WO2014156520A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2014156520A1 WO2014156520A1 PCT/JP2014/055591 JP2014055591W WO2014156520A1 WO 2014156520 A1 WO2014156520 A1 WO 2014156520A1 JP 2014055591 W JP2014055591 W JP 2014055591W WO 2014156520 A1 WO2014156520 A1 WO 2014156520A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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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
- G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
Definitions
- the present invention relates to a photosensitive resin composition, a protective film or an insulating film, a touch panel, and a manufacturing method thereof.
- the sensor substrate of the capacitive touch panel has wiring in which ITO (Indium Tin Oxide) or metal (silver, molybdenum, aluminum, or the like) is patterned on glass.
- ITO Indium Tin Oxide
- metal silver, molybdenum, aluminum, or the like
- an insulating film, ITO A structure having a protective film for protecting a metal is common.
- the protective film is formed of high-hardness inorganic SiO 2 or SiN x or a photosensitive transparent material (Patent Document 1), and the insulating film is often formed of a photosensitive transparent material.
- inorganic materials are formed by high-temperature deposition of SiO 2 or SiN x by CVD (Chemical Vapor Deposition), and the number of processes increases because pattern processing is performed using a resist. was there.
- the touch panel with high reliability cannot be obtained because it has poor moisture and heat resistance and corrodes the underlying metal wiring.
- Photosensitive transparent materials can be expected to reduce costs by reducing the number of processes, but the hardness is insufficient and the heat and heat resistance is low, as with inorganic materials. I had it.
- the cured film obtained from the photosensitive transparent material is exposed to various acidic or alkaline chemicals such as an etching solution for processing ITO or the underlying metal wiring, but if the cured film has low chemical resistance, Peeling or floating occurs at the interface between the cured film and the underlying metal wiring or substrate, which may cause ITO disconnection.
- acidic or alkaline chemicals such as an etching solution for processing ITO or the underlying metal wiring
- the coating liquid of the photosensitive transparent material when stored at room temperature, there is a problem that the material changes in quality during storage and the adhesion to the substrate and chemical resistance are lowered. Therefore, it has high hardness, excellent transparency, moisture and heat resistance, adhesion and chemical resistance, can be patterned with alkaline developer, and has good storage stability of coating liquid, and adhesion and chemical resistance during storage Therefore, there has been a strong demand for a photosensitive transparent material that does not deteriorate the properties.
- a UV curable coating composition containing an alkali-soluble resin, a radical polymerizable compound, a photopolymerization initiator and other additives is known.
- the composition is used for, for example, a color resist by containing a colorant in addition to being used for an overcoat material for a color filter and a spacer material (Patent Documents 2 and 3).
- a photosensitive transparent material containing a polyfunctional epoxy compound Patent Document 3
- a photosensitive transparent material containing a metal chelate compound such as a zirconium compound
- 3 Photosensitive transparent material containing a silane compound having one or four hydrolyzable alkoxy groups
- Patent Document 5 Photosensitive transparent material containing a silane compound having one or four hydrolyzable alkoxy groups
- Patent Document 6 containing a polymer having a (meth) acryl equivalent of 100 to 300 g / eq, a chelate compound, and a silane coupling
- Photosensitive transparent material Patent Document 6
- photosensitive transparent material Patent Document 7
- an alcohol exchange reaction catalyst and a silane coupling agent having two or more hydrolyzable silyl groups or silanol groups
- the cured film obtained has high hardness, excellent transparency, heat and humidity resistance, adhesion and chemical resistance, can be patterned with an alkaline developer, and has good storage stability of the coating liquid during storage.
- an alkaline developer there is no known photosensitive transparent material that satisfies the requirement that adhesion and chemical resistance do not deteriorate.
- the present invention is capable of obtaining a cured film having high hardness, excellent transparency, moist heat resistance, adhesion and chemical resistance, and having good storage stability of the coating liquid and adhesion during storage.
- Another object of the present invention is to provide a photosensitive resin composition capable of alkali development, which has a plurality of performances such that chemical resistance does not deteriorate.
- the present invention is a photosensitive resin composition containing (A) an alkali-soluble resin, (D) a metal chelate compound, and (E) a silane compound.
- Photosensitive resin composition which is an alkali-soluble resin having a heavy bond equivalent, wherein (D) the metal chelate compound is a compound having a specific structure, and (E) the silane compound is a tetrafunctional silane or silane oligomer having a specific structure. Offer things.
- the photosensitive resin composition of the present invention it is possible to obtain a cured film having high hardness and excellent transparency, moisture and heat resistance, adhesion and chemical resistance. Moreover, according to the photosensitive resin composition of the present invention, it is possible to prepare a coating liquid that has good storage stability and does not deteriorate adhesion and chemical resistance during storage.
- the photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (D) a metal chelate compound, and (E) a silane compound, and the (A) alkali-soluble resin is an ethylenically unsaturated double. Having a bonding group, a double bond equivalent of 300 to 5,000 g / mol, the (D) metal chelate compound is a compound represented by the general formula (1), and the (E) silane compound is A silane oligomer obtained by condensing a tetrafunctional silane represented by the general formula (2) or a tetrafunctional silane represented by the general formula (2).
- M represents titanium, zirconium, aluminum, or magnesium
- R 1 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or 6 to 6 carbon atoms
- R 4 to R 7 are each independently And 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.
- the photosensitive resin composition of the present invention contains (A) an alkali-soluble resin.
- the alkali-soluble resin has an ethylenically unsaturated double bond group.
- the double bond equivalent of the alkali-soluble resin is 300 to 5,000 g / mol, preferably 300 to 2,000 g / mol, and more preferably 300 to 1,500 g / mol.
- the double bond equivalent means the resin weight per 1 mol of the ethylenically unsaturated double bond group, and the unit is g / mol.
- the double bond equivalent can be calculated by measuring the iodine value.
- (A) alkali-soluble resins include acrylic resins, polysiloxanes, polyimides, polyamic acids, polyamides, novolac resins, and epoxy resins, but from the ease of introduction of ethylenically unsaturated double bond groups, (A-1) Acrylic resin or (A-2) polysiloxane is preferred. That is, the (A) alkali-soluble resin is preferably selected from (A-1) acrylic resin and (A-2) polysiloxane. (A) As for alkali-soluble resin, multiple types of said resin may be contained.
- (A-1) As the acrylic resin, (A-1) an acrylic resin having a carboxy group is preferable. (A-1) Since the acrylic resin has a carboxy group, pattern processing with an alkaline developer becomes possible. (A-1)
- the carboxylic acid equivalent of the acrylic resin is preferably 280 to 1,400 g / mol, more preferably 300 to 1,100 g / mol, and further preferably 400 to 950 g / mol.
- the carboxylic acid equivalent of the acrylic resin means the weight of the acrylic resin per 1 mol of the carboxy group, and the unit is g / mol. From the value of carboxylic acid equivalent, the number of carboxy groups in the acrylic resin can be determined.
- the carboxylic acid equivalent of the acrylic resin is within the above range, the pattern processability with an alkaline developer is improved, and the pattern shape after development is improved. If the carboxylic acid equivalent is less than 280, the film loss during development is large, and the pattern shape after development may deteriorate. On the other hand, when the carboxylic acid equivalent exceeds 1400, the pattern processability with an alkaline developer is lowered, which may cause a residue after development.
- the weight average molecular weight (hereinafter “Mw”) of the acrylic resin is preferably 2,000 to 100,000 in terms of polystyrene measured by gel permeation chromatography (hereinafter “GPC”). 5,000 to 40,000 is more preferable.
- Mw weight average molecular weight
- GPC gel permeation chromatography
- Mw is in the above range, leveling properties during coating, pattern processability with an alkaline developer, resolution after development, and storage stability of the coating solution are improved.
- Mw is less than 2,000, tack-free performance is deteriorated, the moisture resistance of the coating film after exposure is lowered, film loss during development is increased, and resolution after development may be reduced.
- Mw exceeds 100,000 the leveling property at the time of application is poor and uneven coating occurs, the pattern workability with an alkaline developer is remarkably lowered, and the storage stability of the coating solution may be lowered.
- (A-1) As the acrylic resin, an acrylic resin obtained by radical copolymerization with a (meth) acrylic compound having a carboxy group or a carboxylic anhydride group or another (meth) acrylic ester is preferable.
- the radical polymerization initiator used for radical copolymerization include azo compounds such as 2,2′-azobis (isobutyronitrile) or 2,2′-azobis (2,4-dimethylvaleronitrile), or lauroyl peroxide.
- Organic peroxides such as di-t-butyl peroxide, bis (4-t-butylcyclohexane-1-yl) peroxydicarbonate, t-butyl 2-ethylperoxyhexanoate, methyl ethyl ketone peroxide, benzoyl peroxide or cumene hydroperoxide An oxide is mentioned.
- the conditions for radical copolymerization can be appropriately set. For example, after sufficiently purging the inside of the reaction vessel with nitrogen by bubbling or vacuum degassing, a copolymer component and a radical polymerization initiator are added in a solvent, and 60 The reaction is preferably carried out at ⁇ 110 ° C. for 30 to 500 minutes. When a (meth) acrylic compound having an acid anhydride group is used as a copolymerization component, it is preferable to add a theoretical amount of water and react at 30 to 60 ° C. for 30 to 60 minutes. Moreover, you may use chain transfer agents, such as a thiol compound, as needed.
- Examples of the (meth) acrylic compound having a carboxy group or an acid anhydride group include (meth) acrylic acid, (meth) acrylic anhydride, itaconic acid, itaconic anhydride, mono (2-acryloxyethyl) succinate. ), Mono (2-acryloxyethyl) phthalate or mono (2-acryloxyethyl) tetrahydrophthalate.
- (meth) acrylic acid esters examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth ) Cyclohexyl acrylate, cyclohexenyl (meth) acrylate, (4-methoxy) cyclohexyl (meth) acrylate, (2-isopropyloxycarbonyl) ethyl (meth) acrylate, (meth) acrylic acid (2-cyclopentyloxycarbonyl) ) Ethyl, (meth) acrylic acid (2-cyclohexyloxycarbonyl) ethyl, (meth) acrylic acid (2-cyclohexylenylcarbonyl) ethyl, (meth) acrylic acid [2- (4-methoxycyclohexyl) oxycarbonyl]
- aromatic vinyl compounds such as styrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene or ⁇ -methylstyrene may be used.
- Styrene is preferred because the heat and humidity resistance and heat resistance are improved.
- (A-1) acrylic resin having an ethylenically unsaturated double bond group a radical copolymer of a (meth) acrylic compound having a carboxy group or an acid anhydride group and another (meth) acrylic ester Furthermore, those obtained by a ring-opening addition reaction of an unsaturated compound having an epoxy group in addition to an ethylenically unsaturated double bond group are preferred.
- the catalyst used for the ring-opening addition reaction of an unsaturated compound having an epoxy group include triethylamine, dimethylaniline, tetramethylethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, dimethylbenzylamine or tri-n.
- -Amine-based catalysts such as octyl 7 amine, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium fluoride, alkylureas such as tetramethylurea, alkylguanidines such as tetramethylguanidine, bis ( Tin-based catalysts such as 2-ethylhexanoic acid) tin (II) or di-n-butyltin (IV) dilaurate, titanium-based catalysts such as tetrakis (2-ethylhexanoic acid) titanium (IV), Phosphorus catalysts such as nylphosphine or triphenylphosphine oxide, chromium catalysts such as tris (acetylacetonato) chromium (III), chromium (III) chloride, chromium (III) octenoate
- Examples of the unsaturated compound having an epoxy group include glycidyl (meth) acrylate, ( ⁇ -ethyl) glycidyl (meth) acrylate, (meth) acrylic acid ( ⁇ -n-propyl) glycidyl, and (meth) acrylic acid.
- (A-1) When the acrylic resin has a carboxy group, the (A-1) acrylic resin having no epoxy group is preferred. (A-1) If the acrylic resin has both a carboxy group and an epoxy group, the carboxy group and the epoxy group may react during storage of the coating solution, resulting in a decrease in adhesion or chemical resistance during storage. The storage stability of the coating liquid decreases.
- (A-1) acrylic resins having no epoxy group include (meth) acrylic compounds having a carboxy group or an acid anhydride group, other (meth) acrylic esters having no epoxy group, and aromatics having no epoxy group An acrylic resin obtained by radical copolymerization with one or more copolymerization components selected from group vinyl compounds is preferred.
- the polysiloxane is preferably one obtained by hydrolyzing an organosilane and subjecting it to dehydration condensation by heating or a reaction using an acid or a base.
- the organosiloxane represented by the general formula (3) What is obtained by hydrolyzing and dehydrating and condensing organosilane containing silane and / or organosilane represented by the general formula (4) is more preferable.
- R 8 each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms.
- R 9 to R 13 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an alkyl group having 6 to 15 carbon atoms.
- R 8 is preferably independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- R 9 to R 13 are preferably each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- Examples of the alkyl group represented by R 8 in the general formula (3) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and an n-decyl group. Can be mentioned.
- a cycloalkyl group of R ⁇ 8 > of General formula (3) a cyclopentyl group or a cyclohexyl group is mentioned, for example.
- substituents examples include a halogen, an epoxy group, a glycidyl group, an oxetanyl group, a carboxy group, an amino group, a mercapto group, an isocyanate group, or a succinic anhydride residue.
- Examples of the substituent of the alkyl group represented by R 8 in the general formula (3) include a trifluoromethyl group, a 3,3,3-trifluoropropyl group, a 3-glycidoxypropyl group, and 2- (3,4- (Epoxycyclohexyl) ethyl group, [(3-ethyl-3-oxetanyl) methoxy] propyl group, 1-carboxy-2-carboxypentyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group, or The group of the structure is mentioned.
- Examples of the alkenyl group of R 8 in the general formula (3) and the substituted product thereof include a vinyl group, an allyl group, a 3- (meth) acryloxypropyl group, and a 2- (meth) acryloxyethyl group.
- Examples of the aryl group represented by R 8 in the general formula (3) and the substituted product thereof include phenyl group, 4-tolyl group, 4-hydroxyphenyl group, 4-methoxyphenyl group, 4-t-butylphenyl group, 1- Naphthyl group, 2-naphthyl group, 4-styryl group, 2-phenylethyl group, 1- (4-hydroxyphenyl) ethyl group, 2- (4-hydroxyphenyl) ethyl group or 4-hydroxy-5- (4- A hydroxyphenylcarbonyloxy) pentyl group.
- Examples of the alkyl group of R 9 to R 13 in the general formulas (3) and (4) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
- Examples of the acyl group of R 9 to R 13 in the general formulas (3) and (4) include an acetyl group.
- Examples of the aryl group of R 9 to R 13 in the general formulas (3) and (4) include a phenyl group, a 4-tolyl group, a 4-hydroxyphenyl group, a 4-methoxyphenyl group, and a 4-t-butylphenyl group. Or a 1-naphthyl group is mentioned.
- the content ratio of the monofunctional silane unit represented by the general formula (3) in the polysiloxane is preferably 0 to 10 mol%, more preferably 0 to 5 mol% in terms of Si atom mol ratio.
- the Si atomic mole ratio derived from the monofunctional silane represented by the general formula (3) exceeds 10 mol%, the Mw of the polysiloxane may be lowered.
- the content ratio of the bifunctional silane unit represented by the general formula (3) in the polysiloxane is preferably 0 to 60 mol%, more preferably 0 to 40 mol% in terms of Si atom mol ratio.
- the content ratio of the trifunctional silane unit represented by the general formula (3) in the polysiloxane is preferably 50 to 100 mol%, more preferably 60 to 100 mol% in terms of Si atom mol ratio. If the Si atom mol ratio derived from the trifunctional silane represented by the general formula (3) is less than 50 mol%, the hardness of the cured film may be lowered.
- the content ratio of units can be determined by combining 1 H-nuclear magnetic resonance (hereinafter “NMR”), 13 C-NMR, 29 Si-NMR, IR, TOF-MS, elemental analysis, ash content measurement, and the like. .
- the organosilane represented by the general formula (3) is preferably an organosilane having an aromatic group.
- A-2 Since the polysiloxane has a structure derived from an organosilane having an aromatic group, the pattern shape after development is improved due to the steric hindrance and hydrophobicity of the aromatic group, and crack resistance during thermal curing is improved. In addition, the heat and moisture resistance and chemical resistance of the cured film can be improved.
- organosilane represented by the general formula (3) and having an aromatic group examples include phenyltrimethoxysilane, phenyltriethoxysilane, 4-tolyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, and 4-methoxyphenyl.
- the content ratio of the organosilane unit represented by the general formula (3) and having an aromatic group in the polysiloxane is preferably 3 to 70 mol%, more preferably 5 to 60 mol% in terms of Si atom mol ratio. 10 to 50 mol% is more preferable. If the Si atom molar ratio derived from the organosilane represented by the general formula (3) and having an aromatic group is less than 3 mol%, the pattern shape after development deteriorates, crack resistance during heat curing, Moisture heat resistance or chemical resistance may decrease. On the other hand, when it exceeds 70 mol%, the pattern processability with an alkali developer or the hardness of the cured film may be lowered.
- the content ratio of the organosilane unit represented by the general formula (3) and having an aromatic group in the polysiloxane is 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, TOF. -MS, elemental analysis, and ash content measurement can be combined.
- an organosilane having an ethylenically unsaturated double bond group is also preferable.
- A-2 Since the polysiloxane has an ethylenically unsaturated double bond group derived from organosilane, UV curing at the time of exposure is promoted and the sensitivity is improved, and the crosslinking density after heat curing is improved, The hardness of the cured film can be improved.
- organosilane represented by the general formula (3) and having an ethylenically unsaturated double bond group examples include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyl.
- vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acrylic Roxypropylmethyldimethoxysilane or 4-styryltrimethoxysilane is preferred.
- an organosilane having an acidic group is also preferable.
- A-2 Since the polysiloxane has an organosilane-derived acidic group, generation of residues after development can be suppressed and resolution after development can be improved.
- the acidic group a group exhibiting an acidity of less than pH 6 is preferable. Examples of the group having an acidity of less than pH 6 include a carboxy group, a carboxylic acid anhydride group, a sulfonic acid group, a phenolic hydroxyl group, a hydroxyimide group, or a silanol group. From the viewpoint of improving the resolution after development, a carboxy group or a carboxylic anhydride group is preferred.
- organosilane represented by the general formula (3) and having an acidic group examples include 3-trimethoxysilylpropyl succinic acid, 3-triethoxysilylpropyl succinic acid, 3-trimethoxysilylpropionic acid, 3-triethoxy Silylpropionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilyl Propyl succinic anhydride, 4- (3-trimethoxysilylpropyl) cyclohexane-1,2-dicarboxylic anhydride, 4- (3-triethoxysilylpropyl) cyclohexane-1,2-dicarboxylic anhydride, 4- (3-trimethoxysilylpropyl) phthalic anhydride,
- the content ratio of the organosilane unit represented by the general formula (3) and having an acidic group in the polysiloxane is 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, TOF— It can be determined by combining MS, elemental analysis, ash content measurement, and the like.
- the carboxylic acid equivalent of the polysiloxane is preferably 280 to 1,400 g / mol, more preferably 300 to 1,100 g / mol, and further preferably 400 to 950 g / mol.
- the carboxylic acid equivalent of polysiloxane means the weight of polysiloxane per 1 mol of carboxy groups, and the unit is g / mol. From the carboxylic acid equivalent value, the number of carboxy groups in the polysiloxane can be determined.
- the carboxylic acid equivalent of the polysiloxane is in the above range, the pattern processability with an alkaline developer is improved, and the pattern shape after development is good.
- the carboxylic acid equivalent is less than 280, the film loss during development is large, and the pattern shape after development may deteriorate.
- the carboxylic acid equivalent exceeds 1,400, pattern processability with an alkaline developer is lowered, which may cause generation of a residue after development.
- the (A-2) polysiloxane having no epoxy group is preferred.
- the carboxy group and the epoxy group may react during storage of the coating solution, and adhesion or chemical resistance will decrease during storage. The storage stability of the coating liquid decreases.
- one or more organosiloxanes selected from the organosilane represented by the general formula (3) and the organosilane represented by the general formula (4) having no epoxy group A polysiloxane obtained by hydrolyzing and dehydrating and condensing the organosilane represented by the general formula (3) having a carboxy group or an acid anhydride group together with silane is preferable.
- organosilanes represented by the general formula (3) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyl Trimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltri Ethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane,
- the organosilane unit represented by the general formula (4) By containing the organosilane unit represented by the general formula (4), it is possible to suppress generation of residues after development and improve resolution after development without impairing the heat resistance and transparency of the cured film. . Moreover, the glass transition temperature of polysiloxane becomes high, the reflow of the pattern at the time of thermosetting is suppressed, the pattern shape after thermosetting becomes favorable, and the resolution can be improved.
- organosilane represented by the general formula (4) examples include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane and tetraacetoxysilane.
- Silane Silane, methyl silicate 51 (manufactured by Fuso Chemical Industry Co., Ltd.), M silicate 51, silicate 40 or silicate 45 (all of which are manufactured by Tama Chemical Industry Co., Ltd.) or methyl silicate 51, methyl silicate 53A, ethyl silicate 40 or Examples of the silicate compound include ethyl silicate 48 (all of which are manufactured by Colcoat Co., Ltd.). From the viewpoint of improving the chemical resistance of the cured film by improving the pattern shape after heat curing.
- Tetraethoxysilane, teto -n- propoxysilane, (manufactured by Fuso Chemical Co.) Methyl Silicate 51, M Silicate 51 (manufactured by Tama Chemicals Co.,) or methyl silicate 51 (manufactured by Colcoat Co.) is preferred.
- the content ratio of the organosilane unit represented by the general formula (4) in the polysiloxane is preferably 0 to 30 mol%, more preferably 0 to 20 mol% in terms of Si atom mol ratio.
- Si atom mol ratio derived from the organosilane represented by the general formula (4) exceeds 30 mol%, the crack resistance during thermosetting may be lowered.
- the content ratio of the organosilane unit represented by the general formula (4) in the polysiloxane is 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, TOF-MS, elemental analysis. It can be determined by combining the method and ash content measurement.
- the Mw of the polysiloxane is preferably from 500 to 100,000, more preferably from 500 to 50,000, and even more preferably from 500 to 20,000 in terms of polystyrene measured by GPC.
- Mw is in the above range, leveling properties during coating, pattern processability with an alkaline developer, resolution after development, and storage stability of the coating solution are improved. If Mw is less than 500, tack-free performance is deteriorated, the moisture resistance of the coating film after exposure is lowered, film loss during development is increased, and resolution after development may be lowered. On the other hand, if Mw exceeds 100,000, the leveling property at the time of application is poor and uneven coating occurs, the pattern workability with an alkaline developer is remarkably lowered, and the storage stability of the coating solution may be lowered.
- a solvent and water, and a catalyst as necessary are added to a mixture containing organosilane, and the temperature is 50 to 150 ° C., preferably 90 to 130 ° C.
- a method of heating and stirring for 0.5 to 100 hours can be mentioned.
- hydrolysis by-products alcohols such as methanol
- condensation by-products water
- Examples of the solvent used for the hydrolysis and dehydration condensation of organosilane include the same solvents as described below.
- the amount of the solvent added is preferably 10 to 1,000 parts by weight when the total of the inorganic particles to be reacted with organosilane and organosilane is 100 parts by weight.
- the amount of water added is preferably 0.5 to 2 mol with respect to 1 mol of the hydrolyzable group.
- an acid catalyst or a base catalyst is preferable.
- the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyvalent carboxylic acid, anhydrides thereof, and ion exchange resins.
- the base catalyst examples include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, Examples include diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, alkoxysilane having an amino group, or an ion exchange resin.
- the addition amount of the catalyst is preferably 0.01 to 10 parts by weight when the total of the inorganic particles to be reacted with organosilane and organosilane is 100 parts by weight.
- the (A-2) polysiloxane does not contain the above catalyst, and therefore the catalyst may be removed afterwards.
- a method for removing the catalyst water washing or treatment with an ion exchange resin is preferable from the viewpoint of ease of operation and removability.
- the water washing is a method in which the obtained polysiloxane solution (A-2) is diluted with an appropriate hydrophobic solvent, washed several times with water, and the obtained organic layer is concentrated with an evaporator or the like.
- the treatment with an ion exchange resin refers to a method in which the obtained (A-2) polysiloxane solution is brought into contact with an appropriate ion exchange resin.
- polysiloxane polysiloxane obtained by reacting organosilane represented by general formula (3) and / or organosilane represented by general formula (4) with inorganic particles (Hereinafter, “inorganic particle-containing polysiloxane”) may be used.
- inorganic particle-containing polysiloxane (A-2) in which polysiloxane is bonded to inorganic particles having poor solubility in an alkaline developer, the alkali solubility of the inorganic particles is improved. Pattern workability is not reduced.
- the hydrophobicity of the inorganic particles not only improves the contrast between the exposed and unexposed areas during development, but also increases the glass transition temperature of (A-2) polysiloxane. Reflow can be suppressed, and the pattern shape after development becomes good. Furthermore, since the inorganic particles have a small shrinkage rate at the time of thermosetting, the generation of shrinkage stress can be suppressed, and the crack resistance at the time of thermosetting can be improved.
- Inorganic particles are particles made of a metal compound or a semiconductor compound.
- the metal or semiconductor include an element selected from the group consisting of silicon, lithium, sodium, magnesium, potassium, calcium, strontium, barium, lanthanum, tin, titanium, zirconium, niobium, and aluminum.
- the metal compound or semiconductor compound include halides, oxides, nitrides, hydroxides, carbonates, sulfates, nitrates, and metasilicates of the above metals or semiconductors.
- Reacting organosilane and inorganic particles means that organosilane is hydrolyzed in the presence of inorganic particles and dehydrated to obtain polysiloxane containing inorganic particles.
- the number average particle diameter of the inorganic particles is preferably 1 to 200 nm, more preferably 5 to 70 nm. If the number average particle diameter is less than 1 nm, the effect of improving crack resistance during thermosetting may be insufficient. On the other hand, if the number average particle diameter exceeds 200 nm, the solubility in an alkali developer is lowered, so that the pattern processability in the alkali developer is lowered, causing a residue after development, and light scattering occurs. Therefore, the sensitivity or transparency of the cured film may be reduced.
- the number average particle diameter of the inorganic particles is measured by laser scattering due to Brownian motion of the inorganic particles in the solution using a submicron particle size distribution measuring device (N4-PLUS; manufactured by Beckman Coulter, Inc.). (Dynamic light scattering method).
- inorganic particles include silica particles, lithium fluoride particles, lithium chloride particles, lithium bromide particles, lithium oxide particles, lithium carbonate particles, lithium sulfate particles, lithium nitrate particles, lithium metasilicate particles, lithium hydroxide particles, Sodium fluoride particles, sodium chloride particles, sodium bromide particles, sodium carbonate particles, sodium hydrogen carbonate particles, sodium sulfate particles, sodium nitrate particles, sodium metasilicate particles, sodium hydroxide particles, magnesium fluoride particles, magnesium chloride particles, Magnesium bromide particles, magnesium oxide particles, magnesium carbonate particles, magnesium sulfate particles, magnesium nitrate particles, magnesium hydroxide particles, potassium fluoride particles, potassium chloride particles, potassium bromide particles, potassium carbonate particles, potassium sulfate particles Particles, potassium nitrate particles, calcium fluoride particles, calcium chloride particles, calcium bromide particles, calcium oxide particles, calcium carbonate particles, calcium sulfate particles, calcium nitrate particles, calcium
- the inorganic particles preferably have a functional group capable of reacting with the resin such as a hydroxy group on the surface. If the reactivity between the inorganic particles and the resin of the matrix is good, the inorganic particles are incorporated into the polysiloxane at the time of thermosetting, and the generation of shrinkage stress at the time of thermosetting is suppressed, so the crack resistance at the time of thermosetting is reduced. improves.
- silica particles examples include methanol silica sol having a number average particle diameter (hereinafter, “particle diameter”) of 10 to 20 nm using methanol (MA) as a dispersion medium, and a particle diameter of 10 to 20 nm using isopropyl alcohol (IPA) as a dispersion medium.
- particle diameter a number average particle diameter of 10 to 20 nm using methanol (MA) as a dispersion medium
- IPA isopropyl alcohol
- IPA-ST EG-ST having a particle diameter of 10 to 20 nm using ethylene glycol (EG) as a dispersion medium
- NPC-ST-30 having a particle diameter of 10 to 20 nm using n-propyl cellosolve (NPC) as a dispersion medium
- dimethyl DMAC-ST having a particle diameter of 10 to 20 nm using acetamide (DMAC) as a dispersion medium
- MEK-ST having a particle diameter of 10 to 20 nm using methyl ethyl ketone (MEK) as a dispersion medium
- MIBK methyl isobutyl ketone
- PGM-ST having a particle diameter of 10 to 20 nm as a dispersion medium
- IPA-ST-L having a particle diameter of 45 to 100 nm using IPA as a dispersion medium
- IPA-ST-ZL having a particle diameter of 70 to 100 nm using IPA as a dispersion medium
- Snowtex (registered trademark) OXS having a particle size of 4 to 6 nm in which the dispersion solution is water
- the same OS having a particle size of 8 to 11 nm in which the dispersion solution is water
- the same O having a particle size of 10 to 20 nm in which the dispersion solution is water
- the same OL with a particle size of 40-50 nm in which the dispersion solution is water
- the solution is water, the same XL with a particle size of 40-60 nm, the dispersion solution is water, the
- MP-1040 having a particle size of about 100 nm or MP-2040 having a particle size of about 200 nm in which the dispersion solution is water (all of which are manufactured by Nissan Chemical Industries, Ltd.), particle size 5 using IPA as a dispersion medium OSCAL (registered trademark) -1421 of -10 nm, -1432 of particle diameter 10-20 nm using IPA as a dispersion medium, -1132 of particle diameter 10-20 nm using MA as a dispersion medium, ethylene glycol monomethyl ether (EGME) -1632 having a particle diameter of 10 to 20 nm using a dispersion medium, -1842 having a particle diameter of 10 to 20 nm using MIBK as a dispersion medium, ⁇ -butyrolactone (GBL The same -101 with a particle diameter of 10 to 20 nm using ED as a dispersion medium, -1727BM with a particle diameter of 110 to 130 nm using EG as a dispersion medium,
- CATALOID registered trademark
- -S having a particle diameter of 5 to 80 nm which is water (all of which are manufactured by JGC Catalysts & Chemicals Co., Ltd.), Quattron (registered trademark) PL- having a particle diameter of 5 to 10 nm which is a water dispersion.
- PL-1 with a particle size of 10 to 15 nm in which the dispersion solution is water
- PL-2L with a particle size of 15 to 20 nm in which the dispersion solution is water
- the same PL with a particle size of 30 to 40 nm in which the dispersion solution is water -3
- PL-7 having a particle diameter of 70 to 85 nm in which the dispersion solution is water
- PL-10H having a particle diameter of 80 to 100 nm in which the dispersion solution is water, and a particle diameter of 10 using IPA as a dispersion medium.
- the same PL-1-IPA of 15 nm, the same PL-2L-IPA of 15 to 20 nm in diameter using IPA as a dispersion medium, and the same PL-2L-MA and PGME of 15 to 20 nm in diameter using MA as a dispersion medium are dispersed.
- DAA diacetone alcohol
- PL-2L-BL having a particle diameter of 15 to 20 nm using the same PL-2L-BL or toluene (Tol) as a dispersion medium (all are manufactured by Fuso Chemical Industry Co., Ltd.), and the particle diameter is 100 nm.
- silica (SiO 2) SG-SO100 Korean No. 1
- silica-lithium oxide composite particles examples include lithium silicate 45 (manufactured by Nissan Chemical Industries, Ltd.).
- tin oxide-titanium oxide composite particles examples include Optolake (registered trademark) TR-502 or TR-504 (all of which are manufactured by JGC Catalysts & Chemicals, Inc.).
- silicon oxide-titanium oxide composite particles examples include Optolake (registered trademark) TR-503, TR-513, TR-520, TR-521, TR-527, TR-528, and TR- 529, TR-543 or TR-544 (all of which are manufactured by JGC Catalysts & Chemicals, Inc.).
- titanium oxide particles examples include Optolake (registered trademark) TR-505 (manufactured by JGC Catalysts & Chemicals Co., Ltd.), Tainok (registered trademark) A-6, M-6, and AM-15 (or above, either Manufactured by Taki Chemical Co., Ltd.), nSol (registered trademark) 101-20I, 101-20L, 101-20BL or 107-20I (all of which are manufactured by Nanogram Co., Ltd.), TTO-51 (A ), TTO-51 (B), TTO-55 (A), TTO-55 (B), TTO-55 (C), TTO-55 (D), TTO-V-4 or TTO-W-5 (or above) , All manufactured by Ishihara Sangyo Co., Ltd.), RTTAP15WT% -E10, RTTDNB15WT% -E11, RTTDNB15WT% -E12, RTTDNB15WT% -E13, RTTIBA15
- Zirconium oxide particles include Nano-Use (registered trademark) ZR-30BL, ZR-30BS, ZR-30BH, ZR-30AL, ZR-30AH or OZ-30M (all of which are Nissan Chemical Industries, Ltd.) Or ZSL-M20, ZSL-10T, ZSL-10A or ZSL-20N (all of which are manufactured by Daiichi Rare Element Chemical Co., Ltd.).
- tin oxide particles examples include Cerames (registered trademark) S-8 or S-10 (all of which are manufactured by Taki Chemical Co., Ltd.).
- Examples include niobium oxide particle Vilaral (registered trademark) Nb-X10 (manufactured by Taki Chemical Co., Ltd.).
- examples of other inorganic particles include tin oxide-zirconium oxide composite particles (manufactured by Catalyst Kasei Kogyo Co., Ltd.), tin oxide particles or zirconium oxide particles (all of which are manufactured by Kojundo Chemical Laboratory Co., Ltd.).
- the photosensitive resin composition of the present invention may contain inorganic particles other than the inorganic particles constituting the inorganic particle-containing polysiloxane.
- the content of inorganic particles in the solid content of the photosensitive resin composition of the present invention is usually 5 to 80% by weight, preferably 7 to 70% by weight, more preferably 10 to 60% by weight, and more preferably 15 to 50%. More preferred is weight percent. If the content of the inorganic particles is less than 5% by weight, the pattern shape after development may be deteriorated, or crack resistance at the time of thermosetting, reflow suppression of the pattern, or resolution after thermosetting may be insufficient. is there. On the other hand, if it exceeds 80% by weight, it may cause a residue after development and the transparency of the cured film may be lowered.
- content of an inorganic particle means the total amount of the inorganic particle which comprises inorganic particle containing polysiloxane, and the other inorganic particle.
- content of an inorganic particle is content which occupies for solid content of the photosensitive resin composition of this invention except a solvent.
- the photosensitive resin composition of the present invention preferably contains (B) a radical polymerizable compound as described later, and the present invention when the photosensitive resin composition of the present invention contains (B) a radical polymerizable compound.
- the content of the (A) alkali-soluble resin in the photosensitive resin composition is as follows.
- the total hardness of the (A) alkali-soluble resin and (B) radical polymerizable compound is 100 parts by weight, and the hardness and resistance of the cured film are as follows. From the viewpoint of improving chemical properties, 10 to 80 parts by weight is preferable, 20 to 70 parts by weight is more preferable, and 30 to 60 parts by weight is even more preferable.
- (A) alkali-soluble resin is inorganic particle containing polysiloxane, it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the photosensitive resin composition of the present invention preferably contains (B) a radical polymerizable compound.
- the radically polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bond groups in the molecule, but is preferably a radically polymerizable compound having a (meth) acrylic group that facilitates radical polymerization. .
- polymerization of the (meth) acryl group of the (B) radical polymerizable compound proceeds, and the exposed portion of the photosensitive resin composition is insolubilized in the aqueous alkali solution, thereby forming a pattern.
- the radicals generated from the photopolymerization initiator (C) promote the polymerization of the radical polymerizable compound (B).
- the sensitivity during exposure and the hardness of the cured film are improved.
- the double bond equivalent of the radical polymerizable compound is preferably 80 to 400 g / mol from the viewpoints of sensitivity during exposure and hardness of the cured film.
- radical polymerizable compound examples include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1 10-decanediol di (meth)
- the content of the (B) radical polymerizable compound in the photosensitive resin composition of the present invention is 20 to 90 when the total of (A) the alkali-soluble resin and (B) the radical polymerizable compound is 100 parts by weight. From the viewpoint of improving the hardness and chemical resistance of the cured film, it is preferably 30 to 80 parts by weight, and more preferably 40 to 70 parts by weight.
- (A) alkali-soluble resin is inorganic particle containing polysiloxane
- it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the photosensitive resin composition of the present invention may contain (B-1) a polyfunctional radical polymerizable compound and (B-2) a trifunctional or tetrafunctional radical polymerizable compound as the (B) radical polymerizable compound.
- B-1 The polyfunctional radically polymerizable compound refers to a compound having 5 or more ethylenically unsaturated double bond groups in the molecule.
- B-2) The trifunctional or tetrafunctional radically polymerizable compound refers to a compound having three or four ethylenically unsaturated double bond groups in the molecule.
- the photosensitive resin composition of the present invention further contains a photopolymerization initiator (C) described later, (B-1) a polyfunctional radical polymerizable compound and (B-1) a radical generated from the photopolymerization initiator, (B-2)
- the polymerization of the trifunctional or tetrafunctional radically polymerizable compound is promoted, and the sensitivity at the time of exposure and the hardness of the cured film are improved.
- the double bond equivalent of (B-1) polyfunctional radical polymerizable compound and (B-2) trifunctional or tetrafunctional radical polymerizable compound is 80 to 400 g / in from the viewpoint of sensitivity during exposure and hardness of the cured film. mol is preferred.
- Hardness, chemical resistance and vacuum resistance of the cured film obtained by containing both (B-1) a polyfunctional radical polymerizable compound and (B-2) a trifunctional or tetrafunctional radical polymerizable compound Can be improved.
- This is due to the use of a plurality of radically polymerizable compounds (B) having different numbers of ethylenically unsaturated double bond groups, and they are free without being originally crosslinked due to structural distortion or steric hindrance. This is considered to be because the cross-linking points that are cross-linked are efficiently cross-linked so as to fill the gaps. Therefore, it is estimated that a crosslinking density improves and the hardness, chemical resistance, and vacuum resistance of the obtained cured film improve.
- Examples of (B-1) polyfunctional radical polymerizable compounds include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and tripentaerythritol octa (meth).
- Examples include acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, pentapentaerythritol undeca (meth) acrylate or pentapentaerythritol dodeca (meth) acrylate, but the hardness of the cured film and chemical resistance Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol Descriptor (meth) acrylate or tripentaerythritol octa (meth) acrylate.
- Trifunctional or tetrafunctional radically polymerizable compounds include, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, ethoxylated Examples include glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate or tris ((meth) acryloxyethyl) isocyanuric acid.
- trimethylolpropane tri (meth) acrylate ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri Meth) acrylate, pentaerythritol tetra (meth) acrylate or tris ((meth) acryloxyethyl) isocyanurate are preferred.
- the content of the (B-1) polyfunctional radical polymerizable compound in the photosensitive resin composition of the present invention is preferably 30 to 99% by weight, more preferably 40 to 90% by weight, based on the total amount of the (B) radical polymerizable compound. 50 to 80% by weight is more preferable.
- (B-1) If the content of the polyfunctional radically polymerizable compound is less than 30% by weight, the hardness, chemical resistance and vacuum resistance of the cured film may be lowered. On the other hand, if it exceeds 99% by weight, the effect of improving the hardness, chemical resistance and vacuum resistance of the cured film may be insufficient.
- the content of the (B-2) trifunctional or tetrafunctional radical polymerizable compound in the photosensitive resin composition of the present invention is preferably 1 to 70% by weight based on the total amount of the (B) radical polymerizable compound, and is 10 to 60% by weight. % Is more preferable, and 20 to 50% by weight is more preferable. (B-2) If the content of the trifunctional or tetrafunctional radically polymerizable compound is less than 1% by weight, the effect of improving the hardness, chemical resistance and vacuum resistance of the cured film may be insufficient. On the other hand, if it exceeds 70% by weight, the hardness, chemical resistance and vacuum resistance of the cured film may be lowered.
- the photosensitive resin composition of the present invention may further contain a radical polymerizable compound having a fluorene skeleton.
- the radically polymerizable compound having a fluorene skeleton is a (B) radically polymerizable compound, which means a compound having a fluorene skeleton and a plurality of ethylenically unsaturated double bond groups in the molecule.
- a radically polymerizable compound having a fluorene skeleton a radically polymerizable compound having a (meth) acryl group, which facilitates radical polymerization, is preferable.
- the photosensitive resin composition of the present invention further contains a photopolymerization initiator (C) described later, the radicals generated from the photopolymerization initiator (C) accelerate the polymerization of the radical polymerizable compound having a fluorene skeleton. As a result, the sensitivity during exposure and the hardness of the cured film are improved.
- the chemical resistance, moist heat resistance and heat resistance of the resulting cured film can be improved. It is presumed that the chemical resistance, moist heat resistance and heat resistance of the resulting cured film are improved by the hydrophobicity and chemical stability of the radically polymerizable compound having a fluorene skeleton.
- the double bond equivalent of the radically polymerizable compound having a fluorene skeleton is preferably 200 to 500 g / mol from the viewpoints of sensitivity during exposure and hardness of the cured film.
- fluorene skeleton-containing radical polymerizable compound examples include Ogsol (registered trademark) EA-50P, EA-0200, EA-0250P, EA-500, EA-1000, EA-F5003, EA-F5503.
- EA-F5510 (all of which are manufactured by Osaka Gas Chemical Co., Ltd.), 9,9-bis [4- (2- (meth) acryloxyethoxy) phenyl] fluorene, 9,9-bis [4- ( 3- (meth) acryloxypropoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- (Meth) acryloxyethoxy) -3,5-dimethylphenyl] fluorene or 9,9-bis (4- (meth) acryloxyphenyl) fluorene And the like.
- the content of the radical polymerizable compound having a fluorene skeleton in the photosensitive resin composition of the present invention is (A) when 100 parts by weight of the alkali-soluble resin, or (B) when the radical polymerizable compound is contained.
- the total of (A) alkali-soluble resin and (B) radical polymerizable compound is 100 parts by weight, 0.1 to 20 parts by weight is preferable, and 1 to 10 parts by weight is more preferable. If the content of the radically polymerizable compound having a fluorene skeleton is less than 0.1 parts by weight, the effect of improving chemical resistance, moist heat resistance or heat resistance may be insufficient.
- alkali-soluble resin is inorganic particle containing polysiloxane, it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the photosensitive resin composition of the present invention may further contain a radical polymerizable compound having a carboxy group.
- the radically polymerizable compound having a carboxy group is (B) a radically polymerizable compound, which means a compound having a carboxy group and a plurality of ethylenically unsaturated double bond groups in the molecule.
- the radically polymerizable compound having a carboxy group is preferably a radically polymerizable compound having a (meth) acrylic group, which facilitates radical polymerization.
- the photosensitive resin composition of the present invention further contains a photopolymerization initiator (C) described later, polymerization of a radical polymerizable compound having a carboxy group is accelerated by radicals generated from the photopolymerization initiator (C). As a result, the sensitivity during exposure and the hardness of the cured film are improved.
- C photopolymerization initiator
- the radically polymerizable compound which has a carboxy group by containing the radically polymerizable compound which has a carboxy group, generation
- the carboxy group contained in the radically polymerizable compound having a carboxy group improves the solubility in an alkaline developer, so that it is presumed that generation of a residue after development is suppressed.
- the double bond equivalent of the radical polymerizable compound is preferably 80 to 400 g / mol from the viewpoints of sensitivity during exposure and hardness of the cured film.
- Carboxy group-containing radically polymerizable compounds are produced by reacting a hydroxy group-containing unsaturated compound having a hydroxy group and a plurality of ethylenically unsaturated double bond groups in the molecule with a compound having an acid anhydride group in the molecule. Can be obtained.
- Examples of the hydroxy group-containing unsaturated compound having one or more hydroxy groups and a plurality of ethylenically unsaturated double bond groups in the molecule include trimethylolpropane di (meth) acrylate and ditrimethylolpropane di (meth) acrylate.
- Examples of the compound having an acid anhydride group in the molecule include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride, with succinic anhydride being preferred.
- radical polymerizable compound having a carboxy group examples include Aronix (registered trademark) M-510 and M-520 (both are manufactured by Toagosei Co., Ltd.), succinic acid mono [2,2,2-tris ((Meth) acryloxymethyl) ethyl] or mono [2,2-bis ((meth) acryloxymethyl) -3- [2,2,2-tris ((meth) acryloxymethyl) ethyloxy] propyl succinate ].
- the content of the radical polymerizable compound having a carboxy group in the photosensitive resin composition of the present invention is 1 to 4 when the total of (A) the alkali-soluble resin and (B) the radical polymerizable compound is 100 parts by weight. 40 parts by weight is preferable, and 5 to 30 parts by weight is more preferable. If the content of the radical polymerizable compound having a carboxy group is less than 1 part by weight, the effect of inhibiting the generation of residues after development may be insufficient. On the other hand, if it exceeds 40 parts by weight, it may cause a decrease in hardness of the cured film and a decrease in chemical resistance.
- (A) alkali-soluble resin is inorganic particle containing polysiloxane, it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the photosensitive resin composition of the present invention preferably contains (C) a photopolymerization initiator.
- Examples of the (C) photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl)- 1- (4-morpholinophenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 3,6-bis (2-methyl-2) ⁇ -aminoalkylphenone compounds such as -morpholinopropionyl) -9-octyl-9H-carbazole, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide or Bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) phosphine oxide Any acylphosphine oxide compound, 1-phenylpropane
- an ⁇ -aminoalkylphenone compound an acylphosphine oxide compound, an oxime ester compound, a benzophenone compound having an amino group, or A benzoic acid ester compound having an amino group is preferred.
- benzophenone compound having an amino group examples include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone.
- benzoic acid ester compound having an amino group examples include ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (2-ethylhexyl), and ethyl 4-diethylaminobenzoate.
- the content of the (C) photopolymerization initiator in the photosensitive resin composition of the present invention is (A) when 100 parts by weight of the alkali-soluble resin, or (B) when containing a radical polymerizable compound ( When the total of A) alkali-soluble resin and (B) radical polymerizable compound is 100 parts by weight, it is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight. (C) If the content of the photopolymerization initiator is less than 0.1 parts by weight, UV curing does not proceed sufficiently, film loss during development is large, and resolution after development may be reduced.
- the photosensitive resin composition of the present invention contains (D) a metal chelate compound.
- a metal chelate compound refers to a compound having a central metal and a ligand coordinated to the metal at two or more sites.
- the metal chelate compound reacts with the resin or the like by heat and is incorporated as part of the three-dimensional network structure formed during thermosetting. That is, when relatively large atoms are taken into the cured film, the film density of the cured film increases, and the permeability of moisture and chemicals decreases. I think that.
- a metal chelate compound from the viewpoint of adhesiveness of a cured film, a titanium chelate compound, a zirconium chelate compound, an aluminum chelate compound or a magnesium chelate compound can be mentioned. Zirconium chelate compounds are more preferred.
- metal chelate compounds can be easily obtained by reacting a metal alkoxide with a chelating agent.
- a chelating agent examples include ⁇ -diketones such as acetylacetone, benzoylacetone or dibenzoylmethane, or ⁇ -ketoesters such as ethyl acetoacetate or ethyl benzoylacetate.
- the (D) metal chelate compound of the present invention is a compound represented by the general formula (1).
- M represents titanium, zirconium, aluminum, or magnesium
- R 1 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or 6 to 6 carbon atoms.
- R 1 is preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms
- R 2 and R 3 are each independently hydrogen, An alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxy group is preferable.
- Examples of the compound represented by the general formula (1) include tetrakis (acetylacetonato) titanium (IV), diisopropoxybis (ethylacetoacetate) titanium (IV), and diisopropoxybis (acetylacetonate).
- Titanium chelate compounds such as titanium (IV), tetrakis (acetylacetonato) zirconium (IV), di-n-butoxybis (ethylacetoacetate) zirconium (IV) or tri-n-butoxymono (acetylacetonato) zirconium (IV
- Zirconium chelate compounds such as tris (acetylacetonate) aluminum (III), tris (ethylacetoacetate) aluminum (III), mono (acetylacetonato) bis (ethylacetoacetate) aluminum (II) ), Diisopropoxymono (ethylacetoacetate) aluminum (III) or Preneact® AL-M ((diisopropoxymono (9-octadecanylacetoacetate) aluminum (III), Kawaken Fine Chemicals ( ), Etc., or bis (acetylacetonato) magnesium (II), bis (ethylacetoacetate) magnesium (II
- the content of the (D) metal chelate compound in the photosensitive resin composition of the present invention is (A) when 100 parts by weight of the alkali-soluble resin, or (B) when containing a radical polymerizable compound (A ) When the total of the alkali-soluble resin and the (B) radical polymerizable compound is 100 parts by weight, 0.1 to 10 parts by weight is preferable, and 0.5 to 5 parts by weight is more preferable. (D) If the content of the metal chelate compound is less than 0.1 parts by weight, the effect of improving chemical resistance or moist heat resistance may be insufficient. On the other hand, if it exceeds 10 parts by weight, it may cause a decrease in transparency and generation of a residue after development, and the storage stability of the coating liquid may decrease. In addition, when (A) alkali-soluble resin is inorganic particle containing polysiloxane, it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the photosensitive resin composition of the present invention contains (E) a silane compound.
- a silane compound is a silane oligomer obtained by condensing the tetrafunctional silane represented by the general formula (2) or the tetrafunctional silane represented by the general formula (2).
- a silane compound has an alkoxy silyl group from a viewpoint of the adhesiveness of a cured film, and a chemical-resistant improvement.
- the adhesiveness of the obtained cured film, chemical resistance, heat-and-moisture resistance, and the storage stability of the coating liquid can be improved.
- the silane compound Since the silane compound has many hydrolyzable silyl groups, it functions as a cross-linking agent, the film density of the cured film is increased, and the permeability of moisture and chemicals is decreased. It is considered that the chemical resistance and the heat and humidity resistance of the material are improved. Further, the silanol group can form a covalent bond or a coordinate bond with a hydroxy group on the surface of the underlying substrate. Therefore, it is estimated that the interaction between the cured film and the underlying substrate is increased, and the adhesion and chemical resistance of the resulting cured film are improved.
- R 4 to R 7 each independently represents 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.
- R 4 to R 7 are preferably each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- the silane compound is a silane oligomer obtained by condensing the tetrafunctional silane represented by the general formula (2), by condensing only the tetrafunctional silane represented by the general formula (2) It may be a silane oligomer obtained, or a silane oligomer obtained by condensing a tetrafunctional silane represented by the general formula (2) and another silane compound, that is, represented by the general formula (2). It may be a silane oligomer having a structure derived from tetrafunctional silane.
- the tetrafunctional silane represented by the general formula (2) and other silane compounds may be subjected to dehydration condensation by hydrolyzing part or all of the hydrolyzable silyl groups that they have.
- Examples of the (E) silane compound include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane and tetraacetoxysilane, and methyl silicate 51 ( Fuso Chemical Industry Co., Ltd.), M silicate 51, silicate 40 or silicate 45 (all of which are manufactured by Tama Chemical Industry Co., Ltd.) or methyl silicate 51, methyl silicate 53A, ethyl silicate 40 or ethyl silicate 48 (or more, All of them include silicate compounds such as those manufactured by Colcoat Co., Ltd.
- tetramethoxysilane tetraethoxysilane, tetra-n- Propoxysilane, methylsil Over preparative 51 (Fuso Chemical Co., Ltd.), M Silicate 51 (Tama Chemical Industries, Ltd.) or methyl silicate 51 (Colcoat Co., Ltd.) are preferable, tetramethoxysilane is preferred.
- the content of the (E) silane compound in the photosensitive resin composition of the present invention is (A) when (A) the alkali-soluble resin is 100 parts by weight, or (B) when it contains a radical polymerizable compound.
- the total of the alkali-soluble resin and the (B) radical polymerizable compound is 100 parts by weight, it is preferably 0.1 to 30 parts by weight, and more preferably 1 to 25 parts by weight.
- content of a silane compound is less than 0.1 weight part, the effect of adhesiveness, chemical-resistance, heat-and-moisture resistance, or the storage stability improvement of a coating liquid may be inadequate.
- (A) alkali-soluble resin is inorganic particle containing polysiloxane, it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the photosensitive resin composition of the present invention is further selected from the group consisting of (F) amino group, amide group, ureido group, ketimine group, isocyanate group, mercapto group, isocyanuric ring skeleton, (meth) acryl group and styryl group. It is preferable to contain a silane compound having a substituent (hereinafter referred to as “(F) specific silane compound”). (F) It is preferable that a specific silane compound has an alkoxy silyl group from a viewpoint of the adhesiveness of a cured film, and a chemical-resistant improvement.
- the adhesion and chemical resistance of the resulting cured film can be improved.
- Functional groups such as amino groups, amide groups, ureido groups, ketimine groups, isocyanate groups, mercapto groups, isocyanuric ring skeletons, (meth) acrylic groups, and styryl groups possessed by specific silane compounds can react with resins, etc. It functions as a site that can be coordinated to the surface of the underlying substrate depending on the functional group.
- the hydrolyzable silyl group possessed by the specific silane compound is converted into a silanol group by hydrolysis, and this silanol group can form a covalent bond with a hydroxy group on the surface of the underlying substrate.
- Specific silane compounds include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2- Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2- Aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3- (4-aminophenyl) propyltrimethoxysilane, Nt-butyl-2- (3-trimethoxysilylpropyl) succinimide, 2- (3 -Trimethoxysilylpropyl) -4
- the content of the specific silane compound (F) in the photosensitive resin composition of the present invention is (A) when 100 parts by weight of the alkali-soluble resin, or (B) when containing a radical polymerizable compound (When the total of A) alkali-soluble resin and (B) radical polymerizable compound is 100 parts by weight, 0.1 to 10 parts by weight is preferable, and 0.5 to 7 parts by weight is more preferable. (F) If the content of the specific silane compound is less than 0.1 parts by weight, the effect of improving adhesion or chemical resistance may be insufficient. On the other hand, if it exceeds 10 parts by weight, it may cause residue after development, and the storage stability of the coating liquid may be lowered. In addition, when (A) alkali-soluble resin is inorganic particle containing polysiloxane, it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the photosensitive resin composition of the present invention may contain a solvent.
- the solvent is preferably a compound having an alcoholic hydroxyl group, a compound having a carbonyl group or a compound having three or more ether bonds from the viewpoint of uniformly dissolving each component and improving the transparency of the resulting cured film.
- a compound having a boiling point of 110 to 250 ° C. under atmospheric pressure is more preferable.
- Examples of the compound having an alcoholic hydroxyl group and a boiling point of 110 to 250 ° C. under atmospheric pressure include hydroxyacetone, 4-hydroxy-2-butanone, 3-hydroxy-3-methyl-2-butanone, 4- Hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), methyl lactate, ethyl lactate, lactic acid n-propyl, n-butyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propi Glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol
- diacetone alcohol ethyl lactate, ethylene glycol monomethyl ether, propylene glycol mono Chirueteru, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol or tetrahydrofurfuryl alcohol.
- Examples of the compound having a carbonyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure include, for example, n-butyl acetate, isobutyl acetate, 3-methoxy-n-butyl acetate, 3-methyl-3-methoxy-n -Butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, methyl n-butyl ketone, methyl isobutyl ketone, diisobutyl ketone, 2-heptanone, acetylacetone, cyclopentanone, cyclohexanone, cycloheptanone, ⁇ -butyrolactone, ⁇ - Examples include valerolactone, ⁇ -valerolactone, propylene carbonate, N-methylpyrrolidone, N, N′-dimethylformamide, N, N′-dimethylacetamide or 1,3-dimethyl-2-imi
- Examples of the compound having three or more ether bonds and a boiling point of 110 to 250 ° C. under atmospheric pressure include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol di-n-propyl ether, dipropylene glycol.
- Examples thereof include dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether and dipropylene glycol di-n-propyl ether. From the viewpoint of applicability, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether or dipropylene glycol dimethyl ether is preferable.
- the content of the solvent in the photosensitive resin composition of the present invention may be appropriately adjusted according to the coating method and the like. For example, when film formation is performed by spin coating, 50% of the entire photosensitive resin composition is used. Generally, it is set to ⁇ 95% by weight.
- the photosensitive resin composition of the present invention may further contain a maleimide compound.
- a maleimide compound a general maleimide or maleimide derivative can be used.
- the photosensitive resin composition contains a maleimide compound, the chemical resistance and heat and moisture resistance of the resulting cured film can be improved without impairing the storage stability of the coating liquid.
- the structure derived from maleimide in the maleimide compound is coordinated to the (D) metal chelate compound, and the reactivity is lowered and stabilized. I think that.
- the maleimide compound contributes to the stabilization of the photosensitive resin composition and suppresses the progress of the reaction during storage of the coating liquid, thereby suppressing the decrease in adhesion or chemical resistance. It is presumed that the maleimide compound reacts with a resin or the like by heat to be taken in as a part of a three-dimensional network structure and the crosslinking density is improved. Moreover, it is thought that the chemical resistance of the obtained cured film improves because the structure derived from the maleimide of the maleimide compound functions as a site capable of coordinating with the underlying substrate surface. Furthermore, it is considered that the heat and humidity resistance of the resulting cured film is improved by improving the crosslinking density.
- the maleimide compound preferably has an aromatic cyclic skeleton or an aliphatic cyclic skeleton. It is considered that the chemical resistance, moist heat resistance and heat resistance of the obtained cured film are further improved by the hydrophobicity and chemical stability of the aromatic cyclic skeleton or the aliphatic cyclic skeleton.
- maleimide compounds include maleimide, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, Nn-hexyl.
- N-cyclopentylmaleimide N-cyclohexylmaleimide, N- (2,4-dimethylcyclohexyl) maleimide, N-phenylmaleimide, N- (4-methylphenyl) maleimide, N- (3-methylphenyl) maleimide, N- (2-methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (4-styryl) maleimide N- (4-methoxyphenyl) maleimide, N (3-methoxyphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N- (4-methoxycarbonylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N- (3-hydroxyphenyl) maleimide, N -(2-hydroxyphenyl) maleimide, N- (4-carboxyphenyl) maleimide,
- the content of the maleimide compound in the photosensitive resin composition of the present invention is (A) an alkali-soluble resin when (A) the alkali-soluble resin is 100 parts by weight, or (B) when it contains a radical polymerizable compound. And (B) When the total amount of the radical polymerizable compounds is 100 parts by weight, it is preferably 0.1 to 20 parts by weight, more preferably 1 to 15 parts by weight. If the content of the maleimide compound is less than 0.1 parts by weight, the effect of improving chemical resistance, moist heat resistance or heat resistance may be insufficient. On the other hand, if it exceeds 20 parts by weight, it may cause generation of a residue after development.
- (A) alkali-soluble resin is inorganic particle containing polysiloxane, it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the maleimide compound is more preferably a bismaleimide compound.
- the bismaleimide compound is a compound having two maleimide-derived structures, and has two sites each incorporated as a part of a three-dimensional network structure and two sites capable of coordination with the underlying substrate surface. For this reason, it is considered that the crosslink density and the adhesion to the underlying substrate surface are further improved, and the chemical resistance and heat-and-moisture resistance of the resulting cured film can be further improved.
- the bismaleimide compound preferably has an aromatic cyclic skeleton or an aliphatic cyclic skeleton. It is considered that the chemical resistance, moist heat resistance and heat resistance of the obtained cured film are further improved by the hydrophobicity and chemical stability of the aromatic cyclic skeleton or the aliphatic cyclic skeleton.
- the bismaleimide compound examples include 1,2-bis (maleimido) ethane, 1,3-bis (maleimido) propane, 1,4-bis (maleimido) butane, 1,5-bis (maleimido) pentane, 6-bis (maleimido) hexane, 2,2,4-trimethyl-1,6-bis (maleimido) hexane, N, N′-1,3-phenylenebis (maleimide), 4-methyl-N, N′- 1,3-phenylenebis (maleimide), N, N′-1,4-phenylenebis (maleimide), 3-methyl-N, N′-1,4-phenylenebis (maleimide), 4,4′-bis (Maleimido) diphenylmethane, 3,3′-diethyl-5,5′-dimethyl-4,4′-bis (maleimido) diphenylmethane or 2,2-bis [4- (4-maleimidophenol) P) propane].
- the content of the bismaleimide compound in the photosensitive resin composition of the present invention is (A) alkali-soluble when (A) the alkali-soluble resin is 100 parts by weight, or when (B) a radical polymerizable compound is contained.
- the total of the resin and the (B) radical polymerizable compound is 100 parts by weight, it is preferably 0.1 to 20 parts by weight, and more preferably 1 to 15 parts by weight. If the content of the bismaleimide compound is less than 0.1 parts by weight, the effect of improving chemical resistance, moist heat resistance or heat resistance may be insufficient. On the other hand, if it exceeds 20 parts by weight, it may cause generation of a residue after development.
- (A) alkali-soluble resin is inorganic particle containing polysiloxane, it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the photosensitive resin composition of the present invention may further contain a fluorene compound.
- a fluorene compound By containing a fluorene compound, the chemical resistance, heat-and-moisture resistance, and heat resistance of the cured film obtained can be improved. It is presumed that the fluorene compound is taken in as a part of the three-dimensional network structure by reacting with a resin or the like by heat. And it is estimated that the chemical resistance of the obtained cured film, heat-and-moisture resistance, and heat resistance improve with the hydrophobicity and chemical stability which the fluorene skeleton of a fluorene compound has.
- fluorene compound examples include Ogsol (registered trademark) PG, PG-100, EG, EG-200, EG-210 (all of which are manufactured by Osaka Gas Chemical Co., Ltd.), ONCOAT (registered trademark).
- EX-1010, EX-1011, EX-1012, EX-1020, EX-1020, EX-1030, EX-1040, EX-1050, EX-1051, EX-1020M80 or EX-1020M70 All of the above are manufactured by Nagase ChemteX Corporation), 9,9-bis [4- (2-glycidoxyethoxy) phenyl] fluorene, 9,9-bis [4- (3-glycidoxypropoxy) phenyl ] Fluorene, 9,9-bis [4- (2-glycidoxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-glycyl) Doxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis (4-glycidoxyphenyl) fluorene, 9,9-bis (4-glycidoxy-3-methylphenyl) fluorene, 9,9-bis ( 4-glycidoxy-3,5-d
- OGSOL registered trademark
- PG registered trademark
- PG-100 EG
- EG-200 EG-210
- EG-250 all of which are Osaka Gas Chemical Co., Ltd.
- EX-1010 (registered trademark) EX-1010, EX-1011, EX-1012, EX-1020, EX-1030, EX-1040, EX-1050, EX-1051, EX-1020M80 or EX-1020M70 (all of which are manufactured by Nagase ChemteX Corporation), 9,9-bis [4- (2-glycidoxyethoxy) phenyl] fluorene, 9,9-bis [4- (3-glycidoxypropoxy) phenyl] fluorene, 9,9-bis [4- (2-glycidoxyethoxy) -3-methylphenyl] fluorene, 9, -Bis [4- (2-glycidoxyethoxy) -3,5-dimethylphenyl] fluorene, 9,9-bis (4-glycidoxyphenyl) fluorene, 9,9-bis [4- (2-hydroxy Ethoxy) phenyl] fluorene, 9,9-bis [4- (3-hydroxyprop
- the content of the fluorene compound in the photosensitive resin composition of the present invention is (A) an alkali-soluble resin when (A) the alkali-soluble resin is 100 parts by weight, or (B) a radically polymerizable compound is contained.
- the total amount of the radically polymerizable compound (B) is 100 parts by weight, it is preferably 1 to 30 parts by weight, and more preferably 5 to 25 parts by weight. If the content of the fluorene compound is less than 1 part by weight, the effect of improving chemical resistance, moist heat resistance or heat resistance may be insufficient. On the other hand, if it exceeds 30 parts by weight, it may cause residue after development, and the storage stability of the coating liquid may be lowered.
- (A) alkali-soluble resin is inorganic particle containing polysiloxane, it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the photosensitive resin composition of the present invention may further contain a polyfunctional epoxy compound.
- a polyfunctional epoxy compound By containing a polyfunctional epoxy compound, the chemical resistance, moist heat resistance and heat resistance of the resulting cured film can be improved. It is presumed that the epoxy part of the polyfunctional epoxy compound is taken in as a part of the three-dimensional network structure by reacting with a resin or the like by heat. And it is estimated that the chemical resistance of the obtained cured film, heat-and-moisture resistance, and heat resistance improve with the hydrophobicity and chemical stability which the aromatic cyclic skeleton of a polyfunctional epoxy compound has.
- polyfunctional epoxy compound examples include 1,1-bis (4-glycidoxyphenyl) -1- [4- [1- (4-glycidoxyphenyl) -1-methylethyl] phenyl] ethane, , 2-bis (4-glycidoxyphenyl) propane, 1,1-bis (4-glycidoxyphenyl) -1-phenylethane, 1,1,1-tris (4-glycidoxyphenyl) methane, 1,1,1-tris (4-glycidoxyphenyl) ethane, 1,1-bis (4-glycidoxyphenyl) -1- (1-naphthyl) ethane, 1,1-bis (4-glycide) Xylphenyl) -1- (2-naphthyl) ethane, 1,1-bis (4-glycidoxy-1-naphthyl) -1- (4-glycidoxyphenyl) ethane, 1,1-bis (5-gly
- the content of the polyfunctional epoxy compound in the photosensitive resin composition of the present invention is (A) when alkali-soluble resin is 100 parts by weight, or when (B) a radical polymerizable compound is contained, (A) alkali When the total of the soluble resin and the (B) radical polymerizable compound is 100 parts by weight, it is preferably 1 to 30 parts by weight, and more preferably 5 to 25 parts by weight. If the content of the polyfunctional epoxy compound is less than 1 part by weight, the effect of improving chemical resistance, moist heat resistance or heat resistance may be insufficient. On the other hand, if it exceeds 30 parts by weight, it may cause residue after development, and the storage stability of the coating liquid may be lowered. In addition, when (A) alkali-soluble resin is inorganic particle containing polysiloxane, it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the photosensitive resin composition of the present invention may further contain an isocyanate compound.
- the isocyanate compound here includes a blocked isocyanate compound in which an isocyanate group is blocked.
- the photosensitive resin composition contains an isocyanate compound, the chemical resistance and heat-and-moisture resistance of the resulting cured film can be improved. Since the isocyanate group is a site capable of reacting with a carboxy group or the like in the resin by heat, it is presumed that the isocyanate compound functions as a crosslinking agent. And since an isocyanate compound functions as a crosslinking agent, the film density of a cured film rises and it is estimated that the chemical resistance and wet heat resistance of the obtained cured film improve.
- isocyanate compound examples include hexamethylene diisocyanate, isophorone diisocyanate, tolylene-2,6-diisocyanate, methylenediphenyl-4,4′-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and 1,3-bis (isocyanate methyl).
- tris (6-isocyanatohexyl) isocyanuric acid tris (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl) isocyanuric acid or 1,3,5-tris (6 -Isocyanatohexyl) biuret is preferred.
- the content of the isocyanate compound in the photosensitive resin composition of the present invention is (A) 100 parts by weight of the alkali-soluble resin, or (B) when it contains a radical polymerizable compound, (A) the alkali-soluble resin And (B) When the total amount of radically polymerizable compounds is 100 parts by weight, 0.1 to 10 parts by weight is preferable, and 0.5 to 7 parts by weight is more preferable. If the content of the isocyanate compound is less than 0.1 parts by weight, the effect of improving chemical resistance or moist heat resistance may be insufficient. On the other hand, if it exceeds 10 parts by weight, it may cause residue after development, and the storage stability of the coating liquid may be lowered.
- (A) alkali-soluble resin is inorganic particle containing polysiloxane, it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the photosensitive resin composition of the present invention may further contain a urea compound having an ethylenically unsaturated double bond group.
- a urea compound having an ethylenically unsaturated double bond group By containing the urea compound which has an ethylenically unsaturated double bond group, the chemical resistance and heat-and-moisture resistance of the obtained cured film can be improved.
- the urea site is presumed to function as a site capable of reacting with a resin or the like by heat and capable of coordinating with the underlying substrate surface.
- a crosslinked structure can be formed by radical polymerization with an ethylenically unsaturated double bond group bonded to a resin or the like.
- the urea compound which has an ethylenically unsaturated double bond group functions as a crosslinking agent, the film density of a cured film rises, and the chemical resistance and wet heat resistance of the obtained cured film improve.
- urea compounds having an ethylenically unsaturated double bond group include 1-allylurea, 1-vinylurea, 1-allyl-2-thiourea, 1-vinyl-2-thiourea, 1-allyl-3. -Methyl-2-thiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea or 1-methyl-3- (4-vinylphenyl) -2-thiourea.
- the content of the urea compound having an ethylenically unsaturated double bond group in the photosensitive resin composition of the present invention is as follows: (A) 100 parts by weight of the alkali-soluble resin, or (B) the radical polymerizable compound When contained, when the total of (A) alkali-soluble resin and (B) radical polymerizable compound is 100 parts by weight, 0.1 to 10 parts by weight is preferable, and 0.5 to 7 parts by weight is more preferable. When the content of the urea compound having an ethylenically unsaturated double bond group is less than 0.1 part by weight, the effect of improving chemical resistance or heat and moisture resistance may be insufficient.
- (A) alkali-soluble resin is inorganic particle containing polysiloxane, it is set as 100 weight part including the weight of the inorganic particle which comprises inorganic particle containing polysiloxane.
- the photosensitive resin composition of the present invention may further contain a polymerization inhibitor.
- a polymerization inhibitor By containing a suitable amount of a polymerization inhibitor, generation of residues after development can be suppressed and high resolution can be ensured. It is presumed that the polymerization inhibitor can capture excessive radicals generated from the photopolymerization initiator (C) by light irradiation during exposure, and the progress of excessive radical polymerization can be suppressed.
- polymerization inhibitor examples include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol.
- polymerization inhibitors examples include IRGANOX (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, and 259. 3114, 565, or 295 (all of which are manufactured by BASF).
- the photosensitive resin composition of the present invention may further contain an ultraviolet absorber.
- an ultraviolet absorber By containing an appropriate amount of the ultraviolet absorber, generation of residues after development can be suppressed, high resolution can be ensured, and light resistance of the resulting cured film is improved. This is presumed to be because the ultraviolet absorbent captures scattered light, reflected light, and the like, which are generated during light irradiation during exposure, and the progress of excessive radical polymerization can be suppressed. Moreover, also in the cured film obtained, it is estimated that light resistance improves because an ultraviolet absorber captures the irradiated light.
- a benzotriazole compound As the ultraviolet absorber, a benzotriazole compound, a benzophenone compound, a triazine compound, or the like is preferable from the viewpoint of transparency and non-colorability.
- benzotriazole compound examples include 2- (2′-hydroxyphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) -2H-benzotriazole, 2- (2′-hydroxy -5′-t-butylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -2H-benzotriazole, 2- [2′-hydroxy- 3 ′, 4′-bis (1-methyl-1-phenylethyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-pentylphenyl) -2H-benzo Triazole, 2- (2′-hydroxy-5′-t-octylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-dodecyl) -5'-methylphenyl) -2H-benzotriazole, 2- [2'-
- benzophenone compound examples include 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-octyloxybenzophenone.
- triazine compound examples include 2- (2′-hydroxy-4′-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- [2′-hydroxy-4 ′-(2 -Hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2 ', 4'-dimethylphenyl) -1,3,5-triazine, 2- [2'-hydroxy-4'-[2- Hydroxy-3- (2-ethylhexyloxy) propoxy] phenyl] -4,6-bis (2 ′, 4′-dimethylphenyl) -1,3,5-triazine or 2,4-bis (2′-hydroxy- And 4'-butoxyphenyl) -6- (2 ', 4'-dibutoxy) -1,3,5-triazine.
- the photosensitive resin composition of the present invention may further contain a surfactant.
- a surfactant By containing an appropriate amount of the surfactant, leveling properties at the time of coating can be improved, the occurrence of coating unevenness can be suppressed, and a uniform coating film can be obtained.
- surfactant examples include a fluorine-based surfactant, a silicone-based surfactant, a polyalkylene oxide-based surfactant, and a poly (meth) acrylate-based surfactant.
- fluorine-based surfactant examples include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, Octaethylene glycol bis (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol bis (1,1, 2,2-tetrafluorobutyl) ether, hexapropylene glycol bis (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8, 8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodeca N- [3- (perfluorooctanesulfonamid
- compounds having a fluoroalkyl group or a fluoroalkylene chain at any of the terminal, main chain, and side chain such as monoperfluoroalkylethyl phosphate, can be mentioned.
- Examples of such compounds include MegaFac (registered trademark) F-142D, F-172, F-173, F-183, F-444, F-445, F-470, and F-470.
- F-475, F-477, F-555, or F-559 "(all of which are manufactured by Dainippon Ink & Chemicals, Inc.), Ftop (registered trademark) EF301, 303 or 352 (and above) , All manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.), Florard (registered trademark) FC-430 or FC-431 (all of which are manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 ”(Asahi Glass ( Manufactured by the same company), Surflon (registered trademark) S-382, “SC-101, SC-102, SC-103, SC-104, SC-105, or SC-106 (above, This is also manufactured by AGC Seimi Chemical Co., Ltd.), BM-1000 or BM-1100 (both manufactured by Yusho Co., Ltd.), or NBX-15, FTX-218 or DFX-218 (all manufactured by Co., Ltd.) Neos).
- silicone surfactant examples include SH28PA, SH7PA, SH21PA, SH30PA or ST94PA (all of which are manufactured by Toray Dow Corning Co., Ltd.) or BYK-301, BYK-307, BYK-331, BYK-333. Another example is BYK-345 (all of which are manufactured by Big Chemie Japan Co., Ltd.).
- the content of the surfactant in the photosensitive resin composition of the present invention is generally preferably 0.0001 to 1% by weight of the entire photosensitive resin composition, and is preferable.
- the photosensitive resin composition of the present invention may further contain various curing agents that promote thermal curing of the resin composition.
- the curing agent include nitrogen-containing organic compounds, silicone resin curing agents, metal alkoxides, methylol group-containing melamine derivatives, and methylol group-containing urea derivatives.
- the photosensitive resin composition of the present invention preferably has negative photosensitivity.
- negative photosensitivity coloring during thermosetting can be suppressed, and a cured film with higher transparency can be obtained.
- the crosslinking reaction easily proceeds during UV curing, and it is possible to obtain a cured film excellent in hardness, moist heat resistance, artificial sweat resistance, adhesion, chemical resistance and vacuum resistance. It becomes.
- a typical production method of the photosensitive resin composition of the present invention will be described. For example, an arbitrary (C) photopolymerization initiator, (D) a metal chelate compound, and other solid additives are weighed, an arbitrary solvent is added, and the mixture is stirred and dissolved. Next, add other liquid additives and stir. Next, (A) an alkali-soluble resin and (B) a radical polymerizable compound are added and stirred. Further, (E) a silane compound is added and stirred for 20 minutes to 3 hours to obtain a uniform solution. Then, the photosensitive resin composition of this invention is obtained by filtering the obtained solution.
- the photosensitive resin composition of the present invention is applied on a substrate.
- a substrate for example, a substrate in which a metal oxide such as ITO, a metal such as molybdenum, silver, copper, or aluminum, or CNT (Carbon Nano Tube) is formed on a glass as an electrode or a wiring is used.
- the application method include micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating.
- the coating film thickness varies depending on the coating method, solid content concentration and viscosity of the photosensitive resin composition, but is usually applied so that the film thickness after coating and pre-baking is 0.1 to 15 ⁇ m.
- the substrate coated with the photosensitive resin composition is prebaked to prepare a prebaked film of the photosensitive resin composition.
- Prebaking is preferably performed at 50 to 150 ° C. for 30 seconds to several hours using an oven, a hot plate, or infrared rays. If necessary, after pre-baking at 80 ° C. for 2 minutes, pre-baking at 120 ° C. for 2 minutes may be used for pre-baking in two or more stages.
- exposure is performed using an exposure machine such as a stepper, mirror projection mask aligner (MPA), or parallel light mask aligner (PLA).
- an exposure machine such as a stepper, mirror projection mask aligner (MPA), or parallel light mask aligner (PLA).
- MPA mirror projection mask aligner
- PPA parallel light mask aligner
- the active actinic radiation to be irradiated at the time of exposure ultraviolet rays, visible rays, electron beams, X-rays, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser or the like can be used, but mercury lamp j-ray (wavelength 313 nm). I-line (wavelength 365 nm), h-line (wavelength 405 nm) or g-line (wavelength 436 nm) is preferably used.
- the exposure amount is usually about 10 to 4000 J / m 2 (i-line illuminometer value), and exposure can be performed through a mask having
- baking before development may be performed.
- the baking temperature is preferably 50 to 180 ° C, more preferably 60 to 150 ° C.
- the baking time is preferably 10 seconds to several hours.
- the exposed film is developed for an arbitrary time using an automatic developing device or the like, so that the unexposed portion is removed with a developer and a relief pattern is obtained.
- a known alkali developer is generally used.
- the developer include organic alkaline developer or ammonia, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine.
- An aqueous solution of an alkaline compound such as dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylene diamine or hexamethylene diamine is mentioned. preferable.
- the same solvents as those contained in the photosensitive resin composition alcohols, ketones, ethers, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide or ⁇ -butyrolactone may be used.
- solvents methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate,
- a mixed solution in combination with a poor solvent for the photosensitive resin composition such as ethyl-3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, or ethyl acetate may be used.
- the above-described developer is directly applied to the exposed film, the developer is sprayed and emitted, the exposed film is immersed in the developer, and the exposed film is exposed. It can be performed by a method such as applying ultrasonic waves while being immersed in the developer.
- the exposed film is preferably brought into contact with the developer for 5 seconds to 10 minutes.
- rinsing treatment may be performed by adding alcohols such as ethanol or isopropyl alcohol, esters such as propylene glycol monomethyl ether acetate, or acids such as carbon dioxide, hydrochloric acid or acetic acid to water.
- Methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3- Ethoxypropionate, 2-heptanone or ethyl acetate is preferred.
- middle baking may be performed as necessary. By performing middle baking, effects such as improvement in resolution after thermosetting and control of the pattern shape after thermosetting can be expected.
- Middle baking uses an oven, a hot plate, infrared rays, or the like, and the baking temperature is preferably 60 to 250 ° C, more preferably 70 to 220 ° C.
- the baking time is preferably 10 seconds to several hours.
- a cured film of the photosensitive resin composition of the present invention is obtained by heating at a temperature of 120 to 280 ° C. for 10 minutes to several hours.
- This heat treatment can be performed in an air atmosphere or an inert gas atmosphere such as nitrogen.
- this heat treatment may be performed stepwise, or may be performed continuously for 5 minutes to 5 hours.
- the thickness of the cured film obtained by thermosetting the photosensitive resin composition of the present invention is preferably 0.1 to 15 ⁇ m. Further, when the film thickness is 1.5 ⁇ m, the hardness is preferably 4H or more and the transmittance is preferably 90% or more, and more preferably 95% or more. In addition, the transmittance
- the cured film obtained by thermosetting the photosensitive resin composition of the present invention includes various types such as a protective film for a touch panel, various hard coat materials, a flattening film for TFT, an overcoat for a color filter, an antireflection film, or a passivation film. It can be used for various insulating films such as protective films, optical filters, touch panel insulating films, TFT insulating films, or color filter photo spacers. Among these, since it has high hardness, transparency, chemical resistance, and heat resistance, it can be suitably used as a protective film for a touch panel or an insulating film for a touch panel. Examples of the touch panel system include a resistance film type, an optical type, an electromagnetic induction type, and a capacitance type. In particular, since a particularly high hardness is required for a capacitive touch panel, the cured film of the present invention can be used particularly suitably.
- the cured film obtained by thermosetting the photosensitive resin composition of the present invention has high moisture and heat resistance, it can be suitably used as a metal wiring protective film.
- a metal wiring protective film By forming the cured film of the present invention on the metal wiring, deterioration due to metal corrosion or the like (conductivity, decrease in resistance value, etc.) can be prevented.
- the metal wiring to be protected include one or more selected from the group consisting of molybdenum, silver, copper, aluminum, chromium, titanium, ITO, IZO (Indium Zinc Oxide), AZO (Aluminum Zinc Oxide), ZnO 2 and CNT.
- the metal wiring to contain is mentioned.
- the cured film obtained by thermosetting the photosensitive resin composition of the present invention is a protective film or insulating film for metal wiring containing at least one selected from the group consisting of molybdenum, silver, copper, aluminum and CNT. Preferably used.
- Synthesis Example 2 Synthesis of acrylic resin solution (A-02) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 32.46 g of PGMEA, and 44.05 g (50 mol%) of benzyl methacrylate ), 21.52 g (50 mol%) of methacrylic acid, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, and 0.186 g (0.3 mol%) of 4-methoxyphenol. And 65.90 g of PGMEA was used for polymerization in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-02). PGMEA was added to the obtained acrylic resin solution (A-02) so that the solid content concentration was 35% by weight. The Mw of the acrylic resin was 33,000, the carboxylic acid equivalent was 490, and the double bond equivalent was 800.
- Synthesis Example 4 Synthesis of Acrylic Resin Solution (A-04) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 23.34 g of PGMEA, and 21.52 g (50 mol%) of methacrylic acid 10.01 g (20 mol%) of methyl methacrylate, 15.62 g (30 mol%) of styrene, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, 4-methoxy Using 0.186 g (0.3 mol%) of phenol and 47.39 g of PGMEA, polymerization was performed in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-04). PGMEA was added to the obtained acrylic resin solution (A-04) so that the solid content concentration was 35% by weight. The Mw of the acrylic resin was 20,000, the carboxylic acid equivalent was 500, and the double bond equivalent was 610.
- Synthesis Example 5 Synthesis of acrylic resin solution (A-05) 2,21'-azobis (isobutyronitrile) 0.821 g (1 mol%), PGMEA 23.54 g, methacrylic acid 21.52 g (50 mol%) 26.04 g (50 mol%) of styrene, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, 0.186 g (0.3 mol%) of 4-methoxyphenol, Using 47.80 g of PGMEA, polymerization was performed in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-05). PGMEA was added to the obtained acrylic resin solution (A-05) so that the solid content concentration was 35% by weight. The Mw of the acrylic resin was 12,000, the carboxylic acid equivalent was 490, and the double bond equivalent was 610.
- Synthesis Example 6 Synthesis of acrylic resin solution (A-06) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 23.98 g of PGMEA, and 28.41 g (66 mol%) of methacrylic acid , 4.41 g (4 mol%) of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, 15.62 g (30 mol%) of styrene, and 25.59 g (36 mol%) of glycidyl methacrylate.
- Synthesis Example 7 Synthesis of acrylic resin solution (A-07) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 32.61 g of PGMEA, and 17.22 g (40 mol%) of methacrylic acid , 33.05 g (30 mol%) of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, 15.62 g (30 mol%) of styrene, and 7.11 g (10 mol%) of glycidyl methacrylate.
- Synthesis Example 8 Synthesis of acrylic resin solution (A-08) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 33.28 g of PGMEA, and 16.36 g (38 mol%) of methacrylic acid 35.25 g (32 mol%) of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, 15.62 g (30 mol%) of styrene, 5.69 g (8 mol%) of glycidyl methacrylate.
- Synthesis Example 9 Synthesis of acrylic resin solution (A-09) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 34.94 g of PGMEA, and 14.20 g (33 mol%) of methacrylic acid , 40.76 g (37 mol%) of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, 15.62 g (30 mol%) of styrene and 2.13 g (3 mol%) of glycidyl methacrylate.
- Synthesis Example 10 Synthesis of acrylic resin solution (A-10) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 35.27 g of PGMEA, and 13.77 g (32 mol%) of methacrylic acid , 41.86 g (38 mol%) of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, 15.62 g (30 mol%) of styrene, and 1.42 g (2 mol%) of glycidyl methacrylate.
- the inside of the flask was sufficiently purged with nitrogen by bubbling, and then heated and stirred at 70 ° C. for 5 hours.
- 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, 0.186 g (0.3 mol%) of 4-methoxyphenol, and 55 of PGMEA were added to the obtained solution.
- .54 g was added and stirred with heating at 90 ° C. for 4 hours to obtain an acrylic resin solution (A-11).
- PGMEA was added to the obtained acrylic resin solution (A-11) so that the solid content concentration was 35% by weight.
- the Mw of the acrylic resin was 14,000, the carboxylic acid equivalent was 460, and the double bond equivalent was 690.
- Synthesis Example 12 Synthesis of acrylic resin solution (A-12) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 22.04 g of PGMEA, and 38.74 g (90 mol%) of methacrylic acid 1.10 g (1 mol%) of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, 4.69 g (9 mol%) of styrene, and 42.65 g (60 mol%) of glycidyl methacrylate.
- Synthesis Example 13 Synthesis of polysiloxane solution (A-13) In a three-necked flask, 23.84 g (35 mol%) of methyltrimethoxysilane, 19.83 g (20 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic acid 13.12 g (10 mol%) of anhydride, 41.01 g (35 mol%) of 3-acryloxypropyltrimethoxysilane, and 62.14 g of DAA were charged. Nitrogen was flowed into the flask at 0.05 L / min, and the mixed solution was heated to 40 ° C. in an oil bath while stirring.
- an aqueous phosphoric acid solution in which 0.196 g of phosphoric acid was dissolved in 27.93 g of water was added over 10 minutes.
- the silane compound was hydrolyzed by stirring at 40 ° C. for 30 minutes. Thereafter, the bath temperature was set to 70 ° C. and stirred for 1 hour, and then the bath temperature was raised to 115 ° C. About 1 hour after the start of temperature increase, the internal temperature of the solution reached 100 ° C., and was then heated and stirred for 1-3 hours (internal temperature was 100-110 ° C.).
- the resin solution obtained by heating and stirring for 1 to 3 hours was cooled in an ice bath, and then 2% by weight of an anion exchange resin and a cation exchange resin were added to the resin solution, followed by stirring for 12 hours. After stirring, the anion exchange resin and the cation exchange resin were removed by filtration to obtain a polysiloxane solution (A-13).
- the resulting polysiloxane solution (A-13) had a solid content concentration of 40% by weight, a moisture content of 1.6% by weight, a polysiloxane Mw of 5,500, a carboxylic acid equivalent of 780, and a double bond equivalent.
- 440 The resulting polysiloxane solution (A-13) had a solid content concentration of 40% by weight, a moisture content of 1.6% by weight, a polysiloxane Mw of 5,500, a carboxylic acid equivalent of 780, and a double bond equivalent.
- Synthesis Example 14 Synthesis of Polysiloxane Solution (A-14) 13.62 g (20 mol%) of methyltrimethoxysilane, 34.70 g (35 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride 13.12 g (10 mol%), 41.01 g (35 mol%) of 3-acryloxypropyltrimethoxysilane, 66.62 g of DAA, 27.93 g of water and 0.205 g of phosphoric acid were used. Polymerization was conducted in the same manner to obtain a polysiloxane solution (A-14).
- the resulting polysiloxane solution (A-14) had a solid content concentration of 38% by weight, a moisture content of 2.4% by weight, a polysiloxane Mw of 5,000, a carboxylic acid equivalent of 820, and a double bond equivalent.
- A-14 had a solid content concentration of 38% by weight, a moisture content of 2.4% by weight, a polysiloxane Mw of 5,000, a carboxylic acid equivalent of 820, and a double bond equivalent.
- Synthesis Example 15 Synthesis of polysiloxane solution (A-15) 23.84 g (35 mol%) of methyltrimethoxysilane, 49.67 g (20 mol%) of 1-naphthyltrimethoxysilane (50 wt% IPA solution), 3 -13.12 g (10 mol%) of trimethoxysilylpropyl succinic anhydride, 41.01 g (35 mol%) of 3-acryloxypropyltrimethoxysilane, 66.95 g of DAA, 27.93 g of water, and phosphoric acid Using 0.206 g, polymerization was carried out in the same manner as in Synthesis Example 13 to obtain a polysiloxane solution (A-15).
- the resulting polysiloxane solution (A-15) had a solid content of 39% by weight, a moisture content of 1.8% by weight, a polysiloxane Mw of 5,300, a carboxylic acid equivalent of 830, and a double bond equivalent.
- A-15 had a solid content of 39% by weight, a moisture content of 1.8% by weight, a polysiloxane Mw of 5,300, a carboxylic acid equivalent of 830, and a double bond equivalent.
- Synthesis Example 16 Synthesis of Polysiloxane Solution (A-16) 23.84 g (35 mol%) of methyltrimethoxysilane, 19.83 g (20 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride 13.12 g (10 mol%), 43.46 g (35 mol%) of 3-methacryloxypropyltrimethoxysilane, 64.50 g of DAA, 27.93 g of water and 0.200 g of phosphoric acid were used. Polymerization was conducted in the same manner to obtain a polysiloxane solution (A-16).
- the resulting polysiloxane solution (A-16) had a solid content concentration of 39% by weight, a moisture content of 1.9% by weight, a polysiloxane Mw of 5,300, a carboxylic acid equivalent of 800, and a double bond equivalent.
- A-16 had a solid content concentration of 39% by weight, a moisture content of 1.9% by weight, a polysiloxane Mw of 5,300, a carboxylic acid equivalent of 800, and a double bond equivalent.
- Synthesis Example 17 Synthesis of polysiloxane solution (A-17) 17.03 g (25 mol%) of methyltrimethoxysilane, 19.83 g (20 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride 13.12 g (10 mol%), 41.01 g (35 mol%) of 3-acryloxypropyltrimethoxysilane, 7.61 g (10 mol%) of tetramethoxysilane, 61.80 g of DAA, 28.83 g of water, phosphorus Polymerization was carried out in the same manner as in Synthesis Example 13 using 0.197 g of acid to obtain a polysiloxane solution (A-17).
- the resulting polysiloxane solution (A-17) had a solid content concentration of 41% by weight, a moisture content of 1.6% by weight, a polysiloxane Mw of 5,700, a carboxylic acid equivalent of 780, and a double bond equivalent.
- a solid content concentration of 41% by weight a moisture content of 1.6% by weight
- a polysiloxane Mw of 5,700 a carboxylic acid equivalent of 780
- a double bond equivalent was 440.
- Synthesis Example 18 Synthesis of polysiloxane solution (A-18) 17.03 g (25 mol%) of methyltrimethoxysilane, 19.83 g (20 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride 26.23 g (20 mol%), 41.01 g (35 mol%) of 3-acryloxypropyltrimethoxysilane, 69.50 g of DAA, 28.83 g of water, and 0.208 g of phosphoric acid were used. Polymerization was conducted in the same manner to obtain a polysiloxane solution (A-18).
- the resulting polysiloxane solution (A-18) has a solid content concentration of 42% by weight, a moisture content of 1.4% by weight, a polysiloxane Mw of 5,900, a carboxylic acid equivalent of 430, and a double bond equivalent.
- Synthesis Example 19 Synthesis of polysiloxane solution (A-19) 17.03 g (25 mol%) of methyltrimethoxysilane, 19.83 g (20 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride 13.12 g (10 mol%), 3-acryloxypropyltrimethoxysilane 52.72 g (45 mol%), DAA 66.86 g, water 27.93 g and phosphoric acid 0.205 g were used. Polymerization was conducted in the same manner to obtain a polysiloxane solution (A-19).
- the resulting polysiloxane solution (A-19) had a solid content concentration of 42% by weight, a moisture content of 1.7% by weight, a polysiloxane Mw of 5,800, a carboxylic acid equivalent of 830, and a double bond equivalent.
- a solid content concentration of 42% by weight a moisture content of 1.7% by weight
- a polysiloxane Mw of 5,800 a carboxylic acid equivalent of 830
- a double bond equivalent was 370.
- Synthesis Example 20 Synthesis of Polysiloxane Solution (A-20) 34.06 g (50 mol%) of methyltrimethoxysilane, 19.83 g (20 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride 13.12 g (10 mol%), 23.43 g (20 mol%) of 3-acryloxypropyltrimethoxysilane, 55.06 g of DAA, 27.93 g of water, and 0.181 g of phosphoric acid were used. Polymerization was conducted in the same manner to obtain a polysiloxane solution (A-20).
- the resulting polysiloxane solution (A-20) has a solid content concentration of 39% by weight, a moisture content of 1.8% by weight, a polysiloxane Mw of 5,000, a carboxylic acid equivalent of 700, and a double bond equivalent. Was 700.
- Synthesis Example 21 Synthesis of Polysiloxane Solution (A-21) 40.87 g (60 mol%) of methyltrimethoxysilane, 19.83 g (20 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride Using Synthesis Example 13 using 13.12 g (10 mol%), 11.72 g (10 mol%) 3-acryloxypropyltrimethoxysilane, 50.34 g DAA, 27.93 g water, and 0.171 g phosphoric acid Polymerization was conducted in the same manner to obtain a polysiloxane solution (A-21).
- the resulting polysiloxane solution (A-21) has a solid content concentration of 38% by weight, a moisture content of 1.9% by weight, a polysiloxane Mw of 4,600, a carboxylic acid equivalent of 650, and a double bond equivalent.
- a solid content concentration of 38% by weight 38% by weight
- a moisture content of 1.9% by weight a polysiloxane Mw of 4,600
- a carboxylic acid equivalent of 650 a double bond equivalent.
- Synthesis Example 22 Synthesis of polysiloxane solution (A-22) 42.91 g (63 mol%) of methyltrimethoxysilane, 19.83 g (20 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride 13.12 g (10 mol%), 8.20 g (7 mol%) of 3-acryloxypropyltrimethoxysilane, 48.93 g of DAA, 27.93 g of water and 0.168 g of phosphoric acid were used. Polymerization was conducted in the same manner to obtain a polysiloxane solution (A-22).
- the resulting polysiloxane solution (A-22) has a solid content concentration of 38% by weight, a moisture content of 1.8% by weight, polysiloxane Mw of 4,500, carboxylic acid equivalent of 640, double bond equivalent. Was 1,830.
- Synthesis Example 23 Synthesis of polysiloxane solution (A-23) 45.63 g (67 mol%) of methyltrimethoxysilane, 19.83 g (20 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride 13.12 g (10 mol%), 3.51 g (3 mol%) of 3-acryloxypropyltrimethoxysilane, 47.04 g of DAA, 27.93 g of water and 0.164 g of phosphoric acid were used. Polymerization was conducted in the same manner to obtain a polysiloxane solution (A-23).
- the resulting polysiloxane solution (A-23) has a solid content concentration of 37% by weight, a moisture content of 2.0% by weight, a polysiloxane Mw of 4,400, a carboxylic acid equivalent of 620, and a double bond equivalent.
- A-23 has a solid content concentration of 37% by weight, a moisture content of 2.0% by weight, a polysiloxane Mw of 4,400, a carboxylic acid equivalent of 620, and a double bond equivalent.
- Synthesis Example 24 Synthesis of Polysiloxane Solution (A-24) 46.31 g (68 mol%) of methyltrimethoxysilane, 19.83 g (20 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride 13.12 g (10 mol%), 2.34 g (2 mol%) of 3-acryloxypropyltrimethoxysilane, 46.57 g of DAA, 27.93 g of water and 0.163 g of phosphoric acid were used. Polymerization was conducted in the same manner to obtain a polysiloxane solution (A-24).
- the resulting polysiloxane solution (A-24) has a solid content concentration of 37% by weight, a moisture content of 2.0% by weight, a polysiloxane Mw of 4,300, a carboxylic acid equivalent of 620, and a double bond equivalent. Was 6,150.
- Synthesis Example 25 Synthesis of polysiloxane solution (A-25) 17.03 g (25 mol%) of methyltrimethoxysilane, 19.83 g (20 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride 13.12 g (10 mol%), 41.01 g (35 mol%) of 3-acryloxypropyltrimethoxysilane, 12.32 g (10 mol%) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and DAA Using 66.33 g, 28.83 g of water, and 0.207 g of phosphoric acid, polymerization was performed in the same manner as in Synthesis Example 13 to obtain a polysiloxane solution (A-25).
- the resulting polysiloxane solution (A-25) had a solid content concentration of 42% by weight, a moisture content of 1.5% by weight, a polysiloxane Mw of 5,800, a carboxylic acid equivalent of 830, and a double bond equivalent.
- Synthesis Example 26 Synthesis of polysiloxane solution (A-26) 4.77 g (7 mol%) of methyltrimethoxysilane, 19.83 g (20 mol%) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride 13.12 g (10 mol%), 3-acryloxypropyltrimethoxysilane 73.81 g (63 mol%), DAA 75.35 g, water 27.93 g and phosphoric acid 0.223 g were used. Polymerization was conducted in the same manner to obtain a polysiloxane solution (A-26).
- the resulting polysiloxane solution (A-26) had a solid content concentration of 44% by weight, a moisture content of 1.5% by weight, a polysiloxane Mw of 6,400, a carboxylic acid equivalent of 910, and a double bond equivalent.
- A-26 had a solid content concentration of 44% by weight, a moisture content of 1.5% by weight, a polysiloxane Mw of 6,400, a carboxylic acid equivalent of 910, and a double bond equivalent.
- Synthesis Example 27 Synthesis of Silane Compound Solution (E-1) A three-necked flask was charged with 30.44 g (100 mol%) of tetramethoxysilane and 19.97 g of DAA. Air was passed through the flask at 0.05 L / min, and the mixed solution was heated to 40 ° C. in an oil bath while stirring. While further stirring the mixed solution, an aqueous phosphoric acid solution in which 0.061 g of phosphoric acid was dissolved in 14.42 g of water was added over 10 minutes. After completion of the addition, the silane compound was hydrolyzed by stirring at 40 ° C. for 30 minutes. Thereafter, the bath temperature was raised to 50 ° C. and stirred at 50 ° C. for 1 hour.
- the solution obtained by stirring for 1 hour was cooled in an ice bath, and then 2% by weight of an anion exchange resin and a cation exchange resin were added to the solution, followed by stirring for 12 hours. After stirring, the anion exchange resin and cation exchange resin were removed by filtration to obtain a silane compound solution (E-1).
- the resulting silane compound solution (E-1) had a solid content concentration of 19% by weight and a moisture content of 10% by weight.
- Synthesis Example 28 Synthesis of Silane Compound Solution (E-2) A three-necked flask was charged with 23.53 g (100 mol%) of M silicate 51 (manufactured by Tama Chemical Industry Co., Ltd.) and 19.96 g of DAA. Air was passed through the flask at 0.05 L / min, and the mixed solution was heated to 40 ° C. in an oil bath while stirring. While further stirring the mixed solution, an aqueous phosphoric acid solution in which 0.047 g of phosphoric acid was dissolved in 9.01 g of water was added over 10 minutes. After completion of the addition, the silane compound was hydrolyzed by stirring at 40 ° C. for 30 minutes. Thereafter, the bath temperature was raised to 50 ° C.
- M silicate 51 manufactured by Tama Chemical Industry Co., Ltd.
- silane compound solution (E-2) had a solid content concentration of 22% by weight and a moisture content of 8.0% by weight.
- compositions of Synthesis Examples 1 to 26 are collectively shown in Tables 1 and 2.
- Example 1 The evaluation method in Example 1 is shown below.
- Apparatus Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.) Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6669 MHz ( 29 Si nucleus) Spectrum width: 20000Hz Pulse width: 12 ⁇ s (45 ° pulse) Pulse repetition time: 30.0 s Solvent: acetone-d6 Reference material: Tetramethylsilane Measurement temperature: Room temperature Sample rotation speed: 0.0 Hz (7) Pretreatment of substrate Glass substrate on which three layers of Mo / Al / Mo are formed by sputtering (manufactured by Sanyo Vacuum Industry Co., Ltd .; hereinafter referred to as “MAM substrate”), glass substrate on which ITO is formed by sputtering (Sanyo Vacuum Industry Co., Ltd .; hereinafter referred to as “ITO substrate”) was cleaned with UV-O 3 for 100 seconds using a tabletop optical surface treatment device (PL16-110; manufactured by Sen Special Light Source Co., Ltd.).
- Tempax glass substrate manufactured by AGC Techno Glass Co., Ltd.
- glass substrate on which a single layer Cr film was formed by sputtering single layer Cr film-formed substrate; manufactured by Kuramoto Seisakusho; hereinafter referred to as “Cr substrate”.
- Sensitivity A post-development film of the photosensitive resin composition was produced on the Cr substrate by the method described in Example 1 below. After development, the resolution pattern is observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), and the exposure amount (i-line illuminance) for forming a 30 ⁇ m line-and-space pattern in a 1: 1 width The total value, hereinafter referred to as “optimum exposure amount”) was defined as sensitivity.
- Hardness A cured film of the photosensitive resin composition was produced on the Cr substrate by the method described in Example 1 below. The hardness of the produced cured film was measured based on “JIS K5600-5-4 (1999)” using a manual pencil scratch hardness tester (850-56; manufactured by Coating Tester Co., Ltd.).
- a +: Discolored area of MAM surface 0% and no change in appearance of cured film surface
- a part of the photosensitive resin composition prepared by the method described in Example 1 below was allowed to stand at 23 ° C. for 7 days. After the elapse of 7 days, a cured film of the photosensitive resin composition was prepared on the MAM substrate by the method described in Example 1 below and allowed to stand at 23 ° C. for 7 days. The prepared cured film was measured for adhesion of the cured film to the substrate based on “JIS K5600-5-6 (1999)” in the same manner as described above.
- a cured film of a photosensitive resin composition was prepared on an ITO substrate by the method described in Example 1 below.
- the adhesion of the cured film to the substrate was measured by the same method as in (13) above based on “JIS K5600-5-6 (1999)”.
- a part of the photosensitive resin composition prepared by the method described in Example 1 below was allowed to stand at 23 ° C. for 7 days. After 7 days, a cured film of the photosensitive resin composition was prepared on the ITO substrate after being left for 7 days at 23 ° C. by the method described in Example 1 below.
- a part of the photosensitive resin composition prepared by the method described in Example 1 was left at 23 ° C. for 7 days. After 7 days, a cured film of the photosensitive resin composition was prepared on the ITO substrate after being left for 7 days at 23 ° C. by the method described in Example 1 below.
- Example 1 Under a yellow light, 0.332 g of OXE-01 and 0.0663 g of ZC-150 were weighed, 2.046 g of PGMEA, 2.730 g of MB, and 1.750 g of DAA were added and dissolved by stirring. Next, 0.150 g of a 5 wt% PGMEA solution of BYK-333 was added and stirred. Next, 9.472 g of the acrylic resin solution (A-01) obtained in Synthesis Example 1 (35 wt% PGMEA solution) and 4.144 g of 80 wt% PGMEA solution of DPHA were added and stirred.
- a negative photosensitive resin composition 1 2.652 g of a 5 wt% MB solution of KBM-903 and 1.658 g of a 20 wt% PGMEA solution of KBM-04 were added and stirred to obtain a uniform solution. Then, the obtained solution was filtered with a 0.2 ⁇ m filter to prepare a negative photosensitive resin composition 1.
- the prepared photosensitive resin composition 1 was applied on a substrate by spin coating at an arbitrary rotation number using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.), and then hot plate (SCW-636; Dainippon). Prebaked at 100 ° C. for 3 minutes using Screen Manufacturing Co., Ltd. to prepare a prebaked film having a thickness of about 2.0 ⁇ m.
- MS-A100 manufactured by Mikasa Co., Ltd.
- SCW-636 hot plate
- Pattern exposure was performed with j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp.
- Examples 2 to 68 and Comparative Examples 1 to 10 In the same manner as the photosensitive resin composition 1, photosensitive resin compositions 2 to 78 were prepared with the compositions shown in Tables 3 to 8. Using each of the obtained photosensitive resin compositions, the photosensitive characteristics and the characteristics of the cured film were evaluated in the same manner as in Example 1. The results are summarized in Tables 9-14.
- Example 69 A touch panel member was produced according to the following procedure.
- a film thickness of 150 nm is obtained by sputtering a glass substrate having a thickness of about 1 mm for 12.5 minutes using a sputtering apparatus at an RF power of 1.4 kW and a degree of vacuum of 6.65 ⁇ 10 ⁇ 1 Pa. Then, an ITO film having a surface resistance of 15 ⁇ / ⁇ was formed. Next, a positive photoresist OFPR-800 was applied onto ITO by spin coating at an arbitrary rotation number using a spin coater, and then pre-baked at 80 ° C. for 20 minutes using a hot plate to obtain a film thickness of 1.1 ⁇ m. A resist film was obtained.
- the cured film obtained by thermosetting the photosensitive resin composition of the present invention includes various hard coat films such as a touch panel protective film, an insulating film for touch sensors, a planarizing film for TFTs of liquid crystals and organic EL displays, It is suitably used for metal wiring protective films, insulating films, antireflection films, antireflection films, optical filters, overcoats for color filters, pillar materials, and the like.
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Abstract
Description
本発明の感光性樹脂組成物は、(A)アルカリ可溶性樹脂を含有する。(A)アルカリ可溶性樹脂はエチレン性不飽和二重結合基を有する。(A)アルカリ可溶性樹脂がエチレン性不飽和二重結合基を有することで、露光時のUV硬化が促進されて感度が向上するとともに、熱硬化後の架橋密度が向上し、硬化膜の硬度を向上させることができる。(A)アルカリ可溶性樹脂の二重結合当量としては、300~5,000g/molであり、300~2,000g/molが好ましく、300~1,500g/molがより好ましい。ここで二重結合当量とは、エチレン性不飽和二重結合基1mol当たりの樹脂重量をいい、単位はg/molである。二重結合当量はヨウ素価を測定することで算出できる。二重結合当量が上記範囲であると、熱硬化時の耐クラック性、硬化膜の硬度、耐薬品性及び塗液の保管安定性が向上する。二重結合当量が300に満たないと、塗液の保管安定性又は熱硬化時の耐クラック性が低下する場合がある。一方、二重結合当量が5,000を超えると、硬化膜の硬度又は耐薬品性が低下する場合がある。
R8は、それぞれ独立して、水素、炭素数1~6のアルキル基、炭素数4~7のシクロアルキル基、炭素数2~8のアルケニル基又は炭素数6~10のアリール基が好ましい。R9~R13は、それぞれ独立して、水素、炭素数1~4のアルキル基、炭素数2~4のアシル基又は炭素数6~10のアリール基が好ましい。
R1は、水素、炭素数1~6のアルキル基、炭素数4~7のシクロアルキル基又は炭素数6~10のアリール基が好ましく、R2及びR3は、それぞれ独立して、水素、炭素数1~18のアルキル基、炭素数4~7のシクロアルキル基、炭素数6~10のアリール基、炭素数1~4のアルコキシ基又はヒドロキシ基が好ましい。上記のアルキル基、シクロアルキル基、アリール基及びアルコキシ基は、無置換体又は置換体のいずれであっても構わない。Mは、ジルコニウムが好ましい。
R4~R7は、それぞれ独立して、水素、炭素数1~4のアルキル基、炭素数2~4のアシル基又は炭素数6~10のアリール基が好ましい。
AcOH:酢酸
AD-TMP:ジトリメチロールプロパンテトラアクリレート(新中村化学工業(株)製)
Al-A:アルミキレートA(川研ファインケミカル(株)製;トリス(アセチルアセトナート)アルミニウム(III))
BDG:ブチルジグリコール、ジエチレングリコールモノ-n-ブチルエーテル
BYK-333:シリコーン系界面活性剤(ビックケミー・ジャパン(株)製)
DAA:ジアセトンアルコール
DMSO:ジメチルスルホキシド
DPHA:KAYARAD(登録商標)DPHA(日本化薬(株)製;ジペンタエリスリトールヘキサアクリレート)
EtOH:エタノール
HCl:塩酸
HNO3:硝酸
H3PO4:リン酸
IC-907:IRGACURE(登録商標)907(BASF製;2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノプロパン-1-オン)
IPA:イソプロピルアルコール
ITO:酸化インジウムスズ
KBE-04:テトラエトキシシラン(信越化学工業(株)製)
KBM-04:テトラメトキシシラン(信越化学工業(株)製)
KBM-1403:4-スチリルトリメトキシシラン(信越化学工業(株)製)
KBM-403:3-グリシドキシプロピルトリメトキシシラン(信越化学工業(株)製)
KBM-503:3-メタクリロキシプロピルトリメトキシシラン(信越化学工業(株)製)
KBM-5103:3-アクリロキシプロピルトリメトキシシラン(信越化学工業(株)製)
KBM-803:3-メルカプトプロピルトリメトキシシラン(信越化学工業(株)製)
KBM-903:3-アミノプロピルトリメトキシシラン(信越化学工業(株)製)
KBE-9007:3-イソシアネートプロピルトリエトキシシラン(信越化学工業(株)製)
KBE-9103:3-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(信越化学工業(株)製)
KBM-9659:1,3,5-トリス(3-トリメトキシシリルプロピル)イソシアヌル酸(信越化学工業(株)製)
MAM:Mo/Al/Mo(モリブデン/アルミニウム/モリブデン)
MB:3-メトキシ-1-ブタノール
MEA:モノエタノールアミン、2-アミノエタノール
NaOH:水酸化ナトリウム
N-300:レジスト剥離液(ナガセケムテックス(株)製;MEA/BDG=30/70)
OFPR-800:ポジ型フォトレジスト(東京応化工業(株)製)
OXE-01:IRGACURE(登録商標)OXE-01(BASF製;1-[4-(フェニルチオ)フェニル]オクタン-1,2-ジオン-2-(O-ベンゾイル)オキシム)
PE-3A:ライトアクリレートPE-3A(共栄社化学(株)製;ペンタエリスリトールトリアクリレート)
PE-4A:ライトアクリレートPE-4A(共栄社化学(株)製;ペンタエリスリトールテトラアクリレート)
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
TC-401:オルガチックス(登録商標)TC-401(マツモトファインケミカル(株)製;テトラキス(アセチルアセトナート)チタン(IV))
THF:テトラヒドロフラン
TMAH:水酸化テトラメチルアンモニウム
TMP-A:ライトアクリレートTMP-A(共栄社化学(株)製;トリメチロールプロパントリアクリレート)
TMPU:1-(3-トリメトキシシリルプロピル)尿素
X-12-967YP:2-(3-トリメトキシシリルプロピル)-4-(N-t-ブチル)アミノ-4-オキソブタン酸(信越化学工業(株)製)
ZC-150:オルガチックス(登録商標)ZC-150(マツモトファインケミカル(株)製;テトラキス(アセチルアセトナート)ジルコニウム(IV))
ナーセムMg:ナーセム(登録商標)マグネシウム(日本化学産業(株)製;ビス(アセチルアセトナート)マグネシウム(II))
合成例1 アクリル樹脂溶液(A-01)の合成
フラスコに2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを34.64g仕込んだ。次に、メタクリル酸ベンジルを26.43g(30mol%)、メタクリル酸を21.52g(50mol%)、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イルを22.03g(20mol%)仕込み、室温でしばらく撹拌して、フラスコ内をバブリングによって十分に窒素置換した後、70℃で5時間加熱撹拌した。次に、得られた溶液にメタクリル酸グリシジルを14.22g(20mol%)、ジメチルベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)、PGMEAを70.33g添加し、90℃で4時間加熱撹拌して、アクリル樹脂溶液(A-01)を得た。得られたアクリル樹脂溶液(A-01)に、固形分濃度が35重量%になるようにPGMEAを添加した。アクリル樹脂のMwは30,000、カルボン酸当量は480であり、二重結合当量は840であった。
2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを32.46g、メタクリル酸ベンジルを44.05g(50mol%)、メタクリル酸を21.52g(50mol%)、メタクリル酸グリシジルを14.22g(20mol%)、ジメチルベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)、PGMEAを65.90g使用し、合成例1と同様に重合をして、アクリル樹脂溶液(A-02)を得た。得られたアクリル樹脂溶液(A-02)に、固形分濃度が35重量%になるようにPGMEAを添加した。アクリル樹脂のMwは33,000、カルボン酸当量は490であり、二重結合当量は800であった。
2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを29.29g、メタクリル酸を21.52g(50mol%)、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イルを22.03g(20mol%)、スチレンを15.62g(30mol%)、メタクリル酸グリシジルを14.22g(20mol%)、ジメチルベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)、PGMEAを59.47g使用し、合成例1と同様に重合をして、アクリル樹脂溶液(A-03)を得た。得られたアクリル樹脂溶液(A-03)に、固形分濃度が35重量%になるようにPGMEAを添加した。アクリル樹脂のMwは15,000、カルボン酸当量は510であり、二重結合当量は730であった。
2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを23.34g、メタクリル酸を21.52g(50mol%)、メタクリル酸メチルを10.01g(20mol%)、スチレンを15.62g(30mol%)、メタクリル酸グリシジルを14.22g(20mol%)、ジメチルベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)、PGMEAを47.39g使用し、合成例1と同様に重合をして、アクリル樹脂溶液(A-04)を得た。得られたアクリル樹脂溶液(A-04)に、固形分濃度が35重量%になるようにPGMEAを添加した。アクリル樹脂のMwは20,000、カルボン酸当量は500であり、二重結合当量は610であった。
2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを23.54g、メタクリル酸を21.52g(50mol%)、スチレンを26.04g(50mol%)、メタクリル酸グリシジルを14.22g(20mol%)、ジメチルベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)、PGMEAを47.80g使用し、合成例1と同様に重合をして、アクリル樹脂溶液(A-05)を得た。得られたアクリル樹脂溶液(A-05)に、固形分濃度が35重量%になるようにPGMEAを添加した。アクリル樹脂のMwは12,000、カルボン酸当量は490であり、二重結合当量は610であった。
2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを23.98g、メタクリル酸を28.41g(66mol%)、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イルを4.41g(4mol%)、スチレンを15.62g(30mol%)、メタクリル酸グリシジルを25.59g(36mol%)、ジメチルベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)、PGMEAを48.68g使用し、合成例1と同様に重合をして、アクリル樹脂溶液(A-06)を得た。得られたアクリル樹脂溶液(A-06)に、固形分濃度が35重量%になるようにPGMEAを添加した。アクリル樹脂のMwは16,000、カルボン酸当量は490であり、二重結合当量は410であった。
2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを32.61g、メタクリル酸を17.22g(40mol%)、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イルを33.05g(30mol%)、スチレンを15.62g(30mol%)、メタクリル酸グリシジルを7.11g(10mol%)、ジメチルベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)、PGMEAを66.22g使用し、合成例1と同様に重合をして、アクリル樹脂溶液(A-07)を得た。得られたアクリル樹脂溶液(A-07)に、固形分濃度が35重量%になるようにPGMEAを添加した。アクリル樹脂のMwは14,000、カルボン酸当量は480であり、二重結合当量は1,450であった。
2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを33.28g、メタクリル酸を16.36g(38mol%)、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イルを35.25g(32mol%)、スチレンを15.62g(30mol%)、メタクリル酸グリシジルを5.69g(8mol%)、ジメチルベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)、PGMEAを67.57g使用し、合成例1と同様に重合をして、アクリル樹脂溶液(A-08)を得た。得られたアクリル樹脂溶液(A-08)に、固形分濃度が35重量%になるようにPGMEAを添加した。アクリル樹脂のMwは14,000、カルボン酸当量は480であり、二重結合当量は1,810であった。
2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを34.94g、メタクリル酸を14.20g(33mol%)、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イルを40.76g(37mol%)、スチレンを15.62g(30mol%)、メタクリル酸グリシジルを2.13g(3mol%)、ジメチルベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)、PGMEAを70.94g使用し、合成例1と同様に重合をして、アクリル樹脂溶液(A-09)を得た。得られたアクリル樹脂溶液(A-09)に、固形分濃度が35重量%になるようにPGMEAを添加した。アクリル樹脂のMwは13,000、カルボン酸当量は480であり、二重結合当量は4,820であった。
2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを35.27g、メタクリル酸を13.77g(32mol%)、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イルを41.86g(38mol%)、スチレンを15.62g(30mol%)、メタクリル酸グリシジルを1.42g(2mol%)、ジメチルベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)、PGMEAを71.61g使用し、合成例1と同様に重合をして、アクリル樹脂溶液(A-10)を得た。得られたアクリル樹脂溶液(A-10)に、固形分濃度が35重量%になるようにPGMEAを添加した。アクリル樹脂のMwは13,000、カルボン酸当量は490であり、二重結合当量は6,580であった。
フラスコに2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを27.36g仕込んだ。次に、メタクリル酸を21.52g(50mol%)、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イルを11.02g(10mol%)、スチレンを15.62g(30mol%)、メタクリル酸グリシジルを7.11g(10mol%)仕込み、室温でしばらく撹拌して、フラスコ内をバブリングによって十分に窒素置換した後、70℃で5時間加熱撹拌した。次に、得られた溶液にメタクリル酸グリシジルを14.22g(20mol%)、ジメチルベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)、PGMEAを55.54g添加し、90℃で4時間加熱撹拌して、アクリル樹脂溶液(A-11)を得た。得られたアクリル樹脂溶液(A-11)に、固形分濃度が35重量%になるようにPGMEAを添加した。アクリル樹脂のMwは14,000、カルボン酸当量は460であり、二重結合当量は690であった。
2,2’-アゾビス(イソブチロニトリル)を0.821g(1mol%)、PGMEAを22.04g、メタクリル酸を38.74g(90mol%)、メタクリル酸トリシクロ[5.2.1.02,6]デカン-8-イルを1.10g(1mol%)、スチレンを4.69g(9mol%)、メタクリル酸グリシジルを42.65g(60mol%)、ジメチルベンジルアミンを0.676g(1mol%)、4-メトキシフェノールを0.186g(0.3mol%)、PGMEAを44.75g使用し、合成例1と同様に重合をして、アクリル樹脂溶液(A-12)を得た。得られたアクリル樹脂溶液(A-12)に、固形分濃度が35重量%になるようにPGMEAを添加した。アクリル樹脂のMwは19,000、カルボン酸当量は580であり、二重結合当量は290であった。
三口フラスコにメチルトリメトキシシランを23.84g(35mol%)、フェニルトリメトキシシランを19.83g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-アクリロキシプロピルトリメトキシシランを41.01g(35mol%)、DAAを62.14g仕込んだ。フラスコ内に窒素を0.05L/minで流し、混合溶液を撹拌しながらオイルバスで40℃に加熱した。混合溶液をさらに撹拌しながら、水27.93gにリン酸0.196gを溶かしたリン酸水溶液を10分かけて添加した。添加終了後、40℃で30分間撹拌して、シラン化合物を加水分解させた。その後、バス温を70℃に設定して1時間撹拌した後、続いてバス温を115℃まで昇温した。昇温開始後、約1時間後に溶液の内温が100℃に到達し、そこから1~3時間加熱撹拌した(内温は100~110℃)。1~3時間加熱撹拌して得られた樹脂溶液を氷浴にて冷却した後、陰イオン交換樹脂及び陽イオン交換樹脂を、それぞれ樹脂溶液に対して2重量%加えて12時間撹拌した。撹拌後、陰イオン交換樹脂及び陽イオン交換樹脂をろ過して除去し、ポリシロキサン溶液(A-13)を得た。得られたポリシロキサン溶液(A-13)の固形分濃度は40重量%、水分率は1.6重量%、ポリシロキサンのMwは5,500、カルボン酸当量は780であり、二重結合当量は440であった。
メチルトリメトキシシランを13.62g(20mol%)、フェニルトリメトキシシランを34.70g(35mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-アクリロキシプロピルトリメトキシシランを41.01g(35mol%)、DAAを66.62g、水を27.93g、リン酸を0.205g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-14)を得た。得られたポリシロキサン溶液(A-14)の固形分濃度は38重量%、水分率は2.4重量%、ポリシロキサンのMwは5,000、カルボン酸当量は820であり、二重結合当量は470であった。
メチルトリメトキシシランを23.84g(35mol%)、1-ナフチルトリメトキシシラン(50重量%のIPA溶液)を49.67g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-アクリロキシプロピルトリメトキシシランを41.01g(35mol%)、DAAを66.95g、水を27.93g、リン酸を0.206g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-15)を得た。得られたポリシロキサン溶液(A-15)の固形分濃度は39重量%、水分率は1.8重量%、ポリシロキサンのMwは5,300、カルボン酸当量は830であり、二重結合当量は470であった。
メチルトリメトキシシランを23.84g(35mol%)、フェニルトリメトキシシランを19.83g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-メタクリロキシプロピルトリメトキシシランを43.46g(35mol%)、DAAを64.50g、水を27.93g、リン酸を0.200g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-16)を得た。得られたポリシロキサン溶液(A-16)の固形分濃度は39重量%、水分率は1.9重量%、ポリシロキサンのMwは5,300、カルボン酸当量は800であり、二重結合当量は460であった。
メチルトリメトキシシランを17.03g(25mol%)、フェニルトリメトキシシランを19.83g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-アクリロキシプロピルトリメトキシシランを41.01g(35mol%)、テトラメトキシシランを7.61g(10mol%)、DAAを61.80g、水を28.83g、リン酸を0.197g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-17)を得た。得られたポリシロキサン溶液(A-17)の固形分濃度は41重量%、水分率は1.6重量%、ポリシロキサンのMwは5,700、カルボン酸当量は780であり、二重結合当量は440であった。
メチルトリメトキシシランを17.03g(25mol%)、フェニルトリメトキシシランを19.83g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を26.23g(20mol%)、3-アクリロキシプロピルトリメトキシシランを41.01g(35mol%)、DAAを69.50g、水を28.83g、リン酸を0.208g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-18)を得た。得られたポリシロキサン溶液(A-18)の固形分濃度は42重量%、水分率は1.4重量%、ポリシロキサンのMwは5,900、カルボン酸当量は430であり、二重結合当量は480であった。
メチルトリメトキシシランを17.03g(25mol%)、フェニルトリメトキシシランを19.83g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-アクリロキシプロピルトリメトキシシランを52.72g(45mol%)、DAAを66.86g、水を27.93g、リン酸を0.205g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-19)を得た。得られたポリシロキサン溶液(A-19)の固形分濃度は42重量%、水分率は1.7重量%、ポリシロキサンのMwは5,800、カルボン酸当量は830であり、二重結合当量は370であった。
メチルトリメトキシシランを34.06g(50mol%)、フェニルトリメトキシシランを19.83g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-アクリロキシプロピルトリメトキシシランを23.43g(20mol%)、DAAを55.06g、水を27.93g、リン酸を0.181g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-20)を得た。得られたポリシロキサン溶液(A-20)の固形分濃度は39重量%、水分率は1.8重量%、ポリシロキサンのMwは5,000、カルボン酸当量は700であり、二重結合当量は700であった。
メチルトリメトキシシランを40.87g(60mol%)、フェニルトリメトキシシランを19.83g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-アクリロキシプロピルトリメトキシシランを11.72g(10mol%)、DAAを50.34g、水を27.93g、リン酸を0.171g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-21)を得た。得られたポリシロキサン溶液(A-21)の固形分濃度は38重量%、水分率は1.9重量%、ポリシロキサンのMwは4,600、カルボン酸当量は650であり、二重結合当量は1,310であった。
メチルトリメトキシシランを42.91g(63mol%)、フェニルトリメトキシシランを19.83g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-アクリロキシプロピルトリメトキシシランを8.20g(7mol%)、DAAを48.93g、水を27.93g、リン酸を0.168g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-22)を得た。得られたポリシロキサン溶液(A-22)の固形分濃度は38重量%、水分率は1.8重量%、ポリシロキサンのMwは4,500、カルボン酸当量は640であり、二重結合当量は1,830であった。
メチルトリメトキシシランを45.63g(67mol%)、フェニルトリメトキシシランを19.83g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-アクリロキシプロピルトリメトキシシランを3.51g(3mol%)、DAAを47.04g、水を27.93g、リン酸を0.164g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-23)を得た。得られたポリシロキサン溶液(A-23)の固形分濃度は37重量%、水分率は2.0重量%、ポリシロキサンのMwは4,400、カルボン酸当量は620であり、二重結合当量は4,130であった。
メチルトリメトキシシランを46.31g(68mol%)、フェニルトリメトキシシランを19.83g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-アクリロキシプロピルトリメトキシシランを2.34g(2mol%)、DAAを46.57g、水を27.93g、リン酸を0.163g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-24)を得た。得られたポリシロキサン溶液(A-24)の固形分濃度は37重量%、水分率は2.0重量%、ポリシロキサンのMwは4,300、カルボン酸当量は620であり、二重結合当量は6,150であった。
メチルトリメトキシシランを17.03g(25mol%)、フェニルトリメトキシシランを19.83g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-アクリロキシプロピルトリメトキシシランを41.01g(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(10mol%)、DAAを66.33g、水を28.83g、リン酸を0.207g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-25)を得た。得られたポリシロキサン溶液(A-25)の固形分濃度は42重量%、水分率は1.5重量%、ポリシロキサンのMwは5,800、カルボン酸当量は830であり、二重結合当量は480であった。
メチルトリメトキシシランを4.77g(7mol%)、フェニルトリメトキシシランを19.83g(20mol%)、3-トリメトキシシリルプロピルコハク酸無水物を13.12g(10mol%)、3-アクリロキシプロピルトリメトキシシランを73.81g(63mol%)、DAAを75.35g、水を27.93g、リン酸を0.223g使用し、合成例13と同様に重合をして、ポリシロキサン溶液(A-26)を得た。得られたポリシロキサン溶液(A-26)の固形分濃度は44重量%、水分率は1.5重量%、ポリシロキサンのMwは6,400、カルボン酸当量は910であり、二重結合当量は290であった。
三口フラスコにテトラメトキシシランを30.44g(100mol%)、DAAを19.97g仕込んだ。フラスコ内に空気を0.05L/minで流し、混合溶液を撹拌しながらオイルバスで40℃に加熱した。混合溶液をさらに撹拌しながら、水14.42gにリン酸0.061gを溶かしたリン酸水溶液を10分かけて添加した。添加終了後、40℃で30分間撹拌して、シラン化合物を加水分解させた。その後、バス温を50℃まで昇温し、50℃で1時間撹拌した。1時間撹拌して得られた溶液を氷浴にて冷却した後、陰イオン交換樹脂及び陽イオン交換樹脂を、それぞれ溶液に対して2重量%加えて12時間撹拌した。撹拌後、陰イオン交換樹脂及び陽イオン交換樹脂をろ過して除去し、シラン化合物溶液(E-1)を得た。得られたシラン化合物溶液(E-1)の固形分濃度は19重量%、水分率は10重量%であった。
三口フラスコにMシリケート51(多摩化学工業(株)製)を23.53g(100mol%)、DAAを19.96g仕込んだ。フラスコ内に空気を0.05L/minで流し、混合溶液を撹拌しながらオイルバスで40℃に加熱した。混合溶液をさらに撹拌しながら、水9.01gにリン酸0.047gを溶かしたリン酸水溶液を10分かけて添加した。添加終了後、40℃で30分間撹拌して、シラン化合物を加水分解させた。その後、バス温を50℃まで昇温し、50℃で1時間撹拌した。1時間撹拌して得られた溶液を氷浴にて冷却した後、陰イオン交換樹脂及び陽イオン交換樹脂を、それぞれ溶液に対して2重量%加えて12時間撹拌した。撹拌後、陰イオン交換樹脂及び陽イオン交換樹脂をろ過して除去し、シラン化合物溶液(E-2)を得た。得られたシラン化合物溶液(E-2)の固形分濃度は22重量%、水分率は8.0重量%であった。
重量を測定したアルミカップに樹脂溶液を1g秤量し、ホットプレート(HP-1SA;アズワン(株)製)を用いて250℃で30分間加熱して蒸発乾固させた。加熱後、固形分が残存したアルミカップの重量を測定し、加熱前後の重量の差分から残存した固形分の重量を算出し、樹脂溶液の固形分濃度を求めた。
カールフィッシャー水分率計(MKS-520;京都電子工業(株)製)を用い、滴定試薬としてカールフィッシャー試薬(HYDRANAL(登録商標)-コンポジット5;Sigma-Aldrich製)を用いて、「JIS K0113(2005)」に基づき、容量滴定法により、水分率測定を行った。
GPC分析装置(HLC-8220;東ソー(株)製)を用い、流動層としてTHFを用いてGPC測定を行い、ポリスチレン換算により求めた。
電位差自動滴定装置(AT-510;京都電子工業(株)製)を用い、滴定試薬として0.1mol/LのNaOH/EtOH溶液を用いて、「JIS K2501(2003)」に基づき、電位差滴定法により、酸価を測定して算出した。
「JIS K0070(1992)」に基づき、樹脂のヨウ素価を測定して算出した。
29Si-NMRの測定を行い、オルガノシラン由来のSi全体の積分値に対する、特定のオルガノシラン単位由来のSiの積分値の割合を算出して、それらの含有比率を計算した。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て測定に用いた。29Si-NMR測定条件を以下に示す。
装置:核磁気共鳴装置(JNM-GX270;日本電子(株)製)
測定法:ゲーテッドデカップリング法
測定核周波数:53.6693MHz(29Si核)
スペクトル幅:20000Hz
パルス幅:12μs(45°パルス)
パルス繰り返し時間:30.0s
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:0.0Hz
(7)基板の前処理
Mo/Al/Moの3層をスパッタにより成膜したガラス基板(三容真空工業(株)製;以下、「MAM基板」)、ITOをスパッタにより成膜したガラス基板(三容真空工業(株)製;以下、「ITO基板」)を、卓上型光表面処理装置(PL16-110;セン特殊光源(株)製)を用いて、100秒間UV-O3洗浄後、超純水で洗浄し、圧縮空気のエアーガンで表面の水滴を飛ばし、ホットプレートを用いて、130℃で3分間加熱して脱水ベーク処理をして使用した。テンパックスガラス基板(AGCテクノグラス(株)製)、単層Crをスパッタにより成膜したガラス基板(単層Cr成膜基板;(株)倉元製作所製;以下、「Cr基板」)は、前処理をせずに使用した。
Cr基板上に、下記、実施例1記載の方法で、感光性樹脂組成物の現像後膜を作製した。現像後、FPD検査顕微鏡(MX-61L;オリンパス(株)製)を用いて解像パターンを観察し、30μm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(i線照度計の値、以下、「最適露光量」)を感度とした。
Cr基板上に、下記、実施例1記載の方法で、感光性樹脂組成物の硬化膜を作製した。FPD検査顕微鏡を用いて、作製した硬化膜の解像パターンを観察し、最適露光量における最小パターン寸法を解像度とした。
テンパックスガラス基板上に、下記、実施例1記載の方法で、感光性樹脂組成物の硬化膜を作製した。紫外可視分光光度計(MultiSpec-1500;(株)島津製作所製)を用いて、まずテンパックスガラス基板のみを測定し、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、作製した硬化膜をシングルビームで測定し、ランベルト・ベールの法則に基づいて波長400nmにおける膜厚1.5μm当たりの透過率を求め、リファレンスとの差異から透過率を算出した。
Cr基板上に、下記、実施例1記載の方法で、感光性樹脂組成物の硬化膜を作製した。手動式鉛筆引っかき硬度試験器(850-56;コーティングテスター(株)製)を用いて、「JIS K5600-5-4(1999)」に基づき、作製した硬化膜の硬度を測定した。
MAM基板上に、下記、実施例1記載の方法で、感光性樹脂組成物の硬化膜を作製した。作製した硬化膜について、高度加速寿命測定装置(ハストチャンバー EHS-221MD)を用いたプレッシャークッカー試験(温度=121℃、湿度=100%RH、気圧=2atm)を行い、20時間放置した。プレッシャークッカー試験の20時間後、MAM基板上の、MAM表面が黒く変色した面積及び硬化膜表面の外観変化の有無を目視によって評価した。MAM表面の変色面積及び硬化膜表面の外観変化によって以下のように判定し、A+、A及びBを合格とした。
A+:MAM表面の変色面積=0%、かつ硬化膜表面の外観変化なし
A:MAM表面の変色面積<5%、硬化膜表面の外観変化なし
B:MAM表面の変色面積5~14%、硬化膜表面の外観変化なし
C:MAM表面の変色面積15~34%、硬化膜表面の外観変化なし
D:MAM表面の変色面積35~64%、硬化膜表面の外観変化なし
E:MAM表面の変色面積65~100%、硬化膜表面の外観変化なし
F:MAM表面の変色面積65~100%、硬化膜表面にクラック、あるいは硬化膜が基板から剥離。
MAM基板上に、下記、実施例1記載の方法で、感光性樹脂組成物の硬化膜を作製した。
5B:剥離面積=0%
4B:剥離面積<5%
3B:剥離面積=5~14%
2B:剥離面積=15~34%
1B:剥離面積=35~64%
0B:剥離面積=65~100%
下記、実施例1記載の方法で調製した、感光性樹脂組成物の一部を、23℃で7日間放置した。7日経過後、MAM基板上に、下記、実施例1記載の方法で、23℃で7日放置後の感光性樹脂組成物の硬化膜を作製した。作製した硬化膜を、上記と同様の方法で、「JIS K5600-5-6(1999)」に基づき、硬化膜の基板との密着性を測定した。
ITO基板上に、下記、実施例1記載の方法で、感光性樹脂組成物の硬化膜を作製した。作製した硬化膜を、40℃に加熱した酸薬液(重量比:HCl/HNO3/H2O=50/7.5/42.5)に240秒間浸漬し、水で2分間リンスした。次いで、上記(13)と同様の方法で、「JIS K5600-5-6(1999)」に基づき、硬化膜の基板との密着性を測定した。
ITO基板上に、下記、実施例1記載の方法で、感光性樹脂組成物の硬化膜を作製した。作製した硬化膜を、60℃に加熱したアルカリ薬液(重量比:DMSO/MEA=30/70)に120秒間浸漬し、水で2分間リンスした。次いで、上記(13)と同様の方法で、「JIS K5600-5-6(1999)」に基づき、硬化膜の基板との密着性を測定した。
黄色灯下、OXE-01を0.332g、ZC-150を0.0663g秤量し、PGMEAを2.046g、MBを2.730g、DAAを1.750g添加し、撹拌して溶解させた。次に、BYK-333の5重量%のPGMEA溶液を0.150g添加し、撹拌した。次いで、合成例1で得られたアクリル樹脂溶液(A-01)(35重量%のPGMEA溶液)を9.472g、DPHAの80重量%のPGMEA溶液を4.144g添加して撹拌した。さらに、KBM-903の5重量%のMB溶液を2.652g、KBM-04の20重量%のPGMEA溶液を1.658g添加して撹拌し、均一溶液とした。その後、得られた溶液を0.2μmのフィルターでろ過し、ネガ型の感光性樹脂組成物1を調製した。
感光性樹脂組成物1と同様に、感光性樹脂組成物2~78を表3~8に記載の組成にて調製した。得られた各感光性樹脂組成物を用いて、実施例1と同様に感光特性及び硬化膜の特性の評価を行った。それらの結果を、まとめて表9~14に示す。
以下の手順に従い、タッチパネル部材を作製した。
厚み約1mmのガラス基板に、スパッタリング装置を用いて、RFパワー1.4kW、真空度6.65×10-1Paで12.5分間スパッタリングすることにより、膜厚が150nmで、表面抵抗が15Ω/□のITOを成膜した。次に、ポジ型フォトレジストOFPR-800を、ITO上にスピンコーターを用いて任意の回転数でスピンコーティングにより塗布した後、ホットプレートを用いて80℃で20分間プリベークし、膜厚1.1μmのレジスト膜を得た。作製したレジスト膜を、両面アライメント片面露光装置を用いて、超高圧水銀灯のj線(波長313nm)、i線(波長365nm)、h線(波長405nm)及びg線(波長436nm)を、マスクを介してパターニング露光した後、フォトリソ用小型現像装置を用いて、2.38重量%TMAH水溶液で90秒間現像し、水で30秒間リンスした。その後、40℃に加熱したITOエッチング液(重量比:HCl/HNO3/H2O=18/4.5/77.5)に80秒浸漬してITOをエッチングし、水で2分間リンスした。次いで、50℃に加熱したレジスト剥離液N-300(重量比:MEA/BDG=30/70)に2分間浸漬してレジスト膜を除去し、膜厚150nmのパターン加工されたITO(図1及び図2の符号2)を有するガラス基板を作製した(図1のaに相当)。
(1)で作製したガラス基板上に、感光性樹脂組成物1を用いて、上記、実施例1記載の方法で、感光性樹脂組成物の透明絶縁膜(図1及び図2の符号3)を作製した(図1のbに相当)。
(2)で作製したガラス基板上に、ターゲットとしてモリブデン及びアルミニウム、MAMエッチング液として酸薬液(重量比:H3PO4/HNO3/AcOH/H2O=65/3/5/27)を用い、(1)と同様の方法で、MAM配線(図1及び図2の符号4)を作製した(図1のcに相当)。
(3)で作製したガラス基板上に、感光性樹脂組成物1を用いて、上記、実施例1記載の方法で、感光性樹脂組成物の透明保護膜を作製した。デジタルマルチメータ(CDM-09N;(株)カスタム製)を用いて接続部の導通テスト実施したところ、電流の導通が確認された(図2に相当)。
b:絶縁膜形成後の上面図
c:金属配線形成後の上面図
1:ガラス基板
2:透明電極
3:透明絶縁膜
4:配線電極
5:透明保護膜
Claims (12)
- (A)アルカリ可溶性樹脂、
(D)金属キレート化合物、及び、
(E)シラン化合物、を含有する感光性樹脂組成物であり、
前記(A)アルカリ可溶性樹脂がエチレン性不飽和二重結合基を有し、二重結合当量が300~5,000g/molであり、前記(D)金属キレート化合物が、一般式(1)で表される化合物であり、前記(E)シラン化合物が、一般式(2)で表される四官能シラン又は一般式(2)で表される四官能シランを縮合させることによって得られるシランオリゴマーであることを特徴とする、感光性樹脂組成物。
- 前記(A)アルカリ可溶性樹脂が、エポキシ基を有しないアルカリ可溶性樹脂である、請求項1記載の感光性樹脂組成物。
- 前記(A)アルカリ可溶性樹脂が、(A-1)アクリル樹脂及び(A-2)ポリシロキサンから選ばれる請求項1又は2記載の感光性樹脂組成物。
- さらに(B)ラジカル重合性化合物を含有する、請求項1~3のいずれか一項記載の感光性樹脂組成物。
- さらに(C)光重合開始剤を含有する、請求項1~4のいずれか一項記載の感光性樹脂組成物。
- さらに(F)アミノ基、アミド基、ウレイド基、ケチミン基、イソシアネート基、メルカプト基、イソシアヌル環骨格、(メタ)アクリル基及びスチリル基からなる群から選ばれる置換基を有するシラン化合物を含有する、請求項1~5のいずれか一項記載の感光性樹脂組成物。
- 前記(B)ラジカル重合性化合物が、(B-1)多官能ラジカル重合性化合物及び(B-2)三官能又は四官能ラジカル重合性化合物を含有する、請求項4~6のいずれか一項記載の感光性樹脂組成物。
- 請求項1~7のいずれか一項記載の感光性樹脂組成物を熱硬化させてなる、金属配線の保護膜又は絶縁膜。
- 前記感光性樹脂組成物がネガ型の感光性を有する、請求項8記載の金属配線の保護膜又は絶縁膜。
- 前記金属配線が、モリブデン、銀、銅、アルミニウム及びCNTからなる群から選ばれる一種以上を含有する、請求項8又は9記載の金属配線の保護膜又は絶縁膜。
- 請求項8~10のいずれか一項記載の金属配線の保護膜又は絶縁膜を具備する、タッチパネル。
- 請求項8記載の金属配線の保護膜又は絶縁膜を用いるタッチパネルの製造方法。
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JP6295950B2 (ja) | 2018-03-20 |
JPWO2014156520A1 (ja) | 2017-02-16 |
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