Classifications

• • 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
• • 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
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • 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
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
• • 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
  • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds

Definitions

• the present invention relates to a photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a photosensitive resin composition capable of forming an image having high water repellency and oil repellency on the surface of the cured film, a cured film thereof, and various materials using the cured film.
• This positive photosensitive resin composition is particularly suitable for use as an interlayer insulating film in a liquid crystal display or an EL display, a light shielding material corresponding to an inkjet method, or a partition material.
• a full color display substrate manufacturing technique using an ink jet in a manufacturing process of a display element such as a thin film transistor (TFT) type liquid crystal display element or an organic EL (electroluminescent) element has been actively studied.
• TFT thin film transistor
• organic EL electroluminescent
• a color filter in a liquid crystal display element light is blocked from a section (hereinafter referred to as a bank) that defines pixels that have been patterned in advance, compared to a conventional printing method, electrodeposition method, dyeing method, or pigment dispersion method.
• Patent Document 2 a method has been proposed (Patent Document 2) in which an organic EL display element is manufactured by preparing a bank in advance and dropping an ink serving as a light emitting layer in the same manner.
• the substrate has ink affinity (hydrophilicity) to prevent the ink droplet from overflowing to the adjacent pixel beyond the bank.
• the surface needs to have water repellency.
• the substrate can be made hydrophilic and the bank can be made water repellent by continuous plasma (ozone) treatment such as oxygen gas plasma treatment and fluorine gas plasma treatment.
• ozone continuous plasma
• oxygen gas plasma treatment oxygen gas plasma treatment
• fluorine gas plasma treatment fluorine gas plasma treatment
• the process is complicated.
• a proposal has been made that a fluorine-based surfactant or a fluorine-based polymer is blended with a photosensitive organic thin film (Patent Document 4), but consideration is given not only to photosensitivity but also to coating properties, such as compatibility. Not only is there much to be done, but also the UV ozone treatment during the hydrophilic treatment of the substrate reduces the water repellency of the surface, which is not practical.
• Patent Document 5 Japanese Unexamined Patent Application Publication No. 2015-172742
• Patent Document 6 JP 2012-220860 A
• JP 2000-187111 A Japanese Patent Laid-Open No. 11-54270 JP 2000-353594 A JP-A-10-197715 Japanese Patent Laying-Open No. 2015-172742 JP 2012-220860 A
• the present invention has been made in view of the above circumstances, and the problem to be solved is used for liquid crystal display elements, organic EL display elements, etc., and the surface of the cured film without plasma treatment or UV ozone treatment. It is to form an image of a cured film having high water repellency and high oil repellency, little residue, and high lyophilicity and high oleophilicity on a substrate. In particular, it is to form an image of a cured film that can prevent a situation where an ink droplet overflows to an adjacent pixel beyond a bank in manufacturing a substrate using inkjet.
• the present inventors have found that at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group, and N -Efficient water and liquid repellency on the film surface by forming a cured film from a composition containing a polymer having at least one group selected from alkoxymethylamide groups, blocked isocyanate groups and trialkoxysilyl groups
• the present invention has been completed.
• thermosetting photosensitive resin composition containing the following component (A), component (B), solvent (C) and component (D).
• A) Component Polymer having the following groups (A1) and (A2) (A1) Liquid repellent group (A2) A group selected from N-alkoxymethylamide group, blocked isocyanate group and trialkoxysilyl group, (B) component: alkali-soluble resin, (C) solvent, (D) Component: A compound having a quinonediazide group.
• Component A compound having a quinonediazide group.
• (A3) at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group; Furthermore, the photosensitive resin composition of said 1 or 2 which satisfies at least one of following (Z1) and (Z2).
• the liquid repellent group of the component (A) is at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group.
• the photosensitive resin composition as described in one. 5).
• the photosensitive resin composition as described in any one of 1 to 4 above, wherein the polymer of the component is an acrylic polymer. 6).
• the photosensitive resin composition of said 5 whose number average molecular weight of the acrylic polymer of a component is 2,000-100,000 in polystyrene conversion. 7).
• the positive photosensitive resin composition of the present invention can efficiently impart water repellency and liquid repellency to the film surface, and can form a cured film that does not impair the wettability of the pattern opening during development. it can.
• the photosensitive resin composition of this invention is a positive photosensitive resin composition containing the following (A) component, (B) component, (C) solvent, and (D) component.
• A) Component Polymer having the following groups (A1) and (A2) (A1) Liquid repellent group (A2) A group selected from N-alkoxymethylamide group, blocked isocyanate group and trialkoxysilyl group, (B) component: alkali-soluble resin, (C) solvent, (D) Component: A compound having a quinonediazide group.
• the photosensitive resin composition of the present invention is preferably a polymer in which the component (A) further has the following (A3).
• the photosensitive resin composition of the present invention preferably further satisfies at least one of the following (Z1) and (Z2).
• the alkali-soluble resin of the component (B) further has a self-crosslinkable group or a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. Also have.
• the component (A) is a polymer having the following groups (A1) and (A2).
• examples of the polymer include polyimides, polyamic acids, polyamides, polyureas, polyurethanes, phenol resins, epoxy resins, polysiloxanes, polyesters, and acrylic polymers.
• Preferred polymers include acrylic polymers. Is mentioned.
• the acrylic polymer is obtained by using a monomer having a polymerizable unsaturated group such as an acrylic ester, methacrylic ester, styrene, maleimide, that is, a polymerizable group containing a C ⁇ C double bond in the structure. Refers to the polymer produced.
• Polyamic acid, polyimide, polyamide, and polyurea include polyamic acid obtained by reacting diamine with acid dianhydride, polyimide obtained by imidizing the polyamic acid, polyamide obtained by reacting diamine with dicarboxylic acid anhydride, or diamine. And a polymer obtained from a monomer mixture containing at least one monomer having a fluoroalkyl group or fluoroalkoxy group and at least one monomer having a hydroxy group.
• polyurethane examples include polyurethane obtained by reacting a diol having a fluoroalkyl group or a fluoroalkoxy group and a diol having an amino group with a diisocyanate.
• phenol resin examples include novolak resins obtained by polymerizing phenol having a fluoroalkyl group or fluoroalkoxy group and formaldehyde.
• epoxy resin examples include epoxy resins obtained by reacting bisphenol A and / or bisphenol F having a fluoroalkyl group or fluoroalkoxy group with glycidyl ether when bisphenol A and / or bisphenol F is used.
• a silane monomer mixture containing a trialkoxysilane having a fluoroalkyl group or a dialkoxysilane silane having a fluoroalkyl group and a trialkoxysilane having an amino group or a dialkoxysilane having an amino group is polymerized.
• the obtained polymer is mentioned.
• polyester examples include a polyester obtained by reacting a dicarboxylic acid or tetracarboxylic dianhydride with a diol having a fluoroalkyl group or a fluoroalkoxy group.
• liquid repellent group examples include at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group.
• the fluoroalkyl group has 3 to 10 carbon atoms, preferably a fluoroalkyl group having 4 to 10 carbon atoms.
• a fluoroalkyl group examples include 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, and 3-perfluorobutyl.
• a monomer having a fluoroalkyl group having 3 to 10 carbon atoms may be copolymerized.
• the monomer having a C 3-10 fluoroalkyl group in the case where the component (A) is an acrylic polymer examples include 2,2,2-trifluoroethyl acrylate, 2,2,2-trimethyl Fluoroethyl 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 acrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2- (perfluorohexyl) ethyl acrylate, 2- (perfluorohexyl) ethyl methacrylate, 3- Perfluorohexyl 2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl
• Examples of the polyfluoroether group include an Rf group (a) having a polyfluoroether structure represented by the following formula 1. -(XO) 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
• each unit united by n Y represents the same group or different groups
• Y represents a hydrogen atom (only when a fluorine atom is not bonded to a carbon atom adjacent to an oxygen atom adjacent to Y), a monovalent saturated carbon atom having 1 to 20 carbon atoms
• a hydrogen group or a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms is shown, and n is an integer of 2 to 50.
• the total number of fluorine atoms in Formula 1 is 2 or more.
• X is preferably an alkylene group which is fluorinated by removing one hydrogen atom having 1 to 10 carbon atoms or a perfluorinated alkylene group having 1 to 10 carbon atoms.
• X is a perfluorinated alkylene group having 1 to 10 carbon atoms, and the same group or a different group is defined for each unit surrounded by n.
• Y represents a perfluorinated alkyl group having 1 to 20 carbon atoms.
• n represents an integer of 2 to 50. n is preferably 2 to 30, and more preferably 2 to 15. When n is 2 or more, the liquid repellency is good. When n is 50 or less, the polymer as component (A) is converted from a monomer having an Rf group (a), a hydroxy group, a carboxyl group, an amide group, an amino group, an N-alkoxymethylamide group, a blocked isocyanate group. Alternatively, when the synthesis is performed by copolymerization with a monomer having a trialkoxysilyl group or other monomer, the compatibility of the monomer is improved.
• the total number of carbon atoms in the Rf group (a) having the polyfluoroether structure represented by the formula 1 is preferably 2 to 50, and more preferably 2 to 30.
• the polymer which is (A) component has favorable liquid repellency.
• the polymer as the component (A) is prepared by combining a monomer having an Rf group (a) with a hydroxy group, a carboxyl group, an amide group, an amino group, an N-alkoxymethylamide group, a blocked isocyanate group or a trialkoxysilyl group. In the case of synthesizing by copolymerization with a monomer or other monomer, the compatibility of the monomer becomes good.
• 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 , -(CF 2 ) 5 CF 3 ,-(CF 2 ) 6 CF 3 ,-(CF 2 ) 7 CF 3 ,-(CF 2 ) 8 CF 3 ,-(CF 2 ) 9 CF 3 , and (CF 2 ) 11 CF 3 , — (CF 2 ) 15 CF 3 may be mentioned.
• 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.
• p represents an integer of 2 or 3
• q represents an integer of 1 to 20
• n represents an integer of 2 to 50.
• 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 preferable from the viewpoint of ease of synthesis.
• the Rf groups (a) in the polymer as the component (A) may all be the same or different.
• the silyl ether group means a group in which a hydroxy group of an alcohol is protected with a trialkylsilyl group, and is preferably a group represented by the following formula. -X 4 -Si (O-SiX 1 X 2 X 3 ) 3 (Wherein X 1 , X 2 and X 3 each independently represents an alkyl group having 1 to 3 carbon atoms, and X 4 represents an alkylene group having 1 to 6 carbon atoms.)
• a monomer having a silyl ether group may be copolymerized.
• Examples of the monomer having a silyl ether group when the component (A) is an acrylic polymer include methacryloxypropyltris (trimethylsiloxy) silane and acryloxypropyltris (trimethylsiloxy) silane.
• Examples of the polysiloxane group include a group (a) having a polysiloxane structure represented by Formula 3.
• the group (a) having a polysiloxane structure represented by Formula 3 is referred to as a pSi group (a).
• 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. Since the polymer as the component (A) exhibits good liquid repellency, R 1 and R 2 are preferably hydrogen, a methyl group or a phenyl group, and further, R 1 and R 2 of all siloxy units. Is preferably a methyl group. R 3 may contain a nitrogen atom, an oxygen atom, or the like.
• Examples of the monomer having a pSi group (a) include CH 2 ⁇ CHCOO (pSi) and CH 2 ⁇ C (CH 3 ) COO (pSi). However, pSi represents a pSi group (a).
• the monomer which has pSi group (a) may be used independently, and may use 2 or more types together.
• Examples of various modification methods for reacting a compound having a reactive site with a compound having a pSi group (a) include the following methods.
• a method in which a monomer having an epoxy group is copolymerized in advance and a compound having a carboxyl group at one end and a pSi group at one end is reacted.
• a method in which a monomer having an epoxy group is copolymerized in advance, and then a compound having an amino group at one end and a pSi group at one end is reacted.
• a method in which a monomer having an epoxy group is copolymerized in advance, and a compound having a mercapto group at one end and a pSi group at one end is reacted.
• a method in which a monomer having an amino group is copolymerized in advance, and then a compound having a carboxyl group at one end and a pSi group at one end is reacted.
• a method in which a monomer having an amino group is copolymerized in advance and a compound having an epoxy group at one end and a pSi group at one end is reacted.
• a method in which a monomer having a carboxyl group is copolymerized in advance and a compound having an epoxy group at one end and a pSi group at one end is reacted.
• a method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having an amino group at one end and a pSi group at one end is reacted.
• a group having a divalent polysiloxane structure may be contained in the initiator molecule main chain, and the initiator molecule has a monovalent group at the terminal portion or side chain.
• a group having a polysiloxane structure may be included.
• the initiator in which a group having a divalent polysiloxane structure is contained in the initiator molecular main chain include a compound having a group having a divalent polysiloxane structure and an azo group alternately.
• Examples of commercially available products include VPS-1001 and VPS-0501 (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).
• Examples of the monomer having an N-alkoxymethylamide group when the component (A) is an acrylic polymer include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-ethoxymethyl (meth) And (meth) acrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group such as acrylamide and N-butoxymethyl (meth) acrylamide.
• Examples of the monomer having a blocked isocyanate group when the component (A) is an acrylic polymer include 2- (0- (1′-methylpropylideneamino) carboxyamino) ethyl methacrylate, 2- (3 , 5-dimethylpyrazolyl) carbonylamino) ethyl and the like.
• Examples of the monomer having a trialkoxysilyl group when the component (A) is an acrylic polymer include, for example, 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate, 3- And triethoxysilylpropyl methacrylate.
• the component (A) is preferably a polymer further having (A3) at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group.
• Examples of the monomer having a carboxyl group when the component (A) is an acrylic polymer include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, and mono- (2- ( And methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.
• Examples of the monomer having a hydroxy group when the component (A) is an acrylic polymer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl.
• Examples of the monomer having an amide group when the component (A) is an acrylic polymer include acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and the like. Of these, methacrylamide is preferred.
• Examples of the monomer having an amino group when the component (A) is an acrylic polymer include aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate.
• the method for producing the polymer of the component (A) includes a monomer having a liquid repellent group, for example, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms, A monomer having a polyfluoroether group, a monomer having at least one group selected from the group consisting of an N-alkoxymethylamide group, a blocked isocyanate group and a trialkoxysilyl group, optionally a hydroxy group, a carboxyl group, an amide group, and A monomer having at least one group selected from the group consisting of amino groups, and, if desired, a further monomer other than the above (hereinafter also referred to as other monomer A) in a solvent in the presence of a polymerization initiator at 50 ° C.
• a monomer having a liquid repellent group for example, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms, A monomer having a polyfluoroether group, a mono
• the solvent used will not be specifically limited if it dissolves the monomer which comprises an alkali-soluble polymer, and the polymer which has a specific functional group.
• the solvent described in the (C) solvent mentioned later is mentioned.
• monomer A examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene.
• the polymer having a specific functional group thus obtained is usually in a solution state dissolved in a solvent.
• the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure.
• the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
• the powder of the specific copolymer may be used as it is, or the powder may be redissolved in a solvent (C) described later and used as a solution.
• the amount of the (A1) liquid repellent group introduced is preferably 5 mol% to 60 mol%, and preferably 5 mol% to 40 mol%, based on all repeating units. It is more preferable. When it is less than 5 mol%, the liquid repellent effect may not be achieved. If it is more than 60 mol%, problems such as aggregation may occur.
• the amount of the group selected from (A2) N-alkoxymethylamide group, blocked isocyanate group and trialkoxysilyl group is 5 mol% to 70 mol% with respect to all repeating units. Preferably, it is 5 mol% to 50 mol%. If it is less than 5 mol%, there may be a problem in the heat resistance and solvent resistance of the resulting film. If it is more than 60 mol%, the developability may be affected.
• the amount introduced is based on all repeating units. 5 mol% to 60 mol% is preferable, and 5 mol% to 40 mol% is more preferable. If it is less than 5 mol%, the effect of improving the heat resistance and solvent resistance of the resulting film may not be obtained. If it is more than 60 mol%, the liquid repellent repeating unit will be too small.
• the number average molecular weight of the polymer as the component (A) is preferably 2,000 to 100,000. More preferably, it is 3,000 to 50,000, and still more preferably 4,000 to 10,000. If the number average molecular weight is more than 100,000, a residue may be generated.
• the polymer of component (A) may be a mixture of a plurality of types of specific copolymers.
• the component (B) of the present invention is a resin having an alkali-soluble group.
• the alkali-soluble group include a phenolic hydroxy group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, phosphoric acid, a boronic acid, an active methylene group, and an active methine group.
• the active methylene group refers to a methylene group (—CH 2 —) having a carbonyl group at an adjacent position and having reactivity with a nucleophile.
• the active methine group has a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group in the active methylene group and has reactivity with a nucleophile.
• a group represented by the following formula (b1) is more preferable.
• R represents an alkyl group, an alkoxy group or a phenyl group, and a broken line represents a bond.
• examples of the alkyl group represented by R include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferable.
• examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. Of these, a methyl group, an ethyl group, an n-propyl group, and the like are preferable.
• examples of the alkoxy group represented by R include an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
• examples of such an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group. Of these, a methoxy group, an ethoxy group, an n-propoxy group, and the like are preferable.
• Examples of the group represented by the above formula (b1) include the following structures.
• the broken line represents a bond.
• an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxyl group, and having a number average molecular weight of 2,000 to 50,000 Preferably there is.
• the alkali-soluble resin as the component (B) may be an alkali-soluble resin having such a structure, and is not particularly limited with respect to the main chain skeleton and side chain type of the polymer constituting the resin.
• the alkali-soluble resin (B) has a number average molecular weight in the range of 2,000 to 50,000. If the number average molecular weight exceeds 50,000, the development residue is likely to be generated, and the sensitivity is greatly reduced. On the other hand, if the number average molecular weight is less than 2,000, the development is insufficient. At this time, there is a case where a considerable amount of film loss occurs in the exposed portion, resulting in insufficient curing.
• alkali-soluble resin (B) examples include acrylic resins, polyhydroxystyrene resins, polyimide precursors, and polyimides.
• an alkali-soluble resin composed of a copolymer obtained by polymerizing plural kinds of monomers (hereinafter referred to as a specific copolymer) can also be used as the component (B).
• the alkali-soluble resin as the component (B) may be a blend of a plurality of types of specific copolymers.
• the specific copolymer is a monomer that exhibits alkali solubility, that is, a monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group, and a group of monomers copolymerizable with these monomers. It is a copolymer formed with at least one selected monomer as an essential constituent unit, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is more than 50,000, a residue may be generated.
• the above “monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxy group” includes a monomer having a carboxyl group and a monomer having a phenolic hydroxy group. These monomers are not limited to those having one carboxyl group or one phenolic hydroxy group, and may have a plurality of monomers.
• the monomer having a carboxyl group examples include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl).
• Maleimide N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.
• Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, 4-hydroxyphenyl methacrylate and the like.
• the ratio of the unsaturated carboxylic acid derivative and / or the monomer having a phenolic hydroxy group and a polymerizable unsaturated group in the production of the component (B) alkali-soluble resin is used in the production of the component (B) alkali-soluble acrylic polymer.
• it is preferably 5 to 90 mol%, more preferably 10 to 60 mol%, and most preferably 10 to 30 mol%.
• the unsaturated carboxylic acid derivative is less than 5% by mass, the alkali solubility of the polymer is insufficient.
• the alkali-soluble resin which is the component (B) of the present invention is obtained by further copolymerizing a monomer having a hydroxyalkyl group and a polymerizable unsaturated group from the viewpoint of further stabilizing the pattern shape after curing. It is preferable.
• Examples of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, Examples thereof include 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerol monomethacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone and the like.
• the ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in the production of the component (B) alkali-soluble resin is preferably 10% by mass to 60% by mass, more preferably 5% by mass to 50% by mass, most preferably Preferable is 20% by mass to 40% by mass.
• the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 10% by mass, the effect of stabilizing the pattern shape of the copolymer may not be obtained.
• the amount is 60% by mass or more, the alkali-soluble group of the component (B) may be insufficient, and characteristics such as developability may be deteriorated.
• the alkali-soluble resin which is the component (B) of the present invention is preferably one obtained by further copolymerizing an N-substituted maleimide compound from the viewpoint of increasing the Tg of the copolymer.
• N-substituted maleimide compound examples include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
• the thing which does not have an aromatic ring from a transparency viewpoint is preferable, and what has an alicyclic skeleton from the point of developability, transparency, and heat resistance is more preferable, and a cyclohexyl maleimide is the most preferable especially.
• the ratio of N-substituted maleimide in the production of the alkali-soluble resin as component (B) is preferably 10% by mass to 60% by mass, more preferably 5% by mass to 50% by mass, and most preferably 20% by mass to 40% by mass. %.
• the N-substituted maleimide is less than 10% by mass, the Tg of the copolymer is lowered and the heat resistance may be inferior. In the case of 60% by mass or more, transparency may be lowered.
• the alkali-soluble resin (B) used in the present invention further has a self-crosslinkable group, or a hydroxy group, a carboxyl group, an amide A copolymer further having a group that reacts with at least one group selected from the group consisting of a group and an amino group (hereinafter also referred to as a crosslinkable group) is preferable.
• Examples of the self-crosslinking group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and a blocked isocyanate group.
• crosslinkable group examples include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group.
• the content is 0.1 to 0.9 per repeating unit in the resin of the component (B).
• 0.1 to 0.8 is more preferable.
• the alkali-soluble resin of component (B) is a self-crosslinking group such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl group and blocked isocyanate group, and N-alkoxymethyl.
• a crosslinkable group such as a group, an oxetane group, a vinyl group, and a blocked isocyanate group
• a self-crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, and an alkoxysilyl group. What is necessary is just to copolymerize.
• Examples of unsaturated compounds having radical polymerizability and having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide. Etc.
• Examples of the monomer having radical polymerizability and further having an N-hydroxymethyl group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.
• Examples of the monomer having radical polymerizability and having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane. Can be mentioned.
• Examples of unsaturated compounds having radical polymerizability and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, ⁇ -n-butyl acrylic acid.
• Glycidyl acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, ⁇ -ethylacrylic acid-6
• examples thereof include 7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate and the like.
• glycidyl methacrylate -6,7-epoxyheptyl methacrylate
• o-vinylbenzyl glycidyl ether o-vinylbenzyl glycidyl ether
• m-vinylbenzyl glycidyl ether p-vinylbenzyl glycidyl ether
• 3,4-epoxycyclohexyl methacrylate etc.
• these may be used alone or in combination.
• Examples of the unsaturated compound having radical polymerizability and further having an oxetane group include (meth) acrylic acid ester having an oxetane group.
• monomers 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
• Examples of the monomer having radical polymerizability and further having a vinyl group include 2- (2-vinyloxyethoxy) ethyl acrylate and 2- (2-vinyloxyethoxy) ethyl methacrylate.
• the content is preferably 10% by mass to 70% by mass, particularly preferably 20% by mass to 60% by mass, based on the total of all repeating units.
• this structural unit When this structural unit is less than 10% by mass, the heat resistance and surface hardness of the resulting cured film tend to be reduced. On the other hand, when the amount of this structural unit exceeds 70% by mass, the radiation-sensitive resin composition is stored. The stability tends to decrease.
• the acrylic polymer of component (B) may be a copolymer formed with monomers other than the above-described monomers (hereinafter referred to as other monomers) as constituent units.
• the other monomer may be any one that can be copolymerized with at least one selected from the group consisting of the above-mentioned monomer having a carboxyl group and a monomer having a phenolic hydroxy group.
• monomers include acrylic ester compounds, methacrylic ester compounds, maleimides, acrylamide compounds, acrylonitrile, styrene compounds and vinyl compounds.
• the specific example of the said other monomer is given, it is not limited to these.
• acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2- Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy Butyl acrylate, 2-methyl-2-adamantyl acrylate, 2 Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate,
• methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2- Trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxy Butyl methacrylate, 2 Methyl-2-adamantyl methacrylate, ⁇ -butyl
• acrylamide compound examples include N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxy.
• methyl acrylamide and N-butoxymethyl methacrylamide examples include methyl acrylamide and N-butoxymethyl methacrylamide.
• vinyl compound examples include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2 -Epoxy-5-hexene, 1,7-octadiene monoepoxide and the like.
• styrene compound examples include styrene having no hydroxy group, such as styrene, ⁇ -methylstyrene, chlorostyrene, and bromostyrene.
• the ratio of the other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and further preferably 20% by mass or less. If the amount is more than 80% by mass, the essential components are relatively reduced, so that it is difficult to sufficiently obtain the effects of the present invention.
• the method for obtaining the alkali-soluble resin that is the component (B) used in the present invention is not particularly limited.
• a carboxyl group, a phenolic hydroxy group, and a carboxylic acid or a phenolic hydroxy group are generated by the action of heat or acid.
• a crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, or a blocked isocyanate group, if desired
• solvent in which the coexistence of a polymerization initiator or the like by, by polymerization reaction at a temperature of 50 ° C. to 110 ° C. is obtained.
• the solvent used will not be specifically limited if it dissolves the monomer which comprises alkali-soluble resin, and the acrylic polymer which has a specific functional group.
• the solvent described in the (C) solvent mentioned later is mentioned.
• the acrylic polymer having a specific functional group thus obtained is usually in a solution state dissolved in a solvent.
• the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure.
• the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
• the powder of the specific copolymer may be used as it is, or the powder may be redissolved in a solvent (C) described later and used as a solution.
• polyimide precursors such as polyamic acid, polyamic acid ester, partially imidized polyamic acid, and polyimide such as carboxylic acid group-containing polyimide can be used. If it is soluble, the kind can be used without particular limitation.
• the polyamic acid which is a polyimide precursor, can generally be obtained by polycondensation of (a) a tetracarboxylic dianhydride compound and (b) a diamine compound.
• the (a) tetracarboxylic dianhydride compound is not particularly limited, and specific examples thereof include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′.
• Aromatic tetracarboxylic acid such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetra Carbo Alicyclic tetracarboxylic dianhydrides such as acid dianhydrides, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthal
• the diamine compound (b) is not particularly limited, and examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1 , 3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, Bis (4-amino-3-carboxyphenyl) sulfone, bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′- Diamino-3,3′-dicarboxy-5,5′-dimethylbiphenyl, 4,4′-diamino-3,3′-dicarboxy-5,
• Diamine compound 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene 1,4-diamino-2-mercaptobenzene, bis (4-amino-3-mercaptophenyl) ether, 2,2-bis (3-amino-4-mercaptophenyl) hexafluoropropane and the like having a thiophenol group
• Diamine compounds 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) ) Ether, 4,4′-diaminobiphenyl-3,3′-disulfonic acid, 4,4′-diamino-3,3′-dimethylbiphenyl-6,6′-disulfonic acid and the like di
• the compounding ratio of both compounds that is, (b) the total number of moles of the diamine compound / (a)
• the total number of moles of the tetracarboxylic dianhydride compound is preferably 0.7 to 1.2.
• a carboxylic anhydride when it superposes
• carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid There may be mentioned anhydrides, itaconic anhydride, tetrahydrophthalic anhydride and the like.
• the reaction temperature of the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from -20 ° C to 150 ° C, preferably -5 ° C to 100 ° C.
• the reaction temperature is appropriately selected within the range of 5 to 40 ° C. and the reaction time of 1 to 48 hours.
• the reaction temperature for protecting the terminal amino group with an acid anhydride can be selected from -20 ° C to 150 ° C, preferably -5 ° C to 100 ° C.
• the reaction of the diamine compound and the tetracarboxylic dianhydride compound can be performed in a solvent.
• Solvents that can be used in this case include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, Hexamethyl sulfoxide, m-cresol, ⁇ -butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3 -Ethyl ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol
• the solution containing the polyamic acid thus obtained can be used as it is for the preparation of the photosensitive resin composition. Further, the polyamic acid may be precipitated and isolated in a poor solvent such as water, methanol, ethanol, etc. and recovered for use.
• a poor solvent such as water, methanol, ethanol, etc.
• any polyimide can be used as the component (B).
• the polyimide used in the present invention is obtained by chemically or thermally imidizing 50% or more of a polyimide precursor such as polyamic acid.
• the polyimide used in the positive photosensitive resin composition of the present invention preferably has a group selected from a carboxyl group and a phenolic hydroxy group in order to impart alkali solubility.
• the method of introducing a carboxyl group or a phenolic hydroxy group into polyimide is a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of sealing an amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxy group, Alternatively, a method of setting the imidization rate to 99% or less when imidizing a polyimide precursor such as polyamide acid is used.
• Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization.
• a method of chemical imidization generally, a method of adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting at room temperature to 100 ° C. is used.
• a method for thermal imidization generally, a method in which a polyimide precursor solution is heated while being dehydrated at a temperature of 180 ° C. to 250 ° C. is used.
• a phenol novolac resin can be further used as the alkali-soluble resin of component (B).
• polyester polycarboxylic acid can also be used as the alkali-soluble resin of component (B).
• the polyester polycarboxylic acid can be obtained from an acid dianhydride and a diol by the method described in International Publication No. 2009/051186.
• the acid dianhydride include the above (a) tetracarboxylic dianhydride.
• the diol include bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyl, aromatic diols such as benzene-1,3-dimethanol, benzene-1,4-dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F.
• 1,4-cyclohexanediol 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and other alicyclic diols, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol And the like, and the like.
• the alkali-soluble resin (B) may be a mixture of a plurality of types of alkali-soluble resins.
• the ratio of the component (A) to the component (B) is such that the component (A) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (B).
• the (C) solvent used in the present invention dissolves the (A) component, the (B) component, and the later-described (D) component and (E) component as necessary, and is added as desired (F) ) Components and other additives are dissolved, and the type and structure thereof are not particularly limited as long as the solvent has such a dissolving ability.
• Examples of such a solvent (C) 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.
• (C) 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 safety Is preferable from the viewpoint of high.
• These solvents are generally used as solvents for photoresist materials.
• the 1,2-quinonediazide compound as component (D) is a compound having either a hydroxyl group or an amino group, both a hydroxyl group and an amino group, and these hydroxyl groups or amino groups (of hydroxyl groups and amino groups). In the case of having both, 10 mol% to 100 mol%, particularly preferably 20 mol% to 95 mol% of the total amount) is esterified or amidated with 1,2-quinonediazidesulfonic acid. Compounds can be used.
• 1,2-quinonediazidosulfonic acid examples include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and 1,2-benzoquinone-2- Examples thereof include diazide-4-sulfonic acid, and the 1,2-quinonediazidesulfonic acid chloride can be used in the reaction with the compound having either one or both of the hydroxy group and amino group.
• 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 the compound containing an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.
• Anilines such as 4,4′-diaminophenyl methane, 4,4′-diaminodiphenyl ether, and aminocyclohexane.
• examples of the compound containing both a hydroxyl group and an amino group include 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) Aminophenols such as -5-hydroxyphenyl) hexafluoropropane, 2-aminoethane Lumpur, 3-aminopropanol, mention may be made of alkanolamines,
• 1,2-quinonediazide compounds can be used alone or in combination of two or more.
• the content of the compound having a quinonediazide group of the component (D) in the positive photosensitive resin composition of the photosensitive resin composition of the present invention is 100 parts by mass in total of the component (A) and the component (B). Preferably they are 5 mass parts thru
• the amount is less than 5 parts by mass, the difference in dissolution rate between the exposed portion and the unexposed portion of the positive photosensitive resin composition in the developer becomes small, and patterning by development may be difficult. If the amount exceeds 100 parts by mass, the 1,2-quinonediazide compound will not be sufficiently decomposed by exposure in a short time and the sensitivity will decrease, or the component (D) will absorb light and the transparency of the cured film. May be reduced.
• the component (E) is a cross-linking agent, and is introduced into the composition when the positive photosensitive resin composition of the present invention satisfies the requirement (Z1). More specifically, it is a compound having a structure capable of forming a bridge structure by a thermal reaction with a thermally reactive site (for example, carboxyl group and / or phenolic hydroxyl group) of component (B). Specific examples will be given below, but the present invention is not limited thereto.
• the thermal crosslinking agent include those selected from (E1) a crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group, and (E2) a crosslinkable compound represented by formula (2). preferable. These crosslinking agents can be used alone or in combination of two or more.
• the crosslinkable compound having two or more substituents selected from the alkoxymethyl group and hydroxymethyl group as the component (E1) undergoes a crosslinking reaction by a dehydration condensation reaction when exposed to a high temperature during thermosetting.
• examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.
• alkoxymethylated glycoluril examples include, for example, 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) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
• glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high-condensation type, product name: Beccamin (trade name) manufactured by DIC Corporation) Registered trademark) J-300S, P-955, N) and the like.
• methylated urea resins (trade name: UFR (registered trademark) 65)
• Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV)
• urea / formaldehyde resin high-
• 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: Nicalac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.
• alkoxymethylated melamine examples include, for example, hexamethoxymethylmelamine.
• methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade name: My Coat (registered trademark)) 506, 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd.
• a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group may be used.
• the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned.
• Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.).
• Examples of commercially available products of the benzoguanamine compound include product name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.).
• 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, -Bis (methoxymethyl) phenol, 2,6-bis (methoxymethyl) cresol, 2,6-bis (methoxymethyl) -4-methoxyphenol, 3,3 ', 5,5'-tetrakis (methoxymethyl)
• the acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or the like
• a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or the like
• Polymers produced using methacrylamide compounds can also be used.
• Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl.
• Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
• the weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, more preferably 2,000 to 10,000.
• the positive photosensitive resin composition of this invention can contain the crosslinkable compound represented by following formula (2) as (E2) component. (Wherein k represents an integer of 2 to 10, m represents an integer of 0 to 4, and R 11 represents a k-valent organic group)
• the component (E2) is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by the formula (2). Specific examples thereof include the following formulas E2-1 and E2-2, and commercially available products shown below.
• EX-252 (trade name, manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179 (above, product name, manufactured by CIBA-GEIGY AG), Araldite CY-182, CY-192, CY-184 (above) , CIBA-GEIGY AG (trade name), Epicron 200, 400 (above, DIC Corporation trade name), Epicoat 871, 872 (above, Yuka Shell Epoxy Co., Ltd. trade name), ED -5661, ED-5562 (above, trade name manufactured by Celanese Coating Co., Ltd.), etc. It is possible. Moreover, these crosslinkable compounds can be used individually or in combination of 2 or more types.
• E component (E1) component, (E2)
• the bridge structure by thermal reaction with the heat-reactive part (for example, carboxyl group and / or phenolic hydroxyl group) of component (B) other than what was shown as a component.
• the heat-reactive part for example, carboxyl group and / or phenolic hydroxyl group
• Formable compounds can also be used.
• ethylene glycol diglycidyl ether polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′, -Tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, and N, N, N ', N',-tetraglycidyl-4,4'-diame Epoxy compounds such
• a polymer having two or more structures capable of forming a bridge structure by thermal reaction with the thermally reactive site (for example, carboxyl group and / or phenolic hydroxyl group) of the component (B) is used.
• the thermally reactive site for example, carboxyl group and / or phenolic hydroxyl group
• it can.
• a polymer produced by using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloxypropyltrimethoxy, etc.
• component (E) When the component (B) has a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group, a hydroxy group, a carboxyl group, an amide group, A compound having two or more groups represented by amino groups can be used as the component (E).
• crosslinkable compounds can be used alone or in combination of two or more.
• the content is 1 part by mass to 50 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). Part, preferably 1 part by weight to 40 parts by weight, more preferably 1 part by weight to 30 parts by weight.
• the content of the crosslinkable compound is low, the crosslink density formed by the crosslinkable compound is not sufficient, and therefore the effect of improving the heat resistance after the pattern formation, the solvent resistance, the long-term baking resistance, etc. May not be obtained.
• the rheology modifier, pigment, dye, storage stabilizer, antifoaming agent, adhesion promoter, or It can contain dissolution promoters such as polyphenols and polycarboxylic acids.
• the photosensitive resin composition of the present invention is a photosensitive resin composition containing the following component (A), component (B), component (C) and component (D), and, if desired, component (E) In addition, the composition may further contain one or more of other additives.
• Component A compound having a quinonediazide group.
• the photosensitive resin composition of the present invention is preferably a polymer having, as component (A), at least one group selected from the group consisting of (A3) a hydroxy group, a carboxyl group, an amide group, and an amino group. .
• the photosensitive resin composition of the present invention preferably further satisfies at least one of the following (Z1) and (Z2).
• the alkali-soluble resin of the component (B) further has a self-crosslinkable group or a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. Also have.
• the preferable example of the photosensitive resin composition of this invention is as follows. [1]: It contains 0.1 to 20 parts by weight of component (A), 5 to 100 parts by weight of component (D), and 100 parts by weight of component (B). ) A photosensitive resin composition dissolved in a solvent. [2]: 0.1 parts by mass to 20 parts by mass of the component (A), 5 parts by mass to 100 parts by mass of the component (D) with respect to 100 parts by mass of the component (B). ) A positive photosensitive resin composition dissolved in a solvent, wherein the alkali-soluble resin of component (B) further has a repeating unit having an epoxy group.
• the ratio of the solid content 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, and is, for example, 1% by mass to 80% by mass, Also, for example, 5 mass% to 60 mass%, or 10 mass% to 50 mass%.
• solid content means what remove
• (A) component (specific polymer) is melt
• examples include a method in which an alkali-soluble resin as component B), a 1,2-quinonediazide compound as component (D), and a crosslinking agent as component (E) as necessary are mixed in a predetermined ratio to obtain a uniform solution.
• (C) a solution of a copolymer obtained by a polymerization reaction in a solvent can be used as it is.
• the solution of the component (A) is used as a solution.
• a solvent (C) may be further added for the purpose of adjusting the concentration.
• the (C) solvent used in the process of forming the specific copolymer and the (C) solvent used for concentration adjustment at the time of preparing the positive photosensitive resin composition may be the same, May be different.
• the prepared positive photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 ⁇ m.
• the positive photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-dried in a hot plate or oven to form a coating film can do. Then, a positive photosensitive resin film is formed by heat-treating this coating film.
• a semiconductor substrate for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.
• a heating temperature and a heating time appropriately selected from the range 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 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 ⁇ m to 30 ⁇ m, for example, 0.2 ⁇ m to 10 ⁇ m, and further, for example, 0.3 ⁇ m to 8 ⁇ m. It is.
• a mask having a predetermined pattern is mounted, irradiated with light such as ultraviolet rays, and developed with an alkali developer, so that the exposed portion is washed out and a sharp relief pattern on the end face Is obtained.
• alkaline developer examples include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, and hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline.
• alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide
• hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline.
• a surfactant or the like can be added to these developers.
• a tetraethylammonium hydroxide 0.1 to 2.58 mass% aqueous solution is generally used as a photoresist developer, and this alkaline developer is also used in the photosensitive resin composition of the present invention. It can be developed satisfactorily without causing problems such as swelling.
• any of a liquid piling method, a dipping method, a rocking dipping 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 example, for 20 to 120 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and A patterned film is obtained.
• the pattern forming film is subjected to post-baking for thermosetting, specifically by heating using a hot plate, an oven, etc., thereby providing heat resistance, transparency, and flatness.
• a film having a good relief pattern with excellent water absorption and chemical resistance can be obtained.
• the post-bake is generally processed at a heating temperature selected from the range of 140 ° C. to 270 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.
• the positive photosensitive resin composition of the present invention has a high storage stability, a sufficiently high sensitivity, a very small film loss at an unexposed portion during development, and a coating having a fine pattern. A film can be formed.
• the present invention also relates to a cured film obtained using the above-described photosensitive resin composition.
• the cured film of the present invention can be advantageously used for display elements, and in particular, can be advantageously used as image-forming partition walls for display elements.
• the molecular weight of the polymer is measured as follows. [Measurement of molecular weight of polymer] The measurement of the number average molecular weight and the weight average molecular weight of the polymer was carried out under the following conditions using a GPC system manufactured by JASCO Corporation as a device and Shodex (registered trademark) KF-804L and 803L as columns.
• Mn number average molecular weight
• Mw weight average molecular weight
• MMA methyl methacrylate
• HEMA 2-hydroxyethyl methacrylate
• HPMA 4-hydroxyphenyl methacrylate
• HPMA-QD condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate and 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride
• CHMI N-cyclohexylmaleimide
• PFHMA 2- (perfluorohexyl) ethyl methacrylate
• TMSSMA methacryloxypropyltris (trimethylsiloxy) silane
• MAA methacrylic acid
• MAAm methacrylamide BMAA: N- (butoxymethyl) acrylamide
• MOI-BM 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate
• KBM-503 3-methacrylic acid
• Examples 1 to 18> and ⁇ Comparative Examples 1 to 3> By mixing the components (A) to (E) and the solvent in the composition shown in Table 1, and adjusting the addition amount of the solvent so that the solid content concentration of the final composition is 21.0% by mass, Examples Photosensitive resin compositions 1 to 13 and Comparative Examples 1 and 2 were prepared. Moreover, the photosensitive resin composition of Examples 14-18 and the comparative example 3 was prepared by adjusting the addition amount of a solvent so that the solid content concentration of a final composition might be 17.0 mass%. In addition, the composition ratio in Table 1 represents the ratio in solid content.
• the positive photosensitive resin composition was applied onto ITO-glass using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a thickness of 1.7 ⁇ m.
• the light intensity at 365 nm was measured by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. through a mask in which a rectangular pattern having a length of 50 ⁇ m and a width of 100 ⁇ m was formed on this coating film in a grid pattern so that the bank width was 30 ⁇ m.
• An ultraviolet ray of 5.5 mW / cm 2 was irradiated for a certain time.
• the film was developed by immersing it in a 2.58% TMAH aqueous solution for 20 seconds, and then washed with running ultrapure water for 20 seconds.
• the coating film on which the rectangular pattern was formed was heated at 230 ° C. for 30 minutes to be post-baked and cured.
• About 20 pl of solution was discharged onto the rectangular opening of the obtained cured film using an Inkjet Designer manufactured by Cluster Technology Co., Ltd. with a drive waveform of B, a repetition frequency of 1 kHz, and a drive voltage of 8V.
• the discharge solution the solution described in Japanese Patent Application No. 2016-141326 and Example 1-1 was used. The obtained results are shown in Table 2.

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