WO2011155382A1 - Composition de siloxane photosensible, film durci formé avec cette composition, et élément comportant le film durci - Google Patents

Composition de siloxane photosensible, film durci formé avec cette composition, et élément comportant le film durci Download PDF

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WO2011155382A1
WO2011155382A1 PCT/JP2011/062684 JP2011062684W WO2011155382A1 WO 2011155382 A1 WO2011155382 A1 WO 2011155382A1 JP 2011062684 W JP2011062684 W JP 2011062684W WO 2011155382 A1 WO2011155382 A1 WO 2011155382A1
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group
carbon atoms
compound
cured film
hydrogen
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PCT/JP2011/062684
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Japanese (ja)
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妹尾将秀
藤原建典
福原将
諏訪充史
山本栄悟
内田圭一
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東レ株式会社
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Priority to JP2011535336A priority Critical patent/JP5696665B2/ja
Priority to KR1020127025114A priority patent/KR101761181B1/ko
Priority to CN201180028270.8A priority patent/CN102918460B/zh
Publication of WO2011155382A1 publication Critical patent/WO2011155382A1/fr

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    • 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
    • G03F7/075—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • 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
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • C08G77/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups

Definitions

  • the present invention forms a flattening film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a protective film or insulating film for a touch panel, an interlayer insulating film for a semiconductor element, or a core or cladding material for an optical waveguide.
  • TFT thin film transistor
  • the present invention relates to a photosensitive siloxane composition, a cured film formed therefrom, and an element having the cured film.
  • Patent Document 1 describes a method for increasing the aperture ratio of a display device as a method for realizing higher definition and higher resolution in a liquid crystal display, an organic EL display, or the like. This is a method in which the data line and the pixel electrode can be overlapped by providing a transparent flattening film as a protective film on the TFT substrate, and the aperture ratio is increased as compared with the prior art.
  • a material for such a flattening film for a TFT substrate it is necessary to form a hole pattern of several ⁇ m to 50 ⁇ m in order to connect the TFT substrate electrode and the ITO electrode with high heat resistance and high transparency.
  • a positive photosensitive material is used.
  • Patent Documents 2 and 3 describe a material in which a quinonediazide compound is combined with an acrylic resin as a representative positive photosensitive material.
  • polysiloxane is known as a material having high heat resistance and high transparency.
  • Patent Documents 4, 5, and 6 are combined with a quinonediazide compound to impart positive photosensitivity thereto. These materials have high heat resistance, and a highly transparent cured film can be obtained without generating defects such as cracks even by high-temperature treatment.
  • JP-A-9-152625 (Claim 1) JP 2001-281853 A (Claim 1) Japanese Patent Laid-Open No. 2001-281861 (Claim 1) JP 2006-178436 A (Claim 1) JP 2009-211033 A1 (Claim 1) JP 2010-33005 A (Claim 1)
  • Patent Documents 2 and 3 have insufficient heat resistance, and there is a problem that the cured film is colored by the high-temperature treatment of the substrate and the transparency is lowered.
  • the high transparency and high conductivity of ITO which is a transparent electrode member, are being studied.
  • these acrylic materials are insufficient in heat resistance and cannot form highly transparent ITO with high conductivity.
  • Patent Documents 4, 5, and 6 are not sufficiently resistant to chemicals such as an ITO etching solution and are required to improve chemical resistance.
  • the present invention has been made based on the above circumstances, and is a photosensitive siloxane composition capable of obtaining a cured film having high heat resistance and high transparency characteristics and good chemical resistance. It is an issue to provide.
  • Another object of the present invention is to provide a cured film such as a flattening film for a TFT substrate, an insulating film for a touch panel, and a liquid crystal display device having the cured film formed from the photosensitive siloxane composition. Let it be an issue.
  • an object of the present invention is (a) a polysiloxane synthesized by reacting one or more organosilanes represented by the general formula (1), (b) a quinonediazide compound, (c) a solvent, and (d It is achieved by a photosensitive siloxane composition containing a silicate compound represented by the general formula (2).
  • R 1 represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R 1 may be the same or different.
  • R 2 represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R 2 may be the same (N may represent an integer of 0 to 3)
  • R 3 to R 6 each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
  • P is 2) Represents an integer of ⁇ 10)
  • a cured film having high heat resistance and high transparency and good chemical resistance can be obtained.
  • the obtained cured film can be suitably used as a planarizing film for a TFT substrate or an insulating film for a touch panel.
  • the photosensitive siloxane composition of the present invention is a photosensitive siloxane composition containing (a) polysiloxane, (b) a quinonediazide compound, (c) a solvent, and (d) a silicate compound.
  • the photosensitive siloxane composition of the present invention contains (a) polysiloxane.
  • the polysiloxane used in the present invention is a polysiloxane synthesized by reacting at least one organosilane represented by the general formula (1).
  • R 1 represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R 1 may be the same or different.
  • R 2 represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R 2 may be the same (N may represent an integer of 0 to 3).
  • R 1 represents any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms.
  • the plurality of R 1 may be the same or different from each other.
  • These alkyl groups, alkenyl groups, and aryl groups may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 3, 3 , 3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, [(3-ethyl-3-oxetanyl) methoxy] propyl group, 3-aminopropyl group, Examples include 3-mercaptopropyl group and 3-isocyanatopropyl group.
  • alkenyl group examples include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group.
  • aryl group examples include phenyl, tolyl, p-hydroxyphenyl, 1- (p-hydroxyphenyl) ethyl, 2- (p-hydroxyphenyl) ethyl, 4-hydroxy-5- (p -Hydroxyphenylcarbonyloxy) pentyl group, naphthyl group.
  • R 2 in the general formula (1) is hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, each of the plurality of R 2 are the same But it can be different.
  • These alkyl groups, acyl groups and aryl groups may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
  • Specific examples of the acyl group include an acetyl group.
  • Specific examples of the aryl group include a phenyl group.
  • N in the general formula (1) represents an integer of 0 to 3.
  • organosilane represented by the general formula (1) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyl.
  • a polysiloxane synthesized by reacting a silicate compound (d) described later may be used together with one or more kinds of organosilanes represented by the general formula (1).
  • the pattern resolution is improved by reacting the silicate compound. This is presumably because the incorporation of a polyfunctional silicate compound in the polysiloxane increases the glass transition temperature of the film and suppresses pattern dripping during thermosetting.
  • the mixing ratio in the case of using a silicate compound is not particularly limited, but is preferably 50% or less in terms of the number of moles of Si atoms relative to the number of moles of Si atoms in the whole polymer.
  • the Si atom molar ratio of the silicate compound to the total number of Si atoms in the polymer can be obtained from the integral ratio of the peak derived from the Si—C bond and the peak derived from the Si—O bond in IR.
  • the structure of the monomer other than the silicate compound is determined by 1H-NMR, 13C-NMR, IR, TOF-MS, etc., and further, the gas generated in the elemental analysis method and the remaining ash ( It can be calculated from the ratio of (all assumed to be SiO 2).
  • the content of phenyl groups in the polysiloxane for the purpose of improving the compatibility with the (b) quinonediazide compound described later and forming a uniform cured film without phase separation is preferably at least 30 mol%, more preferably at least 40 mol%, based on Si atoms.
  • the phenyl group content is within this preferred range, the polysiloxane and quinonediazide compound are unlikely to cause phase separation during coating, drying, thermal curing, etc., so the film does not become cloudy and the cured film has high transparency. Is preserved.
  • the content rate of a phenyl group it is preferable that it is 70 mol% or less with respect to Si atom.
  • the content of the phenyl group is within this preferable range, crosslinking during heat curing occurs sufficiently, and the cured film has excellent chemical resistance.
  • the phenyl group content can be determined, for example, by measuring 29Si-NMR of polysiloxane and determining the ratio of the peak area of Si bonded to the phenyl group and the peak area of Si bonded to no phenyl group.
  • the weight average molecular weight (Mw) of the polysiloxane used in the present invention is not particularly limited, but is preferably 1,000 to 100,000 in terms of polystyrene measured by GPC (gel permeation chromatography), more preferably 2, 000 to 50,000. When the Mw is within this preferred range, the coating properties are good and the solubility in the developer during pattern formation is good.
  • the polysiloxane used in the present invention is synthesized by hydrolysis and partial condensation of a monomer such as organosilane represented by the general formula (1).
  • a general method can be used for hydrolysis and partial condensation. For example, a solvent, water and, if necessary, a catalyst are added to the mixture, and the mixture is heated and stirred at 50 to 150 ° C. for about 0.5 to 100 hours. During stirring, if necessary, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be distilled off by distillation.
  • the reaction solvent is not particularly limited, but usually the same solvent as the solvent (c) described later is used.
  • the addition amount of the solvent is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the monomer such as organosilane.
  • the amount of water used for the hydrolysis reaction is preferably 0.5 to 2 moles per mole of hydrolyzable groups.
  • the catalyst added as necessary, but an acid catalyst and a base catalyst are preferably used.
  • the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid or anhydride thereof, and ion exchange resin.
  • the base catalyst examples include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, amino
  • the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, amino
  • the addition amount of the catalyst is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer such as organosilane.
  • the catalyst is not contained in the polysiloxane solution after hydrolysis and partial condensation, and the catalyst can be removed as necessary.
  • a removal method Preferably water washing and / or the process of an ion exchange resin are mentioned.
  • Water washing is a method in which an organic layer obtained by diluting a polysiloxane solution with an appropriate hydrophobic solvent and washing several times with water is concentrated by an evaporator.
  • the treatment with an ion exchange resin is a method of bringing a polysiloxane solution into contact with an appropriate ion exchange resin.
  • the photosensitive siloxane composition of the present invention contains (b) a quinonediazide compound.
  • a quinonediazide compound By containing the quinonediazide compound, it is possible to form a positive type in which the exposed portion is removed with a developer.
  • the quinonediazide compound to be used is not particularly limited, but is a compound in which naphthoquinonediazidesulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group, and the ortho-position and para-position of the phenolic hydroxyl group of the compound are independently hydrogen, or A compound that is any of the substituents represented by the general formula (3) is preferably used.
  • R 7 , R 8 , and R 9 each independently represents any of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, and a substituted phenyl group. Also, R 7 , R 8 , R 9 9 may form a ring.
  • R 7 , R 8 and R 9 each independently represents any of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, and a substituted phenyl group.
  • the alkyl group may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n- Examples include an octyl group, a trifluoromethyl group, and a 2-carboxyethyl group.
  • a hydroxyl group is mentioned as a substituent substituted by a phenyl group.
  • R 7 , R 8 and R 9 may form a ring, and specific examples include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring.
  • oxidative decomposition is also caused by thermal curing. Since it does not occur, a conjugated compound represented by a quinoid structure is not formed, and the cured film is not colored and colorless and transparent are maintained.
  • quinonediazide compounds can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonic acid chloride.
  • Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all manufactured by Honshu Chemical Industry Co., Ltd.).
  • quinonediazide compound is a compound in which naphthoquinonediazidesulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group represented by the general formula (7).
  • R 24 and R 25 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
  • R 26 and R 27 each independently represents a hydrogen atom, Represents any one of an alkyl group having 1 to 8 carbon atoms, an alkoxyl group, a carboxyl group and an ester group, and a plurality of R 26 and R 27 may be the same or different.
  • c and d represent integers of 1 to 5. However, a + c and b + d are integers of 1 to 5, and c ⁇ d and c + d ⁇ 3.
  • the quinonediazide compound in which naphthoquinonediazidesulfonic acid is ester-bonded to the compound having a phenolic hydroxyl group represented by the general formula (7) has a low molecular weight and an asymmetric structure, (a) polysiloxane and (d) The compatibility with the silicate compound is good, and even when a large amount of the quinonediazide compound is added, film turbidity does not occur.
  • the dissolution contrast between the exposed portion and the unexposed portion can be improved, and the reduction of the developed film in the unexposed portion can be suppressed, thereby realizing a highly sensitive pattern formation.
  • Specific examples of the compound having a phenolic hydroxyl group represented by the general formula (7) include the following compounds.
  • 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid can be used. Since 4-naphthoquinonediazide sulfonic acid ester compound has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure. Further, the 5-naphthoquinonediazide sulfonic acid ester compound has absorption in a wide wavelength range and is therefore suitable for exposure in a wide wavelength range.
  • a 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazide sulfonic acid ester compound may be mixed and used.
  • the addition amount of the quinonediazide compound is not particularly limited, but is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the polysiloxane.
  • the addition amount of the quinonediazide compound is within this preferable range, the dissolution contrast between the exposed part and the unexposed part is not too low, and the photosensitive property is realistic.
  • the compatibility between the polysiloxane and the quinonediazide compound is kept good, whitening of the coating film does not occur, and coloring due to decomposition of the quinonediazide compound during thermal curing can be suppressed. Kept.
  • the photosensitive siloxane composition of the present invention contains (c) a solvent.
  • a solvent for example, the compound which has alcoholic hydroxyl group is used.
  • these solvents are used, the polysiloxane and the quinonediazide compound are uniformly dissolved, and even when the composition is applied, the film is not whitened and high transparency can be achieved.
  • the compound having an alcoholic hydroxyl group is not particularly limited, but is preferably a compound having a boiling point of 110 to 250 ° C. under atmospheric pressure.
  • the boiling point is in this preferred range, the amount of residual solvent in the film is small, film shrinkage during curing can be suppressed, and good flatness can be obtained.
  • the drying at the time of the coating film is not too fast, the film surface is not rough and the coating film properties are excellent.
  • the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy- 4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, propylene glycol mono t- Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3-methoxy-1 Butanol, 3-methyl-3-methoxy-1-butanol.
  • the photosensitive siloxane composition of the present invention may contain other solvents as long as the effects of the present invention are not impaired.
  • Other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1- Esters such as butyl acetate and ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetylacetone, diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl Ethers such as ether,
  • the amount of solvent added is not particularly limited, but is preferably in the range of 100 to 1000 parts by mass with respect to 100 parts by mass of polysiloxane.
  • the photosensitive siloxane composition of the present invention contains (d) a silicate compound represented by the general formula (2).
  • R 3 to R 6 each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
  • P is 2) Represents an integer of ⁇ 10)
  • Specific examples of the silicate compound represented by the general formula (2) include methyl silicate 51 (manufactured by Fuso Chemical Industry), M silicate 51, silicate 40, silicate 45 (manufactured by Tama Chemical Industry Co., Ltd.), methyl Examples thereof include silicate 51, methyl silicate 53A, ethyl silicate 40, and ethyl silicate 48 (manufactured by Colcoat Co., Ltd.).
  • methyl silicate 51 manufactured by Fuso Chemical Industry Co., Ltd.
  • M silicate 51 manufactured by Tama Chemical Industry Co., Ltd.
  • methyl silicate 51, and methyl silicate 53A are preferable.
  • p is preferably 3 to 5.
  • methyl silicate 51 (manufactured by Fuso Chemical Industry Co., Ltd.), M silicate 51 (Tama Chemical Industry Co., Ltd.) And methyl silicate 51 (manufactured by Colcoat Co., Ltd.) are preferable.
  • the silicate compound is a highly heat-resistant and highly transparent compound, and has a good compatibility because it is similar in structure to polysiloxane. Since the silicate compound has many Si-OR groups in one molecule, it reacts with the silanol group in the polysiloxane at the time of thermosetting, thereby increasing the degree of cross-linking of the cured film and improving the chemical resistance. .
  • the addition amount of the silicate compound is not particularly limited, but is preferably 3 to 20 parts by mass with respect to 100 parts by mass of the polysiloxane. More preferably, it is 3 to 10 parts by mass.
  • the addition amount of the silicate compound is within this preferable range, the chemical resistance improvement effect is great.
  • the amount of development film reduction in the unexposed area is small, the film thickness uniformity is good.
  • the photosensitive resin composition of the present invention may contain (e) a metal chelate compound represented by the following general formula (6).
  • M is a metal atom.
  • R ⁇ 21> may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, and those substituted products.
  • a plurality of R 22 and R 23 may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, or a substituted product thereof.
  • j represents the valence of the metal atom M
  • k represents an integer of 0 or more and j or less.
  • the development adhesion is improved and the chemical resistance of the obtained cured film is improved.
  • M is a metal atom and is not particularly limited, but from the viewpoint of transparency, titanium, zirconium, aluminum, zinc, cobalt, molybdenum, lanthanum, barium, strontium, magnesium, calcium Metal atoms such as Among these, zirconium or aluminum is preferable from the viewpoint of development adhesion and chemical resistance of the cured film.
  • R 21 is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, octadecanyl group, phenyl group , Vinyl group, allyl group, oleyl group and the like.
  • n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- An octadecyl group and a phenyl group are preferable.
  • R 22 and R 23 are hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, phenyl group, vinyl group, methoxy group, ethoxy group, n -Propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- An octadecyl group, a benzyloxy group, etc. are mentioned.
  • a methyl group, a t-butyl group, a phenyl group, a methoxy group, an ethoxy group, and an n-octadecyl group are preferable because they are easily synthesized and the compound is stable.
  • Examples of the compound represented by the general formula (6) include a zirconium tetra n-propoxide, zirconium tetra n-butoxide, zirconium tetra sec-butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetra (2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium tetramethyl acetoacetate, zirconium tetraethyl acetoacetate, zirconium tetramethyl malonate, zirconium tetraethyl malonate, zirconium tetrabenzoyl acetonate, zirconium Tetradibenzoylmethanate, zirconium mono-n-butoxyacetylacetonate bis (ethylacetoacetate), zirconium Mono n-butoxyethyl ace
  • Aluminum compounds include aluminum trisisopropoxide, aluminum tris n-propoxide, aluminum tris sec-butoxide, aluminum tris n-butoxide, aluminum trisphenoxide, aluminum trisacetylacetonate, aluminum tris (2,2,6,6- Tetramethyl-3,5-heptanedionate), aluminum trisethyl acetoacetate, aluminum trismethyl acetoacetate, aluminum trismethyl malonate, aluminum trisethyl malonate, aluminum ethyl acetate di (isopropoxide), aluminum acetylacetonate ) Di (isopropoxide), aluminum methyl acetoacetate di (isopropoxide), aluminum oct Tadecyl acetoacetate di (isopropylate), aluminum monoacetylacetonate bis (ethyl acetoacetate) and the like can be mentioned.
  • Titanium compounds include titanium tetra n-propoxide, titanium tetra n-butoxide, titanium tetra sec-butoxide, titanium tetraphenoxide, titanium tetraacetylacetonate, titanium tetra (2,2,6,6-tetramethyl-3, 5-heptanedionate), titanium tetramethyl acetoacetate, titanium tetraethyl acetoacetate, titanium tetramethyl malonate, titanium tetraethyl malonate, titanium tetrabenzoyl acetonate, titanium tetradibenzoyl methacrylate, titanium mono n-butoxyacetylacetonate Bis (ethyl acetoacetate), Titanium mono n-butoxyethyl acetoacetate bis (acetylacetonate), Titanium mono n-butoxytris (acetylacetonate), Titanium mono n Butoxytris (acetylacet
  • zirconium tetranormal propoxide zirconium tetranormal butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetra (2,2,6,6-tetra Methyl-3,5-heptanedionate), zirconium tetramethyl malonate, zirconium tetraethyl malonate, zirconium tetraethyl acetoacetate, zirconium dinormalbutoxybis (ethylacetoacetate), zirconium mononormalbutoxyacetylacetonate bis (ethylacetoacetate) )
  • zirconium compounds aluminum trisacetylacetonate, aluminum tris (2,2,6,6-tetramethyl-3,5 Heptanedionate), aluminum trisethyl acetoa
  • the addition amount of the metal chelate compound is not particularly limited, but is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polysiloxane. More preferably, it is 0.3 to 4 parts by weight. By being in the above range, it is possible to achieve both development adhesion and chemical resistance of the cured film at a high level.
  • the photosensitive siloxane composition of the present invention is optionally provided with a silane coupling agent, a crosslinking agent, a crosslinking accelerator, a sensitizer, a thermal radical generator, a dissolution accelerator, a dissolution inhibitor, a surfactant, and a stable agent.
  • a silane coupling agent such as an agent and an antifoaming agent can also be contained.
  • the photosensitive siloxane composition of the present invention may contain a silane coupling agent.
  • a silane coupling agent By containing the silane coupling agent, the adhesion to the substrate is improved.
  • Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltri Ethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxy
  • the addition amount of the silane coupling agent is not particularly limited, but is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polysiloxane. When the addition amount is within this preferred range, the effect of improving the adhesion is sufficient, while the silane coupling agents are difficult to undergo a condensation reaction during storage and do not cause undissolved residue during development.
  • the photosensitive siloxane composition of the present invention may contain a crosslinking agent.
  • the cross-linking agent is a compound that undergoes polysiloxane cross-linking during thermal curing and is incorporated into the resin.
  • the degree of cross-linking of the cured film is increased.
  • the chemical resistance of the cured film is improved, and a decrease in pattern resolution due to pattern dripping during thermosetting is suppressed.
  • R 10 represents any one of hydrogen and an alkyl group having 1 to 10 carbon atoms.
  • a plurality of R 10 in the compound may be the same or different.
  • R 10 represents either hydrogen or an alkyl group having 1 to 10 carbon atoms.
  • a plurality of R 10 in the compound may be the same or different.
  • Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group and n-decyl group.
  • Specific examples of the compound having two or more groups represented by the general formula (4) include the following melamine derivatives and urea derivatives (trade name, manufactured by Sanwa Chemical Co., Ltd.).
  • crosslinking agent may be used individually or may be used in combination of 2 or more type.
  • the addition amount of the crosslinking agent is not particularly limited, but is preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polysiloxane. When the addition amount of the crosslinking agent is within this preferred range, the resin is sufficiently crosslinked. On the other hand, the colorless transparency of the cured film is maintained and the storage stability of the composition is excellent.
  • the photosensitive siloxane composition of the present invention may contain a crosslinking accelerator.
  • a crosslinking accelerator is a compound that promotes crosslinking of polysiloxane during thermal curing, and is a thermal acid generator that generates acid during thermal curing, and a photoacid generator that generates acid during bleaching exposure before thermal curing. Is used.
  • the presence of an acid in the film at the time of thermosetting promotes the condensation reaction of unreacted silanol groups in the polysiloxane, and increases the degree of crosslinking of the cured film. As a result, the chemical resistance of the cured film is improved, and a decrease in pattern resolution due to pattern dripping during thermosetting is suppressed.
  • the thermal acid generator used in the present invention is a compound that generates an acid at the time of thermosetting, and it is preferable that no acid is generated or only a small amount is generated at the time of pre-baking after coating the composition. Therefore, a compound that generates an acid at a pre-bake temperature or higher, for example, 100 ° C. or higher is preferable.
  • a pre-bake temperature or higher for example, 100 ° C. or higher is preferable.
  • thermal acid generator preferably used include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, SI -110L, SI-145L, SI-150L, SI-160L, SI-180L (above trade names, manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenyl Methylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenylbenzylmethylsulfonium trifluor B methanesulfonate, 4-methoxycarbonyloxy-phenyl dimethyl sulfonium triflu
  • the photoacid generator used in the present invention is a compound that generates an acid during bleaching exposure, and is irradiated with an exposure wavelength of 365 nm (i-line), 405 nm (h-line), 436 nm (g-line), or a mixed line thereof. Is a compound that generates an acid. Therefore, although there is a possibility that acid is generated even in pattern exposure using the same light source, since the exposure amount of pattern exposure is smaller than bleaching exposure, only a small amount of acid is generated, which is not a problem.
  • the acid generated is preferably a strong acid such as perfluoroalkylsulfonic acid or p-toluenesulfonic acid, and the quinonediazide compound generating carboxylic acid does not have the function of a photoacid generator here. This is different from the crosslinking accelerator in the present invention.
  • photoacid generators preferably used include SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI-100, and NAI. -1002, NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI-01, PAI-101 , PAI-106, PAI-1001 (trade name, manufactured by Midori Chemical Co., Ltd.), SP-077, SP-082 (trade name, manufactured by ADEKA), TPS-PFBS (trade name, Toyo Gosei) Industrial Co., Ltd.), CGI-MDT, CGI-NIT (trade name, manufactured by Ciba Japan Co., Ltd.), WPAG-281, WP G-336, WPAG-339, WPAG-342, WPAG-344, WPAG-350, WPAG
  • the crosslinking accelerator the above-described thermal acid generator and photoacid generator can be used in combination.
  • the addition amount of the crosslinking accelerator is not particularly limited, but is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the polysiloxane. When the addition amount of the crosslinking accelerator is within this preferable range, the effect is sufficient, while the polysiloxane is not crosslinked during pre-baking or pattern exposure.
  • the photosensitive siloxane composition of the present invention may contain a sensitizer.
  • a sensitizer By containing a sensitizer, the reaction of the naphthoquinone diazide compound, which is a photosensitizer, is promoted to improve sensitivity, and when a photoacid generator is contained as a crosslinking accelerator, reaction during bleaching exposure is performed. Is promoted to improve the chemical resistance and pattern resolution of the cured film.
  • the sensitizer used in the present invention is not particularly limited, but a sensitizer that vaporizes by heat treatment and / or fades by light irradiation is preferably used.
  • This sensitizer is required to have absorption at 365 nm (i-line), 405 nm (h-line), and 436 nm (g-line), which are wavelengths of the light source in pattern exposure and bleaching exposure, but is cured as it is. If the film remains in the film, absorption in the visible light region exists, so that colorless transparency is lowered.
  • the sensitizer used is faded by light irradiation such as a compound (sensitizer) that is vaporized by heat treatment such as thermosetting and / or bleaching exposure.
  • a compound (sensitizer) that is vaporized by heat treatment such as thermosetting and / or bleaching exposure.
  • Compounds (sensitizers) are preferred.
  • the sensitizer that is vaporized by the heat treatment and / or discolored by light irradiation include coumarin such as 3,3′-carbonylbis (diethylaminocoumarin), anthraquinone such as 9,10-anthraquinone, benzophenone, Aromatic ketones such as 4,4′-dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone, benzaldehyde, biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene, triphenylene, pyrene, anthracene, 9-phenylanthracene, 9-methoxyanthracene, 9,10-diphenylanthracene, 9,10-bis (4-methoxyphenyl) anthracene, 9,10-bis (triphenylsilyl) anthracene, 9,10-dimethoxy Nthracene,
  • the sensitizer that is vaporized by heat treatment is preferably a sensitizer that sublimates, evaporates, or thermally decomposes due to thermal decomposition sublimates or evaporates by heat treatment.
  • the vaporization temperature of the sensitizer is preferably 130 ° C. to 400 ° C., more preferably 150 ° C. to 250 ° C.
  • the sensitizer is not easily vaporized during pre-baking, and therefore it is not lost during the exposure process, and the sensitivity can be maintained high.
  • the sensitizer since the sensitizer is vaporized at the time of heat curing, it does not remain in the cured film and can maintain colorless transparency.
  • the vaporization temperature of a sensitizer is preferably 250 ° C. or less.
  • the sensitizer that fades when irradiated with light is preferably a sensitizer that absorbs light in the visible light region when irradiated with light from the viewpoint of transparency.
  • a compound that fades upon irradiation with light is a compound that dimerizes upon irradiation with light.
  • the sensitizer is preferably an anthracene compound in that it can achieve high sensitivity and dimerizes and fades when irradiated with light, and the anthracene compound in which the 9th and 10th positions are hydrogen is unstable to heat. Therefore, 9,10-disubstituted anthracene compounds are preferable. Furthermore, the 9,10-dialkoxyanthracene compound represented by the general formula (5) is preferable from the viewpoint of improving the solubility of the sensitizer and the reactivity of the photodimerization reaction.
  • R 11 to R 18 in the general formula (5) each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an aryl group, an acyl group, or an organic group in which they are substituted.
  • the alkyl group include a methyl group, an ethyl group, and an n-propyl group.
  • the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.
  • Specific examples of the alkenyl group include a vinyl group, an acryloxypropyl group, and a methacryloxypropyl group.
  • R 11 to R 18 are preferably hydrogen or an organic group having 1 to 6 carbon atoms. More preferably, R 11 , R 14 , R 15 , R 18 are preferably hydrogen.
  • R 19 and R 20 in the general formula (5) represent an alkoxy group having 1 to 20 carbon atoms and an organic group in which they are substituted.
  • the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group, and a propoxy group and a butoxy group are preferable from the viewpoint of the solubility of the compound and a fading reaction due to photodimerization.
  • the addition amount of the sensitizer is not particularly limited, but it is preferably added in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the polysiloxane. When the addition amount of the sensitizer is within this preferable range, the transparency is not lowered and the sensitivity is not lowered.
  • a method for forming a cured film using the photosensitive siloxane composition of the present invention will be described.
  • the composition of the present invention is applied onto a base substrate by a known method such as a spinner or a slit, and prebaked with a heating device such as a hot plate or oven.
  • Pre-baking is preferably performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 ⁇ m.
  • UV-visible exposure machine such as a stepper, mirror projection mask aligner (MPA), parallel light mask aligner (PLA), etc., and pass through the desired mask at a wavelength of about 10 to 4000 J / m 2 (wavelength 365 nm equivalent). Pattern exposure.
  • a developing method it is preferable to immerse in a developing solution for 5 seconds to 10 minutes by a method such as shower, dipping or paddle.
  • a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, and tetramethyl hydroxide. Examples include aqueous solutions containing one or more quaternary ammonium salts such as ammonium and choline.
  • dehydration drying baking can be performed at a temperature of 50 to 150 ° C. with a heating device such as a hot plate or oven.
  • bleaching exposure By performing bleaching exposure, the unreacted quinonediazide compound remaining in the film is photodegraded, and the light transparency of the film is further improved.
  • a bleaching exposure method an entire surface is exposed to about 100 to 20000 J / m 2 (converted to a wavelength of 365 nm exposure amount) using an ultraviolet-visible exposure machine such as PLA.
  • the film subjected to bleaching exposure is soft-baked at a temperature of 50 to 150 ° C. for 30 seconds to 30 minutes with a heating device such as a hot plate or oven, if necessary, and then heated with a heating device such as a hot plate or oven.
  • Curing at 450 ° C for about 1 hour forms a flattening film for TFTs in display elements, protective films and insulating films for touch panels, interlayer insulating films in semiconductor elements, and core and cladding materials in optical waveguides. Is done.
  • the cured film produced using the photosensitive siloxane composition of the present invention has a light transmittance of 90% or more per film thickness of 3 ⁇ m at a wavelength of 400 nm, more preferably 92% or more.
  • the light transmittance of the cured film is within this preferable range, when used as a flattening film for a TFT substrate of a liquid crystal display element, the color change does not occur when the backlight passes and the white display becomes yellowish.
  • the light transmittance of the cured film is within this preferable range, when used as a flattening film for a TFT substrate of a liquid crystal display element, the color change does not occur when the backlight passes and the white display becomes yellowish.
  • the white display becomes yellowish.
  • the transmittance per 3 ⁇ m of film thickness at the wavelength of 400 nm is determined by the following method.
  • the composition is spin-coated on a Tempax glass plate at an arbitrary rotation number using a spin coater, and prebaked at 100 ° C. for 2 minutes using a hot plate.
  • the whole surface of the film was exposed to an ultrahigh pressure mercury lamp at 3000 J / m 2 (wavelength 365 nm exposure amount conversion), and thermally cured at 220 ° C. for 1 hour in air using an oven.
  • a 3 ⁇ m cured film is produced.
  • the ultraviolet-visible absorption spectrum of the obtained cured film is measured using “MultiSpec” -1500 manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm is determined.
  • This cured film is suitably used as a planarizing film for TFT substrates such as liquid crystal display elements, protective films and insulating films for touch panels, interlayer insulating films for semiconductor elements, or cores and cladding materials for optical waveguides.
  • the element in the present invention refers to a liquid crystal display element having a cured film as described above, an organic EL display element, a touch panel, a semiconductor element, or an optical waveguide material, and in particular, a liquid crystal display element having a flattening film for a TFT substrate, and Effectively used for a touch panel having an insulating film.
  • 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 64 g (0.1 mol) and 163.35 g of diacetone alcohol (hereinafter abbreviated as DAA) were charged, and 0.535 g of phosphoric acid (0.3% by mass with respect to the charged monomer) was added to 54 g of water while stirring at room temperature. The dissolved aqueous phosphoric acid solution was added over 10 minutes. Thereafter, the flask was immersed in a 40 ° C. oil bath and stirred for 30 minutes, and then the oil bath was heated to 115 ° C. over 30 minutes.
  • DAA diacetone alcohol
  • the resulting polysiloxane solution (a) had a solid content concentration of 40% by mass, and the polysiloxane had a weight average molecular weight of 6500. In addition, the phenyl group content rate in polysiloxane was 50 mol% with respect to Si atom.
  • Synthesis Example 2 Synthesis of polysiloxane solution (b)] In a 500 ml three-necked flask, 40.86 g (0.3 mol) of methyltrimethoxysilane, 99.15 g (0.5 mol) of phenyltrimethoxysilane, and 12.12 of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • the resulting polysiloxane solution (b) had a solid content concentration of 40% by mass, and the polysiloxane had a weight average molecular weight of 10,000. In addition, the phenyl group content rate in polysiloxane was 50 mol% with respect to Si atom.
  • Synthesis of polysiloxane solution (c) In a 500 ml three-necked flask, 88.53 g (0.65 mol) of methyltrimethoxysilane, 49.58 g (0.25 mol) of phenyltrimethoxysilane, and 24. 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • the polysiloxane solution (c) thus obtained had a solid content concentration of 40% by mass, and the weight average molecular weight of the polysiloxane was 9,000. In addition, the phenyl group content rate in polysiloxane was 25 mol% with respect to Si atom.
  • Synthesis Example 4 Synthesis of polysiloxane solution (d)] In a 500 ml three-necked flask, 20.43 g (0.15 mol) of methyltrimethoxysilane, 158.64 g (0.8 mol) of phenyltrimethoxysilane, and 12.12 of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • the polysiloxane solution (d) thus obtained had a solid content concentration of 40% by mass, and the weight average molecular weight of the polysiloxane was 7,000. In addition, the phenyl group content rate in polysiloxane was 80 mol% with respect to Si atom.
  • Synthesis Example 5 Synthesis of acrylic resin solution (a)] A 500 ml flask was charged with 5 g of 2,2′-azobis (isobutyronitrile) and 150 g of PGMEA.
  • the obtained acrylic resin solution (a) had a solid content concentration of 43% by mass, and the acrylic resin had a weight average molecular weight of 31,400.
  • Synthesis Example 6 Synthesis of quinonediazide compound (a)] Under a nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 37.62 g (0.14 mol) of 5-naphthoquinone diazide sulfonyl chloride were added to 1,4-dioxane. Dissolved in 450 g and brought to room temperature.
  • the triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (b) having the following structure.
  • Example 1 25.51 g of the polysiloxane solution (a) obtained in Synthesis Example 1, 0.92 g of the quinonediazide compound (c) obtained in Synthesis Example 8, and M silicate 51 (trade name, manufactured by Tama Chemical Co., Ltd.) as the silicate compound ) 1.02 g, KBM303 (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.20 g as a silane coupling agent, CGI-MDT (as a crosslinking accelerator) 0.10 g (trade name, manufactured by Ciba Japan), 0.05 g of DPA (9,10-dipropoxyanthracene, product name, manufactured by Kawasaki Kasei Kogyo Co., Ltd.) as a sensitizer, 3.44 g of DAA as a solvent, PGMEA 18 .75 g was mixed and stirred under a yellow light to
  • Composition 1 was spin-coated on a silicon wafer and OA-10 glass plate (manufactured by Nippon Electric Glass Co., Ltd.) using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation number, and then hot plate (Dainippon Screen Mfg. Co., Ltd. SCW-636) was pre-baked at 100 ° C. for 2 minutes to prepare a film having a thickness of 3 ⁇ m.
  • PLA parallel light mask aligner
  • PLA-501F manufactured by Canon Inc.
  • the produced film was subjected to pattern exposure with an ultra-high pressure mercury lamp through a gray scale mask for sensitivity measurement, and then automatically Using a developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 80 seconds with ELM-D (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) which is a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Then rinsed with water for 30 seconds. After that, as bleaching exposure, PLA (Canon Co., Ltd.
  • PLA-501F PLA-501F was used, and the entire surface of the film was exposed to 3000 J / m 2 (wavelength 365 nm exposure amount conversion) with an ultrahigh pressure mercury lamp. Thereafter, soft baking was performed at 110 ° C. for 2 minutes using a hot plate, and then cured in an air at 220 ° C. for 1 hour using an oven (Tabba Espec Co., Ltd.) to prepare a cured film.
  • Table 2 shows the evaluation results of the photosensitive characteristics and the cured film characteristics.
  • the evaluation in the table was performed by the following method.
  • the following evaluations (3) to (6) were performed using a silicon wafer substrate, and (8) and (9) were evaluated using an OA-10 glass plate.
  • (4) Calculation of remaining film rate The remaining film rate was calculated according to the following formula.
  • Residual film ratio (%) unexposed film thickness after development / film thickness after pre-baking ⁇ 100 (5) Calculation of sensitivity The exposure amount that forms a 10 ⁇ m line-and-space pattern with a one-to-one width after exposure and development (hereinafter referred to as the optimum exposure amount) was defined as sensitivity. (6) Calculation of resolution The minimum pattern size after development at the optimum exposure amount was taken as post-development resolution, and the minimum pattern size after cure was taken as post-cure resolution. (7) Measurement of mass reduction rate About 100 mg of the composition was placed in an aluminum cell, and a thermal mass measurement apparatus (TGA-50, manufactured by Shimadzu Corporation) was used, and the temperature was increased to 300 ° C.
  • TGA-50 thermal mass measurement apparatus
  • a cured film of the composition was formed on the OA-10 glass plate (pattern exposure was not performed), this sample was measured with a single beam, and the light transmittance at a wavelength of 400 nm per 3 ⁇ m was obtained. The difference was the light transmittance of the cured film.
  • compositions 2 to 17 were produced in the same manner as Composition 1 according to the compositions described in Table 1.
  • methyl silicate 53A used as a silicate compound ethyl silicate 40, ethyl silicate 48 (trade name, manufactured by Colcoat Co., Ltd.), KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) used as a silane coupling agent, Nicalac MX-270 and Nicalac MW-30HM (trade names, manufactured by Sanwa Chemical Co., Ltd.) used as crosslinking agents are compounds having the structures shown below.
  • Example 2 Each composition was evaluated in the same manner as in Example 1 using each composition obtained. However, in the evaluation of Comparative Example 2, the development was performed by shower development for 80 seconds with a 0.4 mass% tetramethylammonium hydroxide aqueous solution (ELM-D diluted with water). The results are shown in Table 2. Since Comparative Examples 1, 2, and 4 do not contain the silicate compound represented by the general formula (2), the chemical resistance of the cured film properties is inferior. Moreover, since the resin is an acrylic resin, the comparative example 3 is inferior in the light transmittance among cured film characteristics.
  • the present invention forms a flattening film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a protective film or insulating film for a touch panel, an interlayer insulating film for a semiconductor element, or a core or cladding material for an optical waveguide. Therefore, it can be suitably used for a photosensitive siloxane composition.
  • TFT thin film transistor

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Abstract

La présente invention concerne une composition de siloxane photosensible, comprenant : (a) un polysyloxane synthétisé par réaction d'au moins un organosilane représenté par la formule générale (1) ; (b) un composé de quinonediazide ; c) un solvant ; et (d) le composé de silicate représenté par la formule générale (2). Dans la formule (1) : R1 représente l'un quelconque des éléments suivants : hydrogène, groupe alkyle ayant de 1 à 10 atomes de carbone, groupe alcényle ayant de 2 à 10 atomes de carbone, ou groupe aryle ayant de 6 à 15 atomes de carbone, la pluralité des R1 pouvant être identiques ou différents ; R2 représente l'un quelconque des éléments suivants : hydrogène, groupe alkyle ayant de 1 à 6 atomes de carbone, groupe acyle ayant de 2 à 6 atomes de carbone, ou groupe aryle ayant de 6 à 15 atomes de carbone, la pluralité des R2 pouvant être identiques ou différents ; et n représente un entier allant de 0 à 3. Dans la formule (2), R3 à R6 représentent chacun indépendamment l'un quelconque des éléments suivants : hydrogène, groupe alkyle ayant de 1 à 6 atomes de carbone, groupe acyle ayant de 2 à 6 atomes de carbone, ou groupe aryle ayant de 6 à 15 atomes de carbone ; et p représente un entier allant de 2 à 10. La composition de siloxane photosensible selon l'invention peut produire un film durci présentant des propriétés de forte résistance à la chaleur et de grande transparence, et dont la résistance chimique est favorable.
PCT/JP2011/062684 2010-06-09 2011-06-02 Composition de siloxane photosensible, film durci formé avec cette composition, et élément comportant le film durci WO2011155382A1 (fr)

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KR1020127025114A KR101761181B1 (ko) 2010-06-09 2011-06-02 감광성 실록산 조성물, 그것으로부터 형성된 경화막 및 경화막을 갖는 소자
CN201180028270.8A CN102918460B (zh) 2010-06-09 2011-06-02 感光性硅氧烷组合物、由其形成的固化膜和具有固化膜的元件

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JP2013203989A (ja) * 2012-03-29 2013-10-07 Nippon Tungsten Co Ltd オルガノポリシロキサン混合体組成物、フィラー含有オルガノポリシロキサン、コーティング塗料及びコーティング体
JP5505569B1 (ja) * 2012-12-11 2014-05-28 東レ株式会社 熱硬化性着色組成物及び硬化膜、その硬化膜を具備したタッチパネル、その熱硬化性着色組成物を用いるタッチパネルの製造方法
WO2014156520A1 (fr) * 2013-03-28 2014-10-02 東レ株式会社 Composition de résine photosensible, film de protection ou film d'isolation, panneau tactile et procédé pour sa fabrication
US9704724B2 (en) 2011-12-26 2017-07-11 Toray Industries, Inc. Photosensitive resin composition and method for producing semiconductor device
JP2019530900A (ja) * 2016-09-28 2019-10-24 サムスン エスディアイ カンパニー, リミテッドSamsung Sdi Co., Ltd. 感光性樹脂組成物、それから形成された硬化膜、および前記硬化膜を有する電子装置
TWI771907B (zh) * 2016-03-25 2022-07-21 盧森堡商Ａｚ電子材料盧森堡有限公司 感光性矽氧烷組成物及硬化膜的形成方法

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WO2014125884A1 (fr) * 2013-02-12 2014-08-21 東レ株式会社 Composition de résine photosensible, film protecteur ou film isolant obtenu par thermodurcissement de ladite composition, écran tactile utilisant ledit film et procédé de production pour ledit écran tactile
JP6666572B2 (ja) * 2015-03-05 2020-03-18 Jsr株式会社 感放射線性組成物及びパターン形成方法
KR102380151B1 (ko) * 2015-08-31 2022-03-28 삼성전자주식회사 박막 트랜지스터, 및 이를 포함하는 전자 장치
TWI606302B (zh) * 2016-10-18 2017-11-21 臺灣永光化學工業股份有限公司 負型感光性樹脂組成物及其用途
KR102497140B1 (ko) * 2018-11-02 2023-02-06 주식회사 엘지화학 아크릴계 에멀젼 점착제 조성물

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JP2008276190A (ja) * 2007-04-06 2008-11-13 Asahi Kasei Electronics Co Ltd ポジ型感光性樹脂組成物
JP2010033005A (ja) * 2008-06-23 2010-02-12 Toray Ind Inc 感光性組成物、それから形成された硬化膜、および硬化膜を有する素子

Cited By (9)

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Publication number Priority date Publication date Assignee Title
US9704724B2 (en) 2011-12-26 2017-07-11 Toray Industries, Inc. Photosensitive resin composition and method for producing semiconductor device
JP2013203989A (ja) * 2012-03-29 2013-10-07 Nippon Tungsten Co Ltd オルガノポリシロキサン混合体組成物、フィラー含有オルガノポリシロキサン、コーティング塗料及びコーティング体
JP5505569B1 (ja) * 2012-12-11 2014-05-28 東レ株式会社 熱硬化性着色組成物及び硬化膜、その硬化膜を具備したタッチパネル、その熱硬化性着色組成物を用いるタッチパネルの製造方法
WO2014091811A1 (fr) * 2012-12-11 2014-06-19 東レ株式会社 Composition de coloration thermodurcissable, film durci, panneau tactile doté dudit film durci et procédé de production de panneau tactile à l'aide de ladite composition de coloration thermodurcissable
KR101938603B1 (ko) 2012-12-11 2019-01-15 도레이 카부시키가이샤 열경화성 착색 조성물 및 경화막, 그 경화막을 구비한 터치 패널, 그 열경화성 착색 조성물을 사용하는 터치 패널의 제조 방법
WO2014156520A1 (fr) * 2013-03-28 2014-10-02 東レ株式会社 Composition de résine photosensible, film de protection ou film d'isolation, panneau tactile et procédé pour sa fabrication
JPWO2014156520A1 (ja) * 2013-03-28 2017-02-16 東レ株式会社 感光性樹脂組成物、保護膜又は絶縁膜、タッチパネル及びその製造方法
TWI771907B (zh) * 2016-03-25 2022-07-21 盧森堡商Ａｚ電子材料盧森堡有限公司 感光性矽氧烷組成物及硬化膜的形成方法
JP2019530900A (ja) * 2016-09-28 2019-10-24 サムスン エスディアイ カンパニー, リミテッドSamsung Sdi Co., Ltd. 感光性樹脂組成物、それから形成された硬化膜、および前記硬化膜を有する電子装置

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CN102918460B (zh) 2015-07-22
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TW201211112A (en) 2012-03-16

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