WO2022168732A1 - Positive-acting photosensitive resin composition - Google Patents

Positive-acting photosensitive resin composition Download PDF

Info

Publication number
WO2022168732A1
WO2022168732A1 PCT/JP2022/003127 JP2022003127W WO2022168732A1 WO 2022168732 A1 WO2022168732 A1 WO 2022168732A1 JP 2022003127 W JP2022003127 W JP 2022003127W WO 2022168732 A1 WO2022168732 A1 WO 2022168732A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
component
photosensitive resin
resin composition
positive photosensitive
Prior art date
Application number
PCT/JP2022/003127
Other languages
French (fr)
Japanese (ja)
Inventor
浩之 大村
佳代 稲見
真 畑中
Original Assignee
日産化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to KR1020237026446A priority Critical patent/KR20230142489A/en
Priority to JP2022579497A priority patent/JPWO2022168732A1/ja
Priority to CN202280013069.0A priority patent/CN116848466A/en
Publication of WO2022168732A1 publication Critical patent/WO2022168732A1/en

Links

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.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials For Photolithography (AREA)

Abstract

[Problem] To obtain a positive-acting photosensitive resin composition which is used for liquid-crystal display elements, organic EL display elements, etc., gives cured films having surfaces with high water repellency and high oil repellency, leaves little residue after patterning even with a high-concentration developing solution, and can form a cured-film image that is reduced in outgassing during high-temperature burning. [Solution] This positive-acting photosensitive resin composition comprises (A) component, which is a polymer having a liquid-repellent group, (B) component, which is an alkali-soluble resin having an N-hydroxyphenyl group, (C) component, which is a 1,2-quinonediazide compound, (D) component, which is a crosslinking agent, and (E) a solvent.

Description

ポジ型感光性樹脂組成物Positive photosensitive resin composition
　本発明は、ポジ型感光性樹脂組成物及びそれから得られる硬化膜に関する。
　より詳細には、パターン形成時の残渣が発生しにくく、高温焼成時のアウトガスの発生が少なく、高い撥水性と撥油性を硬化膜表面に有する画像を形成可能なポジ型感光性樹脂組成物及びその硬化膜、並びに該硬化膜を用いた各種材料に関する。このポジ型感光性樹脂組成物は、特に液晶ディスプレイやＥＬディスプレイ、マイクロＬＥＤディスプレイ等のディスプレイ素子における層間絶縁膜、インクジェット方式に対応した遮光材料や隔壁材料として用いるのに好適である。 TECHNICAL FIELD 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.
　一般に、薄膜トランジスタ（ＴＦＴ）型液晶表示素子、有機ＥＬ（ｅｌｅｃｔｒｏｌｕｍｉｎｅｓｃｅｎｔ）素子等のディスプレイ素子においては、パターン形成された電極保護膜、平坦化膜、絶縁膜等が設けられている。これらの膜を形成する材料としては、感光性樹脂組成物の中でも、必要とするパターン形状を得るための工程数が少なくしかも十分な平坦性を有するという特徴を持つところの感光性樹脂組成物が、従来から幅広く使用されている。 In general, 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. As a material for forming these films, among the photosensitive resin compositions, 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.
　また、ディスプレイ表示素子の作製工程においてインクジェットを用いたフルカラー表示基板作製技術も近年活発に検討されている。たとえば液晶表示素子におけるカラーフィルタ作製に関しては、従来の印刷法、電着法、染色法または顔料分散法に対して、あらかじめパターニングされた画素を規定する区画（以下バンクという）を、光を遮断する感光性樹脂層で形成し、このバンクに囲まれた開口部内にインク滴を滴下するカラーフィルタおよびその製造方法（特許文献１）などが提案されている。また有機ＥＬ表示素子においてもあらかじめバンクを作製し、同様に発光層となるインクを滴下し、有機ＥＬ表示素子を作製する方法（特許文献２）が提案されている。
　しかしインクジェット法でバンクに囲まれたインク滴を滴下する場合、バンクを超えて隣の画素にインク滴が溢れる事態を防ぐため、基板には親インク性（親水性）を持たせ、バンク表面には撥水性を持たせる必要がある。 Also, in recent years, a full-color display substrate manufacturing technique using an inkjet in the manufacturing process of a display device has been actively studied. For example, regarding the production of color filters in liquid crystal display elements, in contrast to the conventional printing method, electrodeposition method, dyeing method, or pigment dispersion method, pre-patterned sections defining pixels (hereinafter referred to as banks) are shielded from light. A color filter formed of a photosensitive resin layer, in which ink droplets are dropped into openings surrounded by banks, and a method for manufacturing the same (Patent Document 1) have been proposed. Also in the case of organic EL display elements, 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).
However, when ink droplets surrounded by banks are applied using the inkjet method, in order to prevent the ink droplets from overflowing over the banks and overflowing into adjacent pixels, the substrate should be ink-philic (hydrophilic), and the surface of the banks should be made to be hydrophilic. should be water repellent.
　上記の目的を達成するため、感光性有機薄膜にフッ素系界面活性剤やフッ素系ポリマーを配合したネガ型感光性樹脂組成物の提案がなされている（特許文献３）が、解像度向上は難しく、ディスプレイ素子の高精細化にはポジ型感光性樹脂の適用が求められている。 In order to achieve the above object, 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 (Patent Document 3). Application of a positive photosensitive resin is required for higher definition of a display element.
　一方、ポジ型のものとしてはアルカリ可溶性ポリマーとしてカルボキシル基を有するポリマーを用いた国際公開２００７－１３２８９０号公報（特許文献４）があるが、使用するアルカリ現像液中の水酸化テトラエチルアンモニウムが高濃度の場合、パターン間に残渣が発生しやすく全ての製造ラインに対応することは難しかった。また、高濃度現像液を用いてもパターン形成可能なポジ型材料としてはフェノール性水酸基を有するアルカリ可溶性ポリマーを用いた特開２００９－２５１３２７号公報や特開２０１５－２１５４４９号公報（特許文献５、６）があるが、耐熱性が低く、焼成時に発生するアウトガスによりディスプレイ素子の寿命低下が起こる等の問題があった。高濃度現像液が使用できるならＴＦＴ形成用レジスト、ＴＦＴ平坦化層などの現像液と共用でき、コスト低減及びプロセスの最適化につながることができるが、現状は難しい。 On the other hand, 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. In addition, as a positive material capable of forming a pattern even using a high-concentration developer, 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.
特開２０００－１８７１１１号公報JP-A-2000-187111 特開平１１－５４２７０号公報JP-A-11-54270 特開２０１５－１７２７４２号公報JP 2015-172742 A 特開２００７－１３２８９０号公報JP 2007-132890 A 特開２００９－２５１３２７号公報JP 2009-251327 A 特開２０１５－２１５４４９号公報JP 2015-215449 A
　本発明は、上記の事情に鑑みなされたものであって、その解決しようとする課題は、液晶表示素子、有機ＥＬ表示素子等に使用され、硬化膜表面に高い撥水性と高い撥油性を有し、高濃度現像液が使用されてもパターン形成後の残渣が少なく、高温焼成時のアウトガス発生が少ない硬化膜の画像を形成可能なポジ型感光性樹脂組成物を提案することにある。 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.
　本発明者らは、上記目的を達成するために鋭意検討した結果、Ｎ－ヒドロキシフェニル基を有するアルカリ可溶性樹脂を用いることで、高濃度の水酸化テトラメチルアンモニウム水溶液を現像液として用いた場合の現像性が向上し、パターン間の残渣発生を抑制、更にフェノール性水酸基含有樹脂で見られるアウトガスが大幅に低減することを見出し、本発明を完成させた。
　本発明の第１形態は、下記（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分及び（Ｅ）溶剤を含有する熱硬化可能なポジ型感光性樹脂組成物であり、
（Ａ）成分：撥液性基を有する重合体、
（Ｂ）成分：Ｎ－ヒドロキシフェニル基を有するアルカリ可溶性樹脂、
（Ｃ）成分：１，２－キノンジアジド化合物、
（Ｄ）成分：架橋剤
（Ｅ）溶剤；
　本発明の第２形態は、（Ｂ）成分はＮ－（ヒドロキシフェニル）アクリルアミド、Ｎ－（ヒドロキシフェニル）メタクリルアミド、又はＮ－（ヒドロキシフェニル）マレイミドから選ばれる少なくとも一種のモノマーに由来する構成単位を含む重合体である第１形態に記載のポジ型感光性樹脂組成物である；
　本発明の第３形態は、（Ａ）成分の上記撥液性基が炭素原子数３乃至１０のフルオロアルキル基、ポリフルオロエーテル基及びポリシロキサン基からなる群より選ばれる少なくとも一種の基である第１形態又は第２形態に記載のポジ型感光性樹脂組成物である；
　本発明の第４形態は、（Ａ）成分の重合体を構成するモノマー単位が上記撥液性基を有する不飽和炭化水素由来の単位である第１形態乃至第３形態のいずれか１つに記載のポジ型感光性樹脂組成物。
　本発明の第５形態は、（Ａ）成分の重合体を構成するモノマー単位が上記撥液性基を有するアルコキシラン化合物由来の単位である第１形態乃至第３形態のいずれか１つに記載のポジ型感光性樹脂組成物である；
　本発明の第６形態は、（Ａ）成分が上記撥液性基および熱硬化性基を有する重合体である第１形態乃至第５形態のいずれか１つに記載のポジ型感光性樹脂組成物である；
　本発明の第７形態は、（Ｄ）成分の架橋剤がエポキシ基またはメトキシメチル基を含む第１形態乃至第６形態のいずれか１つに記載のポジ型感光性樹脂組成物である；
　本発明の第８形態は、（Ｂ）成分のアルカリ可溶性樹脂の数平均分子量がポリスチレン換算で２，０００乃至６０，０００である第１形態乃至第７形態のいずれか１つに記載のポジ型感光性樹脂組成物である；
　本発明の第９形態は、（Ｂ）成分１００質量部に対して、（Ａ）成分が０．１乃至２０質量部含まれることを特徴とする第１形態乃至第８形態のいずれか１つに記載のポジ型感光性樹脂組成物である；
　本発明の第１０形態は、（Ｂ）成分１００質量部に対して、（Ｃ）成分が５乃至１００質量部含まれることを特徴とする第１形態乃至第９形態のいずれか１つに記載のポジ型感光性樹脂組成物である；
　本発明の第１１形態は、（Ｂ）成分１００質量部に対して、（Ｄ）成分が５乃至５０質量部含まれることを特徴とする上第１形態乃至第１０形態のいずれか１つに記載のポジ型感光性樹脂組成物である；
　本発明の第１２形態は、第１形態乃至第１１形態のいずれか１つに記載のポジ型感光性樹脂組成物を用いて得られる硬化膜である；
　本発明の第１３形態は、第１２形態に記載の硬化膜を有する表示素子である；
　本発明の第１４形態は、第１２形態に記載の硬化膜を画像形成用バンクとして有する表示素子である。 As a result of intensive studies to achieve the above object, 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;
In a second form of the present invention, 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
In a third aspect of the present invention, 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 positive photosensitive resin composition according to the first or second embodiment;
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 positive photosensitive resin composition as described.
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. is a thing;
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. A photosensitive resin composition;
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.
　本発明のポジ型感光性樹脂組成物は、硬化膜表面に高い撥水性と高い撥油性を有し、パターン形成後の残渣が少なく、高温焼成時のアウトガス発生が少ない硬化膜を形成することができる。 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.
　本発明の感光性樹脂組成物は、下記（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分及び（Ｅ）溶剤を含有するポジ型感光性樹脂組成物である。
（Ａ）成分：撥液性基を有する重合体、
（Ｂ）成分：Ｎ－ヒドロキシフェニル基を有するアルカリ可溶性樹脂、
（Ｃ）成分：１，２－キノンジアジド化合物、
（Ｄ）成分：架橋剤
（Ｅ）溶剤
　以下、各成分の詳細を説明する。 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.
(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: Crosslinking Agent (E) Solvent Details of each component are described below.
＜（Ａ）成分＞
（Ａ）成分は、撥液性基を有する重合体である。 <(A) Component>
Component (A) is a polymer having a liquid-repellent group.
　本発明において、重合体とはアクリル酸エステル、メタクリル酸エステル、スチレン、マレイミド等の重合性不飽和基、すなわち、構造中に不飽和炭化水素（Ｃ＝Ｃ二重結合）を含む重合性基を有するモノマーを用いて得られるアクリル重合体、または多官能アルコキシシランモノマーの加水分解重縮合によって得られるポリシルセスキオキサンを指す。 In the present invention, the polymer refers to polymerizable unsaturated groups such as acrylic acid esters, methacrylic acid esters, styrene, maleimide, etc., that is, polymerizable groups containing unsaturated hydrocarbons (C=C double bonds) in the structure. polysilsesquioxane obtained by hydrolytic polycondensation of polyfunctional alkoxysilane monomers, or acrylic polymers obtained using monomers having
　上記撥液性基としては、例えば、炭素原子数３乃至１０のフルオロアルキル基、ポリフルオロエーテル基及びポリシロキサン基から選ばれる少なくとも一種の基が挙げられる。 Examples of the liquid-repellent group include at least one group selected from fluoroalkyl groups having 3 to 10 carbon atoms, polyfluoroether groups and polysiloxane groups.
　上記フルオロアルキル基の炭素原子数は３乃至１０であり、好ましくは、炭素原子数４乃至１０のフルオロアルキル基であることが望ましい。
　このようなフルオロアルキル基としては、２，２，２－トリフルオロエチル基、２，２，３，３，３－ペンタフルオロプロピル基、２－（パーフルオロブチル）エチル基、３－パーフルオロブチル－２－ヒドロキシプロピル基、２－（パーフルオロヘキシル）エチル基、３－パーフルオロヘキシル－２－ヒドロキシプロピル基、２－（パーフルオロオクチル）エチル基、３－パーフルオロオクチル－２－ヒドロキシプロピル基、２－（パーフルオロデシル）エチル基、２－（パーフルオロ－３－メチルブチル）エチル基、３－（パーフルオロ－３－メチルブチル）－２－ヒドロキシプロピル基、２－（パーフルオロ－５－メチルヘキシル）エチル基、２－（パーフルオロ－５－メチルヘキシル）－２－ヒドロキシプロピル基、２－（パーフルオロ－７－メチルオクチル）エチル基、及び２－（パーフルオロ－７－メチルオクチル）－２－ヒドロキシプロピル基等が挙げられる。 The fluoroalkyl group has 3 to 10 carbon atoms, preferably 4 to 10 carbon atoms.
Such 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-(perfluoro-5-methylhexyl)-2-hydroxypropyl group, 2-(perfluoro-7-methyloctyl)ethyl group, and 2-(perfluoro-7-methyloctyl)- A 2-hydroxypropyl group and the like can be mentioned.
　本発明の（Ａ）成分である重合体に炭素原子数３乃至１０のフルオロアルキル基を導入するには、炭素原子数３乃至１０のフルオロアルキル基を有するモノマーを共重合させることができる。また、反応部位を有する重合体に炭素原子数３乃至１０のフルオロアルキル基と重合体の反応部位と反応する官能基を有する化合物を反応させることもできる。 In order to introduce a fluoroalkyl group having 3 to 10 carbon atoms into the polymer that is the component (A) of the present invention, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms can be copolymerized. Alternatively, 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.
　上記ポリフルオロエーテル基としては、下記式１で表されるポリフルオロエーテル構造からなるＲｆ基（ａ）が挙げられる。
　　－（Ｘ－Ｏ）ｎ－Ｙ　・・・式１
　式１中、Ｘは、炭素数１～１０の２価飽和炭化水素基又は炭素数１～１０のフルオロ化された２価飽和炭化水素基であって、ｎで括られた単位毎に同一の基又は異なる基を示し、Ｙは、水素原子（Ｙに隣接する酸素原子に隣接する炭素原子にフッ素原子が結合していない場合に限る）、炭素数１～２０の１価飽和炭化水素基又は炭素数１～２０のフルオロ化された１価飽和炭化水素基を示し、ｎは２～５０の整数を示す。ただし、式１におけるフッ素原子の総数は２以上である。 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
In 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.
　式１におけるＸ、Ｙの態様として、好ましくは、Ｘは、炭素数１～１０の水素原子１個を除いてフルオロ化されたアルキレン基又は炭素数１～１０のパーフルオロ化されたアルキレン基であって、ｎで括られた単位毎に同一の基又は異なる基を示し、Ｙは、炭素数１～２０の水素原子１個を除いてフルオロ化されたアルキル基又は炭素数１～２０のパーフルオロ化されたアルキル基を示すものが挙げられる。 As aspects of X and Y in Formula 1, 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. wherein each unit enclosed by n represents the same group or a different group, and 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.
　式１におけるＸ、Ｙの態様として、より好ましくは、Ｘは、炭素数１～１０のパーフルオロ化されたアルキレン基であって、ｎで括られた単位毎に同一の基又は異なる基を示し、Ｙは、炭素数１～２０のパーフルオロ化されたアルキル基を示すものが挙げられる。 As the embodiment of 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.
　式１においてｎは２～５０の整数を示す。ｎは２～３０が好ましく、２～１５がより好ましい。ｎが２以上であると、撥液性が良好である。ｎが５０以下であると、（Ａ）成分である重合体を、Ｒｆ基（ａ）を有するモノマーとその他のモノマーとの共重合によって合成する場合に、モノマーの相溶性が良好となる。 In Formula 1, 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.
　また、式１で表されるポリフルオロエーテル構造からなるＲｆ基（ａ）における炭素原子の総数は２～５０が好ましく、２～３０がより好ましい。当該範囲では、（Ａ）成分である重合体は良好な撥液性を奏する。 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の具体例としては、－ＣＦ２－、－ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ（ＣＦ３）－、－ＣＦ２ＣＦ２ＣＦ２ＣＦ２－、－ＣＦ２ＣＦ２ＣＦ（ＣＦ３）－、及びＣＦ２ＣＦ（ＣＦ３）ＣＦ２－が挙げられる。 Specific examples of X 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の具体例としては、－ＣＦ３、－ＣＦ２ＣＦ３、－ＣＦ２ＣＨＦ２、－（ＣＦ２）２ＣＦ３、－（ＣＦ２）３ＣＦ３、－（ＣＦ２）４ＣＦ３、－（ＣＦ２）５ＣＦ３、－（ＣＦ２）６ＣＦ３、－（ＣＦ２）７ＣＦ３、－（ＣＦ２）８ＣＦ３、－（ＣＦ２）９ＣＦ３、及び（ＣＦ２）１１ＣＦ３、－（ＣＦ２）１５ＣＦ３が挙げられる。 Specific examples of Y 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 .
　式１で表されるポリフルオロエーテル構造からなるＲｆ基（ａ）の好ましい態様としては、式２で表されるＲｆ基（ａ）が挙げられる。 A preferred embodiment of the Rf group (a) having a polyfluoroether structure represented by Formula 1 includes the Rf group (a) represented by Formula 2.
　－Ｃｐ－１Ｆ２（ｐ－１）－Ｏ－（ＣｐＦ２ｐ－Ｏ）ｎ－１－ＣｑＦ２ｑ＋１　・・・式２
式２中、ｐは２又は３の整数を示し、ｎで括られた単位毎に同一の基であり、ｑは１～２０の整数、ｎは２～５０の整数を示す。 −C p−1 F 2(p−1) −O−(C p F 2p −O) n−1 −C q F 2q+1 Formula 2
In Formula 2, p is an integer of 2 or 3, each unit enclosed by n is the same group, q is an integer of 1 to 20, and n is an integer of 2 to 50.
　式２で表されるＲｆ基（ａ）として、具体的には、
－ＣＦ２Ｏ（ＣＦ２ＣＦ２Ｏ）ｎ－１ＣＦ３　（ｎは２～９）、
－ＣＦ（ＣＦ３）Ｏ（ＣＦ２ＣＦ（ＣＦ３）Ｏ）ｎ－１Ｃ６Ｆ１３　（ｎは２～６）、
－ＣＦ（ＣＦ３）Ｏ（ＣＦ２ＣＦ（ＣＦ３）Ｏ）ｎ－１Ｃ３Ｆ７　（ｎは２～６）
が合成の容易さの点から好ましく挙げられる。 As the 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.
　（Ａ）成分である重合体内のＲｆ基（ａ）は、全て同一でもよいし、異なっていてもよい。 All the Rf groups (a) in the polymer that is the component (A) may be the same or different.
　上記ポリシロキサン基としては、式３で示されるポリシロキサン構造を有する基（ｂ）が挙げられる。以下、式３で示されるポリシロキサン構造を有する基（ｂ）をｐＳｉ基（ｂ）という。
　　－（ＳｉＲ１Ｒ２－Ｏ）ｎ－ＳｉＲ１Ｒ２Ｒ３　　・・・式３
（ただし、Ｒ１、Ｒ２は独立に水素、アルキル基、シクロアルキル基またはアリール基を表し、Ｒ３は水素または炭素数１～１０の有機基を表し、ｎは１～２００の整数を表す。）。 Examples of the polysiloxane group include a group (b) having a polysiloxane structure represented by Formula 3. Hereinafter, the group (b) having a polysiloxane structure represented by formula 3 is referred to as pSi group (b).
—(SiR 1 R 2 —O) n —SiR 1 R 2 R 3 Formula 3
(However, 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, and n represents an integer of 1 to 200. .).
　Ｒ１、Ｒ２は独立に水素、アルキル基、シクロアルキル基またはアリール基を表し、またシロキシ単位毎に同一でも異なっていてもよい。（Ａ）成分である重合体が良好な撥液性を奏することから、Ｒ１、Ｒ２は水素、メチル基またはフェニル基の場合が好ましく、さらには、すべてのシロキシ単位のＲ１、Ｒ２がメチル基の場合が好ましい。また、Ｒ３には、窒素原子、酸素原子等が含まれていてもよい。 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. In addition, R 3 may contain a nitrogen atom, an oxygen atom, or the like.
　（Ａ）成分である重合体へのｐＳｉ基（ｂ）の導入方法としては、ｐＳｉ基（ｂ）を有するモノマーを共重合させる方法、反応部位を有する重合体にｐＳｉ基（ｂ）を有する化合物を反応させる各種変性方法、ｐＳｉ基（ｂ）を有する重合開始剤を使用する方法等が挙げられる。 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).
　ｐＳｉ基（ｂ）を有するモノマーとしては、ＣＨ２＝ＣＨＣＯＯ（ｐＳｉ）、ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ（ｐＳｉ）等が挙げられる。ただし、ｐＳｉはｐＳｉ基（ｂ）を表す。ｐＳｉ基（ｂ）を有するモノマーは単独で用いてもよいし、２種以上を併用してもよい。 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.
　反応部位を有する重合体にｐＳｉ基（ｂ）を有する化合物を反応させる各種変性方法としては、例えば、以下の方法が挙げられる。 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.
　エポキシ基を有するモノマーをあらかじめ共重合させ、後に片末端にカルボキシル基を有し片末端にｐＳｉ基を有する化合物を反応させる方法；エポキシ基を有するモノマーをあらかじめ共重合させ、後に片末端にアミノ基を有し片末端にｐＳｉ基を有する化合物を反応させる方法；エポキシ基を有するモノマーをあらかじめ共重合させ、後に片末端にメルカプト基を有し片末端にｐＳｉ基を有する化合物を反応させる方法；およびアミノ基を有するモノマーをあらかじめ共重合させ、後に片末端にカルボキシル基を有し片末端にｐＳｉ基を有する化合物を反応させる方法がある。 A method in which a monomer having an epoxy group is pre-copolymerized and then reacted with a compound having a carboxyl group at one end and a pSi group at one end; a method of reacting a compound having a pSi group at one end; a method of preliminarily copolymerizing a monomer having an epoxy group and then reacting a compound having a mercapto group at one end and a pSi group at one end; and There is a method in which a monomer having an amino group is previously copolymerized, and then reacted with a compound having a carboxyl group at one end and a pSi group at one end.
　また、アミノ基を有するモノマーをあらかじめ共重合させ、後に片末端にエポキシ基を有し片末端にｐＳｉ基を有する化合物を反応させる方法；カルボキシル基を有するモノマーをあらかじめ共重合させ、後に片末端にエポキシ基を有し片末端にｐＳｉ基を有する化合物を反応させる方法；カルボキシル基を有するモノマーをあらかじめ共重合させ、後に片末端にアミノ基を有し片末端にｐＳｉ基を有する化合物を反応させる方法；カルボキシル基を有するモノマーをあらかじめ共重合させ、後に片末端に塩化シリル基を有し片末端にｐＳｉ基を有する化合物を反応させる方法；および水酸基を有するモノマーをあらかじめ共重合させ、後に片末端に塩化シリル基を有し片末端にｐＳｉ基を有する化合物を反応させる方法がある。 Alternatively, a method in which a monomer having an amino group is previously copolymerized and then reacted with a compound having an epoxy group at one end and a pSi group at one end; A method of reacting a compound having an epoxy group and a pSi group at one end; a method of preliminarily copolymerizing a monomer having a carboxyl group and then reacting a compound having an amino group at one end and a pSi group at one end. a method in which a monomer having a carboxyl group is previously copolymerized and then reacted with a compound having a silyl chloride group at one end and a pSi group at one end; There is a method of reacting a compound having a silyl chloride group and a pSi group at one end.
　ｐＳｉ基（ｂ）を有する重合開始剤としては、開始剤分子主鎖中に２価のポリシロキサン構造を有する基が含まれていてもよいし、開始剤分子の末端部分または側鎖に１価のポリシロキサン構造を有する基が含まれていてもよい。開始剤分子主鎖中に２価のポリシロキサン構造を有する基が含まれている開始剤としては、２価のポリシロキサン構造を有する基とアゾ基とを交互に有する化合物等が挙げられる。市販品としては、ＶＰＳ－１００１、ＶＰＳ－０５０１（以上、和光純薬工業社製）が挙げられる。 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.).
　上記（Ａ）成分の重合体において、上記撥液性基の導入量は、全繰り返し単位に対して５乃至６０モル％であることが好ましい。５モル％より過小である場合は、撥液性の効果を奏しない場合がある。６０モル％よりも過大である場合は、凝集などの問題が生じる場合がある。 In the polymer of component (A), 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.
　（Ａ）成分の重合体は、熱硬化性を有する官能基を共重合することで、熱硬化時の（Ａ）成分の開口部への染み出しや分解を抑制することができる。熱硬化性を有する官能基としては、加熱により共有結合を形成する基であれば特に限定はなく、（Ｂ）成分や（Ｄ）成分と反応する官能基でも、（Ａ）成分同士で自己架橋する官能基でもよい。そのような熱硬化性を有する官能基（熱硬化性基）としてはヒドロキシ基、カルボキシル基、アミド基、アミノ基、Ｎ－アルコキシメチル基、Ｎ－ヒドロキシメチル基、アルコキシシリル基、エポキシ基、オキセタン基、ビニル基、メルカプト基、及びブロックイソシアネート基等が挙げられる。 By copolymerizing the thermosetting functional group in the (A) component polymer, it is possible to suppress the (A) component from leaking into the openings and decomposing during thermosetting. The 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.
　上記（Ａ）成分のアクリル重合体の製造方法としては特に限定されないが、撥液性基を有するモノマー、例えば、炭素原子数３乃至１０のフルオロアルキル基を有するモノマー、ポリフルオロエーテル基を有するモノマー及びポリシロキサン基を有するモノマーの少なくとも一種、上記熱硬化性基を有するモノマー並びに所望により前記以外のモノマー（以下その他モノマーＡともいう）とを、重合開始剤存在下の溶剤中において、５０乃至１１０℃の温度下で重合反応させることにより得られる。その際、用いられる溶剤は、アルカリ可溶性アクリル重合体を構成するモノマー及び特定官能基を有するアクリル重合体を溶解するものであれば特に限定されない。具体例としては、後述する（Ｅ）溶剤に記載する溶剤が挙げられる。 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.
　撥液性基を有するラジカル重合性を有するモノマーの具体例としては、２，２，２－トリフルオロエチルアクリレート、２，２，２－トリフルオロエチルメタクリレート、２，２，３，３，３－ペンタフルオロプロピルアクリレート、２，２，３，３，３－ペンタフルオロプロピルメタクリレート、２－（パーフルオロブチル）エチルアクリレート、２－（パーフルオロブチル）エチルメタクリレート、３－パーフルオロブチル－２－ヒドロキシプロピルアクリレート、３－パーフルオロブチル－２－ヒドロキシプロピルメタクリレート、２－（パーフルオロヘキシル）エチルアクリレート、２－（パーフルオロヘキシル）エチルメタクリレート、３－パーフルオロヘキシル－２－ヒドロキシプロピルアクリレート、３－パーフルオロヘキシル－２－ヒドロキシプロピルメタクリレート、２－（パーフルオロオクチル）エチルアクリレート、２－（パーフルオロオクチル）エチルメタクリレート、３－パーフルオロオクチル－２－ヒドロキシプロピルアクリレート、３－パーフルオロオクチル－２－ヒドロキシプロピルメタクリレート、２－（パーフルオロデシル）エチルアクリレート、２－（パーフルオロデシル）エチルメタクリレート、２－（パーフルオロ－３－メチルブチル）エチルアクリレート、２－（パーフルオロ－３－メチルブチル）エチルメタクリレート、３－（パーフルオロ－３－メチルブチル）－２－ヒドロキシプロピルアクリレート、３－（パーフルオロ－３－メチルブチル）－２－ヒドロキシプロピルメタクリレート、２－（パーフルオロ－５－メチルヘキシル）エチルアクリレート、２－（パーフルオロ－５－メチルヘキシル）エチルメタクリレート、２－（パーフルオロ－５－メチルヘキシル）－２－ヒドロキシプロピルアクリレート、２－（パーフルオロ－５－メチルヘキシル）－２－ヒドロキシプロピルメタクリレート、２－（パーフルオロ－７－メチルオクチル）エチルアクリレート、２－（パーフルオロ－７－メチルオクチル）エチルメタクリレート、２－（パーフルオロ－７－メチルオクチル）－２－ヒドロキシプロピルアクリレート、及び２－（パーフルオロ－７－メチルオクチル）－２－ヒドロキシプロピルメタクリレート等が挙げられる。 Specific examples of radically polymerizable monomers having a liquid-repellent group 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-(perfluorooctyl)ethyl acrylate, 2-(perfluorooctyl)ethyl methacrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-(perfluorodecyl)ethyl acrylate, 2-(perfluorodecyl)ethyl methacrylate, 2-(perfluoro-3-methylbutyl)ethyl acrylate, 2-(perfluoro-3-methylbutyl)ethyl methacrylate, 3- (perfluoro-3-methylbutyl)-2-hydroxypropyl acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-5-methylhexyl) ethyl acrylate, 2-(perfluoro-3-methylbutyl) fluoro-5-methylhexyl)ethyl methacrylate, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl acrylate, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl methacrylate, fluoro-7-methyloctyl)ethyl acrylate, 2-(perfluoro-7-methyloctyl)ethyl methacrylate, 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl acrylate, and 2-(perfluoro-7 -methyloctyl)-2-hydroxypropyl methacrylate and the like.
　熱硬化性基を有するラジカル重合性を有するモノマーの具体例としては、アクリル酸、メタクリル酸、クロトン酸、モノ－（２－（アクリロイルオキシ）エチル）フタレート、モノ－（２－（メタクリロイルオキシ）エチル）フタレート、Ｎ－（カルボキシフェニル）マレイミド、Ｎ－（カルボキシフェニル）メタクリルアミド、Ｎ－（カルボキシフェニル）アクリルアミド、ヒドロキシスチレン、Ｎ－（ヒドロキシフェニル）アクリルアミド、Ｎ－（ヒドロキシフェニル）メタクリルアミド、Ｎ－（ヒドロキシフェニル）マレイミド、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、５－アクリロイルオキシ－６－ヒドロキシノルボルネン－２－カルボキシリック－６－ラクトン、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルメタクリレート、５－メタクリロイルオキシ－６－ヒドロキシノルボルネン－２－カルボキシリック－６－ラクトン、２－アミノエチルアクリレート、２－アミノメチルメタクリレート、グリシジルメタクリレート、アクリル酸グリシジル、メタクリル酸グリシジル、α－エチルアクリル酸グリシジル、α－ｎ－プロピルアクリル酸グリシジル、α－ｎ－ブチルアクリル酸グリシジル、アクリル酸－３，４－エポキシブチル、メタクリル酸－３，４－エポキシブチル、アクリル酸－６，７－エポキシヘプチル、メタクリル酸－６，７－エポキシヘプチル、α－エチルアクリル酸－６，７－エポキシヘプチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、３－（メタクリロイルオキシメチル）オキセタン、３－（アクリロイルオキシメチル）オキセタン、３－（メタクリロイルオキシメチル）－３－エチル－オキセタン、３－（アクリロイルオキシメチル）－３－エチル－オキセタン、３－（メタクリロイルオキシメチル）－２－トリフロロメチルオキセタン、３－（アクリロイルオキシメチル）－２－トリフロロメチルオキセタン、３－（メタクリロイルオキシメチル）－２－フェニル－オキセタン、３－（アクリロイルオキシメチル）－２－フェニル－オキセタン、２－（メタクリロイルオキシメチル）オキセタン、２－（アクリロイルオキシメチル）オキセタン、２－（メタクリロイルオキシメチル）－４－トリフロロメチルオキセタン、２－（アクリロイルオキシメチル）－４－トリフロロメチルオキセタン、Ｎ－ブトキシメチルアクリルアミド、Ｎ－イソブトキシメチルアクリルアミド、Ｎ－メトキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－ヒドロキシメチルアクリルアミド、Ｎ－ヒドロキシメチルメタクリルアミド、Ｎ－ヒドロキシエチルアクリルアミド、Ｎ－ヒドロキシエチルメタクリルアミド、１，２－エポキシ－５－ヘキセン、１，７－オクタジエンモノエポキサイ、メタクリル酸２－（０－（１’－メチルプロピリデンアミノ）カルボキシアミノ）エチル、メタクリル酸２－（３，５－ジメチルピラゾリル）カルボニルアミノ）エチル、３－アクリロイルオキシトリメトキシシラン、３－アクリロイルオキシトリエトキシシラン、３－メタクリロイルオキシトリメトキシシラン、３－メタクリロイルオキシトリエトキシシラン等が挙げられる。 Specific examples of 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-6-lactone, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α- Glycidyl n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6-methacrylate ,7-epoxyheptyl, α-ethylacrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-(methacryloyloxymethyl)oxetane, 3 -(Acryloyloxymethyl)oxetane, 3-(Methacryloyloxymethyl)-3-ethyl-oxetane, 3-(Acryloyloxymethyl)-3-ethyl-oxetane, 3-(Methacryloyloxymethyl)-2-trifluoromethyloxetane , 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3-(acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl) ) oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyl oxymethyl)-4-trifluoromethyloxetane, N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-methylolacrylamide, N-hydroxymethylacrylamide, N- Hydroxymethyl methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxy, 2-(0-(1'-methyl methacrylate) propylideneamino)carboxyamino)ethyl, 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate, 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, 3-methacryloyloxytriethoxysilane and the like.
　その他モノマーＡの具体例としては、メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ベンジルメタクリレート、ナフチルメタクリレート、アントリルメタクリレート、アントリルメチルメタクリレート、フェニルメタクリレート、グリシジルメタクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレート、メトキシトリエチレングリコールメタクリレート、２－エトキシエチルメタクリレート、２－アミノメチルメタクリレート、テトラヒドロフルフリルメタクリレート、３－メトキシブチルメタクリレート、γ－ブチロラクトンメタクリレート、２－プロピル－２－アダマンチルメタクリレート、８－メチル－８－トリシクロデシルメタクリレート、８－エチル－８－トリシクロデシルメタクリレート、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、グリシジルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、メトキシトリエチレングリコールアクリレート、２－エトキシエチルアクリレート、２－アミノメチルアクリレート、テトラヒドロフルフリルアクリレート、３－メトキシブチルアクリレート、γ－ブチロラクトンアクリレート、２－プロピル－２－アダマンチルアクリレート、８－メチル－８－トリシクロデシルアクリレート、８－エチル－８－トリシクロデシルアクリレート、Ｎ－シクロヘキシルマレイミド、Ｎ－メチルマレイミド、Ｎ－エチルマレイミド、スチレン、ビニルナフタレン、ビニルアントラセン、及びビニルビフェニル等が挙げられる。 Specific examples of other 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. Glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate , 8-ethyl-8-tricyclodecyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, Methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tri Cyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, N-cyclohexylmaleimide, N-methylmaleimide, N-ethylmaleimide, styrene, vinylnaphthalene, vinylanthracene, vinylbiphenyl and the like.
　このようにして得られる特定官能基を有するアクリル重合体は、通常、溶剤に溶解した溶液の状態である。 The acrylic polymer having a specific functional group obtained in this way is usually in the form of a solution dissolved in a solvent.
　また、上記のようにして得られたアクリル重合体の溶液を、ジエチルエーテルや水等の撹拌下に投入して再沈殿させ、生成した沈殿物を濾過・洗浄した後、常圧又は減圧下で、常温あるいは加熱乾燥することで、特定共重合体の粉体とすることができる。このような操作により、特定共重合体と共存する重合開始剤や未反応モノマーを除去することができ、その結果、精製した特定共重合体の粉体を得られる。一度の操作で充分に精製できない場合は、得られた粉体を溶剤に再溶解して、上記の操作を繰り返し行えば良い。
　本発明においては、上記特定共重合体の粉体をそのまま用いても良く、あるいはその粉体を、たとえば後述する（Ｅ）溶剤に再溶解して溶液の状態として用いても良い。 In addition, 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.
In the present invention, 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.
　上記（Ａ）成分のポリシルセスキオキサンを得る方法は特に限定されないが、撥液性基を有するアルコキシシランと熱硬化性基を有するアルコキシシランと所望によりその他の有機基を有するアルコキシシランとを重縮合して得られるポリシルセスキオキサンが好ましい。 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.
　撥液性基を有するアルコキシシランモノマーの具体例として、トリフルオロプロピルトリメトキシシラン、トリフルオロプロピルトリエトキシシラン、トリデカフルオロオクチルトリメトキシシラン、トリデカフルオロオクチルトリエトキシシラン、ヘプタデカフルオロデシルトリメトキシシラン、ヘプタデカフルオロデシルトリエトキシシラン、２－（パーフルオロヘキシル）エチルトリメトキシシラン、２－（パーフルオロヘキシル）エチルトリエトキシシラン、２－（パーフルオロブチル）エチルトリメトキシシラン、２－（パーフルオロブチル）エチルトリエトキシシラン等が挙げられる。 Specific examples of 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.
　本発明において撥液性基を有するアルコキシシランのうち少なくとも１種を用いればよいが、必要に応じて複数種を用いてもよい。 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.
　熱硬化性基を有するアルコキシシランモノマーの具体例として、アリルトリエトキシシラン、アリルトリメトキシシラン、ジエトキシメチルビニルシラン、ジメトキシメチルビニルシラン、トリエトキシビニルシラン、トリメトキシビニルシラン、ビニルトリス（２－エトキシ）シラン、ビニルトリス（２－メトキシ）シラン、ｍ－スチリルトリエトキシシラン、ｍ－スチリルトリメトキシシラン、ｐ－スチリルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－（Ｎ－スチリルメチル－２－アミノエチルアミノ）プロピルトリメトキシシラン、ジエトキシ（３－グリシジルオキシプロピル）メチルシラン、３－グリシジルオキシプロピル（ジメトキシ）メチルシラン、３－グリシジルオキシプロピル（ジエトキシ）メチルシラン、３－グリシジルオキシプロピルトリメトキシシラン、３－グリシジルオキシプロピルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルリエトキシシラン、３－（２－アミノエチル）プロピルジメトシキシラン、３－（２－アミノエチル）プロピルジエトシキシラン、３－（２－アミノエチルアミノ）プロピルトリメトキシシラン、３－（２－アミノエチルアミノ）プロピルトリエトキシシラン、３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、トリメトキシ［３－（フェニルアミノ）プロピル］シラン、３－メルカプトプロピル（ジメトキシ）メチルシラン、（３－メルカプトプロピル）トリエトキシシラン、（３－メルカプトプロピル）トリメトキシシラン、３－（トリエトキシシリル）プロピルイソシアネート、３－（トリエトキシシリル）プロピルメタクリレート、３－（トリメトキシシリル）プロピルメタクリレート、３－（トリエトキシシリル）プロピルアクリレート、３－（トリメトキシシリル）プロピルアクリレート、２－（トリエトキシシリル）エチルメタクリレート、２－（トリメトキシシリル）チルメタクリレート、２－（トリエトキシシリル）エチルアクリレート、２－（トリメトキシシリル）チルアクリレート、（トリエトキシシリル）メチルメタクリレート、（トリメトキシシリル）メチルメタクリレート、（トリエトキシシリル）メチルアクリレート、（トリメトキシシリル）メチルアクリレート、γ－ウレイドプロピルトリエトキシシラン、γ－ウレイドプロピルトリメトキシシラン、γ－ウレイドプロピルトリプロポキシシラン、（Ｒ）－Ｎ－１－フェニルエチル－Ｎ’－トリエトキシシリルプロピルウレア、（Ｒ）－Ｎ－１－フェニルエチル－Ｎ’－トリメトキシシリルプロピルウレア、１－［３－（トリメトキシシリル）プロピル］ウレア等が挙げられる。 Specific examples of alkoxysilane monomers having a thermosetting group include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, trimethoxyvinylsilane, vinyltris(2-ethoxy)silane, and vinyltris. (2-methoxy)silane, m-styryltriethoxysilane, m-styryltrimethoxysilane, p-styryltriethoxysilane, p-styryltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyl trimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyl(diethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxy Silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyllethoxysilane, 3-(2-aminoethyl)propyldimethoxysilane, 3-(2- aminoethyl)propyldiethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Silane, Trimethoxy[3-(phenylamino)propyl]silane, 3-mercaptopropyl(dimethoxy)methylsilane, (3-mercaptopropyl)triethoxysilane, (3-mercaptopropyl)trimethoxysilane, 3-(triethoxysilyl) Propyl isocyanate, 3-(triethoxysilyl)propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-(triethoxysilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 2-(triethoxysilyl) ethyl methacrylate, 2-(trimethoxysilyl) ethyl methacrylate, 2-(triethoxysilyl) ethyl acrylate, 2-(trimethoxysilyl) ethyl acrylate, (triethoxysilyl) methyl methacrylate, (trimethoxysilyl) methyl methacrylate, ( triethoxysilyl)methyl acrylate, (trimethoxysilyl)methyl acrylate, γ-ureidopropoxy triethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropylurea, (R)-N-1-phenylethyl -N'-trimethoxysilylpropylurea, 1-[3-(trimethoxysilyl)propyl]urea and the like.
　更に熱による架橋反応が起こる３－グリシジルオキシプロピル（ジメトキシ）メチルシラン、３－グリシジルオキシプロピル（ジエトキシ）メチルシラン、３－グリシジルオキシプロピルトリメトキシシランまたは２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシランを用いることも好ましい。 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyl(diethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, which undergoes further thermal crosslinking reaction is also preferred.
　その際、熱硬化性基を有する有機基を有するアルコキシシランを複数種用いてもよい。 At that time, a plurality of alkoxysilanes having an organic group having a thermosetting group may be used.
　その他の有機基を有するアルコキシシランの例としてはテトラメトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、ブチルトリメトキシシラン、ブチルトリエトキシシラン、ペンチルトリメトキシシラン、ペンチルトリエトキシシラン、へプチルトリメトキシシラン、へプチルトリエトキシシラン、オクチルトリメトキシシラン、オクチルトリエトキシシラン、ドデシルトリメトキシシラン、ドデシルトリエトキシシラン、ヘキサデシルトリメトキシシラン、ヘキサデシルトリエトキシシラン、オクタデシルトリメトキシシラン、オクタデシルトリエトキシシランなどのアルキルトリアルコキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ベンジルトリメトキシシラン、ベンジルトリエトキシシランなどの芳香族基を有するトリアルコキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシランなどのジアルコキシシラン、シクロヘキシルトリエトキシシラン、シクロヘキシルトリメトキシシランなどが挙げられる。 Examples of 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 such as trialkoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, cyclohexyltriethoxysilane, cyclohexyltrimethoxysilane, and the like.
　上記（Ａ）成分のポリシルセスキオキサンは撥液性基を含むアルコキシシランを全アルコキシシラン中の好ましくは５～５０モル％含み、熱硬化性基を含むアルコキシシランを全アルコキシシラン中の好ましくは１０～９５モル％含み、残余はその他のアルコキシシランを重縮合して得られる。 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.
　被膜の撥液性及び溶剤耐性を考慮すると、撥液性基を含むアルコキシシランの含有量は１０～４０モル％がより好ましい。熱硬化性基を含むアルコキシシランの含有量は全アルコキシシラン中の３０から８０モル％がより好ましい。 Considering the liquid repellency and solvent resistance of the film, 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.
　上記（Ａ）成分のポリシルセスキオキサンを得る方法としては、例えば撥液性基を含むアルコキシシランと、熱硬化性基を有するアルコキシシランと、必要に応じてその他のアルコキシシランと、有機溶媒を水酸化テトラエチルアンモニウム水溶液の存在下に加熱して重縮合する方法が挙げられる。具体的には、予め有機溶媒に水酸化テトラエチルアンモニウム水溶液を加えて水酸化テトラエチルアンモニウム水溶液の溶液とした後、該溶液を加熱した状態で、上記の各種アルコキシシランを混合する方法である。上記水酸化テトラエチルアンモニウム水溶液の存在量は、使用するアルコキシシランが有する全アルコキシ基量の１モルに対し、好ましくは０．０１～０．２モルとされる。上記加熱は、液温が好ましくは０～１００℃で行うことができ、また、液の蒸発、揮散などが起こらないように、好ましくは還流管を備え付けた容器中の還流下で数十分～十数時間行われる。 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.
　アルコキシシランを複数種用いる場合は、アルコキシシランを予め混合した混合物として混合してもよいし、複数種のアルコキシシランを順次混合してもよい。アルコキシシランを重縮合する際には、仕込んだアルコキシシランの全ケイ素原子を酸化物に換算した濃度（以下、ＳｉＯ２換算濃度と称す）が、４０質量％以下、特に好ましくは１０～３０質量％の範囲で加熱されることが好ましい。このような濃度範囲で任意の濃度を選択することにより、ゲルの生成を抑え、均質なポリシルセスキオキサン含有溶液を得ることができる。 When using multiple types of alkoxysilanes, the alkoxysilanes may be mixed in advance as a mixture, or multiple types of alkoxysilanes may be mixed sequentially. When the alkoxysilane is polycondensed, 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.
　アルコキシシランを重縮合する際に用いられる有機溶媒（以下、重合溶媒とも言う）は、撥液性基を有するアルコキシシランと熱硬化性基を有するアルコキシシランと必要に応じてその他のアルコキシシランを溶解するものであれば特に限定されないが、溶剤（Ｅ）の使用が好ましい。中でも、アルコキシシランの重縮合反応によりアルコールが生成するため、アルコール類やアルコール類と相溶性の良好な有機溶媒が用いられる。 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. Although it is not particularly limited as long as it does, use of the solvent (E) is preferred. Among them, alcohols and organic solvents having good compatibility with alcohols are used because alcohols are generated by the polycondensation reaction of alkoxysilanes.
　上記重合溶媒の具体例としては、メタノール、エタノール、プロパノール、ｎ‐ブタノールなどのアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルなどのグリコールエーテル、テトラヒドロフランなどのエーテルが挙げられる。本発明においては、上記の有機溶媒を複数種混合して用いてもよい。 Specific examples of the polymerization solvent 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. In the present invention, a plurality of types of the above organic solvents may be mixed and used.
　本発明においては、前記方法で得られた特定のポリシルセスキオキサンの溶液をそのまま本発明の感光性樹脂組成物に用いても良いし、必要に応じて、前記方法で得られた特定のポリシルセスキオキサンの溶液を濃縮したり、溶媒を加えて希釈したり、他の溶媒に置換して用いることもできる。 In the present invention, 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.
　前記溶媒を加えて希釈する際に用いる溶媒（添加溶媒とも言う）は、重縮合反応に用いる溶媒やその他の溶媒であってもよい。この添加溶媒は、ポリシルセスキオキサンが均一に溶解している限りにおいては特に限定されず、１種類または２種類以上を任意に選択して使用することができる。このような添加溶媒としては、前記重縮合反応に用いる溶媒に加え、アセトン、メチルエチルケトン、またはメチルイソブチルケトン等のケトン系溶媒、酢酸メチル、酢酸エチル、または乳酸エチルなどのエステル系溶媒などが挙げられる。 The solvent used when adding and diluting the solvent (also referred to as an additive 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. .
　さらに、本発明において、感光性樹脂組成物中にポリシルセスキオキサン以外の重合体を用いる場合、ポリシルセスキオキサン以外の重合体を混合する前にポリシルセスキオキサンの重縮合反応の際に発生するアルコールを常圧または減圧で留去しておくことが好ましい。 Furthermore, in the present invention, when a polymer other than polysilsesquioxane is used in the photosensitive resin composition, 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.
　また、（Ａ）成分である重合体としては、上記アクリル重合体、ポリシルセスキオキサン以外に、ポリイミド、ポリアミック酸、ポリアミド、ポリウレア、ポリウレタン、フェノール、エポキシ、ポリシロキサン、ポリエステル及びアクリル重合体に、キノンジアジド基を導入した重合体が挙げられる。 In addition to the acrylic polymer and polysilsesquioxane described above, 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.
　ポリアミック酸、ポリイミド、ポリアミド、ポリウレアとしては、フルオロアルキル基またはフルオロアルコキシ基を有するジアミンとヒドロキシ基を有するジアミンを、酸二無水物と反応させたポリアミック酸と、ポリアミック酸をイミド化して得られるポリイミド、前記ジアミンをジカルボン酸無水物と反応させて得られるポリアミドまたは前記ジアミンをジイソシアネートと反応させて得られるポリウレアが挙げられる。 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.
　ポリウレタンとしては、フルオロアルキル基またはフルオロアルコキシ基を有するジオールとアミノ基を有するジオールをジイソシアネートと反応させて得られるポリウレタンが挙げられる。 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.
　フェノール樹脂としては、フルオロアルキル基またはフルオロアルコキシ基を有するフェノールと、ホルムアルデヒドを重合させて得られるノボラック樹脂が挙げられる。
エポキシ樹脂としては、フルオロアルキル基またはフルオロアルコキシ基を有するビスフェノールＡ及び／またはビスフェノールＦと、当該ビスフェノールＡ及び／またはビスフェノールＦの時グリシジルエーテルと反応させて得られるエポキシ樹脂が挙げられる。
　ポリシロキサンとしては、フルオロアルキル基を有するトリアルコキシシランまたはフルオロアルキル基を有するジアルコキシシランシランと、アミノ基を有するトリアルコキシシランまたはアミノ基を有するジアルコキシシランシランとを含むシランモノマー混合物を重合させて得られる重合体が挙げられる。 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.
As the polysiloxane, 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
　ポリエステルとしては、フルオロアルキル基またはフルオロアルコキシ基を有するジカルボン酸とフルオロアルキル基またはフルオロアルコキシ基を有するジオールとを反応させて得られるポリエステルが挙げられる。 Examples of 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.
　また、本発明においては、（Ａ）成分のアクリル重合体は、複数種の特定共重合体の混合物であってもよい。 In addition, in the present invention, the (A) component acrylic polymer may be a mixture of a plurality of specific copolymers.
＜（Ｂ）成分＞
　本発明の（Ｂ）成分は、Ｎ－ヒドロキシフェニル基を有するアルカリ可溶性樹脂である。
　上記（Ｂ）成分のアルカリ可溶性樹脂は、斯かる構造を有するアルカリ可溶性樹脂であればよく、樹脂を構成する高分子の主鎖の骨格及び側鎖の種類などについて特に限定されない。 <(B) Component>
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.
　（Ｂ）成分のアルカリ可溶性樹脂は、数平均分子量が２，０００乃至６０，０００の範囲内にあるものが好ましい。数平均分子量が６０，０００を超えて過大なものであると、現像残渣が発生し易くなり、感度が大きく低下する一方、数平均分子量が２，０００未満で過小なものであると、現像の際、露光部の膜減りが相当量発生し、硬化不足になる場合がある。 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.
　（Ｂ）成分のＮ－ヒドロキシフェニル基を有するアルカリ可溶性樹脂としては、例えばアクリル系樹脂、あるいはポリマレイミド系樹脂等が挙げることができる。 Examples of the component (B), the alkali-soluble resin having an N-hydroxyphenyl group, include acrylic resins and polymaleimide resins.
　また、本発明においては、複数種のモノマーを重合して得られる共重合体（以下、特定共重合体と称す。）からなるアルカリ可溶性樹脂を（Ｂ）成分として用いることもできる。この場合、（Ｂ）成分のアルカリ可溶性樹脂は、複数種の特定共重合体のブレンド物であってもよい。 In addition, in the present invention, 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). In this case, the alkali-soluble resin as component (B) may be a blend of a plurality of specific copolymers.
　すなわち、上記の特定共重合体は、Ｎ－ヒドロキシフェニル基を有するモノマーと、これらモノマーと共重合可能なモノマーの群から選択される少なくとも一種のモノマーとを、必須の構成単位として形成された共重合体であって、その数平均分子量が２，０００乃至６０，０００のものである。数平均分子量が６０，０００より過大であると、残渣が生じる場合がある。 That is, 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 polymer having a number average molecular weight of 2,000 to 60,000. A number average molecular weight greater than 60,000 may result in residue.
　上記のＮ－ヒドロキシフェニル基を有するモノマーはＮ－ヒドロキシフェニル基を一個有するものに限らず、複数個有するものでもよい。 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.
　以下、上記モノマーの具体例を挙げるが、これらに限定されるものでない。
　Ｎ－ヒドロキシフェニル基を有するモノマーとしては、例えば、Ｎ－（ヒドロキシフェニル）アクリルアミド、Ｎ－（ヒドロキシフェニル）メタクリルアミド、Ｎ－（ヒドロキシフェニル）マレイミド等が挙げられる。 Specific examples of the above monomers are listed below, but are not limited thereto.
Examples of monomers having an N-hydroxyphenyl group include N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide and the like.
　Ｎ－ヒドロキシフェニル基を有するモノマーと共重合可能なモノマーとしては、例えば、メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ベンジルメタクリレート、ナフチルメタクリレート、アントリルメタクリレート、アントリルメチルメタクリレート、フェニルメタクリレート、グリシジルメタクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレート、メトキシトリエチレングリコールメタクリレート、２－エトキシエチルメタクリレート、２－アミノメチルメタクリレート、テトラヒドロフルフリルメタクリレート、３－メトキシブチルメタクリレート、γ－ブチロラクトンメタクリレート、２－プロピル－２－アダマンチルメタクリレート、８－メチル－８－トリシクロデシルメタクリレート、８－エチル－８－トリシクロデシルメタクリレート、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、グリシジルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、メトキシトリエチレングリコールアクリレート、２－エトキシエチルアクリレート、２－アミノメチルアクリレート、テトラヒドロフルフリルアクリレート、３－メトキシブチルアクリレート、γ－ブチロラクトンアクリレート、２－プロピル－２－アダマンチルアクリレート、８－メチル－８－トリシクロデシルアクリレート、８－エチル－８－トリシクロデシルアクリレート、スチレン、ビニルナフタレン、ビニルアントラセン、ビニルビフェニル、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－メチルマレイミド、Ｎ－エチルマレイミド、Ｎ－メチルアクリルアミド、Ｎ－メチルメタクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジメチルメタクリルアミド、アクリル酸、メタクリル酸、クロトン酸、モノ－（２－（アクリロイルオキシ）エチル）フタレート、モノ－（２－（メタクリロイルオキシ）エチル）フタレート、Ｎ－（カルボキシフェニル）マレイミド、Ｎ－（カルボキシフェニル）メタクリルアミド、Ｎ－（カルボキシフェニル）アクリルアミド、ヒドロキシスチレン、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、５－アクリロイルオキシ－６－ヒドロキシノルボルネン－２－カルボキシリック－６－ラクトン、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルメタクリレート、５－メタクリロイルオキシ－６－ヒドロキシノルボルネン－２－カルボキシリック－６－ラクトン、２－アミノエチルアクリレート、２－アミノメチルメタクリレート、グリシジルメタクリレート、アクリル酸グリシジル、メタクリル酸グリシジル、α－エチルアクリル酸グリシジル、α－ｎ－プロピルアクリル酸グリシジル、α－ｎ－ブチルアクリル酸グリシジル、アクリル酸－３，４－エポキシブチル、メタクリル酸－３，４－エポキシブチル、アクリル酸－６，７－エポキシヘプチル、メタクリル酸－６，７－エポキシヘプチル、α－エチルアクリル酸－６，７－エポキシヘプチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、３－（メタクリロイルオキシメチル）オキセタン、３－（アクリロイルオキシメチル）オキセタン、３－（メタクリロイルオキシメチル）－３－エチル－オキセタン、３－（アクリロイルオキシメチル）－３－エチル－オキセタン、３－（メタクリロイルオキシメチル）－２－トリフロロメチルオキセタン、３－（アクリロイルオキシメチル）－２－トリフロロメチルオキセタン、３－（メタクリロイルオキシメチル）－２－フェニル－オキセタン、３－（アクリロイルオキシメチル）－２－フェニル－オキセタン、２－（メタクリロイルオキシメチル）オキセタン、２－（アクリロイルオキシメチル）オキセタン、２－（メタクリロイルオキシメチル）－４－トリフロロメチルオキセタン、２－（アクリロイルオキシメチル）－４－トリフロロメチルオキセタン、Ｎ－ブトキシメチルアクリルアミド、Ｎ－イソブトキシメチルアクリルアミド、Ｎ－メトキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－ヒドロキシメチルアクリルアミド、Ｎ－ヒドロキシメチルメタクリルアミド、Ｎ－ヒドロキシエチルアクリルアミド、Ｎ－ヒドロキシエチルメタクリルアミド、１，２－エポキシ－５－ヘキセン、１，７－オクタジエンモノエポキサイ、メタクリル酸２－（０－（１’－メチルプロピリデンアミノ）カルボキシアミノ）エチル、メタクリル酸２－（３，５－ジメチルピラゾリル）カルボニルアミノ）エチル、３－アクリロイルオキシトリメトキシシラン、３－アクリロイルオキシトリエトキシシラン、３－メタクリロイルオキシトリメトキシシラン、及び３－メタクリロイルオキシトリエトキシシラン等が挙げられる。 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, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylates, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2- adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, styrene, vinylnaphthalene, vinylanthracene, vinylbiphenyl, N-phenylmaleimide, N-cyclohexylmaleimide, N-methylmaleimide , N-ethylmaleimide, N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, 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, 2-hydroxyethyl acrylate , 2-hydroxypropyl acrylate, 5-acryloyloxy cy-6-hydroxynorbornene-2-carboxylic-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 2-amino Ethyl acrylate, 2-aminomethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl methacrylate, glycidyl alpha-ethyl acrylate, glycidyl alpha-n-propyl acrylate, glycidyl alpha-n-butyl acrylate, glycidyl acrylate-3, 4-epoxybutyl, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl, o- vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane , 3-(acryloyloxymethyl)-3-ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(acryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxy methyl)-2-phenyl-oxetane, 3-(acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4 -trifluoromethyloxetane, 2-(acryloyloxymethyl)-4-trifluoromethyloxetane, N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-methylol acrylamide, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxy, methacrylic acid 2-(0-(1′-methylpropylideneamino)carboxyamino)ethyl, 2-(3,5-dimethylpyrazolyl)carbonyl methacrylate amino)ethyl, 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, 3-methacryloyloxytriethoxysilane, and the like.
　（Ｂ）成分のアルカリ可溶性樹脂の製造におけるＮ－ヒドロキシフェニル基を有するモノマーの比率は、（Ｂ）成分のアルカリ可溶性アクリル重合体の製造に用いる全てのモノマーのうち、好ましくは１０～９０モル％、より好ましくは２０～８５モル％、最も好ましくは３０～８０モル％である。Ｎ－ヒドロキシフェニル基を有するモノマーの比率が１０モル％未満の場合には、重合体のアルカリ溶解性が不足する。 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.
　（Ｂ）成分であるアルカリ可溶性樹脂の製造において、上記その他モノマーの比率は８０重量％以下であることが好ましく、より好ましくは５０重量％以下であり、さらに好ましくは２０重量％以下である。８０重量％よりも多くなると相対的に必須成分が減るため、本発明の効果を十分に得ることが困難になる。 In the production of the alkali-soluble resin as component (B), 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.
　本発明に用いる（Ｂ）成分であるアルカリ可溶性樹脂を得る方法は特に限定されないが、例えば、Ｎ－ヒドロキシフェニル基を有するモノマー、所望によりそれ以外の共重合可能なモノマー及び所望により重合開始剤等を共存させた溶剤中において、５０乃至１１０℃の温度下で重合反応させることにより、得られる。その際、用いられる溶剤は、アルカリ可溶性アクリル重合体を構成するモノマー及び特定官能基を有するアクリル重合体を溶解するものであれば特に限定されない。具体例としては、後述する（Ｅ）溶剤に記載する溶剤が挙げられる。 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.
　このようにして得られるアクリル重合体は、通常、溶剤に溶解した溶液の状態である。 The acrylic polymer obtained in this way is usually in the form of a solution dissolved in a solvent.
　また、上記のようにして得られた特定共重合体の溶液を、ジエチルエーテルや水等の撹拌下に投入して再沈殿させ、生成した沈殿物を濾過・洗浄した後、常圧又は減圧下で、常温あるいは加熱乾燥することで、特定共重合体の粉体とすることができる。このような操作により、特定共重合体と共存する重合開始剤や未反応モノマーを除去することができ、その結果、精製した特定共重合体の粉体を得られる。一度の操作で充分に精製できない場合は、得られた粉体を溶剤に再溶解して、上記の操作を繰り返し行えば良い。
　本発明においては、上記特定共重合体の粉体をそのまま用いても良く、あるいはその粉体を、たとえば後述する（Ｅ）溶剤に再溶解して溶液の状態として用いても良い。 In addition, 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.
In the present invention, 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.
　また、本発明においては、（Ｂ）成分のアルカリ可溶性樹脂は、複数種のアルカリ可溶性樹脂の混合物であってもよい。 In addition, in the present invention, the alkali-soluble resin as component (B) may be a mixture of multiple types of alkali-soluble resins.
　（Ａ）成分と（Ｂ）成分との比率は、（Ｂ）成分１００質量部に対して（Ａ）成分が０．１～２０質量部である。 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).
＜（Ｃ）成分＞
　（Ｃ）成分である１，２－キノンジアジド化合物としては、水酸基又はアミノ基のいずれか一方か、水酸基及びアミノ基の両方を有する化合物であって、これらの水酸基又はアミノ基（水酸基とアミノ基の両方を有する場合は、それらの合計量）のうち、好ましくは１０乃至１００モル％、特に好ましくは２０乃至９５モル％が１，２－キノンジアジドスルホン酸でエステル化、またはアミド化された化合物を用いることができる。 <(C) Component>
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.
　前記水酸基を有する化合物としては例えば、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、ハイドロキノン、レゾルシノール、カテコール、ガリック酸メチル、ガリック酸エチル、１，３，３－トリス（４－ヒドロキシフェニル）ブタン、４，４－イソプロプリデンジフェノール、２，２－ビス（４－ヒドロキシフェニル）プロパン、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、４，４’－ジヒドロキシフェニルスルホン、４，４－ヘキサフルオロイソプロピリデンジフェノール、４，４’，４’’―トリスヒドロキシフェニルエタン、１，１，１－トリスヒドロキシフェニルエタン、４，４’－［１－［４－［１－（４－ヒドロキシフェニル）－１－メチルエチル］フェニル］エチリデン］ビスフェノール、２，４－ジヒドロキシベンゾフェノン、２，３，４－トリヒドロキシベンゾフェノン、２，２’，４，４’－テトラヒドロキシベンゾフェノン、２，３，４，４’－テトラヒドロキシベンゾフェノン、２，２’，３，４，４’－ペンタヒドロキシベンゾフェノン、２，５－ビス（２－ヒドロキシ－５－メチルベンジル）メチルなどのフェノール化合物、エタノール、２－プロパノール、４－ブタノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、２－メトキシエタノール、２－ブトキシエタノール、２－メトキシプロパノール、２－ブトキシプロパノール、乳酸エチル、乳酸ブチルなどの脂肪族アルコール類を挙げることができる。 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). Butane, 4,4-isopropylidenediphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4- Hexafluoroisopropylidenediphenol, 4,4′,4″-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4′-[1-[4-[1-(4-hydroxy Phenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2,3,4 ,4'-tetrahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, phenol compounds such as 2,5-bis(2-hydroxy-5-methylbenzyl)methyl, ethanol, 2-propanol , 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, butyl lactate, etc. can be mentioned.
　また、前記アミノ基を含有する化合物としては、アニリン、ｏ－トルイジン、ｍ－トルイジン、ｐ－トルイジン、４－アミノジフェニルメタン、４－アミノジフェニル、ｏ－フェニレンジアミン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、４，４’－ジアミノフェニルメタン、４，４’－ジアミノジフェニルエーテルなどのアニリン類、アミノシクロヘキサンを挙げることができる。 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.
　さらに、水酸基とアミノ基両方を含有する化合物としては、例えば、ｏ－アミノフェノール、ｍ－アミノフェノール、ｐ－アミノフェノール、４－アミノレゾルシノール、２，３－ジアミノフェノール、２，４－ジアミノフェノール、４，４’－ジアミノ－４’’－ヒドロキシトリフェニルメタン、４－アミノ－４’，４’’－ジヒドロキシトリフェニルメタン、ビス（４－アミノ－３－カルボキシ－５－ヒドロキシフェニル）エーテル、ビス（４－アミノ－３－カルボキシ－５－ヒドロキシフェニル）メタン、２，２－ビス（４－アミノ－３－カルボキシ－５－ヒドロキシフェニル）プロパン、２，２－ビス（４－アミノ－３－カルボキシ－５－ヒドロキシフェニル）ヘキサフルオロプロパンなどのアミノフェノール類、２－アミノエタノール、３－アミノプロパノール、４－アミノシクロヘキサノールなどのアルカノールアミン類を挙げることができる。 Further, 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.
　これらの１，２－キノンジアジド化合物は単独または２種以上の組み合わせで使用することができる。 These 1,2-quinonediazide compounds can be used alone or in combination of two or more.
　本発明のポジ型感光性樹脂組成物における（Ｃ）成分の含有量は、（Ｂ）成分１００質量部に対して、好ましくは５乃至１００質量部、より好ましくは８乃至５０質量部、更に好ましくは１０乃至４０質量部である。５質量部未満の場合、ポジ型感光性樹脂組成物の露光部と未露光部の現像液への溶解速度差が小さくなり、現像によるパターニングが困難である場合がある。また、１００質量部を超えると、短時間での露光で１，２－キノンジアジド化合物が十分に分解されないため感度が低下する場合や、パターン間に残渣が発生する場合がある。 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.
＜（Ｄ）成分＞
　（Ｄ）成分は架橋剤であり、より具体的には、（Ｂ）成分のＮ－ヒドロキシフェニル基と熱反応により橋架け構造を形成しうる構造を有する化合物である。以下、具体例を挙げるがこれらに限定されるものではない。熱架橋剤は、例えば、（Ｄ１）アルコキシメチル基及びヒドロキシメチル基から選ばれる置換基を２個以上有する架橋性化合物や（Ｄ２）下記式（３）で表される架橋性化合物から選ばれるもの及び（Ｄ３）イソシアネート基を２個以上有する架橋剤が好ましい。これらの架橋剤は単独または２種以上の組み合わせで使用することができる。 <(D) Component>
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.
　（Ｄ１）成分のアルコキシメチル基及びヒドロキシメチル基から選ばれる置換基を２個以上有する架橋性化合物は、熱硬化時の高温に曝されると、脱水縮合反応により架橋反応が進行するものである。このような化合物としては、例えば、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、およびアルコキシメチル化メラミン等の化合物、およびフェノプラスト系化合物が挙げられる。 When the crosslinkable compound having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups, which is the component (D1), is exposed to high temperatures during thermosetting, 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.
　アルコキシメチル化グリコールウリルの具体例としては、例えば、１，３，４，６－テトラキス（メトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ブトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ヒドロキシメチル）グリコールウリル、１，３－ビス（ヒドロキシメチル）尿素、１，１，３，３－テトラキス（ブトキシメチル）尿素、１，１，３，３－テトラキス（メトキシメチル）尿素、１，３－ビス（ヒドロキシメチル）－４，５－ジヒドロキシ－２－イミダゾリノン、および１，３－ビス（メトキシメチル）－４，５－ジメトキシ－２－イミダゾリノン等が挙げられる。市販品として、三井サイテック（株）製グリコールウリル化合物（商品名：サイメル（登録商標）１１７０、パウダーリンク（登録商標）１１７４）等の化合物、メチル化尿素樹脂（商品名：ＵＦＲ（登録商標）６５）、ブチル化尿素樹脂（商品名：ＵＦＲ（登録商標）３００、Ｕ－ＶＡＮ１０Ｓ６０、Ｕ－ＶＡＮ１０Ｒ、Ｕ－ＶＡＮ１１ＨＶ）、ＤＩＣ（株）製尿素／ホルムアルデヒド系樹脂（高縮合型、商品名：ベッカミン（登録商標）Ｊ－３００Ｓ、同Ｐ－９５５、同Ｎ）等が挙げられる。 Specific examples of alkoxymethylated glycoluril 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. Commercially available products include compounds such as glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174), methylated urea resin (trade name: UFR (registered trademark) 65 ), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Corporation urea / formaldehyde resin (high condensation type, trade name: Beccamin ( registered trademarks) J-300S, P-955, N) and the like.
　アルコキシメチル化ベンゾグアナミンの具体例としてはテトラメトキシメチルベンゾグアナミン等が挙げられる。市販品として、三井サイテック（株）製（商品名：サイメル（登録商標）１１２３）、（株）三和ケミカル製（商品名：ニカラック（登録商標）ＢＸ－４０００、同ＢＸ－３７、同ＢＬ－６０、同ＢＸ－５５Ｈ）等が挙げられる。 Specific examples of alkoxymethylated benzoguanamine 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.
　アルコキシメチル化メラミンの具体例としては、例えば、ヘキサメトキシメチルメラミン等が挙げられる。市販品として、三井サイテック（株）製メトキシメチルタイプメラミン化合物（商品名：サイメル（登録商標）３００、同３０１、同３０３、同３５０）、ブトキシメチルタイプメラミン化合物（商品名：マイコート（登録商標）５０６、同５０８）、三和ケミカル製メトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＷ－３０、同ＭＷ－２２、同ＭＷ－１１、同ＭＷ－１００ＬＭ、同ＭＳ－００１、同ＭＸ－００２、同ＭＸ－７３０、同ＭＸ－７５０、同ＭＸ－０３５）、ブトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＸ－４５、同ＭＸ－４１０、同ＭＸ－３０２）等が挙げられる。 Specific examples of alkoxymethylated melamine include, for example, hexamethoxymethylmelamine. As commercially available products, 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.
　また、このようなアミノ基の水素原子がメチロール基またはアルコキシメチル基で置換されたメラミン化合物、尿素化合物、グリコールウリル化合物及びベンゾグアナミン化合物を縮合させて得られる化合物であってもよい。例えば、米国特許第６３２３３１０号に記載されているメラミン化合物およびベンゾグアナミン化合物から製造される高分子量の化合物が挙げられる。前記メラミン化合物の市販品としては、商品名：サイメル（登録商標）３０３（三井サイテック（株）製）等が挙げられ、前記ベンゾグアナミン化合物の市販品としては、商品名：サイメル（登録商標）１１２３（三井サイテック（株）製）等が挙げられる。 It may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group. 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.
　フェノプラスト系化合物の具体例としては、例えば、２，６－ビス（ヒドロキシメチル）フェノール、２，６－ビス（ヒドロキシメチル）クレゾール、２，６－ビス（ヒドロキシメチル）－４－メトキシフェノール、３，３’，５，５’－テトラキス（ヒドロキシメチル）ビフェニル－４，４’－ジオール、３，３’－メチレンビス（２－ヒドロキシ－５－メチルベンゼンメタノール）、４，４’－（１－メチルエチリデン）ビス［２－メチル－６－ヒドロキシメチルフェノール］、４，４’－メチレンビス［２－メチル－６－ヒドロキシメチルフェノール］、４，４’－（１－メチルエチリデン）ビス［２，６－ビス（ヒドロキシメチル）フェノール］、４，４’－メチレンビス［２，６－ビス（ヒドロキシメチル）フェノール］、２，６－ビス（メトキシメチル）フェノール、２，６－ビス（メトキシメチル）クレゾール、２，６－ビス（メトキシメチル）－４－メトキシフェノール、３，３’，５，５’－テトラキス（メトキシメチル）ビフェニル－４，４’－ジオール、３，３’－メチレンビス（２－メトキシ－５－メチルベンゼンメタノール）、４，４’－（１－メチルエチリデン）ビス［２－メチル－６－メトキシメチルフェノール］、４，４’－メチレンビス［２－メチル－６－メトキシメチルフェノール］、４，４’－（１－メチルエチリデン）ビス［２，６－ビス（メトキシメチル）フェノール］、４，４’－メチレンビス［２，６－ビス（メトキシメチル）フェノール］等が挙げられる。市販品としても入手が可能であり、その具体例としては、２６ＤＭＰＣ、４６ＤＭＯＣ、ＤＭ－ＢＩＰＣ－Ｆ、ＤＭ－ＢＩＯＣ－Ｆ、ＴＭ－ＢＩＰ－Ａ、ＢＩＳＡ－Ｆ、ＢＩ２５Ｘ－ＤＦ、ＢＩ２５Ｘ－ＴＰＡ（以上、旭有機材工業（株）製）等が挙げられる。 Specific examples of 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′-diol, 3,3′-methylenebis(2-methoxy-5 -methylbenzenemethanol), 4,4′-(1-methylethylidene)bis[2-methyl-6-methoxymethylphenol], 4,4′-methylenebis[2-methyl-6-methoxymethylphenol], 4, 4'-(1-methylethylidene)bis[2,6-bis(methoxymethyl)phenol], 4,4'-methylenebis[2,6-bis(methoxymethyl)phenol] and the like. It is also available as a commercial product, and specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA ( The above, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like can be mentioned.
　さらに、（Ｄ１）成分としては、Ｎ－ヒドロキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－エトキシメチルアクリルアミド、Ｎ－ブトキシメチルメタクリルアミド等のヒドロキシメチル基またはアルコキシメチル基で置換されたアクリルアミド化合物またはメタクリルアミド化合物を使用して製造されるポリマーも用いることができる。 Furthermore, as the component (D1), 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.
　そのようなポリマーとしては、例えば、ポリ（Ｎ－ブトキシメチルアクリルアミド）、Ｎ－ブトキシメチルアクリルアミドとスチレンとの共重合体、Ｎ－ヒドロキシメチルメタクリルアミドとメチルメタクリレートとの共重合体、Ｎ－エトキシメチルメタクリルアミドとベンジルメタクリレートとの共重合体、及びＮ－ブトキシメチルアクリルアミドとベンジルメタクリレートと２－ヒドロキシプロピルメタクリレートとの共重合体等が挙げられる。このようなポリマーの重量平均分子量は、１，０００乃至５０，０００であり、好ましくは、１，５００乃至２０，０００であり、より好ましくは２，０００乃至１０，０００である。 Examples of such polymers 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.
　これらの架橋性化合物は、単独でまたは２種以上を組み合わせて使用することができる。 These crosslinkable compounds can be used alone or in combination of two or more.
　本発明のポジ型感光性樹脂組成物における架橋剤として（Ｄ１）成分を選択した場合の含有量は、（Ｂ）成分１００質量部に対して、好ましくは５乃至５０質量部、より好ましくは１０乃至４０質量部である。５質量部未満の場合、ディスプレイ素子作製工程でアウトガスが増加したり、他の層へポジ型感光性樹脂組成物の成分が溶出したり、素子特性や信頼性が悪化する場合がある。また、５０質量部を超えると、保存安定性が低下したり、現像時の密着性が低下したり、感度が低下する可能性がある。 When 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.
　また本発明のポジ型感光性樹脂組成物は、（Ｄ２）成分として、式（３）で表されるエポキシ基を有する架橋性化合物を含有することができる。
Figure JPOXMLDOC01-appb-C000001
 （式中、ｋは２～１０の整数、ｍは０～４の整数を示し、Ｒ１１はｋ価の有機基を表す） Moreover, 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).
Figure JPOXMLDOC01-appb-C000001
 (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)
　市販品としては、エポリードＧＴ－４０１、同ＧＴ－４０３、同ＧＴ－３０１、同ＧＴ－３０２、セロキサイド２０２１、セロキサイド３０００（ダイセル化学工業（株）製　商品名）、脂環式エポキシ樹脂であるデナコールＥＸ－２５２（ナガセケムッテクス（株）製　商品名）、ＣＹ１７５、ＣＹ１７７、ＣＹ１７９（以上、ＣＩＢＡ－ＧＥＩＧＹ　Ａ．Ｇ製　商品名）、アラルダイトＣＹ－１８２、同ＣＹ－１９２、同ＣＹ－１８４（以上、ＣＩＢＡ－ＧＥＩＧＹ　Ａ．Ｇ製　商品名）、エピクロン２００、同４００（以上、ＤＩＣ（株）製　商品名）、エピコート８７１、同８７２（以上、油化シェルエポキシ（株）製　商品名）、ＥＤ－５６６１、ＥＤ－５６６２（以上、セラニーズコーティング（株）製　商品名）等を挙げることができる。また、これらの架橋性化合物は、単独または２種類以上を組み合わせて用いることができる。 Commercially available products include Epolead GT-401, GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.), and Denacol, an alicyclic epoxy resin. EX-252 (manufactured by Nagase Chemtex Co., Ltd., trade name), CY175, CY177, CY179 (manufactured by CIBA-GEIGY AG, trade name), Araldite CY-182, CY-192, CY-184 ( CIBA-GEIGY AG brand name), Epiclon 200, 400 (manufactured by DIC Corporation), Epicort 871, 872 (manufactured by Yuka Shell Epoxy Co., Ltd. brand name), ED-5661, ED-5662 (these are trade names manufactured by Celanese Coating Co., Ltd.), and the like. Moreover, these crosslinkable compounds can be used individually or in combination of 2 or more types.
　これらのうち、耐熱性、耐溶剤性、および耐長時間焼成耐性等の耐プロセス性の観点からシクロヘキセンオキサイド構造を有する化合物、エポリードＧＴ－４０１、同ＧＴ－４０３、同ＧＴ－３０１、同ＧＴ－３０２、セロキサイド２０２１、セロキサイド３０００が好ましい。 Among them, compounds having a cyclohexene oxide structure, Epolead GT-401, GT-403, GT-301, GT- 302, Celoxide 2021 and Celoxide 3000 are preferred.
　上記架橋剤として（Ｄ２）成分を選択した場合の含有量は、（Ｂ）成分１００質量部に対して５～５０質量部、好ましくは７～４０質量部、より好ましくは１０～３０質量部である。架橋性化合物の含有量が５質量部より少ない場合には、架橋性化合物によって形成される架橋の密度が十分ではないため、ディスプレイ素子作製工程でアウトガスが増加したり、他の層へポジ型感光性樹脂組成物の成分が溶出したり、素子特性や信頼性が悪化する場合がある。一方、５０質量部を超える場合には、未架橋の架橋性化合物が存在し、パターン形成後の耐熱性、耐溶剤性、長時間の焼成に対する耐性等が低下し、また、感光性樹脂組成物の保存安定性が悪くなる場合がある。 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.
＜（Ｅ）溶剤＞
　本発明に用いる（Ｅ）溶剤は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、及び（Ｄ）成分を溶解し、且つ所望により添加される後述のその他添加剤などを溶解するものであり、斯様な溶解能を有する溶剤であれば、その種類及び構造などは特に限定されるものでない。 <(E) Solvent>
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.
　斯様な（Ｅ）溶剤としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテル、プロピレングリコールプロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２－ブタノン、３－メチル－２－ペンタノン、２－ペンタノン、２－ヘプタノン、γ－ブチロラクトン、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、及びＮ－メチルピロリドン等が挙げられる。 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. monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone , ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and and N-methylpyrrolidone.
　これらの溶剤は、一種単独で、または二種以上の組合せで使用することができる。
　これら（Ｅ）溶剤の中、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、２－ヘプタノン、プロピレングリコールプロピルエーテル、プロピレングリコールプロピルエーテルアセテート、乳酸エチル、乳酸ブチル等が、塗膜性が良好で安全性が高いという観点より好ましい。これら溶剤は、一般にフォトレジスト材料のための溶剤として用いられている。 These solvents can be used singly or in combination of two or more.
Among these (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.
＜その他添加剤＞
　更に、本発明のポジ型感光性樹脂組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、レオロジー調整剤、顔料、染料、保存安定剤、消泡剤、密着促進剤、または多価フェノール、多価カルボン酸等の溶解促進剤等を含有することができる。 <Other additives>
Furthermore, 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.
＜ポジ型感光性樹脂組成物＞
　本発明のポジ型感光性樹脂組成物は、下記（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分及び（Ｅ）溶剤を含有するポジ型感光性樹脂組成物であり、且つ、それぞれ所望により、その他添加剤のうち一種以上を更に含有することができる組成物である。
（Ａ）成分：撥液性基を有する重合体、
（Ｂ）成分：Ｎ－ヒドロキシフェニル基を有するアルカリ可溶性樹脂、
（Ｃ）成分：１，２－キノンジアジド化合物、
（Ｄ）成分：架橋剤
（Ｅ）溶剤 <Positive type photosensitive resin composition>
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.
(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
　中でも、本発明のポジ型感光性樹脂組成物の好ましい例は、以下のとおりである。
（Ｂ）成分１００質量部に対して０．１～２０質量部の（Ａ）成分、５乃至１００質量部の（Ｃ）成分、５乃至５０質量部の（Ｄ）成分を含有し、これら成分が（Ｅ）溶剤に溶解されたポジ型感光性樹脂組成物。 Among them, 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.
　本発明のポジ型感光性樹脂組成物における固形分の割合は、各成分が均一に溶剤に溶解している限り、特に限定されるものではないが、例えば１乃至８０質量％であり、また例えば５乃至６０質量％であり、または１０乃至５０質量％である。ここで、固形分とは、ポジ型感光性樹脂組成物の全成分から（Ｅ）溶剤を除いたものをいう。 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. Here, the solid content refers to the total components of the positive photosensitive resin composition excluding (E) the solvent.
　本発明のポジ型感光性樹脂組成物の調製方法は、特に限定されないが、その調製法としては、例えば、（Ａ）成分（特定アクリル共重合体）を（Ｅ）溶剤に溶解し、この溶液に（Ｂ）成分のアルカリ可溶性樹脂、（Ｃ）成分の１，２－キノンジアジド化合物、（Ｄ）成分の架橋剤を所定の割合で混合し、均一な溶液とする方法、或いは、この調製法の適当な段階において、必要に応じてその他添加剤を更に添加して混合する方法が挙げられる。 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.
　本発明のポジ型感光性樹脂組成物の調製にあたっては、（Ｅ）溶剤中における重合反応によって得られる共重合体の溶液をそのまま使用することができ、この場合、この（Ａ）成分の溶液に前記と同様に（Ｂ）成分、（Ｃ）成分、（Ｄ）成分などを入れて均一な溶液とする際に、濃度調整を目的としてさらに（Ｅ）溶剤を追加投入してもよい。このとき、特定共重合体の形成過程で用いられる（Ｅ）溶剤と、ポジ型感光性樹脂組成物の調製時に濃度調整のために用いられる（Ｅ）溶剤とは同一であってもよいし、異なってもよい。 In preparing the positive photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the solvent (E) can be used as it is. When adding components (B), (C), and (D) to form a uniform solution in the same manner as described above, solvent (E) may be additionally added for the purpose of adjusting the concentration. At this time, 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.
　而して、調製されたポジ型感光性樹脂組成物の溶液は、孔径が０．２μｍ程度のフィルタなどを用いて濾過した後、使用することが好ましい。 Therefore, it is preferable to use the prepared solution of the positive photosensitive resin composition after filtering using a filter having a pore size of about 0.2 μm.
＜塗膜及び硬化膜＞
　本発明のポジ型感光性樹脂組成物を半導体基板（例えば、シリコン／二酸化シリコン被覆基板、シリコンナイトライド基板、金属例えばアルミニウム、モリブデン、クロムなどが被覆された基板、ガラス基板、石英基板、ＩＴＯ基板等）の上に、回転塗布、流し塗布、ロール塗布、スリット塗布、スリットに続いた回転塗布、インクジェット塗布などによって塗布し、その後、ホットプレートまたはオーブン等で予備乾燥することにより、塗膜を形成することができる。その後、この塗膜を加熱処理することにより、ポジ型感光性樹脂膜が形成される。 <Coating film and cured film>
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.
　この加熱処理の条件としては、例えば、温度７０℃乃至１６０℃、時間０．３乃至６０分間の範囲の中から適宜選択された加熱温度及び加熱時間が採用される。加熱温度及び加熱時間は、好ましくは８０℃乃至１４０℃、０．５乃至１０分間である。 As the conditions for this heat treatment, for example, 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.
　また、ポジ型感光性樹脂組成物から形成されるポジ型感光性樹脂膜の膜厚は、例えば０．１乃至３０μｍであり、また例えば０．２乃至１０μｍであり、更に例えば０．３乃至５μｍである。 The film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 30 μm, further, for example, 0.2 to 10 μm, further, for example, 0.3 to 5 μm. is.
　上記で得られた塗膜上に、所定のパターンを有するマスクを装着して紫外線等の光を照射し、アルカリ現像液で現像することで、露光部が洗い出されて端面のシャープなレリーフパターンが得られる。 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.
　使用されうるアルカリ性現像液としては、例えば、炭酸カリウム、炭酸ナトリウム、水酸化カリウム、水酸化ナトリウムなどのアルカリ金属水酸化物の水溶液、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、コリンなどの水酸化第四級アンモニウムの水溶液、エタノールアミン、プロピルアミン、エチレンジアミンなどのアミン水溶液等のアルカリ性水溶液が挙げられる。さらに、これらの現像液には、界面活性剤などを加えることもできる。 Examples of alkaline developers that can be used 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. Alkaline aqueous solutions such as aqueous solutions of quaternary ammonium, aqueous solutions of amines such as ethanolamine, propylamine and ethylenediamine are included. Furthermore, a surfactant or the like can be added to these developers.
　上記の中、水酸化テトラエチルアンモニウム０．１乃至２．３８質量％水溶液は、フォトレジストの現像液として一般に使用されており、本発明の感光性樹脂組成物においても、このアルカリ性現像液を用いて、膨潤などの問題をひき起こすことなく良好に現像することができる。好ましくは１．０乃至２．３８質量％水溶液を用いることで、更に効果的にレリーフパターンを得ることができる。 Among the above, 0.1 to 2.38% by mass 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.
　また、現像方法としては、液盛り法、ディッピング法、揺動浸漬法など、いずれも用いることができる。その際の現像時間は、通常、１５乃至１８０秒間である。 In addition, as a developing method, any of a liquid heaping method, a dipping method, a rocking immersion method, and the like can be used. The development time at that time is usually 15 to 180 seconds.
　現像後、ポジ型感光性樹脂膜に対して流水による洗浄を例えば２０乃至１２０秒間行い、続いて圧縮空気もしくは圧縮窒素を用いてまたはスピニングにより風乾することにより、基板上の水分が除去され、そしてパターン形成された膜が得られる。 After development, 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.
　続いて、斯かるパターン形成膜に対して、熱硬化のためにポストベークを行うことにより、具体的にはホットプレート、オーブンなどを用いて加熱することにより、耐熱性、透明性、平坦化性、低吸水性、耐薬品性などに優れ、良好なレリーフパターンを有する膜が得られる。 Subsequently, 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.
　ポストベークとしては、一般に、温度１４０℃乃至２７０℃の範囲の中から選択された加熱温度にて、ホットプレート上の場合には５乃至３０分間、オーブン中の場合には３０乃至９０分間処理するという方法が採られる。 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.
　而して、斯かるポストべークにより、目的とする、良好なパターン形状を有する硬化膜を得ることができる。 Thus, by such post-baking, it is possible to obtain a desired cured film having a favorable pattern shape.
　以上のように、本発明のポジ型感光性樹脂組成物により、保存安定性が高く、十分高感度であり且つ現像の際に未露光部の膜減りが非常に小さく、微細なパターンを有する塗膜を形成することができる。
　またこのように得られる塗膜（硬化膜）は表示素子の画像形成用バンクとして好適に用いることができる。 As described above, 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.
　以下、実施例を挙げて本発明をさらに詳しく説明するが、本発明は、これら実施例に限定されるものではない。なお、数平均分子量及び重量平均分子量の測定は以下の通りである。 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.
［数平均分子量及び重量平均分子量の測定］
　以下の合成例に従い得られた共重合体の数平均分子量及び重量平均分子量を、島津製作所製ＧＰＣ装置（ＳｈｏｄｅｘカラムＫＦ－８０４Ｌおよび８０３Ｌ）を用い、溶出溶媒テトラヒドロフランを流量１ｍｌ／分でカラム中に（カラム温度４０℃）流して溶離させるという条件で測定した。なお、下記の数平均分子量（以下、Ｍｎと称す。）及び重量平均分子量（以下、Ｍｗと称す。）は、ポリスチレン換算値にて表される。 [Measurement of number average molecular weight and weight average molecular weight]
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. The number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) below are expressed in terms of polystyrene.
　以下の実施例で用いる略記号の意味は、次の通りである。
ＭＭＡ：メチルメタクリレート
ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
ＨＰＭＡ：４－ヒドロキシフェニルメタクリレート
ＣＨＭＩ：Ｎ－シクロヘキシルマレイミド
ＭＡＡ：メタクリル酸
ＡＩＢＮ：α、α’－アゾビスイソブチロニトリル
ＱＤ：　α、α、α’－トリス（４－ヒドロキシフェニル）－１－エチル－４－イソプロピルベンゼン１ｍｏｌと１，２－ナフトキノン－２－ジアジド－５－スルホニルクロリド２ｍｏｌとの縮合反応によって合成される化合物
ＧＴ－４０１：ブタンテトラカルボン酸　テトラ（３，４－エポキシシクロヘキシルメチル）　修飾ε－カプロラクトン
マルカリンカーＣＳＴ：丸善石油化学（株）製マルカリンカーＣＳＴ８５１５と７０３０を２：８で混合したスチレン重合体の３０ｗｔ％プロピレングリコールモノメチルエーテル溶液（Ｐ２）
ＨＭＭ：ニカッラクＭＷ－１００ＬＭ（（株）三和ケミカル製ヘキサメトキシメチルメラミン）
ＰＦＨＭＡ：２－（パーフルオロヘキシル）エチルメタクリレート
ＫＢＭ－５０３：３－メタクリロキシプロピルトリエトキシシラン
ＮＨＰＭＡ：Ｎ－（４－ヒドロキシフェニル）メタクリルアミド
ＮＨＰＭＩ：Ｎ－（４－ヒドロキシフェニル）マレイミド
Ｓｔ：スチレン
ＰＦＨＴＭＯＳ：２－（パーフルオロヘキシル）エチルトリメトキシシラン
ＫＢＭ－３０３：２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン
３５ｗｔ％ＴＥＡＨａｑ．：３５ｗｔ％水酸化テトラエチルアンモニウム溶液
ＰＴＭＯＳ：フェニルトリメトキシシラン
１５ＪＷＥＴ：オルガノ社製イオン交換樹脂
ＰＧＭＥ：プロピレングリコールモノメチルエーテル
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＴＨＦ：テトラヒドロフラン Abbreviations used in the following examples have the following meanings.
MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 4-hydroxyphenyl methacrylate CHMI: N-cyclohexylmaleimide MAA: methacrylic acid AIBN: α,α'-azobisisobutyronitrile QD: α,α,α'- 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 ε-caprolactone Marukalinker CST: Marukalinker CST8515 and 7030 manufactured by Maruzen Petrochemical Co., Ltd. 30 wt% propylene glycol monomethyl ether solution of styrene polymer mixed at 2: 8 (P2 )
HMM: Nikaraku MW-100LM (hexamethoxymethyl melamine manufactured by Sanwa Chemical Co., Ltd.)
PFHMA: 2-(perfluorohexyl)ethyl methacrylate KBM-503: 3-methacryloxypropyltriethoxysilane NHPMA: N-(4-hydroxyphenyl)methacrylamide NHPMI: N-(4-hydroxyphenyl)maleimide St: Styrene PFHTMOS : 2-(perfluorohexyl)ethyltrimethoxysilane KBM-303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 35 wt% TEAHaq. : 35 wt% tetraethylammonium hydroxide solution PTMOS: Phenyltrimethoxysilane 15 JWET: Ion exchange resin manufactured by Organo Corporation PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate THF: Tetrahydrofuran
＜合成例１＞
　ＨＰＭＡ　５．００ｇ、ＭＭＡ　１．２８ｇ、ＣＨＭＩ　３．９３ｇ、ＡＩＢＮ　０．３１ｇをＰＧＭＥ　４７．８８ｇに溶解し、９０℃にて２０時間反応させることによりアクリル重合体溶液（固形分濃度１８質量％）を得た（Ｐ１）。得られたアクリル重合体のＭｎは６，０００、Ｍｗは９，５００であった。 <Synthesis Example 1>
5.00 g of HPMA, 1.28 g of MMA, 3.93 g of CHMI, and 0.31 g of AIBN were dissolved in 47.88 g of PGME and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 18% by mass). was obtained (P1). The obtained acrylic polymer had an Mn of 6,000 and an Mw of 9,500.
＜合成例２＞
　ＮＨＰＭＡ　５．００ｇ、ＭＭＡ　１．２８ｇ、ＣＨＭＩ　３．９３ｇ、ＡＩＢＮ　０．３１ｇをＰＧＭＥ　４７．８８ｇに溶解し、９０℃にて２０時間反応させることによりアクリル重合体溶液（固形分濃度１８質量％）を得た（Ｐ３）。得られたアクリル重合体のＭｎは５，０００、Ｍｗは８，１００であった。 <Synthesis Example 2>
5.00 g of NHPMA, 1.28 g of MMA, 3.93 g of CHMI, and 0.31 g of AIBN were dissolved in 47.88 g of PGME and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 18% by mass). was obtained (P3). The obtained acrylic polymer had an Mn of 5,000 and an Mw of 8,100.
＜合成例３＞
　ＮＨＰＭＡ　５．００ｇ、ＭＭＡ　１．０９ｇ、ＣＨＭＩ　３．００ｇ、ＡＩＢＮ　０．２７ｇをＰＧＭＥ　４２．６６ｇに溶解し、９０℃にて２０時間反応させることによりアクリル重合体溶液（固形分濃度１８質量％）を得た（Ｐ４）。得られたアクリル重合体のＭｎは４，５００、Ｍｗは６，３００であった。 <Synthesis Example 3>
5.00 g of NHPMA, 1.09 g of MMA, 3.00 g of CHMI, and 0.27 g of AIBN were dissolved in 42.66 g of PGME and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 18% by mass). was obtained (P4). The obtained acrylic polymer had an Mn of 4,500 and an Mw of 6,300.
＜合成例４＞
　ＮＨＰＭＡ　３．００ｇ、ＨＥＭＡ　１．１１ｇ、ＣＨＭＩ　３．０４ｇ、ＡＩＢＮ　０．１４ｇをＰＧＭＥ　３３．１６ｇに溶解し、９０℃にて２０時間反応させることによりアクリル重合体溶液（固形分濃度１８質量％）を得た（Ｐ５）。得られたアクリル重合体のＭｎは５，６００、Ｍｗは９，３００であった。 <Synthesis Example 4>
3.00 g of NHPMA, 1.11 g of HEMA, 3.04 g of CHMI, and 0.14 g of AIBN were dissolved in 33.16 g of PGME and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 18% by mass). was obtained (P5). The obtained acrylic polymer had an Mn of 5,600 and an Mw of 9,300.
＜合成例５＞
　ＮＨＰＭＡ　３．００ｇ、ＨＥＭＡ　０．９８ｇ、ＣＨＭＩ　２．３４ｇ、ＡＩＢＮ　０．１２ｇをＰＧＭＥ　２９．３２ｇに溶解し、９０℃にて２０時間反応させることによりアクリル重合体溶液（固形分濃度１８質量％）を得た（Ｐ６）。得られたアクリル重合体のＭｎは６，２００、Ｍｗは９，９００であった。 <Synthesis Example 5>
3.00 g of NHPMA, 0.98 g of HEMA, 2.34 g of CHMI, and 0.12 g of AIBN were dissolved in 29.32 g of PGME and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 18% by mass). was obtained (P6). The obtained acrylic polymer had an Mn of 6,200 and an Mw of 9,900.
＜合成例６＞
　ＰＦＨＭＡ　５．００ｇ、ＫＢＭ－５０３　３．８３ｇ、ＨＥＭＡ　１．５１ｇ、ＡＩＢＮ　０．５２ｇをＰＧＭＥ　２５．３２ｇに溶解し、８０℃にて２０時間反応させることによりアクリル重合体溶液（固形分濃度３０質量％）を得た（Ｐ７）。得られたアクリル重合体のＭｎは４８００、Ｍｗは６７００であった。 <Synthesis Example 6>
5.00 g of PFHMA, 3.83 g of KBM-503, 1.51 g of HEMA, and 0.52 g of AIBN were dissolved in 25.32 g of PGME and reacted at 80° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 30 mass %) was obtained (P7). The obtained acrylic polymer had an Mn of 4,800 and an Mw of 6,700.
＜合成例７＞
　ＰＦＨＴＭＯＳ　２．３４ｇ、ＫＢＭ－３０３　２．４６ｇ、ＰＴＭＯＳ　１．９８ｇ、３５ｗｔ％ＴＥＡＨ　０．２１ｇ、Ｈ２Ｏ　０．６８ｇをＴＨＦ　９．２１ｇに溶解し、４０℃にて４時間撹拌した。続いて、ＴＨＦで洗浄した１５ＪＷＥＴ　０．４８ｇを添加し、２５℃にて１時間撹拌した。次いで、廃１５ＪＷＥＴをろ過しシロキサン重合体溶液を得た（Ｐ８）。得られたシロキサン重合体のＭｎは１，９００、Ｍｗは２，４００であった。 <Synthesis Example 7>
2.34 g of PFHTMOS, 2.46 g of KBM-303, 1.98 g of PTMOS, 0.21 g of 35 wt% TEAH, and 0.68 g of H2O were dissolved in 9.21 g of THF and stirred at 40°C for 4 hours. Subsequently, 0.48 g of 15JWET washed with THF was added and stirred at 25° C. for 1 hour. Next, the waste 15JWET was filtered to obtain a siloxane polymer solution (P8). The resulting siloxane polymer had an Mn of 1,900 and an Mw of 2,400.
＜合成例８＞
　ＭＡＡ　１０．９ｇ、ＣＨＭＩ　３５．３ｇ、ＨＥＭＡ　２５．５ｇ、ＭＭＡ　２８．３ｇを使用し、ラジカル重合開始剤としてＡＩＢＮ　５ｇを使用し、これらを溶剤ＰＧＭＥＡ　２００ｇ中において温度９０℃で重合反応させることにより、Ｍｎ４，１００、Ｍｗ７，６００である（Ｂ）成分（特定共重合体）の溶液（特定共重合体濃度：２７．５質量％）を得た（Ｐ９）。得られた特定共重合体のＭｎは４，１００、Ｍｗは７，１００であった。 <Synthesis Example 8>
Using 10.9 g of MAA, 35.3 g of CHMI, 25.5 g of HEMA, and 28.3 g of MMA, and using 5 g of AIBN as a radical polymerization initiator, these were polymerized in 200 g of solvent PGMEA at a temperature of 90°C. , Mn 4,100, and Mw 7,600 (P9). The obtained specific copolymer had an Mn of 4,100 and an Mw of 7,100.
＜合成例９＞
　ＮＨＰＭＩ　３．００ｇ、Ｓｔ　２．０６ｇ、ＣＨＭＩ　０．７１ｇ、ＡＩＢＮ　０．２０ｇをＰＧＭＥ　３３．１６ｇに溶解し、９０℃にて２０時間反応させることによりアクリル重合体溶液（固形分濃度１８質量％）を得た（Ｐ１０）。得られたアクリル重合体のＭｎは６，２００、Ｍｗは１１，７００であった。 <Synthesis Example 9>
3.00 g of NHPMI, 2.06 g of St, 0.71 g of CHMI, and 0.20 g of AIBN were dissolved in 33.16 g of PGME and reacted at 90° C. for 20 hours to obtain an acrylic polymer solution (solid concentration: 18% by mass). was obtained (P10). The obtained acrylic polymer had an Mn of 6,200 and an Mw of 11,700.
＜実施例１乃至５及び比較例１乃至４＞
　次の表１に示す組成に従い、（Ａ）成分の溶液、（Ｂ）成分の溶液、（Ｃ）成分、（Ｄ）成分を所定の割合で（Ｅ）溶剤に溶解し、室温で３時間撹拌して均一な溶液とすることにより、各実施例及び各比較例のポジ型感光性樹脂組成物を調製した。 <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.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
［開口部残渣の評価］
　ポジ型感光性樹脂組成物をＩＴＯ－ガラス上にスピンコーターを用いて塗布した後、温度８０℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．２μｍの塗膜を形成した。この塗膜に１０μｍのラインアンドスペースパターンのマスクを介しキヤノン（株）製紫外線照射装置ＰＬＡ－６００ＦＡにより３６５ｎｍにおける光強度が５．５ｍＷ／ｃｍ２の紫外線を一定時間照射した。その後２．３８％ＴＭＡＨ水溶液に６０秒間浸漬することで現像を行った後、超純水で３０秒間流水洗浄を行った。次いでこのラインアンドスペースパターンが形成された塗膜を温度２３０℃で３０分間加熱することによりポストベークを行い硬化させた。硬化したラインアンドスペースパターンの開口部残渣を（株）日立ハイテクノロジーズ製走査型電子顕微鏡Ｓ－４８００を用いて観察した。得られた結果を表２に示す。この際、パターン内に残渣が残っていなくて特に良好であるものを（◎）、パターン内に残渣が残っていなくて良好なものを（○）、残渣が残っているものを不良（×）と判断した。 [Evaluation of opening residue]
After applying the positive photosensitive resin composition onto ITO-glass using a spin coater, it was pre-baked on a hot plate at a temperature of 80° C. for 120 seconds to form a coating film having a thickness of 1.2 μm. This coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW/cm 2 at 365 nm for a certain period of time using a PLA-600FA ultraviolet light irradiation device manufactured by Canon Inc. through a 10 μm line-and-space pattern mask. Thereafter, the film was developed by being immersed in a 2.38% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Then, 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.
［脱ガス測定用基板の作製］
　ポジ型感光性樹脂組成物をＩＴＯ－ガラス上にスピンコーターを用いて塗布した後、温度８０℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．２μｍの塗膜を形成した。この塗膜を２．３８％ＴＭＡＨ水溶液に６０秒間浸漬することで現像を行った後、超純水で３０秒間流水洗浄を行った。次いでこの塗膜を温度２３０℃で３０分間加熱することによりポストベークを行い硬化させた。 [Preparation of substrate for degassing measurement]
After applying the positive photosensitive resin composition onto ITO-glass using a spin coater, it was pre-baked on a hot plate at a temperature of 80° C. for 120 seconds to form a coating film having a thickness of 1.2 μm. This coating film was developed by immersing it in a 2.38% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Then, this coating film was post-baked by heating at a temperature of 230° C. for 30 minutes to be cured.
［脱ガスの評価］
　作製した脱ガス測定用基板（１０ｍｍ×５０ｍｍ、５枚）を加熱炉内で２５０℃、３０分間加熱した際の脱ガスをＧＣ／ＭＳ（Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｉｅｓ社製、ＧＣ：７８９０Ａ、ＭＳ：５９７５Ｃ）にて分析し、検出されたピーク全成分の面積の総和を計算した。面積が８，０００，０００未満のものを〇、８，０００，０００以上のものを×と判定した。結果を表２に示す。 [Evaluation of degassing]
Degassing when the prepared substrates for degassing measurement (10 mm × 50 mm, 5 sheets) were heated in a heating furnace at 250 ° C. for 30 minutes was measured by GC / MS (manufactured by Agilent Technologies, GC: 7890A, MS: 5975C). The sum of the areas of all detected peak components was calculated. A sample with an area of less than 8,000,000 was rated as ◯, and a sample with an area of 8,000,000 or more was rated as x. Table 2 shows the results.
［撥液性の評価］
　ポジ型感光性樹脂組成物をシリコンウェハ上にスピンコーターを用いて塗布した後、温度８０℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．２μｍの塗膜を形成した。この塗膜を２．３８％ＴＭＡＨ水溶液に６０秒間浸漬することで現像を行った後、超純水で３０秒間流水洗浄を行った。次いでこの塗膜を温度２３０℃で３０分間加熱することによりポストベークを行い硬化させた。この硬化膜上のアニソールの接触角を協和界面科学（株）製Ｄｒｏｐ　Ｍａｓｔｅｒを用いて測定した。接触角が５０度以上のものを〇、５０℃未満のものを×と判定した。得られた結果を表２に示す。 [Evaluation of liquid repellency]
After applying the positive photosensitive resin composition onto a silicon wafer using a spin coater, it was pre-baked on a hot plate at a temperature of 80° C. for 120 seconds to form a coating film having a thickness of 1.2 μm. This coating film was developed by immersing it in a 2.38% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Then, this coating film was post-baked by heating at a temperature of 230° C. for 30 minutes to be cured. The contact angle of anisole on this cured film was measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd. A contact angle of 50° or more was evaluated as ◯, and a contact angle of less than 50°C was evaluated as x. Table 2 shows the results obtained.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２に示すように、実施例１乃至実施例５においては、撥液性を維持しつつ良好な開口部残渣と低い脱ガス量を示した。 As shown in Table 2, in Examples 1 to 5, good residue at openings and a low amount of degassing were exhibited while maintaining liquid repellency.

Claims (14)

  1. 下記（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分及び（Ｅ）溶剤を含有する熱硬化可能なポジ型感光性樹脂組成物。
    （Ａ）成分：撥液性基を有する重合体、
    （Ｂ）成分：Ｎ－ヒドロキシフェニル基を有するアルカリ可溶性樹脂、
    （Ｃ）成分：１，２－キノンジアジド化合物、
    （Ｄ）成分：架橋剤
    （Ｅ）溶剤     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
  2. （Ｂ）成分はＮ－（ヒドロキシフェニル）アクリルアミド、Ｎ－（ヒドロキシフェニル）メタクリルアミド、又はＮ－（ヒドロキシフェニル）マレイミドから選ばれる少なくとも一種のモノマーに由来する構成単位を含む重合体である請求項１に記載のポジ型感光性樹脂組成物。 Component (B) is a polymer containing structural units derived from at least one monomer selected from N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide. 2. The positive photosensitive resin composition according to 1.
  3. （Ａ）成分の上記撥液性基が炭素原子数３乃至１０のフルオロアルキル基、ポリフルオロエーテル基及びポリシロキサン基からなる群より選ばれる少なくとも一種の基である請求項１又は請求項２に記載のポジ型感光性樹脂組成物。 3. The liquid-repellent group of component (A) is at least one group selected from the group consisting of a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group and a polysiloxane group. A positive photosensitive resin composition as described.
  4. （Ａ）成分の重合体を構成するモノマー単位が上記撥液性基を有する不飽和炭化水素由来の単位である請求項１乃至請求項３のいずれか１項に記載のポジ型感光性樹脂組成物。 4. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the monomer unit constituting the polymer of component (A) is a unit derived from an unsaturated hydrocarbon having a liquid-repellent group. thing.
  5. （Ａ）成分の重合体を構成するモノマー単位が上記撥液性基を有するアルコキシラン化合物由来の単位である請求項１乃至請求項３のいずれか１項に記載のポジ型感光性樹脂組成物。 4. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein the monomer units constituting the polymer of component (A) are units derived from the alkoxysilane compound having a liquid-repellent group. .
  6. （Ａ）成分が上記撥液性基および熱硬化性基を有する重合体である請求項１乃至請求項５のいずれか１項に記載のポジ型感光性樹脂組成物。 6. The positive photosensitive resin composition according to any one of claims 1 to 5, wherein component (A) is a polymer having a liquid-repellent group and a thermosetting group.
  7. （Ｄ）成分の架橋剤がエポキシ基またはメトキシメチル基を含む請求項１乃至請求項６のいずれか１項に記載のポジ型感光性樹脂組成物。 7. The positive photosensitive resin composition according to any one of claims 1 to 6, wherein the cross-linking agent of component (D) contains an epoxy group or a methoxymethyl group.
  8. （Ｂ）成分のアルカリ可溶性樹脂の数平均分子量がポリスチレン換算で２，０００乃至６０，０００である請求項１乃至請求項７のいずれか１項に記載のポジ型感光性樹脂組成物。 8. The positive photosensitive resin composition according to any one of claims 1 to 7, wherein the alkali-soluble resin as component (B) has a number average molecular weight of 2,000 to 60,000 in terms of polystyrene.
  9. （Ｂ）成分１００質量部に対して、（Ａ）成分が０．１乃至２０質量部含まれることを特徴とする請求項１乃至請求項８のいずれか１項に記載のポジ型感光性樹脂組成物。 9. The positive photosensitive resin according to any one of claims 1 to 8, wherein 0.1 to 20 parts by mass of component (A) is contained with respect to 100 parts by mass of component (B). Composition.
  10. （Ｂ）成分１００質量部に対して、（Ｃ）成分が５乃至１００質量部含まれることを特徴とする請求項１乃至請求項９のいずれか１項に記載のポジ型感光性樹脂組成物。 10. The positive photosensitive resin composition according to any one of claims 1 to 9, wherein 5 to 100 parts by mass of component (C) is contained with respect to 100 parts by mass of component (B). .
  11. （Ｂ）成分１００質量部に対して、（Ｄ）成分が５乃至５０質量部含まれることを特徴とする上請求項１乃至請求項１０のいずれか１項に記載のポジ型感光性樹脂組成物。 11. The positive photosensitive resin composition according to any one of claims 1 to 10, wherein 5 to 50 parts by mass of component (D) is contained with respect to 100 parts by mass of component (B). thing.
  12. 請求項１乃至請求項１１のいずれか１項に記載のポジ型感光性樹脂組成物を用いて得られる硬化膜。 A cured film obtained using the positive photosensitive resin composition according to any one of claims 1 to 11.
  13. 請求項１２に記載の硬化膜を有する表示素子。 A display device comprising the cured film according to claim 12 .
  14. 請求項１２に記載の硬化膜を画像形成用バンクとして有する表示素子。 A display device comprising the cured film according to claim 12 as an image forming bank.
PCT/JP2022/003127 2021-02-03 2022-01-27 Positive-acting photosensitive resin composition WO2022168732A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020237026446A KR20230142489A (en) 2021-02-03 2022-01-27 Positive photosensitive resin composition
JP2022579497A JPWO2022168732A1 (en) 2021-02-03 2022-01-27
CN202280013069.0A CN116848466A (en) 2021-02-03 2022-01-27 Positive photosensitive resin composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021015970 2021-02-03
JP2021-015970 2021-02-03

Publications (1)

Publication Number Publication Date
WO2022168732A1 true WO2022168732A1 (en) 2022-08-11

Family

ID=82741554

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/003127 WO2022168732A1 (en) 2021-02-03 2022-01-27 Positive-acting photosensitive resin composition

Country Status (5)

Country Link
JP (1) JPWO2022168732A1 (en)
KR (1) KR20230142489A (en)
CN (1) CN116848466A (en)
TW (1) TW202242550A (en)
WO (1) WO2022168732A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012226044A (en) * 2011-04-18 2012-11-15 Hitachi Chem Co Ltd Positive photosensitive resin composition, method for producing resist pattern, semiconductor device and electronic device
WO2013133392A1 (en) * 2012-03-09 2013-09-12 旭硝子株式会社 Positive photosensitive resin composition, partition wall and optical element
JP2016040577A (en) * 2014-08-12 2016-03-24 東京応化工業株式会社 Positive photosensitive resin composition and cured film
JP2019045622A (en) * 2017-08-31 2019-03-22 住友ベークライト株式会社 Photosensitive resin composition, pattern formation method, electronic device production method, polymer, and polymer production method

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3911775B2 (en) 1997-07-30 2007-05-09 セイコーエプソン株式会社 Manufacturing method of organic EL element
JP4138117B2 (en) 1998-12-21 2008-08-20 セイコーエプソン株式会社 Manufacturing method of color filter substrate
JP4453920B2 (en) 2005-11-14 2010-04-21 株式会社不二越 Touch probe contact detection method and apparatus
JP5173543B2 (en) 2008-04-08 2013-04-03 東京応化工業株式会社 Positive photosensitive resin composition
JP6398774B2 (en) 2014-02-18 2018-10-03 Ａｇｃ株式会社 Negative photosensitive resin composition, cured resin film, partition and optical element
JP2015215449A (en) 2014-05-09 2015-12-03 日立化成株式会社 Positive photosensitive resin composition, method for forming ink-repellent bank film using resin composition, and organic electroluminescence display device including bank film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012226044A (en) * 2011-04-18 2012-11-15 Hitachi Chem Co Ltd Positive photosensitive resin composition, method for producing resist pattern, semiconductor device and electronic device
WO2013133392A1 (en) * 2012-03-09 2013-09-12 旭硝子株式会社 Positive photosensitive resin composition, partition wall and optical element
JP2016040577A (en) * 2014-08-12 2016-03-24 東京応化工業株式会社 Positive photosensitive resin composition and cured film
JP2019045622A (en) * 2017-08-31 2019-03-22 住友ベークライト株式会社 Photosensitive resin composition, pattern formation method, electronic device production method, polymer, and polymer production method

Also Published As

Publication number Publication date
TW202242550A (en) 2022-11-01
JPWO2022168732A1 (en) 2022-08-11
CN116848466A (en) 2023-10-03
KR20230142489A (en) 2023-10-11

Similar Documents

Publication Publication Date Title
TWI388929B (en) A negative photosensitive composition, a partition member for an optical element using the same, and an optical element having the partition wall
KR20090010044A (en) Positive photosensitive resin composition and porous film obtained therefrom
JP7406181B2 (en) Photosensitive resin composition
TWI738634B (en) Positive photosensitive resin composition, hardened film and display element
KR101923249B1 (en) Negative photosensitive resin composition, partition wall and optical element
KR20090008326A (en) Positive photosensitive resin composition containing siloxane compound
WO2017188047A1 (en) Resin composition, cured film of same and method for manufacturing same, and solid-state imaging element
TW201321898A (en) Method for manufacturing ink-repellent agent, negative-type photosensitive resin composition, partition wall, and optical device
CN110573963B (en) Photosensitive resin composition
TWI713678B (en) Positive photosensitive resin composition
TWI655501B (en) Negative photosensitive resin composition, partition and optical component
JP2024038456A (en) Formation method of bank pattern
JP7045001B2 (en) Photosensitive resin composition
WO2022168732A1 (en) Positive-acting photosensitive resin composition
WO2024024502A1 (en) Positive-type photosensitive resin composition
WO2024024501A1 (en) Positive photosensitive resin composition
TW202422226A (en) Positive photosensitive resin composition
JP2021135499A (en) Photosensitive resin composition, cured film, liquid-repellent bank, display device, method for manufacturing substrate with partition wall, and method for manufacturing display device
TW202422225A (en) Positive photosensitive resin composition
WO2024038814A1 (en) Positive-type photosensitive resin composition, partition wall, and optical element
JP7324581B2 (en) Bank pattern formation method
WO2023171487A1 (en) Photosensitive resin composition, cured article, display device, and method for producing display device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22749606

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022579497

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 202280013069.0

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22749606

Country of ref document: EP

Kind code of ref document: A1