Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
  • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/52—Amides or imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
  • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
• • 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
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
• • 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
  • G03F7/20—Exposure; Apparatus therefor
  • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/128—Radiation-activated cross-linking agent containing

Definitions

• the present invention relates to a positive photosensitive resin composition and a cured film obtained therefrom. More specifically, a positive photosensitive resin composition that is less likely to generate residue during pattern formation, generates less outgassing during high-temperature baking, and is capable of forming an image having a cured film surface with high water repellency and oil repellency;
• the present invention relates to the cured film and various materials using the cured film.
• This positive photosensitive resin composition is particularly suitable for use as an interlayer insulating film in display devices such as liquid crystal displays, EL displays, and micro LED displays, and as a light-shielding material and barrier rib material compatible with inkjet systems.
• display elements such as thin film transistor (TFT) type liquid crystal display elements and organic EL (electroluminescent) elements are provided with patterned electrode protective films, flattening films, insulating films, and the like.
• TFT thin film transistor
• organic EL electroactive EL
• a photosensitive resin composition characterized by having a small number of steps for obtaining a required pattern shape and having sufficient flatness is preferred. , has been widely used.
• Patent Document 2 a method has been proposed (Patent Document 2) in which a bank is prepared in advance and an ink that will form a light-emitting layer is similarly dropped to prepare an organic EL display element (Patent Document 2).
• the substrate should be ink-philic (hydrophilic), and the surface of the banks should be made to be hydrophilic. should be water repellent.
• Patent Document 3 a proposal has been made for a negative photosensitive resin composition in which a fluorine-based surfactant or fluorine-based polymer is added to a photosensitive organic thin film.
• Application of a positive photosensitive resin is required for higher definition of a display element.
• Patent Document 4 As a positive type, there is WO 2007-132890 (Patent Document 4) using a polymer having a carboxyl group as an alkali-soluble polymer, but the alkaline developer used has a high concentration of tetraethylammonium hydroxide. In the case of , it was difficult to deal with all production lines because residues tend to occur between patterns.
• Patent Document 5 JP-A-2009-251327 and JP-A-2015-215449 using an alkali-soluble polymer having a phenolic hydroxyl group (Patent Document 5, 6), however, there are problems such as low heat resistance and shortening of the life of the display element due to outgassing generated during firing. If a high-concentration developer can be used, it can be used in common with the developer for TFT formation resists, TFT flattening layers, etc., leading to cost reduction and process optimization, but it is difficult at present.
• the present invention has been made in view of the above circumstances.
• Another object of the present invention is to provide a positive photosensitive resin composition capable of forming a cured film image with little residue after pattern formation even when a high-concentration developer is used and little outgassing during high-temperature baking.
• the present inventors have found that by using an alkali-soluble resin having an N-hydroxyphenyl group, a high-concentration tetramethylammonium hydroxide aqueous solution is used as a developer.
• the present inventors have found that developability is improved, the generation of residues between patterns is suppressed, and outgassing seen with phenolic hydroxyl group-containing resins is greatly reduced, and the present invention has been completed.
• a first embodiment of the present invention is a thermosetting positive photosensitive resin composition containing the following components (A), (B), (C), (D) and (E) a solvent, (A) component: a polymer having a liquid-repellent group, (B) component: an alkali-soluble resin having an N-hydroxyphenyl group, (C) component: 1,2-quinonediazide compound, (D) component: cross-linking agent (E) solvent;
• the component (B) is a structural unit derived from at least one monomer selected from N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, or N-(hydroxyphenyl)maleimide.
• the positive photosensitive resin composition according to the first embodiment which is a polymer containing
• the liquid-repellent group of component (A) is at least one group selected from the group consisting of fluoroalkyl groups having 3 to 10 carbon atoms, polyfluoroether groups and polysiloxane groups.
• a fourth aspect of the present invention is any one of the first to third aspects, wherein the monomer units constituting the polymer of component (A) are units derived from unsaturated hydrocarbons having the liquid-repellent group.
• a fifth aspect of the present invention is any one of the first to third aspects, wherein the monomer units constituting the polymer of component (A) are units derived from the above-mentioned alkoxysilane compound having a liquid-repellent group. is a positive photosensitive resin composition of;
• a sixth aspect of the present invention is the positive photosensitive resin composition according to any one of the first to fifth aspects, wherein component (A) is a polymer having a liquid-repellent group and a thermosetting group.
• a seventh aspect of the present invention is the positive photosensitive resin composition according to any one of the first to sixth aspects, wherein the cross-linking agent of component (D) contains an epoxy group or a methoxymethyl group;
• An eighth embodiment of the present invention is the positive type according to any one of the first to seventh embodiments, wherein the component (B), the alkali-soluble resin, has a number average molecular weight of 2,000 to 60,000 in terms of polystyrene.
• the ninth form of the present invention is any one of the first to eighth forms, wherein 0.1 to 20 parts by mass of component (A) is contained with respect to 100 parts by mass of component (B).
• a positive photosensitive resin composition according to; A tenth form of the present invention is any one of the first to ninth forms, characterized in that 5 to 100 parts by mass of component (C) is contained with respect to 100 parts by mass of component (B). is a positive photosensitive resin composition of;
• the eleventh mode of the present invention is characterized in that 5 to 50 parts by mass of component (D) is contained with respect to 100 parts by mass of component (B).
• a positive photosensitive resin composition according to; A twelfth aspect of the present invention is a cured film obtained using the positive photosensitive resin composition according to any one of the first to eleventh aspects;
• a thirteenth aspect of the present invention is a display device having the cured film according to the twelfth aspect;
• a fourteenth form of the present invention is a display element having the cured film according to the twelfth form as an image forming bank.
• the positive photosensitive resin composition of the present invention has high water repellency and high oil repellency on the surface of the cured film, and can form a cured film with less residue after pattern formation and less outgassing during high-temperature baking. can.
• the photosensitive resin composition of the present invention is a positive photosensitive resin composition containing the following components (A), (B), (C), (D) and (E) a solvent.
• E) Solvent Details of each component are described below.
• Component (A) is a polymer having a liquid-repellent group.
• polysilsesquioxane obtained by hydrolytic polycondensation of polyfunctional alkoxysilane monomers, or acrylic polymers obtained using monomers having
• liquid-repellent group examples include at least one group selected from fluoroalkyl groups having 3 to 10 carbon atoms, polyfluoroether groups and polysiloxane groups.
• the fluoroalkyl group has 3 to 10 carbon atoms, preferably 4 to 10 carbon atoms.
• fluoroalkyl groups include 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2-(perfluorobutyl)ethyl group, 3-perfluorobutyl -2-hydroxypropyl group, 2-(perfluorohexyl)ethyl group, 3-perfluorohexyl-2-hydroxypropyl group, 2-(perfluorooctyl)ethyl group, 3-perfluorooctyl-2-hydroxypropyl group , 2-(perfluorodecyl) ethyl group, 2-(perfluoro-3-methylbutyl) ethyl group, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl group, 2-(perfluoro-5-methyl hexyl)ethyl group, 2-(per
• a monomer having a fluoroalkyl group having 3 to 10 carbon atoms can be copolymerized.
• a polymer having a reactive site can be reacted with a compound having a fluoroalkyl group having 3 to 10 carbon atoms and a functional group that reacts with the reactive site of the polymer.
• Examples of the polyfluoroether group include an Rf group (a) having a polyfluoroether structure represented by Formula 1 below. -(X-O) n -Y Formula 1
• X is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorinated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and each unit enclosed by n is the same represents a group or a different group
• Y is a hydrogen atom (limited to the case where a fluorine atom is not bonded to the carbon atom adjacent to the oxygen atom adjacent to Y), a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or It represents a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 to 50. However, the total number of fluorine atoms in Formula 1 is 2 or more.
• X is preferably an alkylene group having 1 to 10 carbon atoms fluorinated by removing one hydrogen atom or a perfluorinated alkylene group having 1 to 10 carbon atoms.
• n represents the same group or a different group
• Y is an alkyl group fluorinated by removing one hydrogen atom having 1 to 20 carbon atoms or a per Examples include those showing fluorinated alkyl groups.
• X and Y in formula 1 more preferably X is a perfluorinated alkylene group having 1 to 10 carbon atoms, and each unit enclosed by n is the same group or a different group.
• Y represents a perfluorinated alkyl group having 1 to 20 carbon atoms.
• n represents an integer from 2 to 50. n is preferably 2-30, more preferably 2-15. Liquid repellency is favorable in n being two or more. If n is 50 or less, the compatibility of the monomers will be good when the polymer as the component (A) is synthesized by copolymerizing the monomer having the Rf group (a) with other monomers.
• the total number of carbon atoms in the Rf group (a) having the polyfluoroether structure represented by formula 1 is preferably 2-50, more preferably 2-30. Within this range, the polymer as component (A) exhibits good liquid repellency.
• X examples include -CF 2 -, -CF 2 CF 2 -, -CF 2 CF 2 CF 2 -, -CF 2 CF(CF 3 )-, -CF 2 CF 2 CF 2 CF 2 -, - CF 2 CF 2 CF(CF 3 )— and CF 2 CF(CF 3 )CF 2 —.
• Y examples include -CF 3 , -CF 2 CF 3 , -CF 2 CHF 2 , -(CF 2 ) 2 CF 3 , -(CF 2 ) 3 CF 3 , -(CF 2 ) 4 CF 3 , -(CF2) 5CF3 , -(CF2) 6CF3 , -( CF2 ) 7CF3 , - ( CF2 ) 8CF3 , -( CF2 ) 9CF3 , and ( CF2 ) 11 CF 3 , —(CF 2 ) 15 CF 3 .
• Rf group (a) having a polyfluoroether structure represented by Formula 1 includes the Rf group (a) represented by Formula 2.
• Rf group (a) represented by formula 2 specifically, - CF 2 O(CF 2 CF 2 O) n-1 CF 3 (n is 2 to 9), - CF(CF 3 )O(CF 2 CF(CF 3 )O) n-1 C 6 F 13 (n is 2 to 6), —CF(CF 3 )O(CF 2 CF(CF 3 )O) n ⁇ 1 C 3 F 7 (n is 2 to 6) is preferred from the viewpoint of ease of synthesis.
• All the Rf groups (a) in the polymer that is the component (A) may be the same or different.
• Examples of the polysiloxane group include a group (b) having a polysiloxane structure represented by Formula 3.
• the group (b) having a polysiloxane structure represented by formula 3 is referred to as pSi group (b).
• pSi group (b) the group (b) having a polysiloxane structure represented by formula 3
• pSi group (b) the group (b) having a polysiloxane structure represented by formula 3
• R 1 and R 2 independently represent hydrogen, an alkyl group, a cycloalkyl group or an aryl group
• R 3 represents hydrogen or an organic group having 1 to 10 carbon atoms
• n represents an integer of 1 to 200. .).
• R 1 and R 2 independently represent hydrogen, an alkyl group, a cycloalkyl group or an aryl group, and may be the same or different for each siloxy unit.
• R 1 and R 2 are preferably hydrogen, a methyl group or a phenyl group because the polymer of component (A) exhibits good liquid repellency. is preferably a methyl group.
• R 3 may contain a nitrogen atom, an oxygen atom, or the like.
• Methods for introducing the pSi group (b) into the polymer that is the component (A) include a method of copolymerizing a monomer having a pSi group (b) and a compound having a pSi group (b) in a polymer having a reactive site. and a method of using a polymerization initiator having a pSi group (b).
• Monomers having a pSi group (b) include CH 2 ⁇ CHCOO(pSi), CH 2 ⁇ C (CH 3 )COO(pSi), and the like. However, pSi represents a pSi group (b). Monomers having a pSi group (b) may be used alone, or two or more of them may be used in combination.
• Examples of various modification methods for reacting a compound having a pSi group (b) with a polymer having a reactive site include the following methods.
• the polymerization initiator having a pSi group (b) may contain a group having a divalent polysiloxane structure in the main chain of the initiator molecule, or may contain a monovalent group in the terminal portion or side chain of the initiator molecule. may contain a group having a polysiloxane structure of Initiator
• the initiator containing a group having a divalent polysiloxane structure in its molecular main chain includes, for example, a compound having a group having a divalent polysiloxane structure and an azo group alternately.
• Commercially available products include VPS-1001 and VPS-0501 (manufactured by Wako Pure Chemical Industries, Ltd.).
• the amount of the liquid-repellent group introduced is preferably 5 to 60 mol % of all repeating units. If it is less than 5 mol %, the liquid-repellent effect may not be obtained. If it is more than 60 mol %, problems such as aggregation may occur.
• thermosetting functional group is not particularly limited as long as it is a group that forms a covalent bond upon heating. It may be a functional group that Examples of such thermosetting functional groups (thermosetting groups) include hydroxy group, carboxyl group, amide group, amino group, N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group and oxetane. groups, vinyl groups, mercapto groups, blocked isocyanate groups, and the like.
• the method for producing the acrylic polymer of component (A) is not particularly limited, but a monomer having a liquid-repellent group, such as a monomer having a fluoroalkyl group having 3 to 10 carbon atoms, or a monomer having a polyfluoroether group. and at least one of the monomers having a polysiloxane group, the monomer having a thermosetting group, and optionally a monomer other than the above (hereinafter also referred to as other monomer A), in a solvent in the presence of a polymerization initiator, 50 to 110 It is obtained by polymerizing at a temperature of °C. At that time, the solvent used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble acrylic polymer and the acrylic polymer having a specific functional group. Specific examples include solvents described in (E) solvent described later.
• radically polymerizable monomers having a liquid-repellent group examples include 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3- Pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2-(perfluorobutyl)ethyl acrylate, 2-(perfluorobutyl)ethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl Acrylates, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2-(perfluorohexyl) ethyl acrylate, 2-(perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluoro Hexyl-2-hydroxypropyl methacrylate, 2-(perfluoroocty
• radically polymerizable monomers having a thermosetting group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl) phthalate, mono-(2-(methacryloyloxy)ethyl ) phthalate, N-(carboxyphenyl) maleimide, N-(carboxyphenyl) methacrylamide, N-(carboxyphenyl) acrylamide, hydroxystyrene, N-(hydroxyphenyl) acrylamide, N-(hydroxyphenyl) methacrylamide, N- (Hydroxyphenyl)maleimide, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5 -methacryloyloxy-6-hydroxynorbornene-2-carboxylic
• monomers A include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and methoxytriethylene.
• the acrylic polymer having a specific functional group obtained in this way is usually in the form of a solution dissolved in a solvent.
• the solution of the acrylic polymer obtained as described above is added to diethyl ether, water, or the like under stirring to reprecipitate, and after filtering and washing the generated precipitate, it is treated under normal pressure or reduced pressure.
• the specific copolymer can be powdered by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If the purification cannot be sufficiently performed in one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
• the powder of the above-mentioned specific copolymer may be used as it is, or the powder may be redissolved, for example, in the solvent (E) described later and used in the form of a solution.
• the method for obtaining the polysilsesquioxane of the component (A) is not particularly limited, but an alkoxysilane having a liquid-repellent group, an alkoxysilane having a thermosetting group, and optionally an alkoxysilane having other organic groups are used. Polysilsesquioxanes obtained by polycondensation are preferred.
• alkoxysilane monomers having a liquid-repellent group include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane.
• Silane heptadecafluorodecyltriethoxysilane, 2-(perfluorohexyl)ethyltrimethoxysilane, 2-(perfluorohexyl)ethyltriethoxysilane, 2-(perfluorobutyl)ethyltrimethoxysilane, 2-(perfluorohexyl)ethyltrimethoxysilane, 2-(perfluorohexyl)ethyltriethoxysilane, fluorobutyl)ethyltriethoxysilane and the like.
• At least one type of alkoxysilane having a liquid-repellent group may be used in the present invention, but a plurality of types may be used as necessary.
• alkoxysilane monomers having a thermosetting group include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, trimethoxyvinylsilane, vinyltris(2-ethoxy)silane, and vinyltris.
• a plurality of alkoxysilanes having an organic group having a thermosetting group may be used.
• alkoxysilanes with other organic groups are tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane.
• butyltriethoxysilane pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyl Alkyltrialkoxysilanes such as trimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane; aromatic groups such as phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane; dialkoxysilanes,
• the polysilsesquioxane of component (A) preferably contains 5 to 50 mol % of alkoxysilane containing a liquid-repellent group in the total alkoxysilane, and preferably contains alkoxysilane containing a thermosetting group in the total alkoxysilane. contains 10 to 95 mol %, and the remainder is obtained by polycondensation of other alkoxysilanes.
• the content of the alkoxysilane containing the liquid repellent group is more preferably 10 to 40 mol%.
• the content of alkoxysilane containing a thermosetting group is more preferably 30 to 80 mol % of the total alkoxysilane.
• a method for obtaining the polysilsesquioxane of component (A) includes, for example, an alkoxysilane containing a liquid-repellent group, an alkoxysilane having a thermosetting group, other alkoxysilanes as necessary, and an organic solvent. is heated in the presence of an aqueous tetraethylammonium hydroxide solution for polycondensation. Specifically, an aqueous tetraethylammonium hydroxide solution is added to an organic solvent in advance to obtain a solution of the aqueous tetraethylammonium hydroxide solution, and then the solution is heated and mixed with the various alkoxysilanes described above.
• the amount of the tetraethylammonium hydroxide aqueous solution present is preferably 0.01 to 0.2 mol per 1 mol of the total amount of alkoxy groups possessed by the alkoxysilane used.
• the above heating can be carried out at a liquid temperature of preferably 0 to 100° C., and preferably for several tens of minutes under reflux in a container equipped with a reflux tube so that the liquid does not evaporate or volatilize. It takes place for dozens of hours.
• the alkoxysilanes may be mixed in advance as a mixture, or multiple types of alkoxysilanes may be mixed sequentially.
• the concentration of all silicon atoms in the charged alkoxysilane converted to oxide (hereinafter referred to as SiO 2 conversion concentration) is 40% by mass or less, particularly preferably 10 to 30% by mass. is preferably heated in the range of By selecting an arbitrary concentration within such a concentration range, gel formation can be suppressed and a homogeneous polysilsesquioxane-containing solution can be obtained.
• the organic solvent (hereinafter also referred to as a polymerization solvent) used for polycondensation of the alkoxysilane dissolves the alkoxysilane having a liquid-repellent group, the alkoxysilane having a thermosetting group, and other alkoxysilanes as necessary.
• a polymerization solvent used for polycondensation of the alkoxysilane.
• the solvent (E) is preferred.
• alcohols and organic solvents having good compatibility with alcohols are used because alcohols are generated by the polycondensation reaction of alkoxysilanes.
• the polymerization solvent examples include alcohols such as methanol, ethanol, propanol and n-butanol, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and propylene glycol monomethyl ether. and ethers such as tetrahydrofuran.
• alcohols such as methanol, ethanol, propanol and n-butanol
• glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and propylene glycol monomethyl ether.
• ethers such as tetrahydrofuran.
• a plurality of types of the above organic solvents may be mixed and used.
• the specific polysilsesquioxane solution obtained by the above method may be used as it is in the photosensitive resin composition of the present invention, or if necessary, the specific polysilsesquioxane solution obtained by the above method may be used.
• a solution of polysilsesquioxane may be concentrated, diluted by adding a solvent, or used by replacing with another solvent.
• the solvent used when adding and diluting the solvent may be the solvent used in the polycondensation reaction or other solvents.
• This additive solvent is not particularly limited as long as the polysilsesquioxane is uniformly dissolved, and one or more of them can be arbitrarily selected and used.
• Examples of such additive solvents include the solvents used in the polycondensation reaction, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ester solvents such as methyl acetate, ethyl acetate, and ethyl lactate. .
• the polycondensation reaction of polysilsesquioxane is carried out before mixing the polymer other than polysilsesquioxane. It is preferable to distill off the alcohol generated at the time under normal pressure or reduced pressure.
• the polymer (A) may be polyimide, polyamic acid, polyamide, polyurea, polyurethane, phenol, epoxy, polysiloxane, polyester, or acrylic polymer. and polymers into which quinonediazide groups have been introduced.
• Polyamic acid, polyimide, polyamide, and polyurea include polyamic acid obtained by reacting a diamine having a fluoroalkyl group or a fluoroalkoxy group and a diamine having a hydroxyl group with an acid dianhydride, and a polyimide obtained by imidizing the polyamic acid. , a polyamide obtained by reacting the diamine with a dicarboxylic anhydride, or a polyurea obtained by reacting the diamine with a diisocyanate.
• Polyurethanes include polyurethanes obtained by reacting a diol having a fluoroalkyl group or a fluoroalkoxy group and a diol having an amino group with a diisocyanate.
• Phenolic resins include novolak resins obtained by polymerizing phenol having a fluoroalkyl group or fluoroalkoxy group with formaldehyde.
• Epoxy resins include epoxy resins obtained by reacting bisphenol A and/or bisphenol F having a fluoroalkyl group or fluoroalkoxy group with glycidyl ether of the bisphenol A and/or bisphenol F.
• a silane monomer mixture containing a trialkoxysilane having a fluoroalkyl group or a dialkoxysilanesilane having a fluoroalkyl group and a trialkoxysilane having an amino group or a dialkoxysilanesilane having an amino group is polymerized.
• Examples include polymers obtained by
• polyesters include polyesters obtained by reacting a dicarboxylic acid having a fluoroalkyl group or a fluoroalkoxy group with a diol having a fluoroalkyl group or a fluoroalkoxy group.
• the (A) component acrylic polymer may be a mixture of a plurality of specific copolymers.
• Component (B) of the present invention is an alkali-soluble resin having an N-hydroxyphenyl group.
• the alkali-soluble resin of component (B) may be any alkali-soluble resin having such a structure, and there are no particular restrictions on the skeleton of the main chain of the polymer constituting the resin and the types of side chains.
• the (B) component alkali-soluble resin preferably has a number average molecular weight within the range of 2,000 to 60,000. If the number average molecular weight is too large, exceeding 60,000, development residues are likely to occur, and the sensitivity is greatly reduced. At that time, a considerable amount of film loss occurs in the exposed area, and curing may be insufficient.
• Examples of the component (B), the alkali-soluble resin having an N-hydroxyphenyl group, include acrylic resins and polymaleimide resins.
• an alkali-soluble resin composed of a copolymer (hereinafter referred to as a specific copolymer) obtained by polymerizing multiple types of monomers can also be used as the component (B).
• the alkali-soluble resin as component (B) may be a blend of a plurality of specific copolymers.
• the above specific copolymer is a copolymer formed of a monomer having an N-hydroxyphenyl group and at least one monomer selected from the group of monomers copolymerizable with these monomers as essential structural units.
• a number average molecular weight greater than 60,000 may result in residue.
• the above monomer having an N-hydroxyphenyl group is not limited to having one N-hydroxyphenyl group, and may have a plurality of N-hydroxyphenyl groups.
• Examples of monomers having an N-hydroxyphenyl group include N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide and the like.
• Monomers copolymerizable with monomers having an N-hydroxyphenyl group include, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, ⁇ -butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl me
• the ratio of the monomer having an N-hydroxyphenyl group in the production of the component (B) alkali-soluble resin is preferably 10 to 90 mol% of all the monomers used in the production of the component (B) alkali-soluble acrylic polymer. , more preferably 20 to 85 mol %, most preferably 30 to 80 mol %. If the ratio of the monomer having an N-hydroxyphenyl group is less than 10 mol %, the alkali solubility of the polymer is insufficient.
• the ratio of the other monomers is preferably 80% by weight or less, more preferably 50% by weight or less, and even more preferably 20% by weight or less. If it exceeds 80% by weight, the amount of essential components is relatively reduced, making it difficult to sufficiently obtain the effects of the present invention.
• the method for obtaining the alkali-soluble resin which is the component (B) used in the present invention, is not particularly limited. can be obtained by polymerizing at a temperature of 50 to 110° C. in a solvent in which At that time, the solvent used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble acrylic polymer and the acrylic polymer having a specific functional group. Specific examples include solvents described in (E) solvent described later.
• the acrylic polymer obtained in this way is usually in the form of a solution dissolved in a solvent.
• the solution of the specific copolymer obtained as described above is added to diethyl ether, water, or the like under stirring to reprecipitate, and after filtering and washing the generated precipitate, Then, the powder of the specific copolymer can be obtained by drying at normal temperature or by heating. By such an operation, the polymerization initiator and unreacted monomers coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If the purification cannot be sufficiently performed in one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
• the powder of the above-mentioned specific copolymer may be used as it is, or the powder may be redissolved, for example, in the solvent (E) described later and used in the form of a solution.
• the alkali-soluble resin as component (B) may be a mixture of multiple types of alkali-soluble resins.
• the ratio of component (A) to component (B) is 0.1 to 20 parts by mass of component (A) per 100 parts by mass of component (B).
• the 1,2-quinonediazide compound as component (C) is either a hydroxyl group or an amino group, or a compound having both a hydroxyl group and an amino group. In the case of having both, preferably 10 to 100 mol%, particularly preferably 20 to 95 mol% of the total amount thereof) is esterified or amidated with 1,2-quinonediazide sulfonic acid. be able to.
• Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris(4-hydroxyphenyl).
• Examples of compounds containing an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine. , 4,4′-diaminophenylmethane, 4,4′-diaminodiphenyl ether and other anilines, and aminocyclohexane.
• compounds containing both hydroxyl group and amino group include, for example, o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4′-diamino-4′′-hydroxytriphenylmethane, 4-amino-4′,4′′-dihydroxytriphenylmethane, bis(4-amino-3-carboxy-5-hydroxyphenyl) ether, bis (4-amino-3-carboxy-5-hydroxyphenyl)methane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)propane, 2,2-bis(4-amino-3-carboxy -5-Hydroxyphenyl)hexafluoropropane, and alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol.
• 1,2-quinonediazide compounds can be used alone or in combination of two or more.
• the content of component (C) in the positive photosensitive resin composition of the present invention is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and still more preferably 100 parts by mass of component (B). is 10 to 40 parts by mass. If the amount is less than 5 parts by mass, the difference in dissolution rate in the developer between the exposed area and the unexposed area of the positive photosensitive resin composition becomes small, and patterning by development may be difficult. On the other hand, when the amount exceeds 100 parts by mass, the 1,2-quinonediazide compound is not sufficiently decomposed by exposure for a short period of time, so that the sensitivity may be lowered or a residue may be generated between patterns.
• Component (D) is a cross-linking agent, more specifically, a compound having a structure capable of forming a cross-linked structure by thermal reaction with the N-hydroxyphenyl group of component (B). Specific examples are given below, but are not limited to these.
• the thermal cross-linking agent is selected from, for example, (D1) a cross-linking compound having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups and (D2) a cross-linking compound represented by the following formula (3). and (D3) a cross-linking agent having two or more isocyanate groups is preferred.
• These cross-linking agents can be used alone or in combination of two or more.
• crosslinkable compound having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups which is the component (D1)
• the crosslinkable reaction proceeds through a dehydration condensation reaction.
• Such compounds include, for example, compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplastic compounds.
• alkoxymethylated glycoluril examples include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4 ,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl) urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone and the like.
• alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine.
• Commercially available products manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (trade names: Nikalac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.
• alkoxymethylated melamine examples include, for example, hexamethoxymethylmelamine.
• Mitsui Cytec Co., Ltd. methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, Cymel 301, Cymel 303, and 350), butoxymethyl type melamine compounds (trade name: Mycoat (registered trademark) ) 506, 508), Sanwa Chemical methoxymethyl type melamine compounds (trade names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl-type melamine compounds (trade names: Nikalac (registered trademark) MX-45, MX-410, MX-302), etc. mentioned.
• a melamine compound examples include high molecular weight compounds made from melamine and benzoguanamine compounds described in US Pat. No. 6,323,310.
• Commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.).
• Commercially available products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 ( (manufactured by Mitsui Cytec Co., Ltd.) and the like.
• phenoplast compounds include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 3 , 3′,5,5′-tetrakis(hydroxymethyl)biphenyl-4,4′-diol, 3,3′-methylenebis(2-hydroxy-5-methylbenzenemethanol), 4,4′-(1-methyl ethylidene)bis[2-methyl-6-hydroxymethylphenol], 4,4′-methylenebis[2-methyl-6-hydroxymethylphenol], 4,4′-(1-methylethylidene)bis[2,6- bis(hydroxymethyl)phenol], 4,4′-methylenebis[2,6-bis(hydroxymethyl)phenol], 2,6-bis(methoxymethyl)phenol, 2,6-bis(methoxymethyl)cresol, 2 ,6-bis(methoxymethyl)-4-methoxyphenol, 3,3′,5,5′-tetrakis(methoxymethyl)biphenyl-4,4,4
• an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or Polymers made using methacrylamide compounds can also be used.
• polymers examples include poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methylmethacrylate, N-ethoxymethyl Copolymers of methacrylamide and benzyl methacrylate, copolymers of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate, and the like are included.
• Such polymers have a weight average molecular weight of 1,000 to 50,000, preferably 1,500 to 20,000, more preferably 2,000 to 10,000.
• crosslinkable compounds can be used alone or in combination of two or more.
• component (D1) is selected as a cross-linking agent in the positive photosensitive resin composition of the present invention
• the content is preferably 5 to 50 parts by mass, more preferably 10 parts by mass, per 100 parts by mass of component (B). to 40 parts by mass. If the amount is less than 5 parts by mass, outgassing may increase during the display element manufacturing process, components of the positive photosensitive resin composition may elute into other layers, and element characteristics and reliability may deteriorate. On the other hand, if it exceeds 50 parts by mass, the storage stability may deteriorate, the adhesion during development may deteriorate, or the sensitivity may deteriorate.
• the positive photosensitive resin composition of the present invention can contain a crosslinkable compound having an epoxy group represented by formula (3) as the component (D2). (Wherein, k is an integer of 2 to 10, m is an integer of 0 to 4, and R 11 represents a k-valent organic group)
• component (D2) When component (D2) is selected as the cross-linking agent, the content is 5 to 50 parts by mass, preferably 7 to 40 parts by mass, more preferably 10 to 30 parts by mass per 100 parts by mass of component (B). be. If the content of the crosslinkable compound is less than 5 parts by mass, the density of the crosslinks formed by the crosslinkable compound is not sufficient. components of the resin composition may be eluted, and device characteristics and reliability may be deteriorated. On the other hand, when it exceeds 50 parts by mass, uncrosslinked crosslinkable compounds are present, and the heat resistance after pattern formation, solvent resistance, resistance to long-term baking, etc. are lowered, and the photosensitive resin composition is also deteriorated. storage stability may deteriorate.
• the solvent (E) used in the present invention dissolves the components (A), (B), (C), and (D), and also dissolves other additives described below that are optionally added.
• the type and structure of the solvent are not particularly limited as long as the solvent has such dissolving ability.
• Examples of such (E) solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol.
• solvents can be used singly or in combination of two or more.
• (E) solvents propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. have good coating properties and are safe. is preferable from the viewpoint of high
• These solvents are commonly used as solvents for photoresist materials.
• the positive photosensitive resin composition of the present invention may optionally contain rheology modifiers, pigments, dyes, storage stabilizers, antifoaming agents, adhesion promoters, or A dissolution accelerator such as polyhydric phenol and polycarboxylic acid may be contained.
• the positive photosensitive resin composition of the present invention is a positive photosensitive resin composition containing the following components (A), (B), (C), (D) and (E) a solvent, In addition, each of these compositions can further contain one or more of other additives as desired.
• solvent solvent
• preferred examples of the positive photosensitive resin composition of the present invention are as follows. 0.1 to 20 parts by mass of component (A), 5 to 100 parts by mass of component (C), and 5 to 50 parts by mass of component (D) per 100 parts by mass of component (B), and these components (E) a positive photosensitive resin composition dissolved in a solvent.
• the proportion of solids in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent. 5 to 60% by mass, or 10 to 50% by mass.
• the solid content refers to the total components of the positive photosensitive resin composition excluding (E) the solvent.
• the method for preparing the positive photosensitive resin composition of the present invention is not particularly limited, but for example, the (A) component (specific acrylic copolymer) is dissolved in the (E) solvent, and this solution is (B) component alkali-soluble resin, (C) component 1,2-quinonediazide compound, and (D) component cross-linking agent are mixed in predetermined proportions to form a uniform solution, or this preparation method. In an appropriate stage, a method of further adding and mixing other additives as necessary may be mentioned.
• the solution of the copolymer obtained by the polymerization reaction in the solvent (E) can be used as it is.
• solvent (E) may be additionally added for the purpose of adjusting the concentration.
• the (E) solvent used in the formation process of the specific copolymer and the (E) solvent used for adjusting the concentration during preparation of the positive photosensitive resin composition may be the same, can be different.
• the prepared solution of the positive photosensitive resin composition after filtering using a filter having a pore size of about 0.2 ⁇ m.
• the positive photosensitive resin composition of the present invention is applied to semiconductor substrates (e.g., silicon/silicon dioxide coated substrates, silicon nitride substrates, substrates coated with metal such as aluminum, molybdenum, chromium, etc., glass substrates, quartz substrates, ITO substrates). etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following the slit, inkjet coating, etc., and then pre-dried on a hot plate or oven to form a coating film. can do. After that, a positive photosensitive resin film is formed by heat-treating this coating film.
• semiconductor substrates e.g., silicon/silicon dioxide coated substrates, silicon nitride substrates, substrates coated with metal such as aluminum, molybdenum, chromium, etc., glass substrates, quartz substrates, ITO substrates.
• spin coating flow coating, roll coating, slit coating, spin coating following the slit, inkjet coating, etc.
• a heating temperature and a heating time appropriately selected from the ranges of a temperature of 70°C to 160°C and a time of 0.3 to 60 minutes are adopted.
• the heating temperature and heating time are preferably 80° C. to 140° C. and 0.5 to 10 minutes.
• the film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 30 ⁇ m, further, for example, 0.2 to 10 ⁇ m, further, for example, 0.3 to 5 ⁇ m. is.
• a mask having a predetermined pattern is attached to the coating film obtained above, and light such as ultraviolet light is irradiated, and the exposed portion is washed out by developing with an alkaline developer, thereby forming a sharp relief pattern on the end face. is obtained.
• alkaline developers examples include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hydroxides such as choline.
• alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide
• tetramethylammonium hydroxide tetraethylammonium hydroxide
• hydroxides such as choline.
• Alkaline aqueous solutions such as aqueous solutions of quaternary ammonium, aqueous solutions of amines such as ethanolamine, propylamine and ethylenediamine are included.
• a surfactant or the like can be added to these developers.
• aqueous solution of tetraethylammonium hydroxide is generally used as a photoresist developer, and the photosensitive resin composition of the present invention is also produced using this alkaline developer. , can be developed satisfactorily without causing problems such as swelling. A relief pattern can be obtained more effectively by preferably using a 1.0 to 2.38% by mass aqueous solution.
• any of a liquid heaping method, a dipping method, a rocking immersion method, and the like can be used as a developing method.
• the development time at that time is usually 15 to 180 seconds.
• the positive photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, followed by air drying using compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and A patterned film is obtained.
• the pattern-formed film is post-baked for thermal curing, specifically by heating using a hot plate, an oven, etc., to improve heat resistance, transparency, and planarization properties. , low water absorption, excellent chemical resistance, etc., and a film having a good relief pattern can be obtained.
• Post-baking is generally performed at a heating temperature selected from the range of 140 ° C. to 270 ° C. for 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven. method is adopted.
• the positive photosensitive resin composition of the present invention provides a coating having high storage stability, sufficiently high sensitivity, very little film loss in unexposed areas during development, and a fine pattern.
• a film can be formed.
• the coating film (cured film) thus obtained can be suitably used as an image forming bank for a display device.
• the present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
• the number average molecular weight and weight average molecular weight are measured as follows.
• the number-average molecular weight and weight-average molecular weight of the copolymer obtained according to the following synthesis examples were measured using a Shimadzu GPC apparatus (Shodex columns KF-804L and 803L), and tetrahydrofuran, an elution solvent, was passed through the column at a flow rate of 1 ml/min. (Column temperature 40° C.) The measurement was carried out under the condition of flowing and eluting.
• Mn number average molecular weight
• Mw weight average molecular weight
• MMA methyl methacrylate
• HEMA 2-hydroxyethyl methacrylate
• HPMA 4-hydroxyphenyl methacrylate
• CHMI N-cyclohexylmaleimide
• MAA methacrylic acid
• AIBN ⁇ , ⁇ '-azobisisobutyronitrile
• QD ⁇ , ⁇ , ⁇ '- Compound GT-401: Butanetetracarboxylic acid synthesized by condensation reaction of 1 mol of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride Tetra (3,4-epoxycyclohexylmethyl) modified ⁇ -caprolactone
• Marukalinker CST Marukalinker CST8515 and 7030 manufactured by Maruzen Petrochemical Co., Ltd.
• the obtained acrylic polymer had an Mn of 5,000 and an Mw of 8,100.
• the obtained acrylic polymer had an Mn of 5,600 and an Mw of 9,300.
• the obtained acrylic polymer had an Mn of 6,200 and an Mw of 11,700.
• Examples 1 to 5 and Comparative Examples 1 to 4> According to the composition shown in Table 1 below, the solution of component (A), the solution of component (B), the component (C), and the component (D) are dissolved in the solvent (E) in a predetermined ratio, and stirred at room temperature for 3 hours. to form a uniform solution, to prepare a positive photosensitive resin composition for each example and each comparative example.
• the coating film on which the line and space pattern was formed was post-baked by heating at a temperature of 230° C. for 30 minutes to cure it. Residues in the openings of the cured line-and-space pattern were observed using a scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation. Table 2 shows the results obtained. At this time, the pattern was particularly good with no residue left ( ⁇ ), the pattern was good with no residue left ( ⁇ ), and the residue was defective (x). I decided.

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