WO2011078106A1 - ポジ型感光性樹脂組成物、それから形成された硬化膜、および硬化膜を有する素子 - Google Patents
ポジ型感光性樹脂組成物、それから形成された硬化膜、および硬化膜を有する素子 Download PDFInfo
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- WO2011078106A1 WO2011078106A1 PCT/JP2010/072865 JP2010072865W WO2011078106A1 WO 2011078106 A1 WO2011078106 A1 WO 2011078106A1 JP 2010072865 W JP2010072865 W JP 2010072865W WO 2011078106 A1 WO2011078106 A1 WO 2011078106A1
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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
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- 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
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- 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
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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
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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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- 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
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
Definitions
- the present invention relates to 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 an insulating film such as a touch panel sensor element, an interlayer insulating film for a semiconductor element, or a flattening film for a solid-state imaging element.
- TFT thin film transistor
- the present invention relates to a photosensitive composition for forming a core and a clad material of an optical waveguide such as a microlens array pattern or an optical semiconductor element, a cured film formed therefrom, and an element having the cured film.
- Patent Document 1 a method for increasing the aperture ratio of a display device is known as a method for realizing higher definition and higher resolution in a liquid crystal display, an organic EL display, and the like (see Patent Document 1).
- 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 hole pattern having a high heat resistance and a high transparency is formed, and a hole pattern of about 50 ⁇ m to several ⁇ m is formed to ensure conduction between the TFT substrate electrode and the ITO electrode.
- a positive photosensitive material is used.
- a typical material a material in which an acrylic resin is combined with a quinonediazide compound (see Patent Documents 2, 3, and 4) is known.
- polysiloxane is known as another material having features such as high heat resistance and high transparency, and a material in which a quinonediazide compound is combined in order to impart positive photosensitivity (Patent Documents 5 and 6).
- This material is highly transparent, and a highly transparent cured film can be obtained without lowering the transparency even when the substrate is treated at high temperature.
- sensitivity, resolution and chemical resistance are sufficient, and there is a strong demand for a positive photosensitive material with higher sensitivity, high resolution and high chemical resistance.
- Patent Document 7 a positive siloxane material using a polysiloxane having a quinonediazide structure
- This material has the problem that the process for incorporating quinonediazide into the polymer structure increases, is complicated, and has low transparency.
- a positive siloxane material Patent Document 8 in which a polysiloxane having a phenolic hydroxyl group in a polymer and a naphthoquinonediazide compound are combined is known.
- This material has the problem of increasing the steps for incorporating phenol into the polymer structure, which is cumbersome and has low transparency. Moreover, it is a 2 layer resist use and this siloxane cured film does not remain in an element.
- the present invention has been made based on the above-mentioned circumstances, has features of high heat resistance and high transparency, can form a pattern with high sensitivity and high resolution, and has excellent chemical resistance.
- a positive photosensitive composition is provided.
- Another object of the present invention is to provide a planarized film for a TFT substrate, an interlayer insulating film, a protective film for a touch panel, an insulating film, a cured film such as a core or a clad material, formed from the above positive photosensitive composition,
- a display element, a semiconductor element, a solid-state imaging element, an optical waveguide, and the like having the cured film are provided.
- a positive photosensitive composition containing (a) a polysiloxane, (b) a naphthoquinone diazide compound, and (c) a solvent, wherein (a) an organosilane represented by the general formula (1) in the polysiloxane Organosilane represented by the general formula (2) in the polysiloxane, wherein the content ratio of the derived structure is 20% or more and 80% or less in terms of the Si atom mole ratio with respect to the number of moles of Si atoms in the whole polysiloxane.
- a positive photosensitive resin composition comprising a derived structure.
- R 1 represents an aryl group having 6 to 15 carbon atoms, and a plurality of R 1 may be the same or different.
- R 2 represents hydrogen, an alkyl group having 1 to 6 carbon atoms, 2 to 6 represents an acyl group of 6 or an aryl group of 6 to 15 carbon atoms, and a plurality of R 2 may be the same or different, and n represents an integer of 1 to 3.
- R 3 to R 6 each independently represent any 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. Represents an integer from 1 to 11.
- the photosensitive composition of the present invention has high heat resistance and high transparency, and is excellent in high chemical resistance.
- the obtained cured film can be suitably used as a planarizing film for TFT substrate, an interlayer insulating film, a protective film for a touch panel, or an insulating film.
- the photosensitive composition of the present invention is a positive photosensitive composition containing (a) a polysiloxane, (b) a naphthoquinonediazide compound, and (c) a solvent, wherein the general formula (a) The content ratio of the structure derived from the organosilane represented by 1) is 20% or more and 80% or less in terms of the Si atom mole ratio with respect to the number of moles of Si atoms in the entire polysiloxane, and (a) the polysiloxane has the general formula ( 2) A positive photosensitive resin composition comprising a structure derived from an organosilane represented by 2).
- the positive photosensitive composition of the present invention comprises (a) one or more organosilanes represented by the following general formula (1) and one or more organosilanes represented by the following general formula (2). Contains polysiloxane synthesized by hydrolyzing and condensing silane.
- R 1 represents an aryl group having 6 to 15 carbon atoms, and the plurality of R 1 may be the same or different. These aryl groups may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition.
- Preferred aryl groups as specific examples of the aryl group and its substituent include phenyl group, tolyl group, naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, fluorenonyl group, pyrenyl group, indenyl group, acenaphthenyl group and the like. Since these aryl groups do not have a phenolic hydroxyl group in the skeleton, they are particularly preferable in terms of high transparency of the cured film.
- a phenyl group More preferred are a phenyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, fluorenonyl group, and acenaphthenyl group, and most preferred is a phenyl 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 1 to 3.
- organosilane represented by the general formula (1) include phenyltrimethoxysilane, phenyltriethoxysilane, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, 1-anthracenyltrimethoxysilane, 9-anthracenyltrimethoxysilane, 9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane, 2-fluorenyltrimethoxysilane, Trifunctional silanes such as 2-fluorenonyltrimethoxysilane, 1-pyrenyltrimethoxysilane, 2-indenyltrimethoxysilane, 5-acenaphthenyltrimethoxysilane, diphenyldimethoxy
- organosilanes may be used alone or in combination of two or more.
- trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the cured film, and phenyltrimethoxysilane and 1-naphthyltrimethoxysilane are preferable.
- the polysiloxane can be used for the purpose of ensuring sufficient compatibility with the naphthoquinonediazide compound described later and forming a uniform cured film without phase separation.
- the ratio derived from the organosilane represented by the general formula (1) is 20% or more and 80% or less, preferably 25% or more and 70% or less in terms of the Si atom mole ratio with respect to the number of moles of Si atoms in the whole polysiloxane. Preferably they are 30% or more and 65% or less.
- the organosilane represented by the general formula (1) is more than 80% in terms of the Si atom molar ratio, crosslinking during thermal curing does not occur sufficiently and the chemical resistance of the cured film is lowered. If it is less than 20%, the compatibility between the polysiloxane and the naphthoquinonediazide compound is deteriorated, and the transparency of the cured film is lowered.
- the organosilane represented by the general formula (1) is less than 20% in terms of the Si atomic molar ratio, the polysiloxane and the naphthoquinonediazide compound cause phase separation during coating, drying, thermosetting, etc. As a result, the transmittance of the cured film decreases.
- the content derived from the organosilane of the general formula (1) is measured, for example, by 29 Si-NMR of polysiloxane, and the peak area of Si bonded to the aryl group in the general formula (1) is bonded to the aryl group. It can be determined from the ratio of the peak area of Si.
- 29 Si-NMR, 1H-NMR, 13C-NMR, IR, TOF-MS, elemental analysis, ash content measurement, and the like can be used in combination.
- R 3 to R 6 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or 6 to 15 carbon atoms.
- 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.
- aryl group examples include a phenyl group.
- M in the general formula (2) is an integer of 1 to 11. If m exceeds 11, a development residue may be generated, which is not preferable. From the standpoint of compatibility between chemical resistance and sensitivity, m is preferably an integer of 1 to 8, more preferably an integer of 3 to 8.
- M silicate 51 (m 4, average)
- silicate 40 (m 5, average)
- methyl silicate 51 (m 4, average)
- methyl silicate 53A (M 7, average)
- ethyl silicate 40 (m 5, average
- the content ratio of the organosilane represented by the general formula (2) in the polysiloxane of (a) is preferably 5% or more and 80% or less in terms of the Si atom mole ratio relative to the number of moles of Si atoms in the entire polysiloxane, more preferably, It is 12% or more and 60% or less, more preferably 25% or more and 60% or less. More preferably, the upper limit is preferably less than 60%.
- the content ratio of the organosilane represented by the general formula (2) is, for example, measured by 29 Si-NMR of polysiloxane, the peak area of Si derived from the tetrafunctional silane in the general formula (2) and the tetrafunctional silane derived Other than the peak area ratio of Si.
- 29 Si-NMR, 1 H-NMR, 13 C-NMR, IR, TOF-MS, elemental analysis, ash content measurement, and the like can be used in combination.
- At least one organosilane represented by the above general formula (1), at least one organosilane represented by the general formula (2), and a general formula ( Polysiloxane synthesized by reacting organosilane containing organosilane represented by 3) may be used.
- R 7 represents either an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and a plurality of R 7 may be the same or different. Also good. These alkyl groups and alkenyl groups may be either unsubstituted or substituted, and can be selected according to the characteristics of the composition.
- alkyl group and its substituent 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- Examples include aminopropyl group, 3-mercaptopropyl group, and 3-isocyanatopropyl group.
- alkenyl group and substituted products thereof include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group.
- R 8 in the general formula (3) 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 8 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.
- L in the general formula (3) represents an integer of 1 to 3.
- organosilane represented by the general formula (3) include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyl Triisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltri Ethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxys
- these organosilanes may be used alone or in combination of two or more.
- trifunctional silanes are preferably used from the viewpoint of crack resistance and hardness of the cured film, and methyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane.
- the content ratio in the case of using the organosilane of the general formula (3) is not particularly limited, but is preferably 50% or less in terms of the Si atom mole ratio relative to the number of moles of Si atoms in the whole polysiloxane.
- the organosilane of the general formula (3) is more than 50%, the compatibility between the polysiloxane and the naphthoquinonediazide compound is deteriorated, and the transparency of the cured film may be lowered.
- one or more types of organosilane represented by the above general formula (1), one or more types of organosilane represented by the general formula (2), and silica particles are reacted.
- the pattern resolution is improved by reacting the silica particles. This is presumably because silica particles are incorporated into polysiloxane, so that the glass transition temperature of the film is increased and the pattern dripping at the time of thermosetting is suppressed.
- the number average particle diameter of the silica particles is preferably 2 nm to 200 nm, more preferably 5 nm to 70 nm. If it is smaller than 2 nm, the effect of improving the pattern resolution is not sufficient, and if it is larger than 200 nm, the cured film is scattered and the transparency is lowered.
- the number average particle diameter of the silica particles is assumed to be a sphere after the silica particles are dried and calcined and the specific surface area of the obtained particles is measured when using the specific surface area conversion value. The particle diameter is obtained from the specific surface area, and the average particle diameter is obtained as a number average.
- the apparatus to be used is not particularly limited, “ASAP” 2020 (trade name, manufactured by Micromeritics) or the like can be used.
- silica particles include IPA-ST having a particle diameter of 12 nm using isopropanol as a dispersion medium, MIBK-ST having a particle diameter of 12 nm using methyl isobutyl ketone as a dispersion medium, and IPA-ST having a particle diameter of 45 nm using isopropanol as a dispersion medium.
- Cataloid with a particle size of 5 to 80 nm in which the dispersion solution is water- S (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.), “Quatron” PL-2L-PGME having a particle diameter of 16 nm using propylene glycol monomethyl ether as a dispersion medium, and 17 nm having a particle diameter of 17 nm using ⁇ -butyrolactone as a dispersion medium.
- the mixing ratio in the case of using silica particles is not particularly limited, but is preferably 50% or less in terms of the Si atom mole ratio relative to the number of moles of Si atoms in the whole polysiloxane.
- silica particles When there are more silica particles than 50%, the compatibility of polysiloxane and a naphthoquinone diazide compound will worsen, and the transparency of a cured film will fall.
- the weight average molecular weight (Mw) of the polysiloxane used in the present invention is not particularly limited, but is preferably 1000 to 100,000, more preferably 1500 to 50,000 in terms of polystyrene measured by GPC (gel permeation chromatography).
- Mw is less than 1000, the coating properties are deteriorated, and when it is greater than 100,000, the solubility in a developer during pattern formation is deteriorated.
- the polysiloxane in the present invention is synthesized by hydrolysis and partial condensation of monomers such as organosilanes represented by the general formulas (1), (2) and (3).
- 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., preferably 90 to 130 ° 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 the same solvent as the solvent (c) described later is usually used.
- the amount of the solvent added is preferably 10 to 1000 parts by weight with respect to 100 parts by weight 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 weight with respect to 100 parts by weight of the monomer such as organosilane.
- the polysiloxane solution after hydrolysis and partial condensation does not contain the catalyst, and the catalyst can be removed as necessary.
- the removal method is not particularly limited, but water washing and / or ion exchange resin treatment is preferable from the viewpoint of easy operation and removability.
- Water washing is a method of concentrating an organic layer obtained by diluting a polysiloxane solution with an appropriate hydrophobic solvent and then washing several times with water with an evaporator or the like.
- the treatment with an ion exchange resin is a method of bringing a polysiloxane solution into contact with an appropriate ion exchange resin.
- the positive photosensitive composition of the present invention contains (b) a naphthoquinonediazide compound.
- the photosensitive composition containing a naphthoquinone diazide compound forms a positive type in which the exposed portion is removed with a developer.
- the naphthoquinone diazide compound to be used is not particularly limited, but is preferably a compound in which naphthoquinone diazide sulfonic 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 independent of each other.
- a compound that is any one of hydrogen, a hydroxyl group, or a substituent represented by the general formulas (5) to (6) is used.
- each of R 14 , R 15 , and R 16 independently represents any of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, and a substituted phenyl group. Further, R 14 , R 15 , and R 16 may form a ring.
- 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.
- substituent on the phenyl group examples include a hydroxyl group and a methoxy group.
- Specific examples of the ring formed by R 14 , R 15 , and R 16 include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring.
- these naphthoquinone diazide compounds can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinone diazide sulfonic acid chloride.
- Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all manufactured by Honshu Chemical Industry Co., Ltd.).
- 4-naphthoquinone diazide sulfonic acid chloride or 5-naphthoquinone diazide sulfonic acid chloride 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.
- Examples of the naphthoquinone diazide compound preferably used in the present invention include compounds represented by the following general formula (4).
- R 9 represents hydrogen or an alkyl group selected from 1 to 8 carbon atoms.
- R 10 , R 11 , R 12 , and R 13 each represent a hydrogen atom, an alkyl group selected from 1 to 8 carbon atoms, an alkoxyl group, a carboxyl group, or an ester group.
- Each R 10 , R 11 , R 12 , R 13 may be the same or different.
- Q represents a 5-naphthoquinonediazidosulfonyl group or a hydrogen atom, and all of Q does not become a hydrogen atom.
- a, b, c, d, e, ⁇ , ⁇ , ⁇ , and ⁇ represent integers of 0 to 4. However, ⁇ + ⁇ + ⁇ + ⁇ ⁇ 2.
- the addition amount of the naphthoquinonediazide compound is not particularly limited, but is preferably 2 to 30 parts by weight, more preferably 3 to 15 parts by weight with respect to 100 parts by weight of the resin (polysiloxane).
- the addition amount of the naphthoquinone diazide compound is less than 1 part by weight, the dissolution contrast between the exposed part and the unexposed part is too low, and the photosensitivity sufficient for practical use is not exhibited. Further, in order to obtain a better dissolution contrast, 5 parts by weight or more is preferable.
- the addition amount of the naphthoquinone diazide compound is more than 30 parts by weight, the coating film may be whitened due to poor compatibility between the polysiloxane and the naphthoquinone diazide compound, or coloring due to decomposition of the quinone diazide compound that occurs during thermal curing may occur. As a result, the colorless transparency of the cured film decreases. Further, in order to obtain a highly transparent film, the content is preferably 15 parts by weight or less.
- the positive photosensitive 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 higher than 250 ° C., the amount of residual solvent in the film increases and film shrinkage during curing increases, and good flatness cannot be obtained.
- the boiling point is lower than 110 ° C., the coating properties deteriorate, such as drying at the time of coating is too fast and the film surface becomes rough.
- 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 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, ethyl acetoacetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, acetylacetone, diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, etc.
- Ethers ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, propylene carbonate, N-methylpyrrolidone, cyclopentanone, Rohekisanon and cycloheptanone and the like.
- the amount of the solvent added is not particularly limited, but is preferably in the range of 100 to 2000 parts by weight with respect to 100 parts by weight of the resin (polysiloxane).
- the photosensitive composition of the present invention may contain 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 stabilizer as necessary. Further, additives such as an antifoaming agent can be contained.
- the photosensitive composition of the present invention may contain a silane coupling agent.
- 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 Propyltrimethoxysilane, 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 weight with respect to 100 parts by weight of the resin (acrylic resin + polysiloxane). If the addition amount is less than 0.1 parts by weight, the effect of improving the adhesion is not sufficient, and if it is more than 10 parts by weight, the silane coupling agents undergo a condensation reaction during storage, causing undissolved residue during development.
- the photosensitive composition of the present invention may contain a surfactant.
- a surfactant By containing the surfactant, coating unevenness is improved and a uniform coating film is obtained.
- Fluorine-based surfactants and silicone-based interface chemicals are preferably used.
- fluorosurfactant examples include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl. Hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1 , 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2 , 8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N- [3- (Perf Oloocty
- silicone surfactants examples include SH28PA, SH7PA, SH21PA, SH30PA, ST94PA (all manufactured by Toray Dow Corning Silicone Co., Ltd.), BYK-333 (manufactured by Big Chemie Japan Co., Ltd.), and the like. It is done.
- the content of the surfactant is generally 0.0001 to 1% by weight in the photosensitive composition.
- the photosensitive composition of the present invention may contain a crosslinking agent.
- the crosslinking agent is a compound that crosslinks an acrylic resin or polysiloxane at the time of thermal curing and is incorporated into the resin.
- the degree of crosslinking 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.
- the compound which has two or more structures selected from the group represented by General formula (7), an epoxy structure, and an oxetane structure is mentioned.
- the combination of the above structures is not particularly limited, but the selected structures are preferably the same.
- R 17 represents either hydrogen or an alkyl group having 1 to 10 carbon atoms.
- a plurality of R 17 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 (7) include the following melamine derivatives and urea derivatives (trade names, manufactured by Sanwa Chemical Co., Ltd.).
- Specific examples of compounds having two or more epoxy structures or oxetane structures include “Epolite” 40E, 100E, 200E, 400E, 70P, 200P, 400P, 1500NP, 80MF, 4000, 3002 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), “Denacol” EX-212L, EX-214L, EX-216L, EX-850L, EX-321L (trade name, Nagase ChemteX ( Co., Ltd.), GAN, GOT, EPPN502H, NC3000, NC6000 (above trade name, Nippon Kayaku Co., Ltd.), “Epicoat” 828, 1002, 1750, 1007, YX8100-BH30, E1256, E4250, E4275 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), “Epiclon” XA-9583, HP4032, N695, HP7200 (trade name, manufactured by Dainippon In
- the addition amount of the crosslinking agent is not particularly limited, but is preferably in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the resin (polysiloxane + acrylic resin).
- the addition amount of the crosslinking agent is less than 0.1 parts by weight, the crosslinking of the resin is insufficient and the effect is small.
- the addition amount of the crosslinking agent is more than 20 parts by weight, the colorless transparency of the cured film is lowered or the storage stability of the composition is lowered.
- the photosensitive 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. If an acid is generated at a temperature lower than the pre-baking temperature, crosslinking of the polysiloxane is likely to occur during pre-baking, and the sensitivity may be lowered, or undissolved residue may be generated during development.
- thermal acid generator preferably used include “Sun-Aid” SI-60, SI-80, SI-100, SI-200, SI-110, SI-145, SI-150, SI-60L, SI- 80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L (above trade name, manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate Benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenylbenzen Examples include methylsulfonium trifluoromethanesulfonate, 4-methoxycarbonyloxyphenyldimethyl
- 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) Kogyo Co., Ltd.), CGI-MDT, CGI-NIT (trade name, manufactured by Ciba Japan Co., Ltd.), WPAG-281, WPAG 336, WPAG-339, WPAG-342, WPAG-344, 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 weight with respect to 100 parts by weight of the resin (polysiloxane). If the addition amount is less than 0.01 parts by weight, the effect is not sufficient, and if it is more than 5 parts by weight, polysiloxane may be crosslinked during pre-baking or pattern exposure.
- the photosensitive 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 solvent 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 vaporized during the pre-baking and may not be present during the exposure process, and the sensitivity may not be increased.
- the vaporization temperature of the sensitizer is preferably 150 ° C. or higher.
- the vaporization temperature of the sensitizer is higher than 400 ° C., the sensitizer does not vaporize during thermal curing and remains in the cured film, and the colorless transparency may be lowered.
- 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 (8) is preferable from the viewpoint of improving the solubility of the sensitizer and the reactivity of the photodimerization reaction.
- R 18 to R 25 in the general formula (8) 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 18 to R 25 are preferably hydrogen or an organic group having 1 to 6 carbon atoms. More preferably, R 18 , R 21 , R 22 , R 25 are preferably hydrogen.
- R 26 and R 27 in the general formula (8) 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 weight with respect to 100 parts by weight of the resin (polysiloxane). If it is out of this range, the transparency is lowered or the sensitivity is lowered.
- the photosensitive composition of the present invention may contain an acrylic resin.
- an acrylic resin By using an acrylic resin, adhesion to the base substrate and pattern processability may be improved.
- an acrylic resin Preferably the polymer of unsaturated carboxylic acid is mentioned.
- unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and the like. These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds.
- Examples of copolymerizable ethylenically unsaturated compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, N-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, n-pentyl acrylate, N-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, benzyl acrylate, benzyl methacrylate, st
- the weight average molecular weight (Mw) of the acrylic resin is not particularly limited, but is preferably 5000 to 50000, more preferably 8000 to 35000 in terms of polystyrene measured by GPC. If Mw is smaller than 5000, pattern reflow occurs during thermal curing, resulting in a decrease in resolution. On the other hand, if Mw is larger than 50000, the polysiloxane and the acrylic resin are phase-separated, and the film becomes cloudy, so that the transmittance of the cured film is lowered.
- the acrylic resin used in the present invention is preferably alkali-soluble, and the acid value of the acrylic resin is preferably 50 to 150 mgKOH / g, more preferably 70 to 130 mgKOH / g. If the resin acid value is less than 50 mgKOH / g, undissolved residue tends to occur during development. On the other hand, if the acid value is larger than 150 mgKOH / g, the film loss in the unexposed area becomes large during development.
- the acrylic resin is preferably an acrylic resin having an ethylenically unsaturated group added to the side chain.
- an acrylic resin having an ethylenically unsaturated group added to the side chain By adding an ethylenically unsaturated group to the side chain, cross-linking of the acrylic resin occurs at the time of thermosetting, and the chemical resistance of the cured film is improved.
- the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group.
- a method for adding an ethylenically unsaturated group to the side chain of an acrylic resin a compound containing a functional group such as a hydroxyl group, an amino group, or a glycidyl group and an ethylenically unsaturated group is used.
- the method of making it react with the carbonyl group in it is mentioned.
- the compound containing a functional group such as a hydroxyl group, amino group or glycidyl group and an ethylenically unsaturated group include 2-hydroxylethyl acrylate, 2-hydroxyethyl methacrylate, 2-aminoethyl acrylate, methacrylic acid.
- Examples include 2-aminoethyl acid, glycidyl acrylate, and glycidyl methacrylate.
- the photosensitive 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 naphthoquinonediazide compound remaining in the film is photodecomposed, 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.
- a flattened film for TFT in the display element By curing for about 1 hour in the range of 450 ° C., a flattened film for TFT in the display element, an interlayer insulating film in the semiconductor element, or a cured film such as a core or cladding material in the optical waveguide is formed.
- a high temperature CVD film such as a Si film or a SiN film on these cured films at 280 ° C. or higher, and high heat resistance and high transparency capable of withstanding this high temperature are demanded. .
- the cured film produced using the photosensitive 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, and still more preferably 95% or more.
- the light transmittance is lower than 90%, when it is used as a planarizing film for a TFT substrate of a liquid crystal display element, a color change occurs when the backlight passes, and the white display becomes yellowish.
- the transmittance per film thickness of 3 ⁇ m 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. Then, as bleaching exposure, using PLA, 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 planarization film for TFT in a display element, an interlayer insulating film in a semiconductor element, an insulating film / protective film for a touch panel, or a core or cladding material in an optical waveguide.
- the element in the present invention refers to a display element, a semiconductor element, or an optical waveguide material having a cured film having high heat resistance and high transparency as described above, and in particular, a liquid crystal having a flattening film for TFT, and an organic EL display Suitable for display elements with sensor elements and touch panel sensor elements.
- DAA diacetone alcohol
- PGMEA propylene glycol monomethyl ether acetate
- GBL ⁇ -butyrolactone
- EDM diethylene glycol methyl ethyl ether
- DPM dipropylene glycol monoether methyl.
- the solid content concentration of the polysiloxane solution and the acrylic resin solution was determined as follows.
- Weight average molecular weight was determined by GPC (Waters 410 type RI detector, fluidized bed: tetrahydrofuran) in terms of polystyrene.
- Ratio of organosilane structure represented by general formula (1) and general formula (2) in polysiloxane 29 Si-NMR was measured, and the ratio of the integrated value with respect to each organosilane was calculated from the total integrated value, and the ratio was calculated.
- the sample (liquid) was injected into a Teflon (registered trademark) NMR sample tube having a diameter of 10 mm and used for measurement.
- the measurement conditions for 29 Si-NMR are shown below.
- Measurement method Gated decoupling method Measurement nuclear frequency: 53.6693 MHz ( 29 Si nucleus), spectral width: 20000 Hz Pulse width: 12 ⁇ sec (45 ° pulse), pulse repetition time: 30.0 sec Solvent: acetone-d6, reference material: tetramethylsilane Measurement temperature: room temperature, sample rotation speed: 0.0 Hz.
- a polysiloxane solution (a) After being immersed in an oil bath at °C and stirred for 30 minutes, the temperature of the oil bath was raised to 115 ° C. over 30 minutes. The internal temperature of the liquid reached 100 ° C., and was then heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (a), while 0.05 l ( In total, 125 g of methanol and water as by-products were distilled out during the reaction. The resulting polysiloxane solution (a) had a solid content concentration of 43% by weight, and the polysiloxane had a weight average molecular weight of 8,500.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 50% in terms of the Si atom molar ratio
- the content ratio of the organosilane represented by the general formula (2) is 15 in terms of the Si atomic mole ratio. %Met.
- a polysiloxane solution (b) 150 liters of methanol and water as by-products were distilled out during the reaction.
- the resulting polysiloxane solution (b) had a solid content concentration of 44% by weight, and the polysiloxane had a weight average molecular weight of 11400.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 50% in terms of Si atom molar ratio
- the content ratio of the organosilane represented by the general formula (2) is 30 in terms of Si atomic mole ratio. %Met.
- the solid content concentration of the obtained polysiloxane solution (c) was 42% by weight, and the weight average molecular weight of the polysiloxane was 12400.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 50% in terms of Si atom molar ratio
- the content ratio of the organosilane represented by the general formula (2) is 40 in terms of Si atomic mole ratio. %Met.
- the solid content concentration of the obtained polysiloxane solution (d) was 39% by weight, and the weight average molecular weight of the polysiloxane was 13500.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 50% in terms of Si atom molar ratio
- the content ratio of the organosilane represented by the general formula (2) is 50 in terms of Si atomic mole ratio. %Met.
- the resulting polysiloxane solution (e) had a solid content concentration of 41% by weight and a polysiloxane weight average molecular weight of 14,900.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 40% in terms of the Si atom molar ratio
- the content ratio of the organosilane represented by the general formula (2) is 60 in terms of the Si atomic mole ratio. %Met.
- the solid content concentration of the obtained polysiloxane solution (f) was 39% by weight, and the weight average molecular weight of the polysiloxane was 9000.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 50% in terms of Si atom molar ratio
- the content ratio of the organosilane represented by the general formula (2) is 30 in terms of Si atomic mole ratio. %Met.
- the resulting polysiloxane solution (g) had a solid content concentration of 42% by weight and a polysiloxane weight average molecular weight of 12,300.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 35% in terms of the Si atom molar ratio
- the content ratio of the organosilane represented by the general formula (2) is 30 in terms of the Si atomic mole ratio. %Met.
- the phosphoric acid aqueous solution in which 10% by weight was dissolved was added over 10 minutes. After soaking in an oil bath and stirring for 30 minutes, the oil bath was heated to 115 ° C. over 30 minutes, 1 hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and then heated and stirred for 2 hours. The temperature was adjusted to 95 to 105 ° C.) to obtain a polysiloxane solution (h), and nitrogen was flowed at 0.05 l (liter) / min during the heating and stirring. Distilled a total of 156 g. The resulting polysiloxane solution (h) had a solid content concentration of 42% by weight and a polysiloxane weight average molecular weight of 9,100.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 25% in terms of the Si atom molar ratio
- the content ratio of the organosilane represented by the general formula (2) is 20 in terms of the Si atomic mole ratio. %Met.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 60% in terms of the Si atom molar ratio
- the content ratio of the organosilane represented by the general formula (2) is 40 in terms of the Si atomic mole ratio. %Met.
- the solid content concentration of the obtained polysiloxane solution (j) was 43% by weight, and the weight average molecular weight of the polysiloxane was 8500.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 50% in terms of the Si atom molar ratio
- the content ratio of the organosilane represented by the general formula (2) is 10 in terms of the Si atomic mole ratio. %Met.
- aqueous phosphoric acid solution in which 0.52 g of phosphoric acid (0.3% by weight based on the charged monomers) was dissolved in 70 g was added over 10 minutes, and then the flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes. Thereafter, the oil bath was heated to 115 ° C. over 30 minutes, and the internal temperature of the solution reached 100 ° C. 1 hour after the start of the temperature increase. Thereafter, the mixture was heated and stirred for 2 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane solution (k), and nitrogen was flowed at 0.05 l (liter) / min during the heating and stirring. A total of 129 g of methanol and water as products were distilled.
- the resulting polysiloxane solution (k) had a solid content concentration of 43% by weight and a polysiloxane weight average molecular weight of 8,500.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 50% in terms of the Si atom molar ratio
- the content ratio of the organosilane represented by the general formula (2) is 10 in terms of the Si atomic mole ratio. %Met.
- Synthesis Example 12 Synthesis of Polysiloxane Solution (l) In a 500 ml three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, (2- (3, 4-Epoxycyclohexyl) ethyltrimethoxysilane (24.64 g, 0.1 mol) and DAA (179.50 g) were charged. While stirring at room temperature, 55.8 g of water was added to 0.54 g of phosphoric acid (0.3% relative to the charged monomer).
- the resulting polysiloxane solution (l) had a solid content concentration of 43% by weight and a polysiloxane weight average molecular weight of 3,200.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 50% in terms of the Si atom molar ratio
- the content ratio of the organosilane represented by the general formula (2) is 0 in terms of the Si atomic mole ratio. %Met.
- the phosphoric acid aqueous solution was added over 10 minutes, and the flask was then immersed in an oil bath at 40 ° C. and stirred for 30 minutes. Then, the temperature of the oil bath was raised to 115 ° C. over 30 minutes, and the internal temperature of the solution reached 100 ° C. 1 hour after the start of the temperature increase, and then the mixture was heated and stirred for 2 hours (the internal temperature was 95 to 105 ° C.)
- a polysiloxane solution (m) was obtained, and while heating and stirring, 0.05 l (liter) / min of nitrogen was flowed in. During the reaction, a total of 120 g of methanol and water as by-products were distilled out.
- the resulting polysiloxane solution (m) had a solid content concentration of 43% by weight, and the polysiloxane had a weight average molecular weight of 9,500.
- the content ratio of the organosilane represented by the general formula (1) in the polysiloxane is 15% in terms of the Si atom molar ratio, and the content ratio of the organosilane represented in the general formula (2) is 20 in terms of the Si atomic mole ratio. %Met.
- Synthesis Example 14 Synthesis of Acrylic Resin Solution (a) A 500 ml flask was charged with 5 g of 2,2′-azobis (isobutyronitrile), 5 g of t-dodecanethiol, and 180 g of PGMEA. Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate were charged, stirred at room temperature, and the atmosphere in the flask was replaced with nitrogen. And stirred for 5 hours.
- the obtained acrylic resin solution (a) had a solid content concentration of 40% by weight, the acrylic resin had a weight average molecular weight of 12000, and an acid value of 91 mgKOH / g.
- Synthesis Example 15 Synthesis of quinonediazide compound (a) Under a dry nitrogen stream, 21.23 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 37.62 g of 5-naphthoquinonediazidesulfonyl acid chloride ( 0.14 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system would not exceed 35 ° C. It stirred at 30 degreeC after dripping for 2 hours.
- TrisP-PA trade name, manufactured by Honshu Chemical Industry Co., Ltd.
- 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 (a) having the following structure.
- Synthesis Example 16 Synthesis of quinonediazide compound (b) Under a dry nitrogen stream, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 15.32 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 26.87 g ( 0.1 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. To this, 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not exceed 35 ° C. It stirred at 30 degreeC after dripping for 2 hours.
- TrisP-HAP trade name, manufactured by Honshu Chemical Industry Co., Ltd.
- 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.
- Synthesis Example 18 Synthesis of quinonediazide compound (d) A quinonediazide compound (d) having the following structure was prepared in the same manner as in Synthesis Example 10 except that the addition amount of 5-naphthoquinonediazidesulfonyl acid chloride was changed to 33.59 g (0.125 mol). Obtained.
- Example 1 21.88 g of the polysiloxane solution (a) obtained in Synthesis Example 1; 0.98 g of the quinonediazide compound (a) obtained in Synthesis Example 9; 2.92 g of DAA as a solvent and 3.96 g of GBL were mixed and stirred under a yellow light. After preparing a uniform solution, it was filtered through a 0.45 ⁇ m filter to prepare Composition 1. The 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 speed, and then hot plate ( Daiwa Screen Manufacturing Co., Ltd.
- SCW-6366 was prebaked at 100 ° C. for 2 minutes to produce a film having a thickness of 3 ⁇ m.
- PLA parallel light mask aligner
- 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 is performed for 60 seconds with ELM-D (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) which is a 2.38 wt% tetramethylammonium hydroxide aqueous solution. Then rinsed with water for 30 seconds.
- AD-2000 manufactured by Takizawa Sangyo Co., Ltd.
- PLA Canon Co., Ltd. PLA-501F
- 3000 J / m 2 wavelength 365 nm exposure amount conversion
- soft baking was performed at 110 ° C. for 2 minutes using a hot plate, and then cured in an air (230 ° C.) for 1 hour using an oven (Tabba Espec Co., Ltd.) to prepare a cured film.
- the evaluation results of photosensitive characteristics and cured film characteristics are shown in Table 2.
- the evaluation in the table was performed by the following method.
- the following evaluations (4) to (8) were performed using a silicon wafer substrate, and (9) to (11) were evaluated using an OA-10 glass plate.
- Residual film ratio (%) unexposed film thickness after development / film thickness after pre-baking ⁇ 100 (6) Calculation of sensitivity After exposure and development, the exposure amount (hereinafter referred to as the optimum exposure amount) for forming a 10 ⁇ m line-and-space pattern in a one-to-one width was defined as sensitivity.
- Example 1 Heat resistance
- the cured film prepared by the method described in Example 1 is scraped off from the substrate, and about 10 mg is put into an aluminum cell, and a thermogravimetric apparatus (TGA-50, manufactured by Shimadzu Corporation) is used in a nitrogen atmosphere. After heating to 150 ° C. at a heating rate of 10 ° C./min and holding the temperature at 150 ° C. for 1 hour, the temperature was raised to 400 ° C. at a heating rate of 10 ° C./min. At this time, the temperature Td1% at which the weight loss was 1% was measured and compared. The higher the Td1%, the better the heat resistance.
- TGA-50 thermogravimetric apparatus
- Examples 2 to 13 and Comparative Examples 1 to 3 Similar to Composition 1, Compositions 2-16 were prepared with the compositions listed in Table 1. Note that KBM303 used as a silane coupling agent was (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, KBM-403 was manufactured by Shin-Etsu Chemical Co., Ltd.) manufactured by Shin-Etsu Chemical Co., Ltd. “Nicarac” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) used as a crosslinking agent is a compound having the structure shown below.
- the transparent electrode As the transparent electrode, a generally used metal oxide such as indium tin oxide (ITO) or tin antimonic acid, or a metal thin film such as gold, silver, copper, or aluminum was used. These transparent conductive electrodes are formed by a conventional method such as a physical method such as vacuum deposition, sputtering, ion plating, ion beam deposition, or chemical vapor deposition.
- ITO is vapor-deposited on a glass substrate with a thickness of about 1 mm, and a resist material is patterned by photolithography, and a rhombus pattern is formed by chemical etching with the above-mentioned ITO etching solution and resist peeling, and a film thickness of 200 ⁇ is transparent.
- a glass substrate having electrodes was produced.
- composition 1 After spin-coating the composition 1 on the part intersecting with the transparent electrode to be formed later, it was pre-baked at 100 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.), and the film thickness was 3 ⁇ m.
- SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.
- a film was prepared. The prepared film was subjected to pattern exposure using an ultra-high pressure mercury lamp through a mask using PLA (PLA-501F manufactured by Canon Inc.), and then subjected to 2 using an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.).
- ELM-D (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is a 38 wt% tetramethylammonium hydroxide aqueous solution, and then rinsed with water for 30 seconds. Then, as bleaching exposure, using PLA, the whole 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, followed by curing in the air at 230 ° C. for 1 hour using an oven (Ibayespec Co., Ltd.) to produce an insulating film.
- ELM-D trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.
- ITO Indium Tin Oxide
- the entire surface was coated with the composition 1 as a transparent protective film to prepare a touch panel element.
- the ends of the electrode group constituting each transparent electrode were each connected to a resistor.
- transparent protective films can be used for example, thermoplastic resins such as acrylic resin, polyvinyl chloride, polyester, polyamide, polycarbonate, fluorine-containing resin, thermosetting resins such as polyurethane, epoxy resin, and polyimide, acrylic UV Examples include curable resins, epoxy ultraviolet curable resins, urethane ultraviolet curable resins, polyester ultraviolet curable resins, photopolymerizable resins such as silicone ultraviolet curable resins, and silicon-based CVD inorganic materials. There is no particular limitation. From the viewpoint of transparency and visibility of the touch panel element, a combination in which the difference in refractive index between the insulating material and the transparent protective film is 0.02 or less, more preferably 0.01 or less is preferable.
- Example 2 Each composition was evaluated in the same manner as in Example 1 using each obtained composition. However, in the evaluation of Comparative Example 2, the development was performed by shower development with a 0.4 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds. The results are shown in Table 2.
- the photosensitive composition of the present invention includes a planarization film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a protective film such as a touch panel sensor, an insulating film, an interlayer insulating film of a semiconductor element, a solid-state imaging element It is used to form a core or cladding material for an optical waveguide such as a flattening film, a microlens array pattern, or an optical semiconductor element.
- TFT thin film transistor
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Abstract
Description
(a)のポリシロキサンにおける一般式(2)で表されるオルガノシランの含有比は、ポリシロキサン全体のSi原子モル数に対するSi原子モル比で5%以上80%以下が好ましく、より好ましくは、12%以上60%以下、さらに好ましくは25%以上60%以下である。さらに好ましくは、上限は60%未満であることが好ましい。80%より多いと、ポリシロキサンとナフトキノンジアジド化合物との相溶性が悪化し、硬化膜の透明性が低下する場合がある。また、5%より少ないと、高耐薬品性を発現し得ない場合がある。一般式(2)で表されるオルガノシランの含有比は、例えば、ポリシロキサンの29Si-NMRを測定し、一般式(2)中の4官能シラン由来のSiのピーク面積と4官能シラン由来以外のSiのピーク面積の比から求めることができる。また、29Si-NMR以外に、1H-NMR、13C-NMR、IR、TOF-MS、元素分析法、灰分測定などを組み合わせて求めることができる。
フェノール性水酸基を有する化合物の具体例としては、以下の化合物が挙げられる(いずれも本州化学工業(株)製)。
さらに、本発明の感光性組成物は必要に応じて、シランカップリング剤、架橋剤、架橋促進剤、増感剤、熱ラジカル発生剤、溶解促進剤、溶解抑止剤、界面活性剤、安定剤、消泡剤などの添加剤を含有することもできる。
シランカップリング剤の具体例としては、メチルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、n-プロピルトリメトキシシラン、n-プロピルトリエトキシシラン、n-ブチルトリメトキシシラン、n-ブチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-アクリロキシプロピルトリメトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、N-フェニル-3-アミノプロピルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリエトキシシラン、〔(3-エチル-3-オキセタニル)メトキシ〕プロピルトリメトキシシラン、〔(3-エチル-3-オキセタニル)メトキシ〕プロピルトリエトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルメチルジメトキシシラン、3-ウレイドプロピルトリエトキシシラン、3-イソシアネートプロピルトリエトキシシラン、3-トリメトキシシリルプロピルコハク酸、N-t-ブチル-3-(3-トリメトキシシリルプロピル)コハク酸イミドなどが挙げられる。
界面活性剤の含有量は、感光性組成物中、0.0001~1重量%とするのが一般的である。
架橋剤に特に制限は無いが、好ましくは一般式(7)で表される基、エポキシ構造、オキセタン構造の群から選択される構造を2個以上有する化合物が挙げられる。上記構造の組み合わせは特に限定されないが、選択される構造は同じものであることが好ましい。
なお、上記の架橋剤は、単独で使用しても、2種以上を組み合わせて使用してもよい。
架橋剤の添加量は特に制限されないが、好ましくは樹脂(ポリシロキサン+アクリル樹脂)100重量部に対して0.1~20重量部の範囲である。架橋剤の添加量が0.1重量部より少ないと、樹脂の架橋が不十分で効果が少ない。一方、架橋剤の添加量が20重量部より多いと、硬化膜の無色透明性が低下したり、組成物の貯蔵安定性が低下したりする。
増感剤の添加量は、特に制限は無いが、好ましくは樹脂(ポリシロキサン)100重量部に対して0.01~5重量部の範囲で添加するのが好ましい。この範囲を外れると、透明性が低下したり、感度が低下したりする。
また、本発明で用いるアクリル樹脂は、アルカリ可溶性であることが好ましく、アクリル樹脂の酸価は好ましくは50~150mgKOH/g、さらに好ましくは70~130mgKOH/gである。樹脂酸価が50mgKOH/gより小さいと、現像時に溶け残りが発生しやすくなってしまう。一方、酸価が150mgKOH/gより大きいと、現像時に未露光部の膜減りが大きくなってしまう。
プリベーク後、ステッパー、ミラープロジェクションマスクアライナー(MPA)、パラレルライトマスクアライナー(PLA)などの紫外可視露光機を用い、10~4000J/m2程度(波長365nm露光量換算)を所望のマスクを介してパターン露光する。
ブリーチング露光した膜を、必要であればホットプレート、オーブンなどの加熱装置で50~150℃の範囲で30秒~30分間ソフトベークを行った後、ホットプレート、オーブンなどの加熱装置で150~450℃の範囲で1時間程度キュアすることで、表示素子におけるTFT用平坦化膜、半導体素子における層間絶縁膜、あるいは光導波路におけるコアやクラッド材といった硬化膜が形成される。近年、これら硬化膜の上に、Si膜やSiN膜などを280℃以上にて高温CVD製膜することが要望されており、この高温に耐えうる高耐熱性、高透明性が要望されている。
この硬化膜は表示素子におけるTFT用平坦化膜、半導体素子における層間絶縁膜、タッチパネル用絶縁膜・保護膜あるいは光導波路におけるコアやクラッド材等に好適に使用される。
PGMEA:プロピレングリコールモノメチルエーテルアセテート
GBL:γ-ブチロラクトン
EDM:ジエチレングリコールメチルエチルエーテル
DPM:ジプロピレングリコールモノエーテルメチル。
アルミカップにポリシロキサン溶液またはアクリル樹脂溶液を1g秤取し、ホットプレートを用いて250℃で30分間加熱して液分を蒸発させた。加熱後のアルミカップに残った固形分を秤量して、アクリル樹脂またはポリシロキサン溶液の固形分濃度を求めた。
重量平均分子量はGPC(Waters社製410型RI検出器、流動層:テトラヒドロフラン)にてポリスチレン換算により求めた。
29Si-NMRの測定を行い、全体の積分値から、それぞれのオルガノシランに対する積分値の割合を算出して、比率を計算した。
試料(液体)は直径10mm のテフロン(登録商標)製 NMR サンプル管に注入し測定に用いた。29Si-NMRの測定条件を以下に示す。
測定核周波数:53.6693 MHz(29Si 核)、スペクトル幅:20000 Hz
パルス幅:12μsec(45°パルス)、パルス繰り返し時間:30.0 sec
溶媒:アセトン-d6、基準物質:テトラメチルシラン
測定温度:室温、試料回転数:0.0 Hz。
500mlの三口フラスコにメチルトリメトキシシランを40.86g(0.30mol)、フェニルトリメトキシシランを99.15g(0.5mol)、(2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランを12.32g(0.05mol)、Mシリケート51((m=4、平均)多摩化学工業株式会社製)を17.63g(0.15mol)、PGMEAを170.77g仕込み、室温で攪拌しながら水53.55gにリン酸0.51g(仕込みモノマーに対して0.3重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから2時間加熱攪拌し(内温は100~110℃)、ポリシロキサン溶液(a)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計125g留出した。
得られたポリシロキサン溶液(a)の固形分濃度は43重量%、ポリシロキサンの重量平均分子量は8500であった。なお、ポリシロキサン中の一般式(1)で表されるオルガノシランの含有比はSi原子モル比で50%、一般式(2)で表されるオルガノシランの含有比はSi原子モル比で15%であった。
500mlの三口フラスコにメチルトリメトキシシランを24.52g(0.18mol)、フェニルトリメトキシシランを118.98g(0.60mol)、(2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランを14.78g(0.06mol)、Mシリケート51((m=4、平均)多摩化学工業株式会社製)を42.30g(0.36mol)、PGMEAを181.89g仕込み、室温で攪拌しながら水62.64gにリン酸0.60g(仕込みモノマーに対して0.3重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから2時間加熱攪拌し(内温は100~110℃)、ポリシロキサン溶液(b)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計150g留出した。
得られたポリシロキサン溶液(b)の固形分濃度は44重量%、ポリシロキサンの重量平均分子量は11400であった。なお、ポリシロキサン中の一般式(1)で表されるオルガノシランの含有比はSi原子モル比で50%、一般式(2)で表されるオルガノシランの含有比はSi原子モル比で30%であった。
500mlの三口フラスコにメチルトリメトキシシランを4.77g(0.035mol)、フェニルトリメトキシシランを69.41g(0.35mol)、(2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランを8.62g(0.035mol)、Mシリケート51((m=4、平均)多摩化学工業株式会社製)を32.90g(0.28mol)、PGMEA104.8gを仕込み、室温で攪拌しながら水35.91gにリン酸0.69g(仕込みモノマーに対して0.6重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから4時間加熱攪拌し(内温は100~110℃)、ポリシロキサン溶液(c)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計97g留出した。
500mlの三口フラスコに、フェニルトリメトキシシランを99.15g(0.50mol)、Mシリケート51((m=4、平均)多摩化学工業株式会社製)を58.75g(0.50mol)、DAAを158.59g仕込み、室温で攪拌しながら水49.5gにリン酸0.79g(仕込みモノマーに対して0.5重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから4時間加熱攪拌し(内温は100~110℃)、ポリシロキサン溶液(d)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計123g留出した。
500mlの三口フラスコにフェニルトリメトキシシランを79.32g(0.40mol)、Mシリケート51((m=4、平均)多摩化学工業株式会社製)を70.50g(0.60mol)、DAAを118.96g仕込み、室温で攪拌しながら水48.60gにリン酸0.90g(仕込みモノマーに対して0.6重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから4時間加熱攪拌し(内温は100~110℃)、ポリシロキサン溶液(e)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計135g留出した。
得られたポリシロキサン溶液(e)の固形分濃度は41重量%、ポリシロキサンの重量平均分子量は14900であった。なお、ポリシロキサン中の一般式(1)で表されるオルガノシランの含有比はSi原子モル比で40%、一般式(2)で表されるオルガノシランの含有比はSi原子モル比で60%であった。
500mlの三口フラスコにメチルトリメトキシシランを20.43g(0.15mol)、フェニルトリメトキシシランを99.15g(0.50mol)、(2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランを12.32g(0.05mol)、テトラメトキシシランを45.67g(0.30mol、m=1)、DAAを228.35g仕込み、室温で攪拌しながら水60.30gにリン酸1.067g(仕込みモノマーに対して0.6重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから4時間加熱攪拌し(内温は100~110℃)、ポリシロキサン溶液(f)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計129g留出した。
500mlの三口フラスコにメチルトリメトキシシランを40.86g(0.30mol)、フェニルトリメトキシシランを69.41g(0.35mol)、(2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランを12.32g(0.05mol)、Mシリケート51((m=4、平均)多摩化学工業株式会社製)を35.25g(0.30mol)、PGMEAを140.37g、メタノールを15.60g仕込み、室温で攪拌しながら水52.20gにリン酸0.63g(仕込みモノマーに対して0.4重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから2時間加熱攪拌し(内温は100~110℃)、ポリシロキサン溶液(g)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計141g留出した。
得られたポリシロキサン溶液(g)の固形分濃度は42重量%、ポリシロキサンの重量平均分子量は12300であった。なお、ポリシロキサン中の一般式(1)で表されるオルガノシランの含有比はSi原子モル比で35%、一般式(2)で表されるオルガノシランの含有比はSi原子モル比で30%であった。
500mlの三口フラスコにメチルトリメトキシシランを44.95g(0.33mol)、フェニルトリメトキシシランを54.53g(0.25mol)、(2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランを13.55g(0.055mol)、Mシリケート51((m=4、平均)多摩化学工業株式会社製)を25.85g(0.22mol)、3-アクリロキシプロピルトリメトキシシラン51.55g(0.22mol)、PGMEAを173.23g、エタノール19.25g仕込み、室温で攪拌しながら水58.41gにリン酸0.95g(仕込みモノマーに対して0.5重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから2時間加熱攪拌し(内温は95~105℃に調整)、ポリシロキサン溶液(h)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計156g留出した。
得られたポリシロキサン溶液(h)の固形分濃度は42重量%、ポリシロキサンの重量平均分子量は9100であった。なお、ポリシロキサン中の一般式(1)で表されるオルガノシランの含有比はSi原子モル比で25%、一般式(2)で表されるオルガノシランの含有比はSi原子モル比で20%であった。
500mlの三口フラスコに、フェニルトリメトキシシランを118.98g(0.60mol)、Mシリケート51((m=4、平均)多摩化学工業株式会社製)を59.61g(0.4mol)、DAAを197.57g仕込み、室温で攪拌しながら水50.40gにリン酸1.07g(仕込みモノマーに対して0.6重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから4時間加熱攪拌し(内温は100~110℃)、ポリシロキサン溶液(i)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計131g留出した。
得られたポリシロキサン溶液(i)の固形分濃度は37重量%、ポリシロキサンの重量平均分子量は10100であった。なお、ポリシロキサン中の一般式(1)で表されるオルガノシランの含有比はSi原子モル比で60%、一般式(2)で表されるオルガノシランの含有比はSi原子モル比で40%であった。
500mlの三口フラスコにメチルトリメトキシシランを47.67g(0.35mol)、フェニルトリメトキシシランを99.15g(0.5mol)、(2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランを12.32g(0.05mol)、Mシリケート51((m=4、平均)多摩化学工業株式会社製)を11.75g(0.10mol)、PGMEAを170.77g仕込み、室温で攪拌しながら水54.00gにリン酸0.53g(仕込みモノマーに対して0.3重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから2時間加熱攪拌し(内温は100~110℃)、ポリシロキサン溶液(j)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計123g留出した。
500mlの三口フラスコにメチルトリメトキシシランを47.67g(0.35mol)、フェニルトリメトキシシランを99.15g(0.5mol)、(2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランを12.32g(0.05mol)、テトラメトキシシランを15.22g(0.10mol、m=1)、PGMEAを170.77g仕込み、室温で攪拌しながら水56.70gにリン酸0.52g(仕込みモノマーに対して0.3重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから2時間加熱攪拌し(内温は100~110℃)、ポリシロキサン溶液(k)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計129g留出した。
500mlの三口フラスコにメチルトリメトキシシランを54.48g(0.40mol)、フェニルトリメトキシシランを99.15g(0.50mol)、(2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランを24.64g(0.1mol)、DAAを179.50g仕込み、室温で攪拌しながら水55.8gにリン酸0.54g(仕込みモノマーに対して0.3重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから2時間加熱攪拌し(内温は100~110℃)、ポリシロキサン溶液(l)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計121g留出した。
得られたポリシロキサン溶液(l)の固形分濃度は43重量%、ポリシロキサンの重量平均分子量は3200であった。なお、ポリシロキサン中の一般式(1)で表されるオルガノシランの含有比はSi原子モル比で50%、一般式(2)で表されるオルガノシランの含有比はSi原子モル比で0%であった。
500mlの三口フラスコにメチルトリメトキシシランを54.48g(0.40mol)、フェニルトリメトキシシランを29.75g(0.15mol)、(2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシランを12.32g(0.05mol)、Mシリケート51((m=4、平均)多摩化学工業株式会社製)を23.50g(0.20mol)、3-アクリロキシプロピルトリメトキシシラン46.86g(0.20mol)、DAAを196.26g仕込み、室温で攪拌しながら水53.10gにリン酸0.33g(仕込みモノマーに対して0.2重量%)を溶かしたリン酸水溶液を10分かけて添加した。その後、フラスコを40℃のオイルバスに浸けて30分攪拌した後、オイルバスを30分かけて115℃まで昇温した。昇温開始1時間後に溶液の内温が100℃に到達し、そこから2時間加熱攪拌し(内温は95~105℃)、ポリシロキサン溶液(m)を得た。なお、加熱攪拌中、窒素を0.05l(リットル)/min流した。反応中に副生成物であるメタノール、水が合計120g留出した。
得られたポリシロキサン溶液(m)の固形分濃度は43重量%、ポリシロキサンの重量平均分子量は9500であった。なお、ポリシロキサン中の一般式(1)で表されるオルガノシランの含有比はSi原子モル比で15%、一般式(2)で表されるオルガノシランの含有比はSi原子モル比で20%であった。
500mlのフラスコに2,2’-アゾビス(イソブチロニトリル)を5g、t-ドデカンチオールを5g、PGMEAを180g仕込んだ。その後、メタクリル酸を30g、ベンジルメタクリレートを35g、トリシクロ[5.2.1.02,6]デカン-8-イルメタクリレートを35g仕込み、室温で攪拌してフラスコ内を窒素置換した後、70℃で5時間加熱攪拌した。次に、得られた溶液にメタクリル酸グリシジルを15g、ジメチルベンジルアミンを1g、p-メトキシフェノールを0.2g添加し、90℃で4時間加熱攪拌し、アクリル樹脂溶液(a)を得た。
得られたアクリル樹脂溶液(a)の固形分濃度は40重量%、アクリル樹脂の重量平均分子量は12000、酸価は91mgKOH/gであった。
乾燥窒素気流下、TrisP-PA(商品名、本州化学工業(株)製)21.23g(0.05mol)と5-ナフトキノンジアジドスルホニル酸クロリド37.62g(0.14mol)を1,4-ジオキサン450gに溶解させ、室温にした。ここに、1,4-ジオキサン50gと混合させたトリエチルアミン15.58g(0.154mol)を系内が35℃以上にならないように滴下した。滴下後30℃で2時間攪拌した。トリエチルアミン塩を濾過し、濾液を水に投入させた。その後、析出した沈殿を濾過で集めた。この沈殿を真空乾燥機で乾燥させ、下記構造のキノンジアジド化合物(a)を得た。
乾燥窒素気流下、TrisP-HAP(商品名、本州化学工業(株)製)15.32g(0.05mol)と5-ナフトキノンジアジドスルホニル酸クロリド26.87g(0.1mol)を1,4-ジオキサン450gに溶解させ、室温にした。ここに、1,4-ジオキサン50gと混合させたトリエチルアミン11.13g(0.11mol)を系内が35℃以上にならないように滴下した。滴下後30℃で2時間攪拌した。トリエチルアミン塩を濾過し、濾液を水に投入させた。その後、析出した沈殿を濾過で集めた。この沈殿を真空乾燥機で乾燥させ、下記構造のキノンジアジド化合物(b)を得た。
乾燥窒素気流下、Ph-cc-AP-MF(商品名、本州化学工業(株)製)15.32g(0.05mol)と5-ナフトキノンジアジドスルホニル酸クロリド37.62g(0.14mol)を1,4-ジオキサン450gに溶解させ、室温にした。ここに、1,4-ジオキサン50gと混合させたトリエチルアミン15.58g(0.154mol)を系内が35℃以上にならないように滴下した。滴下後30℃で2時間攪拌した。トリエチルアミン塩を濾過し、濾液を水に投入させた。その後、析出した沈殿を濾過で集めた。この沈殿を真空乾燥機で乾燥させ、下記構造のキノンジアジド化合物(c)を得た。
5-ナフトキノンジアジドスルホニル酸クロリドの添加量を33.59g(0.125mol)に変更する以外は合成例10と同様に、下記構造のキノンジアジド化合物(d)を得た。
合成例1で得られたポリシロキサン溶液(a)21.88g、合成例9で得られたキノンジアジド化合物(a)0.98g、溶剤としてDAA2.92g、GBL3.96gを黄色灯下で混合、攪拌して均一溶液とした後、0.45μmのフィルターで濾過して組成物1を調製した。
組成物1をシリコンウェハおよびOA-10ガラス板(日本電気硝子(株)製)にスピンコーター(ミカサ(株)製1H-360S)を用いて任意の回転数でスピンコートした後、ホットプレート(大日本スクリーン製造(株)製SCW-636)を用いて100℃で2分間プリベークし、膜厚3μmの膜を作製した。作製した膜をパラレルライトマスクアライナー(以下、PLAと略する)(キヤノン(株)製PLA-501F)を用いて、超高圧水銀灯を感度測定用のグレースケールマスクを介してパターン露光した後、自動現像装置(滝沢産業(株)製AD-2000)を用いて2.38重量%水酸化テトラメチルアンモニウム水溶液であるELM-D(商品名、三菱ガス化学(株)製)で60秒間シャワー現像し、次いで水で30秒間リンスした。その後、ブリーチング露光として、PLA(キヤノン(株)製PLA-501F)を用いて、膜全面に超高圧水銀灯を3000J/m2(波長365nm露光量換算)露光した。その後、ホットプレートを用いて110℃で2分間ソフトベークし、次いでオーブン(タバイエスペック(株)製IHPS-222)を用いて空気中230℃で1時間キュアして硬化膜を作製した。
ラムダエースSTM-602(商品名、大日本スクリーン製)を用いて、屈折率1.50で測定を行った。
残膜率は以下の式に従って算出した。
残膜率(%)=現像後の未露光部膜厚÷プリベーク後の膜厚×100
(6)感度の算出
露光、現像後、10μmのライン・アンド・スペースパターンを1対1の幅に形成する露光量(以下、これを最適露光量という)を感度とした。
最適露光量における現像後の最小パターン寸法を現像後解像度、キュア後の最小パターン寸法をキュア後解像度とした。
実施例1記載の方法で作成した硬化膜を基板から削りとり、アルミセルに約10mg入れ、熱重量測定装置(TGA-50、(株)島津製作所製)を用い、窒素雰囲気中、昇温速度10℃/分で150℃まで加熱し150℃で1時間温度保持した後、昇温速度10℃/分で400℃まで昇温した。この際に重量減少が1%となる温度Td1%を測定し、比較した。Td1%が高いほど、耐熱性は良好である。
MultiSpec-1500(商品名、(株)島津製作所)を用いて、まずOA-10ガラス板のみを測定し、その紫外可視吸収スペクトルをリファレンスとした。次に実施OA-10ガラス板上に組成物の硬化膜を形成(パターン露光は行わない)し、このサンプルをシングルビームで測定し、3μmあたりの波長400nmでの光透過率を求め、リファレンスとの差異を硬化膜の光透過率とした。
光透過率で用いた硬化膜を300℃で250秒熱処理を行い、その硬化膜に1mm間隔にてカッターナイフで10x10のマス目を作製した。その後、ITOエッチング液(塩酸/塩化カリウム/水=5/7/98(重量比))に50℃で300秒浸漬した、その後、そのマス目上にセロハンテープを密着させ、剥がしたときのマス目の残りの状態を観察した。観察評価として、マス目の残存率とした。×:100%剥がれ、△×:40%未満で残存、△△:40%以上~60%未満で残存、△:60%以上~80%未満で残存、〇:80%以上95%未満で残存、◎:95%以上残存とした。
(11)高温熱処理後の光透過率の測定
MultiSpec-1500(商品名、(株)島津製作所)を用いて、まずOA-10ガラス板のみを測定し、その紫外可視吸収スペクトルをリファレンスとした。次にOA-10ガラス板上に組成物の硬化膜を形成(パターン露光は行わない)し、さらに、この硬化膜を330℃で300秒熱処理を行い、このサンプルをシングルビームで測定し、3μmあたりの波長400nmでの光透過率を求め、リファレンスとの差異を硬化膜の光透過率とした。
組成物1と同様に、組成物2~16を表1に記載の組成にて調製した。なお、シランカップリング剤として用いたKBM303は信越化学工業(株)製の(2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、KBM-403は、信越化学工業(株)製の3-グリシドキシプロピルトリメトキシシランである。架橋剤として用いた“ニカラック”MX-270、(商品名、三和ケミカル(株)製)は下記に示した構造の化合物である。また、架橋促進剤として用いた、CGI-MDT(商品名、チバジャパン(株)製))、WPAG-469(商品名、和光純薬工業(株)製)は4-メチルフェニルジフェニルスルホニウムパーフルオロブタンスルホナート20%PGMEA溶液、増感剤として用いたDPA(商品名、川崎化成工業(株)製)は9,10-ジプロポキシアントラセンである。
(12)タッチパネル素子作製方法
タッチパネル素子作製方法について一例を説明する。透明電極には一般に使用されるインジウム錫酸化物(ITO)、錫アンチモン酸等の金属酸化物、または金、銀、銅、アルミニウム等の金属の薄膜を使用した。これらの透明導電極は、真空蒸着、スパッタリング、イオンプレーティング、イオンビーム蒸着等の物理的方法や化学的気相成長法など、従来より行われている方法によって形成される。
結果を表2に示す。
2:透明電極(下ITO)
3:透明絶縁膜
4:透明電極(上ITO)
5:透明保護膜
Claims (10)
- (a)ポリシロキサン、(b)ナフトキノンジアジド化合物、および(c)溶剤を含有するポジ型感光性組成物であって、
(a)ポリシロキサンにおける一般式(1)で表されるオルガノシラン由来の構造の含有比が、ポリシロキサン全体のSi原子モル数に対するSi原子モル比で20%以上80%以下であり、かつ(a)ポリシロキサン中に一般式(2)で表されるオルガノシラン由来の構造を含むことを特徴とするポジ型感光性樹脂組成物。
- (a)ポリシロキサンにおいて、一般式(2)で表されるオルガノシラン由来の構造をポリシロキサン全体のSi原子モル数に対するSi原子モル比で12%以上60%以下の範囲で含むことを特徴とする請求項1または2に記載のポジ型感光性組成物。
- (a)ポリシロキサンにおいて、一般式(1)のR1が、フェニル基、トリル基、ナフチル基、アントラセニル基、フェナントレニル基、フルオレニル基、フルオレノンイル基、ピレニル基、インデニル基、アセナフテニル基のうちのいずれかの基であることを特徴とする請求項1~3記載のいずれかに記載のポジ型感光性組成物。
- (a)ポリシロキサンにおいて、一般式(2)のmが、2~11の整数であることを特徴とする請求項1~4記載のいずれかに記載のポジ型感光性組成物。
- (b)ナフトキノンジアジド化合物が、(a)ポリシロキサン100重量部対して、3~15重量部であることを特徴とする請求項1~5のいずれかに記載のポジ型感光性組成物。
- (b)ナフトキノンジアジド化合物が、下記一般式(4)で表されるナフトキノンジアジド化合物であることを特徴とする請求項1~6のいずれかに記載のポジ型感光性組成物。
- 請求項1~7のいずれかに記載のポジ型感光性組成物から形成された硬化膜であって、波長400nmにおける膜厚3μmあたりの光透過率が90%以上である硬化膜。
- 請求項8に記載の硬化膜を具備する素子。
- 請求項9に記載の素子が、液晶表示素子、有機EL表示素子、タッチパネル用センサー素子、半導体素子、固体撮像素子または光半導体素子のいずれかである素子。
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SG2012046835A SG181913A1 (en) | 2009-12-22 | 2010-12-20 | Positive photosensitive resin composition, cured film formed from same, and element having cured film |
JP2011525337A JPWO2011078106A1 (ja) | 2009-12-22 | 2010-12-20 | ポジ型感光性樹脂組成物、それから形成された硬化膜、および硬化膜を有する素子 |
KR1020127016058A KR101739607B1 (ko) | 2009-12-22 | 2010-12-20 | 포지티브형 감광성 수지 조성물, 그것으로부터 형성된 경화막, 및 경화막을 갖는 소자 |
CN201080058514.2A CN102667625B (zh) | 2009-12-22 | 2010-12-20 | 正型感光性树脂组合物、由该组合物形成的固化膜及具有固化膜的元件 |
US13/513,270 US20120237873A1 (en) | 2009-12-20 | 2010-12-20 | Positive photosensitive resin composition, cured film formed from the same, and device having cured film |
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JP2013020530A (ja) * | 2011-07-13 | 2013-01-31 | Dainippon Printing Co Ltd | タッチセンサパネル部材、タッチセンサパネル部材を備えた表示装置、及びタッチセンサパネル部材の製造方法 |
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KR20120102090A (ko) | 2012-09-17 |
CN102667625B (zh) | 2015-11-25 |
KR101739607B1 (ko) | 2017-05-24 |
JPWO2011078106A1 (ja) | 2013-05-09 |
TW201131293A (en) | 2011-09-16 |
TWI490642B (zh) | 2015-07-01 |
CN102667625A (zh) | 2012-09-12 |
SG181913A1 (en) | 2012-07-30 |
US20120237873A1 (en) | 2012-09-20 |
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