Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • 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
  • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
  • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
• • 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
  • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
• • 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
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

• the present invention relates to a positive photosensitive composition using a polysiloxane compound, further relates to a cured product using the positive photosensitive composition, and a method for producing a permanent resist using the positive photosensitive composition. It is.
• liquid crystal display devices and organic EL display devices are increasing due to the progress of the information society and the spread of multimedia systems.
• an active matrix substrate provided with a switching element such as a thin film transistor (TFT) for each pixel is used.
• TFT thin film transistor
• On the active matrix substrate a large number of scanning wirings and signal wirings intersecting these scanning wirings through an insulating film are formed.
• the scanning wiring, signal wiring, insulating film, etc. of the active matrix substrate are formed by repeating patterning by photolithography on a conductive film or insulating film formed by sputtering, CVD, coating, or the like (for example, patents) References 1 and 2).
• a photoresist is used for photolithography, and a resist (permanent resist) that is used as an insulating film or a protective film without being peeled after patterning has also been developed.
• a permanent resist is used for an active matrix substrate, not only chemical resistance (acid resistance, alkali resistance, solvent resistance) but also high heat resistance and chemical resistance after a high heat history are required. This is due to the following reasons. That is, in an active matrix substrate, a TFT having a polycrystalline silicon thin film as an active layer is formed on a glass substrate which is an insulating substrate, and the polycrystalline silicon thin film is covered with an insulating film.
• the heat resistance in the conventional permanent resist is a heat resistance that can withstand soldering on a printed wiring board at a temperature of 260 ° C. for several minutes (see, for example, Patent Document 4). It differs greatly from the heat resistance required for resists and the chemical resistance after high heat history.
• silicone resins are excellent in transparency, insulation, heat resistance, chemical resistance, etc.
• photoresists based on silicone resins have also been developed.
• a photoresist based on a silicone resin into which a phenolic hydroxyl group or a cyclic siloxane structure is introduced has been studied.
• a conventionally known photoresist based on a silicone resin into which a phenolic hydroxyl group or a cyclic siloxane structure is introduced is excellent in heat resistance and chemical resistance after high-temperature heat history, but the film loss during development is large.
• the development margin in the development process (the width of time for which the development time is optimal) is narrow. Since the developer permeates easily and peels off, it is necessary to strictly control the development time, which is problematic in terms of product yield.
• an object of the present invention is to provide a positive photosensitive composition that is excellent in heat resistance and chemical resistance after high temperature thermal history, has little film loss during development, and has a large development margin in the development process, and this positive photosensitive composition
• An object of the present invention is to provide a permanent resist using an object and a method for producing the permanent resist.
• the present invention (A) Silanol group-containing polysiloxane having a structure obtained by hydrolyzing and condensing a cyclic siloxane compound represented by the following general formula (1) and an alkoxysilane compound represented by the following general formula (2) as the component (A) Compound, (B) As a component, a compound having at least two epoxy-containing organic groups, The object is achieved by providing a positive photosensitive composition characterized by containing diazonaphthoquinones as component (C) and an organic solvent as component (D).
• this invention achieves the said objective by providing the hardened
• the positive photosensitive composition is applied to a target material, pre-baked, exposed, alkali developed, then bleached, and then post-baked at a temperature of 120 to 400 ° C.
• the above object is achieved by providing a method for producing a permanent resist characterized by the following.
• the present invention also provides a liquid crystal display device and an organic EL display device having an active matrix substrate having a permanent resist obtained by using the positive photosensitive composition as an insulating layer or a planarizing film. To do.
• a positive photosensitive composition having excellent heat resistance and chemical resistance after high-temperature heat history, little film loss during development, and a large development margin in the development process, and the positive photosensitive composition It is possible to provide a method for producing a permanent resist using A permanent resist made of a cured product of the positive-type positive-type photosensitive composition is suitable as an insulating layer or a planarizing film for liquid crystal display devices and organic EL display devices having an active matrix substrate.
• the component (A) according to the present invention has a structure obtained by subjecting the cyclic siloxane compound represented by the general formula (1) and the arylalkoxysilane compound represented by the general formula (2) to a hydrolysis / condensation reaction. It is a silanol group-containing polysiloxane compound.
• the cyclic siloxane compound represented by the general formula (1) will be described.
• a plurality of R 1 s may be the same as or different from each other, and R 2 , R 3 and X may be the same or different from each other when there are a plurality of R 1 s. May be.
• R 1 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
• alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, t-butyl and the like.
• aryl group having 6 to 10 carbon atoms include phenyl, ethylphenyl, tolyl, cumenyl, xylyl, pseudocumenyl, mesityl, t-butylphenyl, benzyl, phenethyl and the like.
• R 1 is preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or phenyl, more preferably methyl, ethyl, or phenyl, and most preferably methyl in view of industrial availability.
• R 2 represents a divalent hydrocarbon group having 2 to 10 carbon atoms.
• the divalent hydrocarbon group having 2 to 10 carbon atoms include ethylene, propylene, 1-methylethylene, 2-methylethylene, tetramethylene, pentamethylene, 3-methylpentamethylene, hexamethylene, octamethylene, decamethylene, cyclohexane 1,4-diyl, 2-phenylethane-1,2'-diyl, 2-phenylethane-1,4'-diyl, 2-phenylpropane-1,4'-diyl, etc. From the viewpoint of availability and heat resistance, ethylene, 2-methylethylene and 2-phenylethane-1,4′-diyl are preferable, ethylene and 2-methylethylene are more preferable, and ethylene is most preferable.
• R 3 represents a divalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
• the divalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms include ethylene, propylene, 1-methylethylene, 2-methylethylene, tetramethylene, pentamethylene, 3-methylpentamethylene, hexamethylene, octamethylene, Decamethylene and the like are mentioned, and R 3 is preferably ethylene, 2-methylethylene or propylene, more preferably ethylene, from the viewpoint of industrial availability and heat resistance.
• Position of the phenolic hydroxyl groups of the benzene ring linked to the R 3, relative to R 3, ortho, meta-position may be either para-position, heat resistance higher, easy industrial availability of raw materials For this reason, it is preferably in the ortho or para position relative to R 3 , and more preferably in the para position.
• X represents a group represented by the general formula (3), a group represented by the general formula (4), or a group represented by the general formula (5).
• R 6 represents an alkyl group having 1 to 4 carbon atoms.
• Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, and t-butyl.
• R 6 represents an alkoxysilane compound represented by the general formula (2) Methyl and ethyl are preferable, and methyl is more preferable.
• R 7 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
• Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R 1 , and R 7 is preferably methyl or phenyl because the heat resistance is further improved. More preferred is methyl.
• b represents a number of 1 to 3, preferably 2 to 3, and more preferably 3 because of good reaction with the alkoxysilane compound represented by the general formula (2).
• R 9 represents an alkyl group having 1 to 4 carbon atoms
• R 10 represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.
• the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified for R 1 .
• R 9 is preferably methyl or ethyl, more preferably methyl, because of good reactivity with the alkoxysilane compound represented by the general formula (2).
• R 10 is preferably methyl or phenyl, more preferably methyl, because the heat resistance is further improved.
• c represents a number of 1 to 3, preferably 2 to 3, and more preferably 3, because of good reaction with the alkoxysilane compound represented by the general formula (2).
• d represents a number of 1 or 2, and when R 10 represents a residue obtained by removing a vinyl group from a divinyl compound having a molecular weight of 1000 or less, d is 1, and R 10 represents a vinyl group from a trivinyl compound having a molecular weight of 1000 or less. In the case of representing an excluded residue, d is 2.
• R 8 represents a residue obtained by removing a vinyl group from a divinyl compound or trivinyl compound having a molecular weight of 1000 or less.
• a divinyl compound or trivinyl compound is a compound represented by the following general formula (4a), and examples thereof include compounds represented by the following general formulas (6) to (12).
• R 13 to R 16 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
• alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include groups exemplified by R 1 , and methyl, ethyl, propyl, and phenyl are preferable because of better heat resistance. Methyl, ethyl, and phenyl are more preferable, and methyl is most preferable.
• f represents a number from 0 to 6, and is preferably a number from 0 to 2, more preferably a number from 0 to 1, since industrial availability is easy.
• preferred compounds include dimethyldivinylsilane, diethyldivinylsilane, diphenyldivinylsilane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-tetraethyl-1,3-divinyldisiloxane, 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane, 1,1,3,3,5,5-hexamethyl- 1,5-divinyltrisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-divinyltrisiloxane, 1,1,3,3,5,5-hexaphenyl-1,5-divinyl And trisiloxane, 1,1,3,3,5,5,7,7-octamethyl-1,7-divinyltetrasiloxane, and the like.
• 1,1,3,3-tetramethyl-1,3-divinyl More preferred are disiloxane, 1,1,3,3-tetraethyl-1,3-divinyldisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-divinyltrisiloxane, More preferred is 3,3-tetramethyl-1,3-divinyldisiloxane.
• R 17 to R 19 each independently represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
• alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include groups exemplified by R 1 , and methyl, ethyl, propyl, and phenyl are preferable because of better heat resistance. Methyl, ethyl, and phenyl are more preferable, and methyl is most preferable.
• g represents a number from 1 to 4
• h represents a number from 0 to 4.
• g is a number of 1 to 2 and h is a number of 0 to 2, more preferably a number of g is 1 and h is 0 to 1.
• preferable compounds include tris (dimethylvinylsiloxy) methylsilane, tris (dimethylvinylsiloxy) phenylsilane, tris ⁇ (dimethylvinylsiloxy) dimethylsiloxy ⁇ methylsilane, and the like. Tris (dimethylvinylsiloxy) methylsilane is more preferable.
• R 20 and R 21 each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms
• d has the same meaning as in the general formula (4).
• the alkyl group having 1 to 10 carbon atoms and the aryl group having 6 to 10 carbon atoms include groups exemplified by R 1 , and methyl and ethyl are preferable because of better heat resistance. preferable.
• preferred compounds are 1,2-bis (dimethylvinylsilyl) benzene, 1,3-bis (dimethylvinylsilyl) benzene, and 1,4-bis (dimethylvinyl).
• Silyl) benzene 1,2-bis (diethylvinylsilyl) benzene, 1,3-bis (diethylvinylsilyl) benzene, 1,4-bis (diethylvinylsilyl) benzene, 1,3,5-tris (dimethylvinyl) Silyl) benzene), 1,3,5-tris (diethylvinylsilyl) benzene) and the like, and are easy to obtain industrially and have better heat resistance. More preferred are vinylsilyl) benzene and 1,4-bis (dimethylvinylsilyl) benzene, and 1,4-bis (dimethylvinylsilyl) benzene. A further preferred.
• d is synonymous with General formula (4).
• Examples of the compound represented by the general formula (9) include 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 1,2,4-trivinylbenzene, 1,3,5-tri Examples thereof include vinylbenzene, and 1,4-divinylbenzene is preferred because it is easily available industrially and has better heat resistance.
• d is synonymous with General formula (4).
• Examples of the compound represented by the general formula (10) include 1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane, 1,2,4-trivinylcyclohexane, 1,3,5-tri Examples thereof include vinylcyclohexane, and 1,4-divinylcyclohexane is preferred because it is easily available industrially and has better heat resistance.
• R 22 represents an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an allyl group.
• Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R 1 .
• R 22 is preferably methyl, ethyl, or allyl, more preferably methyl or allyl, because of better heat resistance.
• preferable compounds include diallyl methyl isocyanurate, diallyl ethyl isocyanurate, triallyl isocyanurate, and triallyl isocyanurate is more preferable.
• R 23 to R 25 each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.
• alkyl group having 1 to 10 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified as R 1 , and methyl, ethyl, propyl, and phenyl are preferable because of better heat resistance. Methyl, ethyl, and phenyl are more preferable, and methyl is most preferable.
• d has the same meaning as in the general formula (4), and i represents a number from 0 to 4 where d + i is 3 to 6.
• d + i is preferably a number of 4 to 5, more preferably 4.
• preferred compounds include 2,2,4,6-tetramethyl-4,6-divinylcyclotrisiloxane, 2,2,4,4,6,8- Hexamethyl-6,8-divinylcyclotetrasiloxane, 2,2,4,4,6,6,8,10-octamethyl-8,10-divinylsilopentasiloxane, 2,4,6-trimethyl-2,4 Examples thereof include 6-trivinylcyclotrisiloxane and 2,2,4,6,8-pentamethyl-4,6,8-trivinylcyclotetrasiloxane.
• the divinyl compound or trivinyl compound having a molecular weight of 1000 or less capable of providing the group represented by R 8 in the general formula (4) has been described in detail above.
• compounds represented by the general formulas (9) to (11) are preferable, 1,4-divinylbenzene, 1,2,4-trivinylcyclohexane, triallyl isocyanurate are more preferable, and 1,4 -Divinylbenzene is most preferred.
• R 11 and R 12 represent an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
• Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R 1 in the general formula (1), and the aryl having 6 to 10 carbon atoms is easy to produce. Group is preferred, with phenyl being preferred.
• e represents a number of 1 to 10 and is preferably a number of 1 to 5 and more preferably a number of 1 to 3 because production is easy.
• X is preferably a group represented by general formula (3) because it is easy to produce and has good heat resistance.
• the cyclic siloxane compound represented by the general formula (1) may be used alone or in combination of two or more. If the ratio of n to m is too small, the film loss during development is large and the development margin in the development process is small. If it is too large, the resist residue during development increases. Is preferably 10 to 10, more preferably 2.8 to 9, and most preferably 3 to 8.
• the cyclic siloxane compound represented by the general formula (1) includes, for example, a cyclic siloxane compound represented by the following general formula (1a), a carboxylic acid compound represented by the following general formula (13), and the following general formula (14).
• the phenol compound represented is hydrosilylated to obtain an intermediate represented by the general formula (1b), and the intermediate represented by the above general formulas (3) to (5) is further introduced into the intermediate. be able to.
• cyclic siloxane compounds represented by the general formula (1a) include, for example, 2,4,6-trimethylcyclotrisiloxane, 2,4,6-triethylcyclotrisiloxane, 2,4, 6-triphenylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,2,4,6,8-pentamethylcyclotetrasiloxane, 2,2,2,4,4,6, 8-hexamethylcyclotetrasiloxane, 2,4,6,8-tetraethylcyclotetrasiloxane, 2,4,6,8-tetraphenylcyclotetrasiloxane, 2-ethyl-4,6,8-trimethylcyclotetrasiloxane, 2-phenyl-4,6,8-trimethylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclo 2,4,6,8,10-pentaethylcyclopentas
• carboxylic acid compound represented by the general formula (13) examples include acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8- Nonenic acid, 9-decenoic acid, 10-undecenoic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2-allylbenzoic acid, 3-allylbenzoic acid, 4-allylbenzoic acid, 2 -Isopropenyl benzoic acid, 3-isopropenyl benzoic acid, 4-isopropenyl benzoic acid and the like are listed, and are easily available industrially.
• Acrylic acid, methacrylic acid and 4-vinylbenzoic acid are preferred, and acrylic acid and methacrylic acid are more preferred. Only 1 type may be used for the carboxylic acid compound represented by General formula (13), and 2 or more types may be used for it.
• phenol compound represented by the general formula (14) examples include 2-vinylphenol, 3-vinylphenol, 4-vinylphenol, 2-allylphenol, 3-allylphenol, 4-allylphenol, 2-isopropenyl. Phenol, 3-isopropenylphenol, 4-isopropenylphenol, etc. are listed, and since they are easily available industrially, 2-vinylphenol, 3-vinylphenol, 4-vinylphenol, 4-isopropenylphenol are 2-vinylphenol and 4-vinylphenol are more preferable, and 4-vinylphenol is most preferable. Only 1 type may be used for the phenol compound represented by General formula (14), and 2 or more types may be used for it.
• the hydrosilylation reaction between the cyclic siloxane compound represented by the general formula (1a), the carboxylic acid compound represented by the general formula (13), and the phenol compound represented by the general formula (14) is preferably performed using a catalyst.
• the hydrosilylation catalyst include a platinum-based catalyst, a palladium-based catalyst, and a rhodium-based catalyst.
• platinum catalysts include chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, etc., platinum-olefin complexes, platinum-carbonylvinylmethyl complexes (Ossko catalysts), platinum-divinyltetramethyldisiloxane complexes.
• platinum-cyclovinylmethylsiloxane complex platinum-octylaldehyde complex
• platinum-phosphine complex for example, Pt [P (C 6 H 5 ) 3 ] 4 , PtCl [P (C 6 H 5 ) 3 ] 3 , Pt [P (C 4 H 9 ) 3 ) 4 ], platinum-phosphite complexes (eg Pt [P (OC 6 H 5 ) 3 ] 4 ), Pt [P (OC 4 H 9 ) 3 ] 4 ), Dicarbonyldichloroplatinum and the like.
• the palladium catalyst or rhodium catalyst include compounds containing a palladium atom or a rhodium atom instead of the platinum atom of the platinum catalyst. These may be used alone or in combination of two or more.
• the hydrosilylation catalyst is preferably a platinum-based catalyst from the viewpoint of reactivity, more preferably a platinum-divinyltetramethyldisiloxane complex and a platinum-carbonylvinylmethyl complex, and most preferably a platinum-carbonylvinylmethyl complex.
• the amount of the catalyst used is preferably 5% by mass or less, more preferably 0.0001 to 1.0% by mass, most preferably 0.001 to 0.1% by mass of the total amount of each raw material from the viewpoint of reactivity.
• the reaction conditions for the hydrosilylation are not particularly limited, and may be carried out under the conditions known in the art using the above catalyst. From the viewpoint of the reaction rate, it is preferably carried out at room temperature (25 ° C.) to 130 ° C.
• a conventionally known solvent such as hexane, methyl isobutyl ketone, cyclopentanone, propylene glycol monomethyl ether acetate may be used.
• preferable compounds among the alkoxysilane compounds represented by the general formula (3a) include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylethyldimethoxysilane, vinylphenyldimethoxysilane and the like. In view of further improving heat resistance and adhesion, vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldimethoxysilane are preferable, and vinyltrimethoxysilane is more preferable. Only 1 type may be used for the alkoxysilane compound represented by General formula (3a), and 2 or more types may be used for it.
• preferable compounds among the alkoxysilane compounds represented by the general formula (4b) include, for example, trimethoxysilane, triethoxysilane, dimethoxymethylsilane, dimethoxyethylsilane, dimethoxyphenylsilane, and the like. Therefore, trimethoxysilane, triethoxysilane, methyldimethoxysilane, ethyldimethoxysilane, and phenyldimethoxysilane are preferable, trimethoxysilane and triethoxysilane are more preferable, and trimethoxysilane is most preferable. Only 1 type may be used for the alkoxysilane compound represented by General formula (4b), and 2 or more types may be used for it.
• the SiH group of the intermediate represented by the general formula (1b) is represented by the following general formula (5a). What is necessary is just to make the silanediol represented to react.
• silane diols represented by the general formula (5a) preferable examples include dimethyl silane diol, diethyl silane diol, diisopropyl silane diol, methyl phenyl silane diol, diphenyl silane diol, and the like. Diol and diphenylsilane diol are preferable, and diphenylsilane diol is more preferable.
• the reaction may be performed using an organometallic catalyst.
• organometallic catalyst include an organotin catalyst, an organoplatinum catalyst, an organozinc catalyst, and an organoaluminum catalyst, and an organotin catalyst is preferred.
• organic tin catalyst examples include tin octylate, tin naphthenate, tin stearate, tin versatate, dibutyltin laurate, triphenyltin acetate, and tributyltin chloride, and tin octylate, tin naphthenate, and tin stearate are preferable. Further, tin octylate is more preferable.
• the amount of the organometallic catalyst used is preferably 0.001 to 1% by mass, more preferably 0.002 to 0.1% by mass, based on the amount of each raw material used.
• R 4 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms
• R 5 represents an alkyl group having 1 to 4 carbon atoms.
• Examples of the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms include the groups exemplified for R 1 in the general formula (1).
• R 4 is preferably methyl, ethyl, or phenyl, more preferably methyl or phenyl, and most preferably phenyl because heat resistance is further improved.
• R 5 is preferably methyl, ethyl or propyl, more preferably methyl, because of excellent reactivity.
• alkoxysilane compound represented by the general formula (2) examples include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, and phenyltrimethoxy.
• Silane phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, ethylphenyldimethoxysilane, ethylphenyldiethoxysilane, diphenyldimethoxysilane , Diphenyldiethoxysilane and the like, and the heat resistance and adhesion are further improved, so that phenyltrimethoxysilane, phenyltriethoxy Orchids, phenylmethyl dimethoxysilane and phenyl methyl diethoxy silane are preferable, phenyl trimethoxysilane and phenyl triethoxysilane are more preferable, phenyl trimethoxysilane is most preferred.
• the hydrolysis / condensation reaction of the cyclic siloxane compound represented by the general formula (1) and the arylalkoxysilane compound represented by the general formula (2) may be carried out by a so-called sol-gel reaction. And an alkoxysilyl group may be hydrolyzed and condensed.
• the solvent used at this time is not particularly limited, and specific examples include water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, toluene, and the like. These can be used alone or in combination of two or more.
• the alkoxysilyl groups are hydrolyzed with water to form silanol groups (Si—OH groups), and the generated silanol groups or silanol groups and alkoxysilyl groups condense. It progresses by.
• Examples of the acid and base catalyst used in the hydrolysis / condensation reaction include inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid; formic acid, acetic acid, oxalic acid, citric acid, methanesulfonic acid, benzenesulfonic acid, p- Organic acids such as toluenesulfonic acid and monoisopropyl phosphate; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; amine compounds (organic bases) such as trimethylamine, triethylamine, monoethanolamine and diethanolamine Etc. These catalysts may be used alone or in combination of two or more.
• inorganic acids such as hydrochloric acid, phosphoric acid and sulfuric acid
• formic acid acetic acid, oxalic acid, citric acid, methanesulfonic acid, benzenesulfonic acid, p- Organic acids such as toluenesulfonic
• the temperature of the hydrolysis / condensation reaction varies depending on the type of solvent, the type and amount of the catalyst, etc., but is preferably 30 to 100 ° C., more preferably 40 to 80 ° C., and most preferably 45 to 70 ° C.
• the silanol group-containing polysiloxane compound which is the component (A) according to the present invention is characterized by having a silanol group.
• the content of the silanol group in the component (A) is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, more preferably 5 to Most preferably, it is 20 mass%.
• the silanol group is quantified by trimethylsilylation of the silanol group with trimethylchlorosilane or the like and quantifying the amount of increase in mass before and after the reaction (TMS method), a near infrared spectrophotometer (JP 2001-208683 A, JP 2003 2003 A). -35667) and 29 Si-NMR (see JP 2007-217249 A) and the like.
• the solution is preferably used in the form of a solution containing the component (A) after solvent concentration or the like.
• the weight average molecular weight of the silanol group-containing polysiloxane compound is preferably from 1,000 to 50,000 because the solubility or dispersibility in an alkali developer is decreased and the resist residue on the substrate surface after alkali development is increased. More preferably, it is ⁇ 25000, and most preferably 3000-15000.
• the mass average molecular weight refers to a polystyrene-reduced mass average molecular weight when GPC analysis is performed using tetrahydrofuran (hereinafter referred to as THF) as a solvent.
• THF tetrahydrofuran
• the reaction ratio between the cyclic siloxane compound represented by the general formula (1) and the alkoxysilane compound represented by the general formula (2) is:
• the molar ratio of the alkoxysilane compound represented by the general formula (2) is preferably 0.5 to 10 with respect to the cyclic siloxane compound represented by the general formula (1), more preferably 1 to 7. Most preferred is 5-6. When this ratio is lower than 0.5, the hardness of the cured product may be insufficient. When it is higher than 10, the resist residue on the substrate surface after alkali development may increase.
• the silanol group-containing polysiloxane compound (A) is subjected to hydrolysis / condensation reaction with the cyclic siloxane compound represented by the general formula (1) and the arylalkoxysilane compound represented by the general formula (2). Although it is a compound consisting of the structure obtained, it is not always necessary to use the cyclic siloxane compound represented by the general formula (1) when producing the silanol group-containing polysiloxane compound of the component (A).
• a compound in which a group is masked with an acid-dissociable protecting group that is, a compound represented by the following general formula (1p) and an arylalkoxysilane compound represented by the general formula (2) are reacted to form an arylalkoxysilane compound
• (A) component silanol group-containing polysiloxane It is also possible to obtain a thing.
• the description in the case of using the cyclic siloxane compound represented by general formula (1) is applicable suitably. .
• Examples of the acid-dissociable protecting group for carboxyl group and phenol group include t-butyl group, 1-ethoxyethyl group, acetyl group, t-butoxycarbonyl group and the like, and t-butyl group is preferable.
• Such an acid dissociable protecting group can be removed under acidic conditions, and it is preferable to use hydrochloric acid, trifluoroacetic acid, boron trifluoride or the like as a catalyst.
• an organic solvent capable of dissolving 1% by mass or more of water at 25 ° C. is preferable.
• examples of such an organic solvent include methanol, ethanol, and propanol.
• Alcohols such as isopropanol; 1-methoxy-ethanol, 1-ethoxy-ethanol, 1-propoxy-ethanol, 1-isopropoxy-ethanol, 1-butoxy-ethanol, 1-methoxy-2-propanol, 3-methoxy- Ether alcohols such as 1-butanol and 3-methoxy-3-methyl-1-butanol; 1-methoxy-ethyl acetate, 1-ethoxy-ethyl acetate, 1-methoxy-2-propyl acetate, 3-methoxy-1- Butyl acetate, 3-methoxy-3-methyl-1-butyl Acetates of ether alcohols such as cetate; ketones such as acetone and methyl ethyl ketone; 4-hydroxy-2-butanone, 3-hydroxy
• methanol, ethanol, propanol, methyl ethyl ketone, 1,4-dioxane, tetrahydrofuran, and 1-methoxy-2-propanol acetate are preferable.
• the compound represented by the general formula (1p) is a compound represented by the following general formula (13p) instead of the compound represented by the general formula (13), instead of the cyclic siloxane compound represented by the general formula (1a), Instead of the compound represented by the general formula (14), a compound represented by the following general formula (14p) is hydrosilylated to form an intermediate represented by the following general formula (1 bp).
• the groups represented by the general formulas (3) to (5) may be introduced into the represented intermediate as in the case of the intermediate represented by the general formula (1b).
• the epoxy group of the compound having at least two epoxy-containing organic groups as the component (B) contained in the positive photosensitive composition of the present invention examples include aliphatic epoxy groups such as the following formulas (15) to (16), and the following formulas (17) to (19 ) And the like, and aromatic epoxy groups such as the following formulas (20) to (21), and the like.
• the fat A group epoxy group is preferred, and a 1,2-epoxypropyl group (glycidyl group) of the formula (15) is more preferred.
• the epoxy-containing organic group which the compound which is (B) component has should just contain these epoxy groups, for example, these epoxy groups themselves may be sufficient, and these epoxy groups are hydrocarbons. It may be a group formed by combining one or more linking groups such as a group, an ether group, and an ester group. Especially, it is preferable that the compound which is (B) component is a compound which has a glycidyl ether group as an epoxy-containing organic group.
• Preferred compounds having at least two glycidyl ether groups as component (B) include glycidyl ethers of polyhydric phenol compounds, glycidyl ethers of polyhydric alcohol compounds, siloxane compounds having glycidyl ether groups, and the like. Is more preferable, a siloxane compound having a glycidyl ether group is preferable.
• Examples of the siloxane compound having at least two glycidyl ether groups include a linear siloxane compound represented by the following general formula (22), a cyclic siloxane compound represented by the following general formula (23), and the following general formula (24 ), A hydrolyzed / condensed reaction product of an alkoxysilane having a glycidyl ether group, among others, a cyclic siloxane compound represented by the general formula (23) and a cyclic represented by the general formula (24).
• a siloxane compound is preferable, and a cyclic siloxane compound represented by the general formula (24) is more preferable.
• G represents a group having a glycidyl ether group
• R 26 to R 30 represent an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be the same or different.
• Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified as R 1 in the general formula (1). Methyl, ethyl and phenyl are preferable because of better heat resistance. More preferred is methyl.
• Y 1 represents a group having a glycidyl ether group or a methyl group
• j represents a number from 0 to 1000
• k represents a number from 0 to 1000.
• Y 1 represents a group having a glycidyl ether group.
• a compound having a carbon-carbon double bond and a glycidyl ether group having reactivity with the SiH group is added to the linear compound represented by the following general formula (22a). It can be produced by hydrosilylation reaction.
• the compound having a carbon-carbon double bond having reactivity with the SiH group and a glycidyl ether group include vinyl glycidyl ether, allyl glycidyl ether, 5-glycidoxypropyl-2-norbornene, and the like. Allyl glycidyl ether is preferred due to industrial availability and hydrosilylation reactivity.
• the conditions for the hydrosilylation reaction may be the same as those for obtaining the intermediate represented by the general formula (1b).
• the epoxy equivalent of the linear siloxane compound represented by General formula (22) is 1000 or less, More preferably, it is 700 or less, Most preferably, it is 350 or less.
• an epoxy equivalent means the mass (gram number) of the epoxy compound containing 1 equivalent of epoxy groups.
• the molecular weight of the linear siloxane compound represented by the general formula (22) is not particularly limited. However, when the molecular weight is too large, the solubility or dispersibility in an alkali developer is lowered, and a resist residue is formed on the substrate surface after alkali development. Since it may remain, the mass average molecular weight is preferably 20000 or less, more preferably 15000 or less, and most preferably 10,000 or less.
• R 31 to R 33 each represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be the same or different.
• Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified for R 1 .
• R 31 to R 33 are preferably methyl, ethyl and phenyl, more preferably methyl and phenyl, and most preferably methyl because of better heat resistance.
• q represents a number of 2 to 6, and r represents a number of 0 to 4 where q + r is 3 to 6. In view of industrial availability, q + r is preferably 4 to 6, more preferably 4 to 5, and most preferably 4.
• R is preferably 0.
• the cyclic siloxane compound represented by the general formula (23) is obtained by hydrolyzing a cyclic compound represented by the following general formula (23a) with a compound having a carbon-carbon double bond having reactivity with a SiH group and a glycidyl ether group. It can manufacture by making it react.
• the conditions for the hydrosilylation reaction may be the same as those for obtaining the intermediate represented by the general formula (1b).
• Examples of the cyclic compound represented by the general formula (23a) include compounds exemplified by the cyclic compound represented by the general formula (1a), 2,2,4,6-tetramethylcyclotrisiloxane, 2,2,4, 4,6,8-hexamethylcyclotetrasiloxane, 2,2,4,4,6,6,8,10-octamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,2,4 , 6,8-pentamethylcyclotetrasiloxane and the like.
• R 34 represents an alkyl group having 1 to 4 carbon atoms or a phenyl group.
• Examples of the alkyl group having 1 to 4 carbon atoms include the alkyl groups exemplified for R 1 .
• R 34 is preferably methyl, ethyl and phenyl, more preferably methyl and phenyl, and most preferably methyl, because of better heat resistance.
• R 35 represents a residue obtained by removing a vinyl group from a divinyl compound or trivinyl compound having a molecular weight of 1000 or less.
• divinyl compound or trivinyl compound having a molecular weight of 1000 or less a divinyl compound having a molecular weight of 1000 or less exemplified in the general formula (4) or A trivinyl compound etc. are mentioned.
• the divinyl compound or trivinyl compound providing the group represented by R 35 the compounds represented by the general formulas (9) to (11) are preferable from the viewpoint of industrial availability and heat resistance of the cured product. 1,4-divinylbenzene, 1,2,4-trivinylcyclohexane and triallyl isocyanurate are more preferred, and 1,4-divinylbenzene is most preferred.
• G represents a group having a glycidyl ether group
• s represents a number of 2 to 5.
• s is preferably a number of 2 to 4, and more preferably 3, because industrial raw materials are easily available.
• t represents a number of 1 or 2, and when R 35 is a residue obtained by removing a vinyl group from a divinyl compound having a molecular weight of 1000 or less, t is 1 and a residue obtained by removing the vinyl group from a trivinyl compound having a molecular weight of 1000 or less. In the case of a radical, t is 2.
• the cyclic siloxane compound represented by the general formula (24) is represented by the following general formula (24b) by subjecting the cyclic compound represented by the following general formula (24a) to a hydrosilylation reaction with a divinyl compound or trivinyl compound having a molecular weight of 1000 or less.
• the intermediate SiH group represented by the general formula (24b) is hydrosilylated with a compound having a carbon-carbon double bond reactive with the SiH group and a glycidyl ether group. can do.
• the conditions for the hydrosilylation reaction may be the same as those for obtaining the intermediate represented by the general formula (1b).
• Examples of the cyclic compound represented by the general formula (24a) include compounds exemplified by the cyclic compound represented by the general formula (1a), and examples of the divinyl compound or trivinyl compound having a molecular weight of 1000 or less include those represented by the general formula (4). Examples thereof include the compounds exemplified for R 8 .
• the hydrolysis / condensation reaction product of the alkoxysilane having the glycidyl ether group is obtained by hydrolyzing the alkoxysilane having a glycidyl ether group by a known method, for example, the method described in the hydrolysis / condensation reaction described in the component (A). It is a compound obtained by decomposition / condensation reaction.
• alkoxysilane having a glycidyl ether group examples include glycidylalkoxysilane compounds such as glycidyltrimethoxysilane and glycidyltriethoxysilane; glycidylalkoxysilane compounds such as 2-glycidoxyethyltrimethoxysilane and 2-glycidoxyethylmethyldimethoxysilane.
• Cidoxyethylalkoxysilane compound 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylphenyldimethoxysilane, bis (3 -Glycidoxypropyl) dimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylethyldiethoxysila 3-glycidoxypropylalkoxysilane compounds such as 3-glycidoxypropylphenyldiethoxysilane and bis (3-glycidoxypropyl) diethoxysilane; 2- (4-glycidoxyphenyl) ethyltrimethoxysilane 2- (4-glycidoxyphenyl) ethylalkoxysilane compounds such
• 3-glycidoxypropylalkoxy Silane compounds are preferred.
• 3-glycidoxypropylalkoxysilane compounds 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, bis (3-glycidoxypropyl) dimethoxysilane, 3-glycidoxypropyl Triethoxysilane is more preferable, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are still more preferable, and 3-glycidoxypropyltrimethoxysilane is most preferable.
• alkoxysilane having a glycidyl ether group In addition to the alkoxysilane having a glycidyl ether group, another alkoxysilane compound having no glycidyl ether group may be used in combination. .
• the epoxy equivalent is preferably 1000 or less, more preferably 700 or less, and most preferably 350 or less.
• the molecular weight of the alkoxysilane hydrolysis / condensation reaction product having a glycidyl ether group is not particularly limited. However, if the molecular weight is too large, the solubility or dispersibility in an alkali developer decreases, and the substrate surface after alkali development. In view of the fact that a resist residue may remain, the mass average molecular weight is preferably 20000 or less, more preferably 15000 or less, and most preferably 10,000 or less.
• the hydrolysis / condensation reaction product of alkoxysilane having a glycidyl ether group preferably has a silanol group.
• the content of silanol groups in the hydrolysis / condensation reaction product of the alkoxysilane having a glycidyl ether group is preferably 1 to 30% by mass, and more preferably 3 to 25% by mass.
• a hydrolysis / condensation reaction product of an alkoxysilane having a glycidyl ether group using a trialkoxysilane compound in the reaction may have a bridged structure by Si—O—Si bond. There may be a ladder-like (ladder-like), cage-like or annular structure.
• the hydrolysis / condensation reaction product of the alkoxysilane having a glycidyl ether group is the same reaction as the hydrolysis / condensation reaction between the cyclic siloxane compound represented by the general formula (1) and the alkoxysilane compound represented by the general formula (2). It can be manufactured according to conditions.
• the content of the compound having at least two epoxy-containing organic groups as the component (B) is 1 to 50 parts by mass with respect to 100 parts by mass of the component (A). It is preferably 2 to 40 parts by mass, more preferably 5 to 30 parts by mass.
• the diazonaphthoquinones that are the component (C) of the present invention are not particularly limited as long as they are diazonaphthoquinones compounds that are known to be usable in photosensitive materials, but among them, hydrogen atoms of compounds having a phenolic hydroxyl group Is preferably a compound substituted with the following formula (25) (4-diazonaphthoquinonesulfonic acid ester) or a compound substituted with the following formula (26) (5-diazonaphthoquinonesulfonic acid ester).
• Preferred examples of such diazonaphthoquinones include, for example, compounds represented by the following formulas (27) to (32) and their positional isomers.
• the group represented by the formula (25) has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure, and the group represented by the formula (26) has absorption in a wide wavelength range. Therefore, since it is suitable for exposure in a wide range of wavelengths, it is preferable to select either the group represented by the formula (25) or the group represented by the formula (26) depending on the wavelength to be exposed.
• the content of the diazonaphthoquinones as component (C) is 0.1 to 20 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the silanol group-containing polysiloxane compound as component (A). However, it is preferable from the viewpoint of developability and fine processability of a permanent resist obtained from the positive photosensitive composition of the present invention.
• the organic solvent (D) that can be used in the present invention dissolves or disperses the above (A) silanol group-containing polysiloxane compound, (B) a compound having at least two epoxy-containing organic groups, and (C) diazonaphthoquinones.
• the organic solvent is not particularly limited as long as the organic solvent can be used, but an organic solvent capable of dissolving 1% by mass or more of water at 25 ° C. is preferable.
• ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ethylene carbonate, propylene carbonate, dimethyl carbonate and the like can be mentioned.
• the organic solvent used in the elimination reaction of the protecting group is used as it is. It may be used as an organic solvent.
• the content of the organic solvent as component (D) is 10 to 10000 parts by weight, more preferably 100 to 1000 parts by weight, based on 100 parts by weight of the (A) silanol group-containing polysiloxane compound. From the viewpoints of formability when a permanent resist is formed using the positive photosensitive composition and physical properties of the obtained permanent resist.
• the positive photosensitive composition of the present invention dissolves or dissolves (A) a silanol group-containing polysiloxane compound, (B) a compound having at least two epoxy-containing organic groups, (C) diazonaphthoquinones and (D) an organic solvent. Although it is dispersed, if necessary, it can be used after being filtered through a filter having a pore diameter of about 0.2 ⁇ m, for example.
• the positive photosensitive composition of the present invention includes a plasticizer, a thixotropic agent, a photoacid generator, a thermal acid generator, a dispersant, and an antifoaming agent as necessary. And optional components such as pigments and dyes. From the viewpoint of not impairing the effects of the present invention, the total content of arbitrary components is preferably 30 parts by mass or less with respect to 100 parts by mass of the (A) silanol group-containing polysiloxane compound.
• the positive photosensitive composition of the present invention can be cured in the same manner as conventionally known positive photosensitive compositions. For example, if it is cured through the following steps (1) to (6), And a cured product having excellent chemical resistance after high-temperature heat history. A cured product obtained by curing the positive photosensitive composition of the present invention is suitable for a permanent resist. Below, the preferable method of manufacturing a permanent resist using the positive photosensitive composition of this invention is demonstrated.
• a method of directly applying the positive photosensitive composition of the present invention to the target material, and a support such as polyethylene terephthalate (PET) After applying to a body film, there is a method in which a solvent is evaporated to form a layer of a positive photosensitive composition to form a dry film resist (DFR), and the DFR is bonded to a target material.
• a method for direct application will be described. This method includes the following (1) coating film forming step, (2) pre-baking step, (3) exposure step, (4) development step, (5) bleaching exposure step, and (6) post-baking step.
• the positive photosensitive composition of this invention is apply
• the target material to which the positive photosensitive composition of the present invention is applied to form a coating film has chemical resistance to an organic solvent or the like in the positive photosensitive composition, and (4) development treatment with an alkaline solution in the development step (6)
• the material is not particularly limited as long as the material has resistance to heat treatment in the post-bake process, and glass, metal, semiconductor, and the like can be used as target materials.
• a TFT surface of a liquid crystal display that requires a permanent resist as an insulating layer can be exemplified as a preferable one.
• the application method is not particularly limited, and various methods such as spin coating, dip coating, knife coating, roll coating, spray coating, and slit coating can be used.
• pre-baking step After the step (1), pre-baking is performed to remove (D) the organic solvent from the positive photosensitive composition layer applied to the target material.
• the pre-baked positive-type photosensitive composition layer is hardly soluble in an alkaline solution, and the portion irradiated with light by irradiating light in the next exposure step (hereinafter sometimes referred to as an exposed portion) is alkaline. It becomes soluble.
• the pre-baking temperature varies depending on the type of organic solvent used. If the temperature is too low, the residual amount of the organic solvent increases, which may cause a reduction in exposure sensitivity and resolution, and the temperature is too high.
• the entire coating film is cured by pre-baking, so that the solubility in the alkaline developer in the portion irradiated with light is lowered, and as a result, the exposure sensitivity and resolution may be lowered. 70 to 120 ° C. is more preferable.
• the pre-baking time varies depending on the type of organic solvent used and the pre-baking temperature, but is preferably 30 seconds to 10 minutes, more preferably 1 to 5 minutes.
• Pre-baking may be carried out as it is after the positive photosensitive composition of the present invention is applied to the target material. However, since the physical properties and chemical resistance after the high heat history of the permanent resist are further improved, pre-baking is performed. In addition, the organic solvent is volatilized so that the concentration of the organic solvent in the positive photosensitive composition layer is 5% by mass or less at room temperature to less than 60 ° C. under normal pressure or reduced pressure, and then prebaked. It is preferable.
• the thickness of the positive photosensitive composition layer after pre-baking varies depending on the application in which the permanent resist is used, and is not particularly limited, but is preferably 0.1 ⁇ m to 100 ⁇ m, more preferably 0.3 ⁇ m to 10 ⁇ m.
• Exposure process is a process of irradiating patterned light with respect to the pre-baked positive photosensitive composition layer, and improving the alkali solubility of an exposed part.
• the pre-baked positive photosensitive composition layer is poorly soluble in alkaline solution, but diazonaphthoquinones in the exposed part are decomposed by light irradiation and converted into indenecarboxylic acid, which is dissolved and dispersed in the alkaline solution. Is possible.
• Irradiation light is not particularly limited, and may be light having an energy amount capable of improving the alkali solubility of the light irradiated portion of the pre-baked positive photosensitive composition layer, for example, 10 to 1000 mJ / cm 2 , 40 to 300 mJ / cm 2 is preferable.
• the wavelength of the irradiation light may be visible light or ultraviolet light, and is not particularly limited. However, when 4-diazonaphthoquinonesulfonic acid esters are used as (C) diazonaphthoquinones, the wavelength is narrow with i-line (365 nm) as the main component.
• i-line 365 nm
• h-line 405 nm
• g-line 436 nm
• Irradiation may be performed using a high-pressure mercury lamp or the like.
• the patterning method of the irradiation light is not particularly limited and may be a conventionally known method, for example, a light irradiation method through a photomask or the like, and a selective light irradiation method using laser light. But you can.
• the development step is a step of forming a predetermined pattern by removing a portion of the exposure step that has been irradiated with light and improved alkali solubility using a developer.
• a developing method for example, any method such as a liquid filling method, a dipping method, a shower method, a spray method, or the like can be used.
• the development time varies depending on the type and molecular weight of the (A) silanol group-containing polysiloxane compound and (B) the compound having at least two epoxy-containing organic groups, the temperature of the developer, and the like, but is usually 30 to 180 seconds.
• the developer used in the development step is not particularly limited as long as the exposed portion can be removed by dissolving or dispersing in the solution.
• sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate Inorganic alkalis such as ammonia
• primary amines such as ethylamine and n-propylamine
• secondary amines such as diethylamine and di-n-propylamine
• tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine
• Tertiary alkanolamines such as dimethylethanolamine, methyldiethanolamine, triethanolamine
• pyrrole piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene 1,5-diazabicyclo 4.3.0] -5-nonene and other cyclic tertiary amine
• alkaline aqueous solutions may further contain an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant.
• a water-soluble organic solvent such as methanol and ethanol and / or a surfactant.
• the entire positive-type photosensitive composition layer (hereinafter sometimes referred to as a resist layer) remaining after the alkali solution treatment is irradiated with light so as to have visible light transmittance. It is a process to improve.
• the resist layer is colored light yellow to light brown because it contains (C) diazonaphthoquinones.
• the remaining unreacted (C) diazonaphthoquinones are photodegraded to change to indenecarboxylic acid which does not absorb in the visible light region, and the visible light transmittance is improved.
• Irradiating light in bleaching exposure step is not particularly limited, for example, 10 ⁇ 1000mJ / cm 2, preferably may be irradiated with light of 40 ⁇ 600mJ / cm 2.
• the wavelength of the irradiation light may be visible light or ultraviolet light, and is not particularly limited.
• the wavelength of the irradiation light can be selected according to the (C) diazonaphthoquinones used. preferable.
• the resist layer subjected to bleaching exposure has improved visible light transmittance but also improved alkali solubility.
• the bleaching-exposed resist layer is heat-treated at 120 ° C. or more to thermally cross-link the silicone resin in the resist layer, thereby requiring heat resistance and chemical resistance required as a permanent resist. , Imparts aging resistance.
• the compound having at least two epoxy groups as the component (B) of the positive photosensitive composition functions as a cross-linking agent and can obtain chemical resistance after a high heat history that has never been obtained.
• the post-bake is preferably performed in an inert gas atmosphere such as nitrogen, helium or argon.
• the post-baking is preferably performed at a temperature of 120 to 400 ° C., more preferably 120 to 350 ° C., most preferably 200 to 350 ° C. for 15 minutes to 2 hours.
• the positive photosensitive composition of the present invention may be directly applied to a target material such as a semiconductor substrate as described above.
• the positive photosensitive composition is applied to a support film to form a coating film, and a dry film resist.
• a support film for example, polyethylene terephthalate (PET), polyethylene, polypropylene, and the like can be used, but a PET film is preferable because of excellent thermal characteristics and mechanical characteristics as the support film.
• PET polyethylene terephthalate
• the film thickness of the support film is usually 1 ⁇ m to 5 mm, preferably 10 ⁇ m to 100 ⁇ m.
• the thickness of the coating film formed on the support film varies depending on the application and is not particularly limited, but is 0.1 ⁇ m to 100 ⁇ m, preferably 0.3 ⁇ m to 10 ⁇ m.
• pre-baking is performed in the same manner as in the above (2) pre-baking step to remove the solvent in the coating film, and a protective film is laminated on the coating film surface to prepare a dry film resist.
• the permanent resist obtained from the positive photosensitive composition of the present invention is not only excellent in transparency, insulation, heat resistance and chemical resistance, but also after a high-temperature heat history (high heat history) of about 300 to 350 ° C.
• Insulating film or planarizing film (especially interlayer insulating film) for active matrix substrates used in liquid crystal display devices, organic EL display devices, etc., especially polycrystalline silicon because of its excellent transparency, insulation and chemical resistance It is extremely useful as an interlayer insulating film for an active matrix substrate having a TFT having a thin film as an active layer.
• the permanent resist obtained from the positive photosensitive composition of the present invention can also be used for an interlayer insulating film of a semiconductor element. It can also be used for wafer coating materials (surface protective film, bump protective film, MCM (multi-chip module) interlayer protective film, junction coating) and package materials (sealing material, die bonding material) for semiconductor elements. .
• the permanent resist obtained from the positive photosensitive composition of the present invention is also useful as an insulating film for semiconductor elements, multilayer wiring boards and the like.
• semiconductor elements individual semiconductor elements such as diodes, transistors, compound semiconductors, thermistors, varistors, thyristors, DRAM (Dynamic Random Access Memory), SRAM (Static Random Access Memory), EPROM (Erasable Programmable) ⁇ Read only memory (ROM), mask ROM (mask read only memory), EEPROM (electrically erasable programmable read only memory), memory elements such as flash memory, microprocessor, DSP, ASIC, etc.
• Theoretical circuit elements integrated circuit elements such as compound semiconductors represented by MMIC (monolithic microwave integrated circuit), hybrid integrated circuits (hybrid IC), light emitting diodes Such a photoelectric conversion element such as a charge coupled device and the like.
• MMIC monolithic microwave integrated circuit
• hybrid IC hybrid integrated circuits
• light emitting diodes Such a photoelectric conversion element such as a charge coupled device and the like.
• the multilayer wiring board include a high-density wiring board such as MCM.
• the present invention will be further described with reference to examples below, but the present invention is not limited to these examples.
• the content of silanol groups was determined by reacting the sample with trimethylchlorosilane in a pyridine solution to change the silanol groups to trimethylsilyl ether groups, and then treating with a tetramethylammonium hydroxide ((CH 3 ) 4 NOH) aqueous solution. It was determined by hydrolyzing the —O—Si bond and calculating backward from the rate of mass increase after the reaction.
• Production Example 2 Intermediate a2 In Production Example 1, Production Example 1 was performed except that 102 g (0.5 mol) of 4-vinylbenzoic acid-t-butyl ester was used instead of 64.1 g (0.5 mol) of acrylic acid-t-butyl ester. Intermediate a2 was obtained by performing the same operation as in Example 1.
• Production Example 3 Intermediate a3
• the amount of acrylic acid-t-butyl ester used was 64.1 g (0.5 mol) to 38.4 g (0.3 mol), and the amount of 4-t-butoxystyrene used was 352 g (2 mol).
• Production Example 4 Intermediate a′1 In Production Example 1, 204 g (1 mol) of 4-vinylbenzoic acid-t-butyl ester was used instead of 64.1 g (0.5 mol) of acrylic acid-t-butyl ester, and 4-t-butoxystyrene Except having changed the usage-amount from 352g (2 mol) to 264g (1.5 mol), operation similar to manufacture example 1 was performed and intermediate a'1 was obtained.
• Production Example 5 Intermediate a′2
• the amount of acrylic acid-t-butyl ester used was changed from 64.1 g (0.5 mol) to 19.2 g (0.15 mol), and the amount of 4-tert-butoxystyrene used was 352 g (2 Mol) to 414 g (2.35 mol), and the same operation as in Production Example 1 was performed to obtain an intermediate a′2.
• Production Example 6 Polysiloxane compound A1 In a glass reaction vessel equipped with a thermometer and a stirrer, 200 g of toluene as a solvent, 65.6 g (0.1 mol) of intermediate a1, 22.1 g (0.15 mol) of trimethoxyvinylsilane, and platinum as a catalyst -0.001 g of divinyltetramethyldisiloxane complex (Karstedt catalyst) was added and reacted at 60 ° C. for 10 hours with stirring to introduce a group represented by the general formula (3).
• phenyltrimethoxysilane was added as a compound represented by the general formula (2), and 50 g of 5% oxalic acid aqueous solution was added while stirring with ice cooling to 5 to 10 ° C. The solution was added dropwise over 30 minutes and further stirred at 10 ° C. for 15 hours.
• Reflux dehydration and dealcoholization treatment at 50 ° C. under reduced pressure, and solvent exchange with 1-methoxy-2-propanol acetate (hereinafter referred to as PGMEA) was performed at 25 ° C. under reduced pressure to obtain a 25% PGMEA solution. .
• Production Example 7 Polysiloxane compound A2 In Production Example 6, instead of 65.6 g (0.1 mol) of Intermediate a1, the same operation as in Production Example 6 was carried out except that 69.4 g (0.1 mol) of Intermediate a2 was used. A 30% PGMEA solution of polysiloxane compound A2 as component (A) was obtained. The mass average molecular weight of the polysiloxane compound A2 by GPC analysis was 6500, and the silanol group content was 5.4% by mass.
• Production Example 8 Polysiloxane compound A3
• the same procedure as in Production Example 6 was performed, except that 65.4 g (0.1 mol) of intermediate a3 was used instead of 65.6 g (0.1 mol) of intermediate a1.
• a 30% PGMEA solution of polysiloxane compound A3 as component (A) was obtained.
• the polysiloxane compound A3 had a mass average molecular weight of 6,300 and a silanol group content of 5.4% by mass by GPC analysis.
• Production Example 9 Polysiloxane compound A4 In a glass reaction vessel equipped with a thermometer and a stirrer, 200 g of toluene as a solvent, 65.6 g (0.1 mol) of intermediate a1, and 39 g of divinylbenzene as a divinyl compound represented by the general formula (4a) (0 3 mol), and 0.001 g of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) as a catalyst, and the mixture is allowed to react at 60 ° C. for 10 hours with stirring to obtain an intermediate represented by the general formula (1c) Got.
• Production Example 10 Polysiloxane compound A5 In a glass reaction vessel equipped with a thermometer and a stirrer, 200 g of dioxane as a solvent, 65.6 g (0.1 mol) of intermediate a1, 43.2 g (0.2 mol) of diphenylsilanediol, octylic acid as a catalyst After 0.025 g of tin was added and dissolved, the mixture was reacted at 60 ° C. for 10 hours to introduce a group represented by the general formula (5).
• Production Example 11 Polysiloxane compound A′1
• Production Example 6 the same procedure as in Production Example 6 was used, except that 70.8 g (0.1 mol) of intermediate a′1 was used instead of 65.6 g (0.1 mol) of intermediate a1.
• a comparative 30% PGMEA solution of polysiloxane compound A′1 was obtained.
• the mass average molecular weight of the polysiloxane compound A′1 by GPC analysis was 6500, and the silanol group content was 5.4% by mass.
• Production Example 12 Polysiloxane compound A′2
• the same procedure as in Production Example 6 was used, except that 67.3 g (0.1 mol) of intermediate a′2 was used instead of 65.6 g (0.1 mol) of intermediate a1.
• a comparative 30% PGMEA solution of polysiloxane compound A′2 was obtained.
• the mass average molecular weight of the polysiloxane compound A′2 by GPC analysis was 6400, and the silanol group content was 5.4% by mass.
• Epoxy compound B1 (compound represented by formula (23))
• 200 g of toluene as a solvent 120 g (0.5 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 228 g (2 mol) of allyl glycidyl ether, and After adding 9 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) and reacting at 50-60 ° C. for 15 hours with stirring, the solvent is distilled off under reduced pressure at 60 ° C., and the epoxy compound as component (B) B1 was obtained.
• the analytical value of the epoxy equivalent of the epoxy compound B1 was 174.
• Epoxy compound B2 (compound represented by formula (24)) In a glass reaction vessel equipped with a thermometer and a stirring device, 250 g of toluene as a solvent, 144 g (0.6 mol) of 2,4,6,8-tetramethylcyclotetrasiloxane, 52 g (0.4 mol) of divinylbenzene, After adding 194 g (1.7 mol) of allyl glycidyl ether and 9 mg of platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst), the mixture was reacted at 50-60 ° C. for 15 hours with stirring, and then the solvent was reduced in pressure at 60 ° C. It was distilled off to obtain an epoxy compound B2 as component (B). Epoxy compound B2 had a weight average molecular weight of 1500 and an analysis value of epoxy equivalent of 244.
• Epoxy compound B3 In a glass reaction vessel equipped with a thermometer and a stirrer, 200 g of toluene, 134 g (1 mol) of 1,1,3,3-tetramethyldisiloxane, 52 g (0.4 mol) of divinylbenzene, 194 g of allyl glycidyl ether ( 1.7 mol) and 9 mg of a platinum-divinyltetramethyldisiloxane complex (Karstedt catalyst) were added, and the mixture was reacted at 50-60 ° C. for 15 hours with stirring. The solvent was distilled off from this reaction solution under reduced pressure at 60 ° C. to obtain an epoxysilane compound B3 as component (B).
• Epoxy compound B3 had a weight average molecular weight of 1500 and an epoxy equivalent weight of 244.
• Examples 1 to 10 and Comparative Examples 1 to 3 Using the compounds obtained in the above production examples, the positive photosensitive compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were prepared after blending in the proportions shown in Table 1 and filtering. In addition, the solvent was added so that it might become the value in a table
• (C) component and (D) component of Table 1 are as follows, respectively.
• test specimens were prepared by the following procedure for preparing test specimens.
• Method for preparing test piece A positive photosensitive composition is applied on a glass substrate by spin coating so that the film thickness becomes 3 to 4 ⁇ m, and then the solvent is volatilized and pre-baked at 100 ° C. for 3 minutes to obtain a test piece. Using.
• test pieces evaluation of optimum development time and development margin, evaluation of alkali resistance after high heat history, evaluation of resist residue, and evaluation of film reduction rate were performed by the following methods.
• a photomask having a line width of 5 ⁇ m was placed on the glass substrate, and 90 mJ with an ultrahigh pressure mercury lamp. / Cm 2 (wavelength 365 nm exposure conversion).
• the development time was changed from 30 seconds to every 5 seconds, and the evaluation of the optimum development time and development margin was evaluated according to the following procedure. That is, for each positive photosensitive composition, 15 test pieces were prepared and subjected to patterning exposure, and then these test pieces were immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at a liquid temperature of 25 ° C. After 30 seconds from the start of immersion, one sheet was taken out every 5 seconds. The taken-out test piece was immediately washed with running ultrapure water for 1 minute and air-dried.
• the air-dried test piece was observed, and the shortest development time necessary for the line width to be 5 ⁇ m was set as the optimal development time, and the time from the optimal development time until the 5 ⁇ m line pattern was peeled off was set as the development margin.
• the results are shown in Table 2.
• test piece of the positive photosensitive composition was subjected to patterning exposure, and then developed by a shower development method (shower pressure 0.05 MPa) using a 2.38 mass% tetramethylammonium hydroxide aqueous solution having a liquid temperature of 25 ° C.
• the development time was the optimum development time for each positive photosensitive composition determined in the previous evaluation.
• it was washed with running ultrapure water for 1 minute and air-dried.
• the air-dried test piece was subjected to bleaching exposure under the condition of 200 mJ / cm 2 (wavelength 365 nm exposure conversion) using an ultrahigh pressure mercury lamp.
• post-baking was performed by heating at 230 ° C. for 60 minutes in an air atmosphere to form a permanent resist film, and further, heat treatment was performed at 350 ° C. for 30 minutes in a nitrogen atmosphere.
• ⁇ Change rate of light transmittance is less than 3% and change rate of film thickness is less than 10%, and excellent in alkali resistance even after high heat history.
• ⁇ Change rate of light transmittance is less than 5% and change rate of film thickness is less than 20%, but change rate of light transmittance is less than 3% and change rate of film thickness is not less than 10%. Slightly inferior in alkali resistance after history.
• X Change rate of light transmittance is 5% or more or change rate of film thickness is 10% or more, and is inferior in alkali resistance after a high heat history.
• Each positive photosensitive composition was subjected to patterning exposure using three test pieces each, and then subjected to a shower development method (shower pressure 0. 0) using a 2.38 mass% tetramethylammonium hydroxide aqueous solution having a liquid temperature of 25 ° C. 05 MPa).
• the development time was the optimum development time for each positive photosensitive composition determined in the previous evaluation. Immediately after the development, it was washed with running ultrapure water for 1 minute and air-dried.
• the air-dried test piece was irradiated with 200 mJ / cm 2 (wavelength 365 nm exposure equivalent) of light using a super-high pressure mercury lamp as bleaching exposure, and then post-baked at 230 ° C. for 60 minutes in an air atmosphere to form a permanent resist film. Formed.
• Each test piece was cut, the cut surface was observed using a scanning electron microscope, the presence or absence of a resist residue in a portion where the glass substrate was exposed by development was examined, and the resist residue was evaluated according to the following evaluation criteria. The results are shown in Table 2 (Evaluation criteria) ⁇ : Resist residue is not seen in all three test pieces.
• X Resist residue is observed on 1 to 3 of the 3 test pieces.

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