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
• • 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
  • C08F220/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
  • C08F220/70—Nitriles; Amides; Imides
• • 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
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
  • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
  • H05B33/22—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

• the present invention relates to a positive photosensitive resin composition and a cured film formed from it.
• a positive photosensitive resin composition is difficult to generate residue during pattern formation, has high water and oil repellency on the surface of the cured film, and can form a cured film that spreads well without overflowing the organic functional ink within the enclosed pattern.
• the present invention relates to a positive photosensitive resin composition, 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 display elements such as liquid crystal displays, EL displays, and micro LED displays, and as light-shielding materials and barrier rib materials 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 protection films, flattening films, insulating films, and the like.
• TFT thin film transistor
• organic EL electroactive EL
• photosensitive resin compositions are used as materials for forming these films, as they require a small number of steps to obtain the required pattern shape and have sufficient flatness. , has been widely used for a long time.
• the substrate is made to have ink-philic properties (hydrophilicity), and the bank surface is must be water repellent.
• Patent Document 5 a negative photosensitive resin composition in which a fluorine-based surfactant or a fluorine-based polymer is blended with a photosensitive organic thin film has been proposed (Patent Document 5), but it is difficult to improve the resolution. Positive-type photosensitive resins are required to achieve higher definition in display elements.
• the present invention has been made in view of the above circumstances, and the problem to be solved is to provide a cured film surface with high water repellency and high oil repellency when used in liquid crystal display elements, organic EL display elements, etc.
• a positive photosensitive resin composition that can form a cured film that has high inkjet wettability, high contact angle, and high flatness in the half-exposed area. It's about proposing things.
• the present inventors found that by mixing different types of alkali-soluble polymers, that is, by using an alkali-soluble resin having an N-hydroxyphenyl group in addition to a conventional alkali-soluble polymer, Carboxylic acid, which has high acidity, and a large amount of phenol, which has low acidity, can weaken the permeation inhibiting effect of a low-concentration developer due to alkali-insoluble groups, and the pattern is developed while being dissolved in the low-concentration developer.
• a first embodiment of the present invention is a positive photosensitive material capable of forming a cured film containing the following components (A1), (A2), (B), (C), (D) and (E) solvent.
• the component (A1) is an alkali-soluble compound obtained by copolymerizing a monomer mixture containing at least the compounds of the above (A1-I), the following (A1-II), and (A1-III).
• the positive photosensitive resin composition according to the first embodiment is an acrylic polymer; (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A1-III) an N-substituted maleimide compound;
• the component (A1) comprises a monomer mixture containing at least the compounds (A1-I), (A1-II), (A1-III), and the following (A1-IV).
• the positive photosensitive resin composition according to the second embodiment which is an alkali-soluble acrylic polymer obtained by polymerization; (A1-IV) a monomer having a phenolic hydroxyl group and a polymerizable unsaturated group;
• a fourth aspect of the present invention is a positive photosensitive resin according to the third aspect, wherein (A1-IV) the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group is p-hydroxyphenyl (meth)acrylate. is a composition;
• the component (A1) is an alkali-soluble acrylic polymer having a number average molecular weight of 2,000 to 30,000 in terms of polystyrene.
• the component (A2) is derived from at least one monomer selected from N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, or N-(hydroxyphenyl)maleimide.
• the component (A2) is an alkali-soluble resin having a number average molecular weight of 2,000 to 60,000 in terms of polystyrene.
• the positive photosensitive material according to any one of the first to seventh aspects, wherein the component (B) is a surfactant made of a polymer having a liquid-repellent group. is a resin composition;
• a ninth aspect of the present invention is the positive photosensitive resin according to the eighth aspect, wherein the liquid repellent group is at least one group selected from the group consisting of a fluoroalkyl group, a polyfluoroether group, and a polysiloxane group.
• a tenth aspect of the present invention is described in the eighth or ninth aspect, wherein the monomer unit constituting the polymer having a liquid repellent group is a monomer unit derived from an unsaturated hydrocarbon having the liquid repellent group.
• An eleventh form of the present invention is any one of the eighth to tenth forms, wherein the monomer units constituting the polymer having the liquid repellent group are monomer units derived from the alkoxylan compound having the liquid repellent group.
• the positive photosensitive resin composition according to one of the above; A twelfth aspect of the present invention is a surfactant according to any one of the eighth to eleventh aspects, wherein the component (B) is a surfactant made of a polymer having the liquid repellent group and a thermosetting group.
• the positive photosensitive resin composition described above; A thirteenth aspect of the present invention is a positive photosensitive material according to any one of the first to twelfth aspects, wherein the component (D) is a crosslinking agent made of a compound containing an epoxy group or a methoxymethyl group.
• a fourteenth form of the present invention is the first to thirteenth forms, wherein the component (B) is contained in 0.05 to 20 parts by mass with respect to a total of 100 parts by mass of the components (A1) and (A2).
• a fifteenth embodiment of the present invention is any one of the first to fourteenth embodiments, wherein the component (C) is contained in 5 to 100 parts by mass with respect to a total of 100 parts by mass of the components (A1) and (A2).
• the positive photosensitive resin composition according to one of the above; A sixteenth embodiment of the present invention is any one of the first to fifteenth embodiments, wherein the component (D) is contained in 5 to 50 parts by mass with respect to a total of 100 parts by mass of the components (A1) and (A2).
• the positive photosensitive resin composition according to one of the above; A seventeenth aspect of the present invention is a cured film formed from the positive photosensitive resin composition according to any one of the first to sixteenth aspects;
• An eighteenth aspect of the present invention is a display element having the cured film according to the seventeenth aspect;
• a nineteenth aspect of the present invention is a display element having the cured film according to the seventeenth aspect 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, leaves little residue after pattern formation even when using a low concentration developer, has high inkjet wettability, and has high oil repellency on the surface of the cured film.
• a cured film with a contact angle can be formed. Furthermore, it is also possible to form a cured film with high flatness in the half-exposed area.
• the photosensitive resin composition of the present invention is a positive type capable of forming a cured film containing the following components (A1), (A2), (B), (C), (D) and (E) solvent. It is a photosensitive resin composition.
• (A1) Component an alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least the following (A1-I); preferably the following compounds (A1-I), (A1-II), and (A1-III) An alkali-soluble acrylic polymer obtained by copolymerizing a monomer mixture containing alkali-soluble acrylic polymer, (A1-I) Unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride, (A1-II) Monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A1-III) N-substituted maleimide compound (however, N-(hydroxyphenyl)maleimide shall be (A1-IV)),
• Component (A1) is an alkali-soluble acrylic polymer obtained by polymerizing a monomer mixture containing at least (A1-I) an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride. Preferably, it is obtained by copolymerizing a monomer mixture containing at least the above (A1-I), (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, and (A1-III) an N-substituted maleimide compound. It is an alkali-soluble acrylic polymer.
• a monomer mixture containing at least the monomers (A1-I), (A1-II), (A1-III), and (A1-IV) having a phenolic hydroxyl group and a polymerizable unsaturated group is copolymerized. This is the resulting alkali-soluble acrylic polymer.
• the alkali-soluble acrylic polymer as the component (A1) may be any alkali-soluble acrylic polymer, and there are no particular limitations on the main chain skeleton and the type of side chains of the polymer constituting the acrylic polymer.
• the alkali-soluble acrylic polymer of component (A1) has a number average molecular weight of more than 30,000, the flattening performance against steps will decrease, while if the number average molecular weight is less than 2,000, it will have too low a number average molecular weight. If it is, curing may be insufficient during heat curing and solvent resistance may decrease. Therefore, the number average molecular weight is within the range of 2,000 to 30,000.
• the method for synthesizing the alkali-soluble acrylic polymer as component (A1) is simple, for example, by polymerizing a monomer mixture containing (A1-I) an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride. be. In some cases, it is a method of copolymerizing a monomer mixture containing the above (A1-I), (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, and (A1-III) an N-substituted maleimide compound. .
• a monomer mixture containing monomers having a phenolic hydroxyl group and a polymerizable unsaturated group (A1-I), (A1-II), (A1-III), and (A1-IV) is copolymerized. This is the way to do it.
• monomers constituting component (A1) are listed below, but the invention is not limited to these.
• examples of the monomer having an unsaturated carboxylic acid as the component (A1-I) 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, etc.
• Monomers containing unsaturated carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, etc. etc.
• 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, - Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, etc. It will be done.
• N-substituted maleimide compound examples include N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
• Examples of the monomer having a phenolic hydroxyl group and a polymerizable unsaturated group as the component (A1-IV) include p-hydroxystyrene, ⁇ -methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-(hydroxyphenyl ) acrylamide, N-(hydroxyphenyl) methacrylamide, p-hydroxyphenyl acrylate, p-hydroxyphenyl methacrylate, etc., and these can be used alone or in combination of two or more. Among these, monomers selected from p-hydroxyphenyl acrylate and p-hydroxyphenyl methacrylate are preferred.
• the acrylic polymer of component (A1) when obtaining the acrylic polymer of component (A1), it is possible to copolymerize with the monomers (A1-I), (A1-II), (A1-III) and (A1-IV). , and other monomers A can be used together.
• Specific examples of other monomers A include acrylic ester compounds, methacrylic ester compounds, maleimide, acrylamide compounds, acrylonitrile, and styrene compounds.
• Specific examples of other monomer A compounds are listed below, but the invention is not limited thereto.
• acrylic ester compounds 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, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate,
• methacrylic acid ester compounds 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, ⁇ -butyrolactone methacrylate, 8-methyl-8-tricyclode
• acrylamide compound examples include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-butoxy.
• styrene compound examples include styrene without a hydroxyl group, such as styrene, ⁇ -methylstyrene, chlorostyrene, and bromostyrene.
• the method for obtaining the alkali-soluble acrylic polymer used in the present invention is not particularly limited, for example, the alkali-soluble monomer (A1-I), preferably (A1-II), (A1-III), (A1-IV), It is obtained by carrying out a polymerization reaction at a temperature of 50 to 110° C. in a solvent in which other copolymerizable monomers and, if desired, a polymerization initiator are present.
• the solvent used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble acrylic polymer and the alkali-soluble acrylic polymer having a specific functional group.
• specific functional groups include carboxy groups, acid anhydrides, and the like.
• Specific examples of the solvent to be used include the solvents described in (E) Solvent described below.
• the alkali-soluble acrylic polymer having a specific functional group obtained in this way is called a specific copolymer, and is usually in the form of a solution dissolved in a solvent.
• the solution of the specific copolymer obtained as described above is poured into diethyl ether, water, etc. under stirring to cause reprecipitation, and the resulting precipitate is filtered and washed, and then under normal pressure or reduced pressure.
• powder of the specific copolymer can be obtained.
• the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved 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 in, for example, the below-mentioned solvent (E) and used in the form of a solution.
• E below-mentioned solvent
• the acrylic polymer as the component (A1) may be a mixture of multiple types of specific copolymers.
• Component (A2) of the present invention is an alkali-soluble resin having an N-hydroxyphenyl group and no carboxy group.
• the alkali-soluble resin of the component (A2) may be any alkali-soluble resin having such a structure, and there are no particular limitations on the main chain skeleton and the type of side chains of the polymer constituting the resin.
• Component (A2) is preferably an alkali-soluble resin having a number average molecular weight within the range of 2,000 to 60,000. If the number average molecular weight is too high (more than 60,000), development residues are likely to be generated and the sensitivity will be greatly reduced, while if the number average molecular weight is too small (less than 2,000), development will be difficult. In this case, a considerable amount of film loss may occur in the exposed areas, resulting in insufficient curing.
• alkali-soluble resin having an N-hydroxyphenyl group and no carboxy group as component (A2) examples include acrylic resins and polymaleimide resins.
• an alkali-soluble resin made of a copolymer obtained by polymerizing multiple types of monomers can also be used as the component (A2).
• the alkali-soluble resin of component (A2) may be a blend of multiple types of copolymers.
• the above-mentioned copolymer contains at least one type of monomer selected from the group of monomers having an N-hydroxyphenyl group and no carboxyl group, and monomers having no carboxyl group that are copolymerizable with these monomers. It is a copolymer formed with a monomer as an essential structural unit, and has a number average molecular weight of 2,000 to 60,000. If the number average molecular weight is more than 60,000, a residue may be produced.
• the above-mentioned monomer having an N-hydroxyphenyl group and not having a carboxy group is not limited to one having one N-hydroxyphenyl group, but may have a plurality of N-hydroxyphenyl groups.
• Examples of monomers having an N-hydroxyphenyl group and no carboxy group include N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, etc. .
• Examples of monomers having no carboxy group that can be copolymerized with monomers having an N-hydroxyphenyl group and no carboxy group include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, and Tolyl methacrylate, anthryl methyl 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, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate
• the ratio of monomers having an N-hydroxyphenyl group but not having a carboxy group in the production of the alkali-soluble resin as the component (A2) is as follows: Preferably it is 10 to 90 mol%, more preferably 20 to 85 mol%, most preferably 30 to 80 mol%. If the ratio of the monomer having an N-hydroxyphenyl group and no carboxy group is less than 10 mol%, the alkali solubility of the polymer will be insufficient.
• the proportion of the monomer having no carboxyl group that can be copolymerized with the monomer having an N-hydroxyphenyl group and no carboxyl group is 80% by weight. It is preferably at most 50% by weight, more preferably at most 20% by weight. If it exceeds 80% by weight, the essential components will be relatively reduced, making it difficult to obtain the full effect of the present invention.
• the method for obtaining the alkali-soluble resin, which is the component (A2) used in the present invention is not particularly limited. It is obtained by carrying out a polymerization reaction at a temperature of 50 to 110° C. in a solvent in which a monomer having no carboxyl group and, if desired, a polymerization initiator and the like are present. At this time, the solvent used is not particularly limited as long as it dissolves the monomer and alkali-soluble resin constituting the alkali-soluble resin, which is the component (A2). Specific examples include the solvents listed in (E) Solvent below.
• the alkali-soluble resin thus obtained is usually in the form of a solution dissolved in a solvent.
• the alkali-soluble resin solution obtained as described above may be reprecipitated by adding it to diethyl ether, water, etc. under stirring, and the resulting precipitate is filtered and washed, and then the solution is placed under normal pressure or reduced pressure. By drying at room temperature or by heating, it can be made into an alkali-soluble resin powder. By such an operation, the polymerization initiator and unreacted monomer coexisting with the alkali-soluble resin can be removed, and as a result, purified powder of the alkali-soluble resin can be obtained. If sufficient purification cannot be achieved in one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
• the powder of the alkali-soluble resin described above may be used as it is, or the powder may be redissolved in, for example, the below-mentioned solvent (E) and used in the form of a solution.
• E below-mentioned solvent
• the alkali-soluble resin of component (A2) may be a mixture of multiple types of alkali-soluble resins.
• Component (B) is a surfactant made of a polymer having a liquid-repellent group.
• liquid-repellent group examples include at least one group selected from fluoroalkyl groups, polyfluoroether groups, and polysiloxane groups.
• Examples of the fluoroalkyl group include an Ra group having a fluoroalkyl structure represented by the following formula 1. -X-Y...Formula 1
• X represents a single bond or an optionally substituted divalent saturated hydrocarbon group
• Y represents a fluorinated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
• the total number of fluorine atoms in Formula 1 is 3 or more.
• the number of carbon atoms is not particularly limited as long as it does not impair the liquid repellency, but is preferably 1 to 20, more preferably 1 to 10.
• the number of carbon atoms in the fluoroalkyl group is not particularly limited as long as it does not impair the liquid repellency, but is preferably from 1 to 40, more preferably from 1 to 30, even more preferably from 4 to 10. be.
• fluoroalkyl groups include trifluoromethyl group, 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-methyl
• a monomer having a fluoroalkyl group can be copolymerized. Further, a polymer having a reactive site can be reacted with a compound having a fluoroalkyl group and a functional group that reacts with the reactive site of the polymer.
• polyfluoroether group examples include an Rf group (a) having a polyfluoroether structure represented by the following formula 2. -(PO) n -Q ...Formula 2
• P 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 group or a different group
• Q is a hydrogen atom (limited to cases where a fluorine atom is not bonded to a carbon atom adjacent to an oxygen atom adjacent to Q), 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.
• the total number of fluorine atoms in Formula 2 is 2 or more.
• P is preferably a fluorinated alkylene group having 1 to 10 carbon atoms except for one hydrogen atom or a perfluorinated alkylene group having 1 to 10 carbon atoms.
• each unit enclosed by n represents the same group or a different group
• Q is a fluorinated alkyl group having 1 to 20 carbon atoms except for one hydrogen atom, or a perfluorinated group having 1 to 20 carbon atoms. Examples include those showing a fluorinated alkyl group.
• P is a perfluorinated alkylene group having 1 to 10 carbon atoms, and each unit surrounded by n represents the same group or a different group.
• Q represents a perfluorinated alkyl group having 1 to 20 carbon atoms.
• n represents an integer from 2 to 50. n is preferably 2 to 30, more preferably 2 to 15. When n is 2 or more, liquid repellency is good. If n is 50 or less, the compatibility of the monomers will be good when the polymer as component (B) is synthesized by copolymerization of the monomer having the Rf group (a) and other monomers.
• the total number of carbon atoms in the Rf group (a) consisting of a polyfluoroether structure represented by Formula 2 is preferably 2 to 50, more preferably 2 to 30. Within this range, the polymer as component (B) exhibits good liquid repellency.
• P 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 -, - Examples thereof include CF 2 CF 2 CF (CF 3 )- and CF 2 CF (CF 3 )CF 2 -.
• Q 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 and -(CF 2 ) 15 CF 3 are included.
• Rf group (a) having a polyfluoroether structure represented by Formula 2 includes the Rf group (a) represented by Formula 3.
• Rf group (a) represented by formula 3 -CF 2 O (CF 2 CF 2 O) n-1 CF 3 (n is 2 to 9), -CF( CF3 )O( CF2CF ( CF3 )O) n -1 C6F13 (n is 2 to 6), -CF( CF3 )O( CF2CF ( CF3 )O) n - 1 C3F7 (n is 2 to 6) are preferred from the viewpoint of ease of synthesis.
• the Rf groups (a) in the polymer that is component (B) may all be the same or different.
• Examples of the polysiloxane group include a group (b) having a polysiloxane structure represented by Formula 4.
• the group (b) having a polysiloxane structure represented by Formula 4 will be referred to as pSi group (b).
• pSi group (b) the group (b) having a polysiloxane structure represented by Formula 4 will be referred to as pSi group (b).
• pSi group (b) having a polysiloxane structure represented by Formula 4 will be referred to as pSi group (b).
• pSi group (b) having a polysiloxane structure represented by Formula 4 will be referred to as pSi group (b).
• pSi group (b) having a polysiloxane structure represented by Formula 4 will be referred to as pSi group (b).
• R 1 and R 2 independently represent hydrogen, an alkyl group, a cycloalkyl group, or an aryl group, and each siloxy unit may be the same or different. Since the polymer as component (B) exhibits good liquid repellency, R 1 and R 2 are preferably hydrogen, methyl group, or phenyl group, and moreover, R 1 and R 2 of all siloxy units is preferably a methyl group. Further, R 3 may contain a nitrogen atom, an oxygen atom, or the like.
• Methods for introducing pSi groups (b) into the polymer that is component (B) include methods of copolymerizing monomers having pSi groups (b), and methods for introducing pSi groups (b) into a polymer having a reactive site. Examples include various modification methods in which a polymer is reacted with a polymer, a method in which a polymerization initiator having a pSi group (b) is used, and the like.
• the monomer having pSi group (b) may be used alone, or two or more types may be used in combination.
• Examples of various modification methods in which a polymer having a reactive site is reacted with a compound having a pSi group (b) 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 group having a monovalent polysiloxane structure in the terminal portion or side chain of the initiator molecule.
• a group having a polysiloxane structure may be included.
• Examples of the initiator containing a group having a divalent polysiloxane structure in the main chain of the initiator molecule include compounds having alternating groups having a divalent polysiloxane structure and an azo group.
• 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% based on the total repeating units. If the amount is less than 5 mol%, the liquid repellency may not be effective. If the amount is more than 60 mol%, problems such as aggregation may occur.
• thermosetting functional group is not particularly limited as long as it forms a covalent bond when heated, and even a functional group that reacts with component (A1), component (A2), or component (D) can be used. It may also be a functional group that self-crosslinks between components.
• thermosetting functional groups include hydroxy group, carboxyl group, amide group, amino group, N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, and oxetane group. group, vinyl group, mercapto group, blocked isocyanate group, and the like.
• the method for producing the acrylic polymer having a liquid-repellent group as the component (B) is not particularly limited, but monomers having a liquid-repellent group and having radical polymerizability, such as monomers having a fluoroalkyl group, polyfluoroether groups, etc. and at least one kind of monomer having a polysiloxane group, a radically polymerizable monomer having a thermosetting group, and optionally a monomer other than the above (hereinafter also referred to as "other monomer B") in the presence of a polymerization initiator. It is obtained by carrying out a polymerization reaction in a solvent at a temperature of 50 to 110°C.
• the solvent used is not particularly limited as long as it dissolves the monomer constituting the acrylic polymer having a liquid repellent group, which is component (B), and the acrylic polymer having a liquid repellent group.
• Specific examples include the solvents listed in (E) Solvent below.
• radically polymerizable monomers having a liquid-repellent group include 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, and 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-perfluoro Hexyl-2-hydroxypropyl methacrylate, 2-(perfluorooctyl
• thermosetting group examples include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, and mono-(2-(methacryloyloxy)ethyl).
• monomers B 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 liquid-repellent group obtained in this way is usually in the form of a solution dissolved in a solvent.
• the solution of the acrylic polymer having a liquid-repellent group obtained as described above is poured into diethyl ether, water, etc. under stirring to cause reprecipitation, and the resulting precipitate is filtered and washed.
• an acrylic polymer powder having a liquid-repellent group can be obtained.
• the purified powder of the acrylic polymer having a liquid repellent group can be removed. can get. If sufficient purification cannot be achieved 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 acrylic polymer having a liquid-repellent group may be used as it is, or the powder may be redissolved in, for example, the solvent (E) described later and used as a solution. good.
• the acrylic polymer having a liquid repellent group as the component (B) may be a mixture of acrylic polymers having multiple types of liquid repellent groups.
• the method for obtaining the polysiloxane of the component (B) is not particularly limited. Polysiloxanes obtained by condensation are preferred.
• alkoxysilane monomers having a liquid-repellent group include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, and heptadecafluorodecyltrimethoxysilane.
• Silane heptadecafluorodecyltriethoxysilane, 2-(perfluorohexyl)ethyltrimethoxysilane, 2-(perfluorohexyl)ethyltriethoxysilane, 2-(perfluorobutyl)ethyltrimethoxysilane, 2-(perfluorohexyl)ethyltriethoxysilane, Examples include fluorobutyl)ethyltriethoxysilane.
• At least one type of alkoxysilane having a liquid-repellent group may be used, but multiple 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.
• alkoxysilanes having other organic groups examples include tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and 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 polysiloxane of component (B) preferably contains an alkoxysilane containing a liquid repellent group at 5 to 70 mol% of the total alkoxysilane, and preferably contains an alkoxysilane containing a thermosetting group at 10 to 70 mol% of the total alkoxysilane. It contains 95 mol%, and the remainder is obtained by polycondensing other alkoxysilanes.
• the content of alkoxysilane containing a liquid repellent group is more preferably 10 to 60 mol%.
• the content of the alkoxysilane containing a thermosetting group is more preferably 30 to 80 mol% of the total alkoxysilane.
• an alkoxysilane containing a liquid-repellent group, an alkoxysilane having a thermosetting group, other alkoxysilanes as necessary, and an organic solvent are hydroxylated.
• examples include a method of polycondensation by heating in the presence of an aqueous tetraethylammonium solution.
• the method is to add an aqueous tetraethylammonium hydroxide solution to an organic solvent in advance to obtain a solution of the aqueous tetraethylammonium hydroxide solution, and then mix the various alkoxysilanes described above while heating the solution.
• 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 contained in the alkoxysilane used.
• the above heating can be carried out at a liquid temperature of preferably 0 to 100°C, and preferably under reflux in a container equipped with a reflux pipe for several tens of minutes to prevent evaporation or volatilization of the liquid. It will last over ten hours.
• the alkoxysilanes may be mixed in advance as a mixture, or multiple types of alkoxysilanes may be mixed one after another.
• SiO 2 equivalent concentration the concentration of all silicon atoms in the charged alkoxysilane converted into oxides. It is preferable to heat within the range of . By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous polysiloxane-containing solution can be obtained.
• the organic solvent used when polycondensing alkoxysilane dissolves an alkoxysilane having a liquid repellent group, an alkoxysilane having a thermosetting group, and other alkoxysilanes as necessary.
• polymerization solvent dissolves an alkoxysilane having a liquid repellent group, an alkoxysilane having a thermosetting group, and other alkoxysilanes as necessary.
• solvent (E) it is preferable to use the solvent (E).
• alcohol is produced by the polycondensation reaction of alkoxysilane, alcohols and organic solvents having good compatibility with alcohols are used.
• the polymerization solvent examples include alcohols such as methanol, ethanol, propanol, and n-butanol, and 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 mixture of two or more of the above organic solvents may be used.
• the solution of the specific polysiloxane obtained by the above method may be used as it is in the photosensitive resin composition of the present invention, or if necessary, the solution of the specific polysiloxane obtained by the above method may be used as it is in the photosensitive resin composition of the present invention.
• the solution can be concentrated, diluted by adding a solvent, or replaced with another solvent.
• the solvent used when diluting by adding the solvent may be a solvent used in a polycondensation reaction or another solvent.
• the additive solvent is not particularly limited as long as the polysiloxane is uniformly dissolved therein, and one or more types can be arbitrarily selected and used.
• Examples of such additive solvents include, in addition to the solvent used in the polycondensation reaction, ketone solvents such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, and ester solvents such as methyl acetate, ethyl acetate, or ethyl lactate. .
• the alcohol generated during the polycondensation reaction of polysiloxane is heated under normal pressure or It is preferable to distill it off under reduced pressure.
• examples of the polymer as component (B) include polyamic acids, polyimides, polyamides, polyureas, polyurethanes, phenolic resins, epoxy resins, polyesters, and liquid-repellent polymers.
• examples include polymers in which a quinonediazide group is introduced into an acrylic polymer having a functional group.
• Polyamic acids, polyimides, polyamides, and polyureas include polyamic acids obtained by reacting diamines having fluoroalkyl or fluoroalkoxy groups and diamines having hydroxyl groups with acid dianhydrides, and polyimides obtained by imidizing polyamic acids. , a polyamide obtained by reacting the diamine with a dicarboxylic anhydride, or a polyurea obtained by reacting the diamine with a diisocyanate.
• polyurethane examples 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 resin examples include novolac resins obtained by polymerizing formaldehyde and a phenol having a fluoroalkyl group or a fluoroalkoxy group.
• 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.
• 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 ratio of component (B) to components (A1) and (A2) is 0.05 to 20 parts by mass of component (B) per 100 parts by mass of the total of component (A1) + component (A2). .
• the 1,2-quinonediazide compound which is component (C) is a compound having either a hydroxyl group or an amino group, or both a hydroxyl group and an amino group, When 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 gallic acid, ethyl gallic acid, 1,3,3-tris(4-hydroxyphenyl) Butane, 4,4-isopropridendiphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4- Hexafluoroisopropylidene diphenol, 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-trihydroxybenzophen
• the compounds containing the amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine. , 4,4'-diaminophenylmethane, anilines such as 4,4'-diaminodiphenyl ether, and aminocyclohexane.
• examples of compounds 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 Examples include aminophenols such as -5-hydroxyphenyl)hexafluoropropane, and alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohex
• 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 parts by mass, based on a total of 100 parts by mass of components (A1) and (A2).
• the amount is from 80 parts by mass, more preferably from 10 to 60 parts by mass.
• 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.
• it exceeds 100 parts by mass the 1,2-quinonediazide compound may not be sufficiently decomposed by short exposure, resulting in lower sensitivity or generation of residue between patterns.
• Component (D) is a crosslinking agent, and more specifically, it is a compound having a structure that can form a crosslinked structure by thermal reaction with the N-hydroxyphenyl group of component (A2). Specific examples will be given below, but the invention is not limited to these.
• the thermal crosslinking agent is selected from, for example, (D1) a crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group, and (D2) a crosslinkable compound represented by the following formula (5). and (D3) a crosslinking agent having two or more isocyanate groups is preferred. These crosslinking agents can be used alone or in combination of two or more.
• crosslinkable compound having two or more substituents selected from the alkoxymethyl group and hydroxymethyl group of component (D1) When the crosslinkable compound having two or more substituents selected from the alkoxymethyl group and hydroxymethyl group of component (D1) is exposed to high temperatures during thermosetting, the crosslinking reaction proceeds through a dehydration condensation reaction.
• examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast 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) Examples include urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone.
• glycoluril compounds products names: Cymel (registered trademark) 1170, Powder Link (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd.
• methylated urea resins product name: UFR (registered trademark) 65).
• butylated urea resin product name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV
• urea/formaldehyde resin manufactured by DIC Corporation (high condensation type, product name: Beckamine ( Examples include registered trademarks) J-300S, P-955, N), etc.
• alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine.
• Commercially available products include Mitsui Cytec Co., Ltd. (product name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (product names: Nikalac (registered trademark) BX-4000, BX-37, and BL-). 60, BX-55H), etc.
• alkoxymethylated melamine examples include hexamethoxymethylmelamine and the like.
• Commercially available products include methoxymethyl type melamine compounds (trade name: Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350), butoxymethyl type melamine compounds (trade name: Mycoat (registered trademark)) manufactured by Mitsui Cytec Co., Ltd.
• methoxymethyl type melamine compounds manufactured by Sanwa Chemical (trade name: Nikalak (registered trademark) MW-30, Nikalak MW-22, Nikalak MW-11, Nikalak MW-100LM, MS-001, Nikalak (registered trademark) MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade name: Nikalac (registered trademark) MX-45, MX-410, MX-302), etc. Can be mentioned.
• a melamine compound examples include high molecular weight compounds made from melamine and benzoguanamine compounds as described in US Pat. No. 6,323,310.
• Examples of commercial products of the melamine compound include the trade name Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercial products of the benzoguanamine compound include the trade name Cymel (registered trademark) 1123 (trade name). (manufactured by Mitsui Cytec Co., Ltd.), etc.
• 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'-d
• 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.
• Such polymers include, for example, poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, and N-ethoxymethyl.
• Examples 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 from 1,000 to 50,000, preferably from 1,500 to 20,000, more preferably from 2,000 to 10,000.
• crosslinking compounds can be used alone or in combination of two or more.
• the content is preferably 5 to 50 parts by mass based on a total of 100 parts by mass of component (A1) + component (A2). Parts by weight, more preferably 10 to 40 parts by weight. If the amount is less than 5 parts by mass, outgas may increase during the display element manufacturing process, components of the positive photosensitive resin composition may be eluted into other layers, and element characteristics and reliability may deteriorate. Moreover, if it exceeds 50 parts by mass, storage stability may be reduced, adhesion during development may be reduced, and sensitivity may be reduced.
• the positive photosensitive resin composition of the present invention can contain, as component (D2), a crosslinkable compound having an epoxy group represented by formula (5).
• component (D2) a crosslinkable compound having an epoxy group represented by formula (5).
• k represents an integer of 2 to 10
• m represents an integer of 0 to 4
• R 11 represents a k-valent organic group
• Epolead GT-401 Epolead GT-403, Epolead GT-301, Epolead GT-302, Celloxide 2021P, Celloxide 3000 (trade name, manufactured by Daicel Corporation), and Denacol EX-, an alicyclic epoxy resin.
• 252 trade name manufactured by Nagase Chemtechs Co., Ltd.
• Epiclon 200 Epolead GT-403
• Epiclon 400 trade names manufactured by DIC Corporation
• Epicort 871, 872 trade names manufactured by Yuka Shell Epoxy Co., Ltd.
• ED-5661 ED-5662
• Epolead GT-401 Epolead GT-403, Epolead GT-301, Epolead GT- 302, Celoxide 2021P, and Celoxide 3000 are preferred.
• component (D2) When component (D2) is selected as the crosslinking agent, the content is 5 to 50 parts by mass, preferably 7 to 40 parts by mass, and more preferably is 10 to 30 parts by mass. 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, resulting in increased outgas during the display element manufacturing process or loss of positive exposure to other layers. Components of the synthetic resin composition may be eluted, and device characteristics and reliability may deteriorate. On the other hand, if it exceeds 50 parts by mass, uncrosslinked crosslinkable compounds will be present, and the heat resistance after pattern formation, solvent resistance, resistance to long-term baking, etc. will decrease, and the photosensitive resin composition Storage stability may deteriorate.
• the (E) solvent used in the present invention dissolves the (A1) component, (A2) component, (B) component, (C) component, and (D) component, and other additives as described below that are added as desired.
• the type and structure of the solvent are not particularly limited as long as it has such dissolving ability.
• Such (E) solvents include, for example, 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 alone 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. This 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, pigments, storage stabilizers, antifoaming agents, adhesion promoters, as long as the effects of the present invention are not impaired. , or a solubility promoter such as polyhydric phenol or polyhydric carboxylic acid.
• the positive photosensitive resin composition of the present invention is capable of forming a cured film containing the following components (A1), (A2), (B), (C), (D) and (E) solvent.
• the composition is a positive photosensitive resin composition, and can further contain one or more other additives, if desired.
• Component (A1) an alkali-soluble acrylic polymer obtained by copolymerizing at least the following (A1-I); preferably at least the following (A1-I), the following (A1-II), and the following (A1-III) It is an alkali-soluble acrylic polymer obtained by copolymerizing; more preferably, at least the following (A1-I), the following (A1-II), the following (A1-III), and the following (A1-IV) are copolymerized.
• an alkali-soluble acrylic polymer obtained by (A1-I) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride, (A1-II) a monomer having a hydroxyalkyl group and a polymerizable unsaturated group, (A1-III) N-substituted maleimide compound, (A1-IV) Monomer having a phenolic hydroxyl group and a polymerizable unsaturated group (A2) Component: an alkali-soluble resin having an N-hydroxyphenyl group and not having a carboxyl group, (B) Component: surfactant, Component (C): 1,2-quinonediazide compound, (D) Component: Crosslinking agent (E) Solvent
• preferred examples of the positive photosensitive resin composition of the present invention are as follows. 0.05 to 20 parts by mass of component (B), 5 to 100 parts by mass of component (C), and 5 to 50 parts by mass of (D) for a total of 100 parts by mass of component (A1) + component (A2). A positive photosensitive resin composition containing components and these components being dissolved in (E) a solvent.
• the solid content ratio 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, but is, for example, 1 to 80% by mass, and, for example, 5 to 60% by weight, or 10 to 50% by weight.
• the solid content refers to all the 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, component (B) (polymer) is dissolved in (E) solvent, and (A1 )
• component (B) polymer
• (A2) polymer
• the alkali-soluble acrylic polymer as the component, the alkali-soluble resin as the component (A2), the 1,2-quinonediazide compound as the component (C), and the crosslinking agent as the component (D) are mixed in a predetermined ratio to form a uniform solution.
• method or a method in which other additives are further added and mixed as necessary at an appropriate stage of this preparation method.
• the solution of the copolymer obtained by the polymerization reaction in the (E) solvent can be used as it is; in this case, the solution of the (B) component can be used as is.
• the (E) solvent used in the copolymer formation process and the (E) solvent used for concentration adjustment during the preparation of the positive photosensitive resin composition may be the same or different. It's okay.
• the prepared solution of the positive photosensitive resin composition is 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 can be applied to semiconductor substrates (e.g., silicon/silicon dioxide-coated substrates, silicon nitride substrates, substrates coated with metals 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 slit coating, inkjet coating, etc., and then pre-drying on a hot plate or oven to form a coating film. can do. Thereafter, 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 metals such as aluminum, molybdenum, chromium, etc., glass substrates, quartz substrates, ITO substrates.
• spin coating flow coating, roll coating, slit coating, spin coating following slit coating, inkjet coating,
• a heating temperature and heating time appropriately selected from a 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°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, and further, for example, 0.3 to 5 ⁇ m. It is.
• a mask with a predetermined pattern is attached to the coating film obtained above, and by irradiating it with light such as ultraviolet rays and developing it with an alkaline developer, the exposed areas are washed out and a sharp relief pattern is formed on the edge surface. is obtained.
• a positive photosensitive resin film formed from the positive photosensitive resin composition of the present invention can also be applied to a gray scale mask and a halftone mask. By simply attaching a grayscale mask or halftone mask with a predetermined pattern to the coating film obtained above, irradiating it with light such as ultraviolet rays, and developing it with an alkaline developer, one material is sufficient. A lyophilic portion and a lyophobic portion having flatness can be formed.
• alkaline developers examples include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide; hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline Examples include alkaline aqueous solutions such as quaternary ammonium aqueous solutions and amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers.
• alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide
• hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline
• alkaline aqueous solutions such as quaternary ammonium aqueous solutions and amine aqueous solutions such as ethanolamine, propylamine, and
• a 0.1 to 3% by mass aqueous solution of tetramethylammonium hydroxide is generally used as a developer for photoresists, and this alkaline developer is also used in the photosensitive resin composition of the present invention.
• Good development can be achieved without causing problems such as swelling.
• a relief pattern can be obtained more effectively.
• any of the liquid piling method, dipping method, rocking immersion method, etc. can be used.
• the developing 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, and then air-dried using compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and A patterned membrane is obtained.
• the pattern-formed film is post-baked for thermosetting, specifically by heating using a hot plate, oven, etc., to improve heat resistance, transparency, and flattening properties. , a film with excellent low water absorption, chemical resistance, etc., and a good relief pattern can be obtained.
• Post-baking is generally carried out 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 for 15 to 90 minutes when in an oven. This method is adopted.
• the positive photosensitive resin composition of the present invention has high storage stability, sufficiently high sensitivity, very little film loss in unexposed areas during development, and coatings with fine patterns. A film can be formed. Further, the coating film (cured film) obtained in this way has a characteristic that there is almost no pattern residue. Therefore, it is suitable for use as a light-shielding material or partition wall material compatible with inkjet systems, along with various films such as interlayer insulating films, protective films, and insulating films in liquid crystal displays and organic EL displays.
• Residue evaluation Equipment Scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation (5) Contact angle evaluation device: Drop Master manufactured by Kyowa Interface Science Co., Ltd. (6) Wettability evaluation Device: Inkjet Designer manufactured by Cluster Technology Co., Ltd. (7) Evaluation of flatness of half exposed area Equipment: Semiconductor motorized inspection microscope MX61A manufactured by Olympus Corporation
• MMA methyl methacrylate
• HEMA 2-hydroxyethyl methacrylate
• HPMA 4-hydroxyphenyl methacrylate
• CHMI N-cyclohexylmaleimide
• MAA methacrylic acid
• AIBN ⁇ , ⁇ '-azobisisobutyronitrile
• QD 4,4'-[4 -(4-Hydroxyphenyl)butane-2,2-diyl]
• the coating film on which the line and space pattern was formed was post-baked and cured by heating at a temperature of 230° C. for 30 minutes.
• the opening residue of the cured line-and-space pattern was observed using a scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation, and evaluated according to the following criteria. Note that assuming actual specifications, at least B is required, and A is desirable. A: Particularly good with no residue within the pattern B: Good with no residue within the pattern C: There is residue within the pattern
• the film was developed by immersing it in a 0.40% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds.
• the coating film on which the rectangular pattern was formed was post-baked and cured by heating at a temperature of 230° C. for 30 minutes.
• a fixed shot (approximately 3 pL per shot) of the organic functional ink prepared in Synthesis Example 7 was discharged into the opening of the cured rectangular pattern and air-dried to form an organic functional film.
• the state of the organic functional film was observed using an optical microscope and evaluated according to the following criteria. Note that assuming actual specifications, at least B is required, and A is desirable.
• B Good without repelling or overflowing after 6 shots
• C Repelling or overflowing occurring after 6 shots
• the film was developed by immersing it in a 0.40% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds.
• the coating film on which the rectangular pattern was formed was post-baked and cured by heating at a temperature of 230° C. for 30 minutes. The surface of the cured rectangular pattern was observed using an optical microscope and evaluated according to the following criteria.
• C Peeling or unevenness occurring
• the cured films made of the positive photosensitive compositions of Comparative Examples 1 and 3, in which A1-1 and A1-2 were used as the alkali-soluble acrylic polymer A1 and no alkali-soluble resin A2 were used showed inkjet wettability. It was shown that the contact angle was inferior.
• the cured film made of the positive photosensitive composition of Comparative Example 5 in which A1-2 was used as the alkali-soluble acrylic polymer A1 and the alkali-soluble resin A2 was not used the cured film had excellent inkjet wettability and contact angle; It was shown that the flatness of the half-exposed area was poor.
• Comparative Examples 2 and 4 in which A1-1 was used as the alkali-soluble acrylic polymer A1, A2-1 was used as the alkali-soluble resin A2, and no surfactant was added, showed excellent residue but poor inkjet wettability and contact angle. It was done.

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• 2023
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