Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • 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
  • G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
• • 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
• • 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 resin composition for forming a flattening film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a protective film or insulating film such as a touch panel sensor element, or an interlayer insulating film of a semiconductor element.
• TFT thin film transistor
• a protective film or insulating film such as a touch panel sensor element
• an interlayer insulating film of a semiconductor element is related with the adhesion improving agent suitable for.
• the negative photosensitive composition using the same, the cured film formed from it, and the member for touch panels which has the cured film.
• Non-patent Document 1 Non-patent Document 1
• the composition of the hard coat material is a polymerizable group-containing oligomer, monomer, photopolymerization initiator, and other additives.
• Oligomer and monomer are cross-linked by radical polymerization by UV irradiation to obtain a high hardness film. Since this hard coat material requires a short time for curing, use of this hard coat material improves productivity. Furthermore, since a negative photosensitive material having a general radical polymerization mechanism can be used, there is an advantage that the manufacturing cost is reduced.
• the base may have a pattern made of a metal film such as ITO (Indium Tin Oxide) film or Mo (Molybdenum). Many. Therefore, it is a desirable characteristic that the negative photosensitive resin has good adhesion to ITO and Mo for use in various display elements and capacitive touch panels.
• a capacitive touch panel that has been attracting attention in recent years has a large area occupied by an ITO film or a metal film on a base, and a hard coat material that solves this problem has been demanded.
• Patent Document 1 As a method for improving adhesiveness, a method of adding a silane coupling agent is well known (Patent Document 1).
• aminoalkylsilane has a high effect of improving adhesiveness and is useful.
• aminoalkylsilane is useful because it has a high effect of improving adhesiveness, but if it is added in an increased amount to increase the effect of improving adhesiveness, it is insolubilized in an alkaline developer by standing for a long time after pre-baking. This is regarded as a problem in mass production.
• An object of the present invention is to provide a composition which is excellent in adhesion with a substrate surface composed of a metal or an inorganic substance and does not become insoluble in an alkaline developer even if left for a long time after pre-baking.
• the present inventors have focused on silane coupling agents in order to solve the above problems, and have found that silane coupling agents having a specific structure contribute to the solution of the problems.
• the present invention has the following configuration.
• R 1 represents a monovalent organic group or fluoro group having 1 to 30 carbon atoms.
• R 1 may have a substituent.
• R 2 represents 1 carbon atom.
• R 3 may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group, and a phenoxy group. (At least one of R 3 is selected from an alkoxy group having 1 to 6 carbon atoms and a hydroxyl group.)
• R 4 represents a monovalent .R 4 where an aryl group is good .
• R 5 may have a substituent divalent organic group having 1 to 6 carbon atoms of 1 to 12 carbon atoms .
• R 6 May be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group, or a phenoxy group, wherein at least one of R 6 is 1 carbon atom Selected from alkoxy groups of 6 to 6 and hydroxyl groups.
• the negative photosensitive composition of the present invention is excellent in improving adhesion to a substrate surface composed of a metal or an inorganic substance, and does not become insoluble in an alkaline developer even if left for a long time after pre-baking. Furthermore, since the silane coupling agent in the present invention can be used together with a cardo resin, it also has an effect of providing a composition containing a cardo resin excellent in adhesion to a substrate surface composed of a metal or an inorganic substance. .
• the negative photosensitive resin composition of the present invention comprises at least (A) a silane coupling agent represented by the general formula (1) or (2), (B) an alkali-soluble resin, and (C) a polyfunctional acrylic monomer. (D) radical photopolymerization initiator is contained, It is characterized by the above-mentioned.
• the negative photosensitive composition of the present invention has a silane coupling agent represented by the following general formula (A) general formula (1) or general formula (2).
• R 1 represents a monovalent organic group or fluoro group having 1 to 30 carbon atoms.
• R 2 represents a divalent organic group having 1 to 6 carbon atoms.
• R 3 May be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group, or a phenoxy group, wherein at least one of R 3 is 1 carbon atom Selected from alkoxy groups of 6 to 6 and hydroxyl groups.
• R 4 represents a monovalent .R 4 where an aryl group is good .
• R 5 may have a substituent divalent organic group having 1 to 6 carbon atoms of 1 to 12 carbon atoms .
• R 6 May be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group, or a phenoxy group, wherein at least one of R 6 is 1 carbon atom Selected from alkoxy groups of 6 to 6 and hydroxyl groups.
• R 1 and R 4 may have a substituent such as an alkoxy group, an aryl group, a phenoxy group, or a halogen group.
• R 3 R 6, methoxy, ethoxy, butoxy are preferred, with methoxy group from the viewpoint of availability of raw materials, an ethoxy group are preferable.
• silane coupling agent represented by the general formula (1) examples include 3- (trimethoxysilyl) propane-1-aminium ethanesulfonic acid, 10-camphorsulfonic acid 3- (trimethoxysilyl) propane-1 -Aminium, 10-camphorsulfonic acid 3- (triethoxysilyl) propane-1-aminium, trifluoromethanesulfonic acid 3- (trimethoxysilyl) propane-1-aminium, and the like.
• silane coupling agent represented by the general formula (2) examples include 3- (trimethoxysilyl) propane-1-aminium benzenesulfonate, 3- (trimethoxysilyl) propane-1 4-methylbenzenesulfonate -Aminium, 3- (triethoxysilyl) propane-1-aminium 4-methylbenzenesulfonate, and the like.
• silane coupling agents When these silane coupling agents are added to the negative photosensitive resin, they may be used alone or mixed.
• silane coupling agents As a method for producing these silane coupling agents, a method in which aminoalkylsilane and alkyl (aryl) sulfonic acid are reacted by mixing them in an organic solvent at room temperature is preferable from the viewpoint of ease of production. Although a small amount of unreacted substances may remain in this synthesis method, it does not significantly affect the adhesion improving effect and can be used without separation and purification. However, in order to reduce the residual amount of aminosilane, it is preferable to design a large molar ratio of alkyl (aryl) sulfonic acid.
• the amount of (A) silane coupling agent added is 0.5 to 0.5 with respect to the total amount of resin components of the negative photosensitive resin composition, that is, (B) alkali-soluble resin and (C) polyfunctional acrylic monomer. 10% by mass is preferable, and 1 to 5% by mass is more preferable. If the amount is less than 0.5% by mass, the effect of improving the adhesiveness is not sufficient. If the amount is more than 15% by mass, a fine pattern is hardly dissolved in alkali development, and the resolution may be lowered.
• alkali-soluble resin examples include polysiloxane, acrylic resin, vinyl ether resin, polyhydroxystyrene, novolac resin, polyimide, polyamide, cardo resin, and the like.
• the (B) alkali-soluble resin it is preferable that at least a part of the ethylenically unsaturated double bond group is introduced in order to increase the hardness of the cured film.
• polysiloxane, acrylic resin, and cardo resin are more preferable because of the ease of introduction of the ethylenically unsaturated double bond group. Moreover, you may contain 2 or more types of these polymers. In order to increase the chemical resistance or the refractive index, it is more preferable to contain a cardo resin.
• a reaction product obtained by hydrolyzing and condensing a trifunctional alkoxysilane compound is particularly preferable.
• the following are mentioned as a trifunctional alkoxysilane compound.
• the ethylenically unsaturated double bond group can be easily introduced into the polysiloxane, and the hardness of the cured film is increased. Is more preferable.
• (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth) acrylic acid Cyclohexyl, cyclohexenyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate, 2-cyclopropyloxycarbonylethyl (meth) acrylate, 2-cyclopentyloxycarbonylethyl (meth) acrylate, (meth) acrylic acid 2-cyclohexyloxycarbonylethyl, (meth) acrylic acid 2-cyclohexenyloxycarbonylethyl, (meth) acrylic acid 2- (4-methoxycyclohexyl)
• Aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and ⁇ -methylstyrene may be copolymerized with the above (meth) acrylic acid or (meth) acrylic acid ester. .
• an ethylenically unsaturated double bond group can be introduced by addition reaction of an epoxy compound having an ethylenically unsaturated double bond group with (meth) acrylic acid.
• an epoxy compound having an ethylenically unsaturated double bond group include the following compounds.
• CR-TR1, CR-TR2, CR-TR3, CR-TR4, CR-TR5, CR-TR6 or more, Osaka Gas Chemical.
• the content of the (B) alkali-soluble resin is not particularly limited, and can be arbitrarily selected depending on the desired film thickness and application.
• the alkali-soluble resin is preferably added in an amount of 10 to 70% by mass with respect to the solid content of the negative photosensitive resin composition.
• the negative photosensitive composition of the present invention contains (C) a polyfunctional monomer.
• the polyfunctional monomer refers to a compound having at least two ethylenically unsaturated double bonds in the molecule. Considering the ease of radical polymerization, a multi-sensitive monomer having an acrylic group is preferable.
• Specific examples include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylic acid ester, propylene phthalate anhydride Oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin modified epoxy di (meth) acrylate, oligomer such as alkyd modified (meth) acrylate, or tripropylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaeryth Tall tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaery
• the negative photosensitive resin composition of the present invention contains (D) a photo radical polymerization initiator.
• a photo radical polymerization initiator Any radical photopolymerization initiator may be used as long as it is decomposed and / or reacted by light (including ultraviolet rays and electron beams) to generate radicals.
• light including ultraviolet rays and electron beams
• ⁇ -aminoalkylphenone compounds include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1 -(4-morpholin-4-yl-phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and the like.
• acylphosphine oxide compound examples include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-( 2,4,4-trimethylpentyl) -phosphine oxide and the like.
• oxime ester compound examples include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O -Benzoyloxime)], 1-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, ethanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) and the like.
• 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 p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate and the like.
• the content of the radical photopolymerization initiator is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more in the solid content of the negative photosensitive resin composition. Moreover, 20 mass% or less is preferable and 10 mass% or less is more preferable. By setting it as the said range, radical hardening can fully be advanced and elution of the residual radical polymerization initiator etc. can be prevented and solvent resistance can be ensured.
• the negative photosensitive resin composition of the present invention may contain a polymerization inhibitor.
• a polymerization inhibitor By containing a polymerization inhibitor, the storage stability of the composition is improved, and the resolution after development is improved in applications requiring pattern processing.
• Specific examples of the polymerization inhibitor include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di (t-butyl) -p-cresol, phenothiazine, 4-methoxyphenol and the like.
• the content of the polymerization inhibitor is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more in the solid content of the negative photosensitive resin composition.
• it is preferably 5% by mass or less, and more preferably 1% by mass or less.
• the negative photosensitive resin composition of the present invention may contain a solvent.
• a compound having an alcoholic hydroxyl group or a cyclic compound having a carbonyl group is preferably used in that each component can be dissolved uniformly and the transparency of the resulting coating film can be improved. Two or more of these may be contained. Further, a compound having a boiling point of 110 to 250 ° C. under atmospheric pressure is more preferable.
• boiling point By setting the boiling point to 110 ° C. or higher, drying proceeds moderately at the time of coating, and a good coating without uneven coating can be obtained. On the other hand, when the boiling point is 250 ° C. or lower, the amount of residual solvent in the film can be reduced, and film shrinkage during thermosetting can be further reduced, so that better flatness can be obtained.
• Specific examples of the compound having an alcoholic hydroxyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2- Butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl Examples include ether, propylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, 3-methoxy-1-butanol, and 3-methyl-3-methoxy-1-butanol.
• diacetone alcohol is preferable from the viewpoint of storage stability
• propylene glycol mono t-butyl ether is preferable from the viewpoint of step coverage.
• cyclic compound having a carbonyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure examples include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, Examples include cycloheptanone. Among these, ⁇ -butyrolactone is preferable.
• the negative photosensitive resin composition of the present invention may contain various solvents such as acetates, ketones and ethers other than those described above.
• the content of the solvent is not particularly limited, and any amount can be used depending on the coating method.
• the amount of solvent is generally 50 to 95% by mass of the entire negative photosensitive resin composition.
• the negative photosensitive resin composition of the present invention may contain various curing agents that accelerate the curing of the resin composition or facilitate the curing.
• curing agent A well-known thing can be used. Specific examples include nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, and methylolated urea derivatives. Two or more of these may be contained. Of these, metal chelate compounds, methylolated melamine derivatives, and methylolated urea derivatives are preferably used in view of the stability of the curing agent and the processability of the obtained coating film.
• the negative photosensitive resin composition of the present invention may contain various surfactants such as a fluorine-based surfactant and a silicone-based surfactant in order to improve the flowability during coating.
• various surfactants such as a fluorine-based surfactant and a silicone-based surfactant in order to improve the flowability during coating.
• a fluorine-type surfactant, a silicone type surfactant, a polyalkylene oxide type surfactant, a poly (meth) acrylate type surfactant etc. can be used. Two or more of these may be used.
• fluorosurfactants include “Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477 (above, Dainippon Ink & Chemicals, Inc.) NBX-15 and FTX-218 (manufactured by Neos) are preferably used.
• silicone surfactants BYK-333, BYK-301, BYK-331, BYK-345, BYK-307 (manufactured by BYK Japan Japan Co., Ltd.) are preferably used.
• a typical method for producing the negative photosensitive resin composition of the present invention will be described.
• a silane coupling agent represented by the general formula (1) or (2) (B) an alkali-soluble resin, (C) a polyfunctional acrylic monomer, (D) a radical photopolymerization initiator, and If necessary, other additives are added to an arbitrary solvent and dissolved by stirring, and then the resulting solution is filtered to obtain a negative photosensitive resin composition.
• the method for forming a cured film using the negative photosensitive resin composition of the present invention will be described with an example.
• the negative photosensitive resin composition of the present invention is applied on a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, hot plate, Pre-bake with a heating device such as an oven.
• Pre-baking is preferably performed at 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 ⁇ m.
• exposure is performed using an exposure machine such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA).
• the exposure intensity is about 10 to 4000 J / m 2 (wavelength 365 nm exposure amount conversion), and this light is irradiated through or without a desired mask.
• the exposure light source is not limited, and ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.
• the exposed portion can be dissolved by development to obtain a negative pattern.
• a developing method it is preferable to immerse in a developing solution for 5 seconds to 10 minutes by a method such as showering, dipping or paddle.
• a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. And aqueous solutions containing one or more quaternary ammonium salts such as choline.
• this film is heated in the range of 140 to 320 ° C. for 15 minutes to 1 hour with a heating device such as a hot plate or oven.
• the cured film obtained by curing the negative photosensitive resin composition of the present invention is used as a touch panel protective film, a touch panel insulating film, various hard coat materials, an antireflection film, and an optical filter. Further, since it has negative photosensitivity, it is suitably used for TFT flattening films, insulating films, antireflection films, color filter overcoats, column materials, etc. for liquid crystals and organic EL displays. Among these, in particular, it can be suitably used as a touch panel protective film or a touch panel insulating film that requires adhesion after heat treatment and chemical treatment to a substrate not containing Si, such as ITO or molybdenum. Examples of the touch panel system include a resistance film type, an optical type, an electromagnetic induction type, and a capacitance type. Since the electrostatic capacity type touch panel particularly requires chemical treatment resistance, the cured film of the present invention can be preferably used.
• the hardness is preferably 4H or more
• the transmittance is 95% or more
• the resolution is preferably 20 ⁇ m or less.
• the hardness and transmittance can be adjusted by selecting the exposure amount and the thermosetting temperature.
• Synthesis Example 2 Synthesis of Silane Coupling Agent Solution (a-2) 1.902 g (10 mmol) of p-toluenesulfonic acid monohydrate and 1.793 g (10 mmol) of 3-aminopropyltrimethoxysilane were added to 64.983 g of MB. The mixture was stirred at room temperature for 15 minutes to obtain a 5% MB solution (a-2) of 3- (trimethoxysilyl) propane-1-aminium 4-methylbenzenesulfonate.
• Synthesis Example 3 Synthesis of silane coupling agent solution (a-3) To 77.944 g of MB, 2.323 g (10 mmol) of 10-camphorsulfonic acid and 1.793 g (10 mmol) of 3-aminopropyltrimethoxysilane were added for 15 minutes at room temperature. And a 5% MB solution (a-3) of 3- (trimethoxysilyl) propane-1-aminium 10-camphorsulfonic acid was obtained.
• Synthesis Example 4 Preparation of Silane Coupling Agent Solution (a-4) 1.793 g (10 mmol) of 3-aminopropyltrimethoxysilane was added to 34.067 g of MB, and the mixture was stirred for 15 minutes at room temperature. A 5% MB solution (a-4) was obtained.
• Synthesis Example 5 Synthesis of Silane Coupling Agent Solution (a-5) 0.981 g (10 mmol) of concentrated sulfuric acid and 1.793 g (10 mmol) of 3-aminopropyltrimethoxysilane were added to 52.706 g of MB and stirred at room temperature for 15 minutes. As a result, a 5% MB solution (a-5) of 3- (trimethoxysilyl) propane-1-aminium hydrogen sulfate was obtained.
• Synthesis Example 6 Synthesis of Silane Coupling Agent Solution (a-6) 0.961 g (10 mmol) of methanesulfonic acid and 1.793 g (10 mmol) of 3-aminopropyltrimethoxysilane were added to 52.326 g of MB and 15 minutes at room temperature. Stirring gave a 5% MB solution (a-6) of 3- (trimethoxysilyl) propane-1-aminium methanesulfonate.
• Synthesis Example 7 Synthesis of Siloxane Resin Solution (b-1) 13.62 g (0.1 mol) of methyltrimethoxysilane, 118.98 g (0.6 mol) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic acid 39 .39 g (0.15 mol), ⁇ -methacryloxypropyltrimethoxysilane 35.16 g, and DAA 140.87 g were added to a 500 mL three-necked flask.
• Synthesis Example 8 Synthesis of Acrylic Resin Solution (b-2) A 500 mL flask was charged with 3 g of 2,2′-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate). Thereafter, 30 g of methacrylic acid, 22.48 g of styrene, and 25.13 g of cyclohexyl methacrylate were added. Thereafter, the mixture was stirred at room temperature for a while, and the atmosphere in the flask was replaced with nitrogen, followed by heating and stirring at 70 ° C. for 5 hours.
• 2,2′-azobis isobutyronitrile
• PGMEA propylene glycol methyl ether acetate
• MAM substrate A cured film having a film thickness of 1.5 ⁇ m produced on this substrate (hereinafter referred to as MAM substrate) is cured with the MAM substrate in accordance with JIS “K5400” 8.5.2 (1990) grid tape method.
• JIS “K5400” 8.5.2 (1990) grid tape method The adhesion of the film was evaluated.
• 11 parallel straight lines of 11 vertical and horizontal directions were drawn at 1 mm intervals so as to reach the substrate of the glass plate with a cutter knife, and 100 squares of 1 mm ⁇ 1 mm were produced. .
• Condition 1 60 ° C., 80 seconds
• Condition 2 60 ° C., 5 minutes
• Condition 3 85 ° C., 5 minutes
• the chemical resistance was evaluated in four stages as follows. 3: Both conditions 1, 2 and 3 have chemical resistance 2: Condition 1 and 2 have chemical resistance 1: Only condition 1 has chemical resistance 0: No condition has chemical resistance (3) Development after pre-baking Sex change (Development margin after pre-baking)
• the ITO substrate was spin-coated at an arbitrary rotation number using a spin coater (1H-360S manufactured by Mikasa Corporation), and the substrate was heated at 110 ° C. using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Pre-baking was performed for 2 minutes to produce four films having a thickness of 1.5 ⁇ m.
• the time taken for the subsequent exposure process was divided into four types, 30 minutes, 6 hours, 12 hours, and 24 hours.
• Exposure was performed with a mask gap of 100 ⁇ m.
• an automatic developing device AD-2000, manufactured by Takizawa Sangyo Co., Ltd.
• shower development was performed for 90 seconds with a 0.4% by mass tetramethylammonium hydroxide aqueous solution ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.).
• a pattern with a width of 50 ⁇ m can be resolved even after being left after pre-baking. There was a margin left after pre-baking.
• Example 1 Under a yellow light, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irgacure (registered trademark) 907” manufactured by Ciba Specialty Chemicals, Inc. IC907.)) 1.557 g, 4,4-bis (diethylamino) benzophenone (hereinafter referred to as EK) 0.173 g was dissolved in DAA 15.000 g, MB 5.914 g, and PGMEA 30.000 g. Dipentaerythritol hexaacrylate (trade name “Kayarad (registered trademark) DPHA” manufactured by Shin Nippon Kayaku Co., Ltd.
• EK 4,4-bis (diethylamino) benzophenone
• silane coupling agent solution (a- 1) 6.922 g, 8.652 g of a 1% by weight PGMEA solution of 4-t-butylcatechol, 21.630 g of a siloxane resin solution (b-1), BYK-333 which is a silicone surfactant (BIC Chemie Japan K.K.) 1.500 g of a 1% by mass solution of PGMEA (manufactured) was added and stirred, followed by filtration through a 0.45 ⁇ m filter to obtain a negative photosensitive resin composition (N-1).
• DPHA silane coupling agent solution
• the obtained negative photosensitive resin composition (N-1) was spin-coated on the MAM substrate and the ITO substrate using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation speed. Thereafter, these substrates were pre-baked for 2 minutes at 110 ° C. using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a film having a thickness of 1.5 ⁇ m.
• the produced film was exposed at an exposure amount of 200 mJ (i-line) using a parallel light mask aligner (PLA-501F manufactured by Canon Inc.) and an ultrahigh pressure mercury lamp as a light source. Then, using an automatic developing device (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed for 90 seconds with a 0.4% by mass tetramethylammonium hydroxide aqueous solution ELM-D (manufactured by Mitsubishi Gas Chemical Co., Ltd.). Then rinsed with water for 30 seconds. Finally, a cured film was prepared by curing in an air at 220 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222). About the obtained cured film, MAM adhesiveness and TOK106 tolerance were evaluated by the said method. The development margin after pre-baking was evaluated by the above method.
• Example 2 The same procedure as in Example 1 was conducted except that 1.731 g of the silane coupling agent solution (a-2) was used instead of 6.922 g of the silane coupling agent solution (a-1), and the negative photosensitive resin composition (N -2) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-2).
• Example 3 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 1 except that 6.922 g of the silane coupling agent solution (a-2) was used instead of 6.922 g of the silane coupling agent solution (a-1). -3) was obtained. The obtained negative photosensitive resin composition (N-3) was evaluated in the same manner as in Example 1.
• Example 4 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 1 except that 20.766 g of the silane coupling agent solution (a-2) was used instead of 6.922 g of the silane coupling agent solution (a-1). -4) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-4).
• Example 5 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 1 except that 6.922 g of the silane coupling agent solution (a-3) was used instead of 6.922 g of the silane coupling agent solution (a-1). -5) was obtained. Using the obtained negative photosensitive resin composition (N-5), evaluation was performed in the same manner as in Example 1.
• Example 6 Under a yellow light, 1.557 g of IC907 and 0.173 g of EK were dissolved in DAA17.597 g, MB5.914 g, and PGMEA30.000 g. To this solution, 10.382 g of DPHA, 6.922 g of silane coupling agent solution (a-2), 8.652 g of 1% by weight PGMEA solution of 4-t-butylcatechol, and 17.303 g of acrylic resin solution (b-2) Then, 1.500 g of a 1% by mass PGMEA solution of BYK-333 (manufactured by Big Chemie Japan Co., Ltd.), a silicone surfactant, was added and stirred. Next, filtration was performed with a 0.45 ⁇ m filter to obtain a negative photosensitive resin composition (N-6). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-6).
• Example 7 A negative photosensitive resin composition (N-7) was obtained in the same manner as in Example 6 except that the amount of 6.922 g of the silane coupling agent solution (a-2) was changed to 20.766 g. Evaluation was carried out in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-7).
• Example 8 Under a yellow light, IC9071.557 g of IC907 and 0.173 g of EK were dissolved in DAA 15.000 g, MB 5.914 g, and PGMEA 27.405 g.
• 8.502 g of a cardo resin solution (b-3) and 1.500 g of a 1% by mass PGMEA solution of BYK-333 (manufactured by Big Chemie Japan Co., Ltd.), a silicone surfactant were added and stirred.
• filtration was performed with a 0.45 ⁇ m filter to obtain a negative photosensitive resin composition (N-8). Evaluation was carried out in the same manner as in Example 1 using the obtained negative photosensitive
• Example 9 Under a yellow light, 1.557 g of IC907 and 0.173 g of EK were dissolved in 25.000 g of DAA, 5.914 g of MBA, and 20.000 g of PGMEA. To this solution, 8.652 g of DPHA, 6.922 g of the silane coupling agent solution (a-1), 8.652 g of a 1% by mass PGMEA solution of 4-t-butylcatechol, and 21.630 g of cardo resin solution (b-3) Then, 1.500 g of a 1% by mass PGMEA solution of BYK-333 (manufactured by Big Chemie Japan Co., Ltd.), a silicone surfactant, was added and stirred. Next, filtration was performed with a 0.45 ⁇ m filter to obtain a negative photosensitive resin composition (N-9).
• N-9 negative photosensitive resin composition
• Example 10 The same procedure as in Example 9 was conducted except that 6.922 g of the silane coupling agent solution (a-2) was used instead of 6.922 g of the silane coupling agent solution (a-1), and a negative photosensitive resin composition (N -10) was obtained. Evaluation was carried out in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-10).
• Example 11 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 9 except that 6.922 g of the silane coupling agent solution (a-3) was used instead of 6.922 g of the silane coupling agent solution (a-1). -11) was obtained. The obtained negative photosensitive resin composition (N-11) was used for evaluation in the same manner as in Example 1.
• Example 12 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 9 except that 20.766 g of the silane coupling agent solution (a-2) was used instead of 6.922 g of the silane coupling agent solution (a-1). -12) was obtained. Using the obtained negative photosensitive resin composition (N-12), evaluation was performed in the same manner as in Example 1.
• Comparative Example 1 A negative photosensitive resin composition (N-13) was obtained in the same manner as in Example 1 except that 6.922 g of the silane coupling agent solution (a-1) was not added. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-13).
• Comparative Example 2 The negative photosensitive resin composition (N) was prepared in the same manner as in Example 1 except that 6.922 g of the silane coupling agent solution (a-4) was used instead of 6.922 g of the silane coupling agent solution (a-1). -14) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-14).
• Comparative Example 3 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 1 except that 20.766 g of the silane coupling agent solution (a-4) was used instead of 6.922 g of the silane coupling agent solution (a-1). -15) was obtained. Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (N-15).
• Comparative Example 4 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 1 except that 6.922 g of the silane coupling agent solution (a-5) was used instead of 6.922 g of the silane coupling agent solution (a-1). -16) was obtained. The obtained negative photosensitive resin composition (N-16) was used for evaluation in the same manner as in Example 1.
• the negative photosensitive resin composition (N) was prepared in the same manner as in Example 1 except that 6.922 g of the silane coupling agent solution (a-6) was used instead of 6.922 g of the silane coupling agent solution (a-1). -17) was obtained. The obtained negative photosensitive resin composition (N-17) was used for evaluation in the same manner as in Example 1.
• Comparative Example 6 A negative photosensitive resin composition (N-18) was obtained in the same manner as in Example 6 except that 6.922 g of the silane coupling agent solution (a-3) was not added. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-18).
• Comparative Example 7 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 6 except that 20.766 g of the silane coupling agent solution (a-4) was used instead of 6.922 g of the silane coupling agent solution (a-3). -19) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-19).
• Comparative Example 8 A negative photosensitive resin composition (N-20) was obtained in the same manner as in Example 9 except that 6.922 g of the silane coupling agent solution (a-1) was not added. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-20).
• Comparative Example 9 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 9 except that 6.922 g of the silane coupling agent solution (a-4) was used instead of 6.922 g of the silane coupling agent solution (a-1). -21) was formulated. However, the solution was cloudy and could not be filtered with a 0.45 ⁇ m filter. When the solution was allowed to stand at room temperature for 1 day, generation of a slight precipitate was confirmed. Therefore, evaluation of MAM adhesion, TOK106 resistance, and development margin after pre-baking was not performed.
• Comparative Example 10 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 9 except that 6.922 g of the silane coupling agent solution (a-5) was used instead of 6.922 g of the silane coupling agent solution (a-1). ⁇ 22) was prepared. However, the solution was cloudy and could not be filtered with a 0.45 ⁇ m filter. When the solution was allowed to stand at room temperature for 1 day, generation of a slight precipitate was confirmed. Therefore, evaluation of MAM adhesion, TOK106 resistance, and development margin after pre-baking was not performed.
• Comparative Example 11 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 9 except that 6.922 g of the silane coupling agent solution (a-6) was used instead of 6.922 g of the silane coupling agent solution (a-1). -23) was formulated. However, the solution was cloudy and could not be filtered with a 0.45 ⁇ m filter. When the solution was allowed to stand at room temperature for 1 day, generation of a slight precipitate was confirmed. Therefore, evaluation of MAM adhesion, TOK106 resistance, and development margin after pre-baking was not performed.
• the present invention is suitably used for a negative photosensitive resin composition, a cured film using the same, and a touch panel device having the same.

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