisting of an organic EL luminescent material, a hole injection material, and a hole transport material is dropped as a functional ink into pixels, and then dried. By doing so, an organic EL light emitting layer can be formed.
• step (II) of forming a second electrode on the functional layer will be explained.
• a second electrode is formed to cover the entire partition wall and functional layer.
• methods for forming the second electrode include sputtering, vapor deposition, and the like. Note that it is preferable to form the second electrode with a uniform layer thickness without any disconnection.
• the molecular weights of the alkali-soluble resins (b2) and (b3) synthesized in Synthesis Examples 15 and 16 were measured using the above-mentioned GPC device using N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as the developing solvent.
• NMP N-methyl-2-pyrrolidone
• Mn number average molecular weight
• the obtained substrate with dried photosensitive resin was inspected for defects using a wafer surface inspection device (WM-10; manufactured by Topcon Co., Ltd.).
• the wave height and particle size of the signal associated with particle detection are calibrated.
• the number of defects of 0.5 ⁇ m or more calculated using a standard polystyrene latex sphere with a particle size of 0.5 ⁇ m is determined as follows, and A is Excellent, B as good, C as passing, and D as poor.
• Evaluation of liquid repellency To measure the contact angle, 3 ⁇ L of PGMEA was dropped onto the partition wall pattern 4 in FIG. 1, and the contact angle was measured. The measurement was carried out using a contact angle measuring device DMs-401 (manufactured by Kyowa Kaimen Kagaku Co., Ltd.) by the sessile drop method at 23° C. in accordance with JIS R 3257
• the measurement results of the PGMEA contact angle on the cured product were judged as follows: A was excellent, B was good, C was acceptable, and D was bad. A: The contact angle is 45° or more B: The contact angle is 35° or more and less than 45° C: The contact angle is 25° or more and less than 35° D: The contact angle is less than 25° (4) Evaluation of ink wettability of the opening Will be described later A compound (HT-1) using methyl benzoate as a solvent was applied to the region (opening) surrounded by the partition walls of the substrate on which the partition pattern 5 in FIG. of ink (7% by mass) was dropped, and the wetting and spreading properties of the ink at the openings were observed.
• the number of dropped ink droplets required for the ink to wet and spread over the entire surface of the opening was counted.
• the volume per drop of the ink used in this evaluation was 8 pl.
• the ink wettability of the opening is judged according to the following criteria: excellent (A) where the ink spreads over the entire surface of the opening with an amount of 2 to 4 drops of ink dropped; (B) is considered good if the ink spreads over the entire surface of the opening, and (C) is considered good if the ink spreads over the entire surface of the opening when 7 to 8 drops of ink are dropped. If the ink was repelled (D) or if the ink oozed out of the pixel (E), it was judged as defective.
• a compound (HT-2) using 4-methoxytoluene as a solvent was dropped into the area surrounded by the partition walls using an inkjet device, and then baked at 190°C to form a hole transport layer.
• a transport layer was formed.
• a mixture of Compound (GH-1) and Compound (GD-1) using 4-methoxytoluene as a solvent was dropped onto the area surrounded by the partition walls using an inkjet device, and then heated to 130°C. was fired to form a light-emitting layer.
• a compound (ET-1) and a compound (LiQ) were sequentially laminated as electron transport materials by a vacuum evaporation method at a volume ratio of 1:1 to form an organic EL layer 6.
• a compound (LiQ) was deposited to a thickness of 2 nm, and then Mg and Ag were deposited to a thickness of 10 nm at a volume ratio of 10:1 to form the second electrode 7.
• a cap-shaped glass plate was bonded using an epoxy resin adhesive under a low-humidity nitrogen atmosphere for sealing, thereby producing a 5 mm square organic EL display device on one substrate.
• the organic EL display device produced by the above method was driven to emit light at 10 mA/cm 2 with direct current, and the initial light emitting area was observed. Furthermore, it was kept at 80°C for 500 hours, and then the light was emitted again by direct current drive at 10mA/ cm2 , and it was confirmed that there was no change in the light emitting area. The durability was judged as shown below, with A being excellent and B being good. , C was accepted, and D was accepted as defective.
• a substrate with partition walls on which the partition pattern 4 in FIG. 1 was formed was prepared by the method described below, and XPS analysis was performed at any point within 100 ⁇ m from the end of the opening of the cured material in the partition pattern 4.
• XPS X-ray photoelectron spectroscopy
• XPS X-ray photoelectron spectroscopy
• TfTMS tridecafluorooctyltrimethoxysilane
• DPhDMS dimethoxydiphenylsilane
• NapTMS 1-naphthyltrimethoxysilane
• HfTES 4-(2-hydroxy-1,1,1,3,3,3-hexafluoroisopropyl)-1-
• BHEDOS 1,3-bis(1,2-dihydroxyethyl)disiloxane-1,1,3,3-tetraol
• TMSSucA 3-trimethoxysilylpropylsuccinic anhydride
• MTMS Methyltrimethoxysilane
• TEOS Tetraethoxysilane (f-1): CF 3 CF 2 O (CF 2 CF 2 O) 2 (CH 2 ) 3 Si(OCH 3 ) 3 (f-2): (OCH 3 ) 3 Si(CH 2 ) 3 OCF 2
• MW-100LM 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine (“Nicalak” (registered trademark) MW-100LM, manufactured by Sanwa Chemical Co., Ltd.) ⁇ Organic solvent> PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether.
• Synthesis Example 1 Synthesis of liquid repellent material (P-1) In a 1,000 mL three-necked flask equipped with a reflux tube, add 79.61 g (0.17 mol) of TfTMS, 122.19 g (0.50 mol) of DPhDMS, and MTMS. 27.24 g (0.20 mol), 27.08 g (0.13 mol) TEOS, 264.09 g PGMEA, and 29.34 g methanol were added, and while stirring at 40°C, 47.34 g water and 1 phosphoric acid were added. A phosphoric acid solution containing 0.28 g (0.5% by mass based on the monomer charged) was added using a dropping funnel.
• the flask was immersed in a 70°C oil bath and stirred for 60 minutes, and then the temperature of the oil bath was raised to 130°C over 15 minutes.
• the internal temperature of the solution reached 100°C, and from there it was heated and stirred for 3 hours (internal temperature was 100 to 125°C) to obtain a liquid repellent material (P-1).
• nitrogen was flowed at a rate of 0.070 (liter)/min during the temperature rise and heating and stirring.
• the weight average molecular weight was 2,100.
• Synthesis examples 2 to 7 Liquid repellent materials (P-2) to (P-7) were obtained in the same manner as in Synthesis Example 1, except that the components and amounts of alkoxysilanes listed in Table 1 were changed.
• the weight average molecular weights of the liquid repellent materials (P-2) to (P-7) are listed in Table 1.
• a 200 mL three-necked flask was purged with nitrogen, and tetraethylene glycol dimethyl ether was added to 119 25.0 g of CF 3 CF 2 OCF 2 CF 2 OCF 2 COF and 16.4 g of CsF were charged, and the mixture was stirred at 50° C. for 1 hour under a nitrogen atmosphere. While maintaining the temperature at 50°C, 13.0 g of allyl bromide was added dropwise. Thereafter, the flask was immersed in an 80° C. oil bath under a nitrogen atmosphere to react for 12 hours.
• reaction product residue was distilled using a Kugelrohr apparatus at 140° C. to 190° C. and 200 Pa to obtain HfTES, ie, tridecafluorooctyltrimethoxysilane, as a colorless liquid.
• Synthesis Example 11 Synthesis of liquid repellent material (Ac-1) 100 g of cyclohexanone was added to a glass reaction vessel equipped with a stirring device, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet, and the mixture was heated under a nitrogen gas atmosphere. The temperature was raised to 110°C.
• Synthesis Example 12 Synthesis of liquid repellent material (Ac-2) CF 3 O (CF 2 O) 2 (CF 2 CF 2 O) was placed in a glass reaction vessel equipped with a stirring device, a reflux condenser, a dropping funnel, and a thermometer. ) 3 20 g of perfluoroalkylene ether compound having a hydroxyl group at one end represented by CF 2 CH 2 CH 2 OH, 10 g of diisopropyl ether as a solvent, 0.006 g of p-methoxyphenol as a polymerization inhibitor, and 3 triethylamine as a neutralizing agent. .3g was charged.
• Synthesis Example 13 Synthesis of liquid repellent material (Ac-3) In a glass reaction vessel equipped with a stirring device, a reflux condenser, a dropping funnel, and a thermometer, a peroxide having hydroxyl groups at both ends represented by formula (40) was added. 20 g of a fluoroalkylene ether compound, 10 g of diisopropyl ether as a solvent, 0.006 g of p-methoxyphenol as a polymerization inhibitor, and 3.3 g of triethylamine as a neutralizing agent were charged.
• c and d represent the number of repeating units, the average value of c is 5, and the average value of d is 8.
• the average number of fluorine atoms in the compound of the above formula is 46.
• the mass average molecular weight of the compound of the above formula by GPC is 5,800.
• c and d represent the number of repeating units, the average value of c is 5, and the average value of d is 8.
• the average number of fluorine atoms in the compound of the above formula is 46.
• methyl isobutyl ketone 160 g was charged as a solvent into a glass reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen gas inlet, and the temperature was raised to 105°C while stirring under a nitrogen stream. It was warm.
• a monomer solution in which 20 g of the compound represented by formula (41) was dissolved in 80 g of methyl isobutyl ketone, a monomer solution in which 80 g of glycidyl methacrylate was dissolved in 80 g of methyl isobutyl ketone, and t-butylperoxy-2- as a polymerization initiator were added.
• Synthesis Example 15 Synthesis of alkali-soluble resin (b2) Under a stream of dry nitrogen, 88.8 g (0.20 mol) of 2,2-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride was dissolved in 500 g of NMP. .
• 96.7 g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 14 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added to 100 g of NMP. and reacted at 20°C for 1 hour, and then at 50°C for 2 hours.
• Synthesis Example 16 Synthesis of alkali-soluble resin (b3) Under a stream of dry nitrogen, 41.3 g (0.16 mol) of diphenyl ether-4,4'-dicarboxylic acid and 43.0 g (0.16 mol) of 1-hydroxy-1,2,3-benzotriazole were mixed. 0.16 mol of a mixture of dicarboxylic acid derivatives obtained by reacting 2g (0.32 mol) with 73.3 g (0.20 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane.
• Synthesis Example 18 Synthesis of quinonediazide compound (c1) Under a stream of dry nitrogen, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 33.58 g of 4-naphthoquinonediazide sulfonyl acid chloride (0.125 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. To this, 12.65 g (0.125 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the reaction system did not rise above 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours.
• TrisP-PA trade name, manufactured by Honshu Chemical Industry Co., Ltd.
• the triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried in a vacuum dryer to obtain a naphthoquinone diazide compound (c1). The esterification rate of this naphthoquinone diazide compound was 83%.
• FIG. 1 shows a schematic diagram of the substrate used for evaluation.
• a 10 nm thick ITO transparent conductive film was formed on the entire surface of the alkali-free glass plate 1 by sputtering and etched as the first electrode 2. Further, an auxiliary electrode 3 was also formed at the same time in order to take out the second electrode.
• the obtained substrate was ultrasonically cleaned for 10 minutes using "Semico Clean” (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.), washed with ultrapure water, and dried to obtain a substrate.
• each component was mixed at the compounding ratio shown in Tables 2 and 3 under a yellow light, and thoroughly stirred at room temperature to dissolve. Thereafter, the obtained solution was filtered through a filter with a pore size of 0.2 ⁇ m to obtain photosensitive resin compositions W1 to W27.
• the obtained photosensitive resin compositions W1 to W27 were applied onto the substrate by a spin coating method, and prebaked for 2 minutes on a hot plate at 120° C. to form a dry coating film with a thickness of about 2 ⁇ m.
• the film was developed with a 2.38 mass% aqueous solution of TMAH for 60 seconds, and then with water.
• a barrier rib pattern 4 was prepared on the substrate in which an opening with a width of 70 ⁇ m and a length of 260 ⁇ m was arranged at one place in the center.
• a partition wall pattern 5 was formed, which was arranged at a pitch of 155 ⁇ m in the direction and a pitch of 465 ⁇ m in the length direction, and each opening had a shape that exposed the first electrode.
• the substrate on which the partition wall pattern 4 and the partition wall pattern 5 were formed was heated at 250° C. for 1 hour in a nitrogen atmosphere using a clean oven (manufactured by Koyo Thermo Systems Co., Ltd.) to cure it.
• a clean oven manufactured by Koyo Thermo Systems Co., Ltd.
• Example 24 The cured product of photosensitive resin composition W15 was subjected to XPS analysis by the method described in ⁇ Method for measuring property (iv) by X-ray photoelectron spectroscopy (XPS) analysis>, and the obtained F atoms and Si Table 6 shows the elemental concentrations (atom%).
• XPS X-ray photoelectron spectroscopy
• Examples 25 to 27 Comparative Examples 5 and 6
• the same evaluation as in Example 24 was performed except that the photosensitive resin composition W15 was changed to one of W17, W18, W19, W25, and W26.
• the evaluation results are shown in Table 6.
• the cured product of the present invention can be used for electronic components such as organic EL display devices, liquid crystal display devices, semiconductor devices, and multilayer wiring boards. Specifically, partition walls of organic EL elements, flattening layers of substrates with drive circuits of display devices using organic EL elements, color filters of liquid crystal devices, black matrices of liquid crystal devices, and rewiring spaces of semiconductor devices or semiconductor components. interlayer insulating film for semiconductors, passivation film for semiconductors, surface protection film for semiconductor elements, interlayer insulating film for multilayer wiring for high-density packaging, wiring protection insulating layer for circuit boards, on-chip microlenses for solid-state imaging devices, and various displays and solid-state imaging devices. It is suitably used for applications such as a flattening layer for devices.
• Examples of electronic devices having a surface protective film, interlayer insulating film, etc. on which the cured product of the present invention is disposed include MRAMs with low heat resistance. Furthermore, it can be preferably used for partition walls and insulating layers of display devices such as LCDs (liquid crystal displays), ECDs (electrochromic displays), and OLEDs (organic EL displays). More preferably, it can be used as a partition wall of a display device in which a functional layer is formed by applying functional ink in a region (pixel) surrounded by a grid-like partition wall formed on a substrate using an inkjet.
• the cured product of the present invention has good liquid repellency and prevents ink applied by an inkjet method from penetrating into adjacent pixels, thereby reducing the occurrence of display defects. Furthermore, since the cured product of the present invention has a small amount of outgassing at high temperatures, the functional layer contains an organic EL material containing at least one selected from the group consisting of an organic EL luminescent material, a hole injection material, and a hole transport material. It can be suitably used for EL display devices.
• the substrate with partition walls having partition walls containing the cured product of the present invention has good liquid repellency on the surface of the cured product, so that the area on the first electrode where at least a part of the cured product is open has functionality. It can be suitably used in a display device in which a functional layer is formed by applying ink using an inkjet method.
• the organic EL display device includes at least one type selected from the group consisting of an organic EL light emitting material, a hole injection material, and a hole transport material in the functional layer. It can be suitably used for.
• Second electrode Substrate 9 Flattening layer 10 Patterned first electrode 11 Cured product 12 Surface opposite to the interface where the first electrode and the cured product are in contact 13 Interface 14 where the first electrode and the cured product are in contact Perpendicular to the interface where the first electrode and the cured product are in contact and from the substrate The direction is a range of 100 to 200 nm starting from the interface where the first electrode and the cured product are in contact, and is perpendicular to the interface where the first electrode and the cured product are in contact, and the direction from the substrate to the cured product, and the first electrode 100 nm starting from the interface where the cured product contacts 16 First stage of cured product 17 Second stage of cured product

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