CN113474730A

CN113474730A - Negative photosensitive resin composition, method for producing cured film using same, and touch panel

Info

Publication number: CN113474730A
Application number: CN202080016528.1A
Authority: CN
Inventors: 福崎雄介; 妹尾将秀
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2019-03-05
Filing date: 2020-03-02
Publication date: 2021-10-01
Also published as: WO2020179744A1; TWI837317B; JPWO2020179744A1; TW202035471A; KR102675832B1; JP7405075B2; KR20210135217A

Abstract

The invention provides a negative photosensitive resin composition which has high resolution, can form a cured film which has high pencil hardness, excellent chemical resistance and weather resistance and can inhibit the generation of external gas during electrode or wiring processing even if the cured film is cured at a low temperature of below 150 ℃. The present invention is a negative photosensitive resin composition comprising: (A) a silicone resin having a radical polymerizable group; (B) a monomer having a radical polymerizable group; and (C) a photo radical polymerization initiator having an absorption peak in a region of a wavelength of 350 to 370, wherein the absorbance at the wavelength of 400 is 10% or less of the absorbance at the wavelength of 365.

Description

Negative photosensitive resin composition, method for producing cured film using same, and touch panel

Technical Field

The present invention relates to a negative photosensitive resin composition containing a silicone resin having a radical polymerizable group, a monomer having a radical polymerizable group, and a photo radical polymerization initiator, and a method for producing a cured film using the same, and a touch panel.

Background

In recent years, touch panels have been widely used as input means. The touch panel includes a display unit such as a liquid crystal panel, a touch panel sensor for detecting information input to a specific position, and the like. Touch panel systems are broadly classified into resistive film systems, electrostatic capacitance systems, optical systems, electromagnetic induction systems, ultrasonic wave systems, and the like, according to a method of detecting an input position. Among them, the capacitive touch panel is widely used for reasons such as optical brightness, excellent design, simple structure, and excellent function. A transparent electrode substrate having a transparent electrode formed on a substrate is used for a display portion of a touch panel, and Indium Oxide (ITO) doped with Tin has been conventionally used as the transparent electrode. In order to enable a large screen of a touch panel and detection by pen touch (pen touch), further reduction in resistance is required, but ITO has a high resistivity. Therefore, in recent years, a touch panel having an electrode called a Metal Mesh (Metal Mesh) in which conductive wires made of a conductive Metal such as copper or a copper alloy are arranged in a Mesh shape has been proposed. However, since copper is easily oxidized at a high temperature to form an oxide film and the resistance value is increased, a material that can be cured at a low temperature of 150 ℃ or lower is required as a material for an insulating layer or a protective layer of the touch panel.

Therefore, as a photosensitive resin composition which is excellent in pattern processability and which provides sufficient chemical resistance and substrate adhesion even when cured at a low temperature of 150 ℃ or lower, for example, a photosensitive resin composition comprising a photoreactive resin containing an ethylenically unsaturated group and a carboxyl group, a specific epoxy compound, a specific polyfunctional epoxy compound and a photopolymerization initiator has been proposed (for example, see patent document 1).

Further, as a raw material composition of an insulating coating film excellent in adhesion force or chemical resistance, a composition for an insulating material containing a siloxane oligomer having a crosslinkable functional group, a photopolymerization initiator, and an adhesion promoter containing an aluminum and/or zirconium complex compound (for example, see patent document 2) and the like have been proposed.

On the other hand, as photo radical polymerization initiators, benzoic acid type, benzophenone type, thioxanthone type, acetophenone type, and acylphosphine type are known. Recently, oxime ester type photo radical polymerization initiators have also been introduced (see patent documents 3 and 4).

[ Prior art documents ]

[ patent document ]

[ patent document 1] International publication No. 2017/110689

[ patent document 2] International publication No. 2014/185435

[ patent document 3] Japanese patent application publication No. 2009-519991

[ patent document 4] Japanese patent laid-open publication No. 2014-522394

Disclosure of Invention

Problems to be solved by the invention

According to the technique described in patent document 1, a cured film excellent in chemical resistance and substrate adhesion can be obtained even when cured at a low temperature, but there is a problem that pencil hardness and weather resistance of the cured film are insufficient, and an outgas is generated at the time of wiring processing due to the remaining unreacted radical polymerizable group. Further, according to the technique described in patent document 2, a cured film having excellent pencil hardness can be obtained, but there is a problem that resolution (resolution) is insufficient. Further, since the cured film has insufficient crosslinking density, there is a problem that chemical resistance is insufficient such that an etching solution penetrates into an insulating film when an electrode is formed on the insulating film.

The present invention has been made in view of the problems of the prior art, and an object of the present invention is to provide a negative photosensitive resin composition which has a high resolution, and which can form a cured film having high pencil hardness, excellent chemical resistance and weather resistance, and capable of suppressing the generation of outgas during electrode or wiring processing, even when cured at a low temperature of 150 ℃.

Means for solving the problems

The object of the present invention is achieved by the following means.

First, the following negative photosensitive resin composition was obtained. A negative photosensitive resin composition comprising: (A) a silicone resin having a radical polymerizable group, (B) a monomer having a radical polymerizable group, and (C) a photo radical polymerization initiator, wherein the photo radical polymerization initiator has a light absorption peak in a wavelength region of 350 to 370nm, and the absorbance at a wavelength of 400nm is 10% or less of the absorbance at a wavelength of 365 nm.

The characteristics of the negative photosensitive resin composition disclosed in the present invention include the following inventions.

A method for producing a cured film, comprising: the method for producing a negative photosensitive resin composition of the present invention includes a step of coating a negative photosensitive resin composition of the present invention on a substrate, a step of exposing the composition to light, and a step of curing the exposed composition at a temperature of 150 ℃.

A touch panel comprises a substrate, an electrode and/or wiring containing copper, and a cured film obtained by curing the negative photosensitive resin composition of the present invention.

Effects of the invention

The negative photosensitive resin composition of the present invention has a high resolution, and even when cured at a low temperature of 150 ℃ or lower, the negative photosensitive resin composition of the present invention can provide a cured film which has high pencil hardness, excellent chemical resistance and weather resistance, and can suppress the generation of outgas during electrode or wiring processing.

Detailed Description

The present invention will be described in more detail below.

The negative photosensitive resin composition of the present invention is characterized by containing at least: (A) a silicone resin having a radical polymerizable group (hereinafter, may be simply referred to as "(a) silicone resin"); (B) a monomer having a radical polymerizable group; and (C) a photo radical polymerization initiator (hereinafter, may be simply referred to as "(C) photo radical polymerization initiator") having an absorption peak in a region of a wavelength of 350nm to 370nm, and an absorbance at a wavelength of 400nm being 10% or less of an absorbance at a wavelength of 365 nm. By containing (a) a silicone resin and (C) a photo radical polymerization initiator, radical polymerization of (a) a radical polymerizable group of the silicone resin and (B) a monomer having a radical polymerizable group is performed in a light irradiation part, and negative pattern processing that does not dissolve the light irradiation part is possible. (A) The silicone resin contains a siloxane skeleton having high heat resistance and weather resistance in its main chain and a radical polymerizable group, and also undergoes a silanol condensation reaction even at 150 ℃ or lower, so that the crosslinking density of the cured film can be increased, the chemical resistance and weather resistance can be improved, and the pencil hardness can be increased.

On the other hand, in the case of the conventionally known negative photosensitive resin composition, there is a problem that crosslinking cannot be sufficiently performed at a curing temperature of 150 ℃ or lower, and chemical resistance of the film is lowered. In contrast, in the present invention, in exposure using a normal ultra-high pressure mercury lamp or a Light Emitting Diode (LED) as a light source, which has a strong bright-line emission spectrum in i-rays (wavelength 365nm), a photo radical polymerization initiator having an absorption peak in a wavelength region of 350nm to 370nm is used, whereby the concentration of radicals generated in a light irradiation part is increased, and the reaction of radical polymerizable groups is promoted. Therefore, the crosslinking density of the film obtained by photocuring can be increased, and pencil hardness or chemical resistance can be improved. Further, since the residual unreacted radical polymerizable group can be suppressed, the weather resistance can be improved and the amount of outgas during electrode or wiring processing can be reduced.

Further, the photo radical polymerization initiator of the present invention, in which the absorbance at a wavelength of 400nm is 10% or less of the absorbance at a wavelength of 365nm, can suppress absorption of long-wavelength light, which is a main cause of lowering the resolution, and thus can improve the resolution.

In the present invention, as a photo radical polymerization initiator that selectively absorbs in the wavelength region of i-ray, attention is paid to the absorbance at each wavelength, and the absorbance at a wavelength of 400nm is selected as an index of the absorbance in the wavelength region of h-ray (405nm) or g-ray (436nm) having an emission spectrum of a longer wavelength than that of i-ray. The absorbance at a wavelength of 400nm being 10% or less of the absorbance at a wavelength of 365nm means that light in a wavelength region where i-ray is selectively absorbed.

The negative photosensitive resin composition of the present invention contains (a) a siloxane resin. The silicone resin refers to a polymer comprising a repeating unit having a siloxane skeleton. The silicone resin (a) in the present invention has a radical polymerizable group, and is preferably a hydrolysis-condensation product of an organosilane compound having a radical polymerizable group. For the hydrolysis condensation reaction, it is preferable that a hydrolyzable group is directly bonded to a silicon atom of the organic silane compound. Examples of the hydrolyzable group include an alkoxy group and a carboxyl group.

From the viewpoint of further improving chemical resistance, the weight average molecular weight (Mw) of the (a) silicone resin is preferably 500 or more, more preferably 1,000 or more. On the other hand, from the viewpoint of improving solubility in a developer at the time of forming a pattern, Mw of the (a) silicone resin is preferably 10,000 or less, more preferably 5,000 or less. Here, the Mw of the silicone resin (a) is a polystyrene equivalent value measured by Gel Permeation Chromatography (GPC).

Examples of the radical polymerizable group include a vinyl group, an α -methylvinyl group, an allyl group, a styryl group, and a (meth) acryloyl group. From the viewpoint of further improving pencil hardness of the cured film or sensitivity in pattern processing, a (meth) acryloyl group is preferable.

The double bond equivalent of the silicone resin (a) is preferably 150g/mol or more, and more preferably 200g/mol or more, from the viewpoint of improving adhesion to a substrate as a base. On the other hand, from the viewpoint of further increasing the crosslinking density of the cured film, further improving chemical resistance, and further improving pencil hardness, the double bond equivalent of the (a) silicone resin is preferably 2,000g/mol or less, and more preferably 1,500g/mol or less. As described above, the (meth) acryloyl group is preferred, and therefore, although not necessarily, two kinds of functional groups are present, the equivalent weight of the double bond in the total of the acryloyl group and the methacryloyl group is preferably 2,000g/mol or less, more preferably 1,500g/mol or less, from the viewpoint of further increasing the crosslinking density of the cured film, further improving the chemical resistance, and further improving the pencil hardness. Here, the double bond equivalent of the silicone resin can be calculated by measuring the iodine value.

Examples of the organic silane compound having a radical polymerizable group include: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi (methoxyethoxy) silane, allyltrimethoxysilane, allyltriethoxysilane, allyltris (methoxyethoxy) silane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi (methoxyethoxy) silane, styryltrimethoxysilane, styryltriethoxysilane, styryltris (methoxyethoxy) silane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldi (methoxyethoxy) silane, vinylmethyldimethoxysilane, vinylmethyldi (ethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi (ethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi (ethoxysilane, vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldi (vinylmethyldimethoxysilane), 3-methoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi (methoxyethoxy) silane, vinylmethyldi (vinylmethyldi) silane, vinylmethyldi) and (e) silane, vinylmethyldi (e) silane, vinylmethyldi (e), vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldi (vinyltriethoxysilane, vinylmethyldi (vinyltriethoxysilane, vinylmethyldi (e), vinylmethyldi (e), vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldi (vinyltriethoxysilane, vinylmethyldi (e), vinylmethyldi (vinyltriethoxysilane, vinylmethyldi (e), and (e), vinylmethyldi (e), vinyltriethoxysilane), vinylmethyldi (vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane), vinyltriethoxysilane, vinylmethyldi (e), and (e), 3-acryloxypropyltris (methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltris (methoxyethoxy) silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyl (methoxyethoxy) silane and the like. Two or more of these may also be used. Among these, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane are preferable from the viewpoint of further improving the pencil hardness of the cured film and the sensitivity in pattern processing.

(A) The silicone resin may also be a hydrolytic condensate of the organosilane compound having a radical polymerizable group and another organosilane compound. The latter organosilane compound is also preferably a compound in which a hydrolyzable group is directly bonded to a silicon atom. Examples of the hydrolyzable group include an alkoxy group and a carboxyl group.

Examples of the other organosilane compounds include: methyltrimethoxysilane, methyltriethoxysilane, methyltris (methoxyethoxy) silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, methyl-tri (methoxy-ethoxy) silane, methyl-tripropoxysilane, methyl-triisopropoxysilane, methyl-tributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, methyl-triethoxysilane, methyl-N-aminopropyltrimethoxysilane, methyl-N-ethoxysilane, ethyl-3-N-aminopropyltrimethoxysilane, N-trimethoxysilane, N-di (di-diglycidyl) trimethoxysilane, N-glycidyloxy-trimethoxysilane, and the like, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 2-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 1-glycidoxyethyltrimethoxysilane, 1-glycidoxyethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 1-glycidoxypropyltrimethoxysilane, 1-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, and the like, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltriisopropoxysilane, 3-glycidoxypropyltributoxysilane, 3-glycidoxypropyltri (methoxyethoxy) silane, 1-glycidoxybutyltrimethoxysilane, 2-glycidoxybutyltriethoxysilane, 3-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, (3, 4-epoxycyclohexyl) methyltrimethoxysilane, (3, 4-epoxycyclohexyl) methyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltripropoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltributoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriphenoxysilane, 3- (3, 4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3, 4-epoxycyclohexyl) propyltriethoxysilane, 4- (3, 4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3, 4-epoxycyclohexyl) butyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriphenoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 2-epoxycyclohexyl) triethoxysilane, 3, 4-epoxycyclohexyl) triethoxysilane, 3, 4-epoxycyclohexyl) triethoxysilane, and (3-epoxycyclohexyl) butyltriethoxysilane, 4-epoxycyclohexyl) triethoxysilane, 4-epoxycyclohexyl) butyltrimethoxysilane, 2-epoxycyclohexyl) triethoxysilane, and (3, 4-epoxycyclohexyl) triethoxysilane, and a mixture thereof, Dimethyldimethoxysilane, dimethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, 1-glycidoxyethylmethyldimethoxysilane, 1-glycidoxyethylmethyldiethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethylmethyldiethoxysilane, 1-glycidoxypropylmethyldimethoxysilane, 1-glycidoxypropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, 1-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethylsilane, 2-hydroxyethylmethyldimethoxysilane, 1-glycidoxyethylmethyldimethoxysilane, a, 2-glycidoxypropylmethyldimethoxysilane, 2-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropoxysilane, 2-glycidoxypropylmethyldibutyloxysilane, 3-glycidoxypropylmethyldi (methoxyethoxy) silane, 3-glycidoxypropylethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, perfluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctylpropyltriethoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, bis (trifluoromethyl) dimethoxysilane, bis (trifluoropropyl) diethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, perfluoropropyltriethoxysilane, perfluorooctyltriethoxysilane, perfluorooctyldimethoxysilane, perfluoroethyldimethoxysilane, bis (trifluoropropyldimethoxysilane, perfluoropropyldimethoxysilane, perfluoroethyldimethoxysilane, perfluoroethylsilane, perfluoroethyldimethoxysilane, perfluoroethylsilane, perfluoroethyldimethoxysilane, perfluoroethylsilane, perfluoroethyldimethoxysilane, perfluoroethylsilane, perfluoroethyltriethoxysilane, perfluoroethylsilane, perfluoroethyltriethoxysilane, perfluoroethylsilane, perfluoropropyltriethoxysilane, perfluoroethylsilane, perfluoropropyltriethoxysilane, perfluoroethylsilane, perfluoropropyltriethoxysilane, perfluoroethylsilane, perfluoroethyl, Heptadecafluorodecylmethyldimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl cyclohexyl dicarboxylic anhydride, 3-trimethoxysilylpropyl phthalic anhydride, and the like. Two or more of these may also be used. Of these, methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are preferable.

The (a) siloxane resin of the present invention can be obtained by subjecting the organosilane compound to hydrolytic condensation. For example, the silanol compound can be obtained by hydrolyzing an organosilane compound having a hydrolyzable group and then condensing the obtained silanol compound in the presence or absence of an organic solvent.

In the negative photosensitive resin composition of the present invention, it is preferable that (a) the silicone resin is not completely condensed and a hydrolyzable group or silanol group remains, because the composition is further cured after patterning. When these functional groups disappear, the polymer becomes high in molecular weight and is further crosslinked, which makes it difficult to dissolve or disperse the polymer in a solvent or to mix the polymer with other additives.

The conditions for the hydrolysis reaction may be appropriately set in consideration of the scale of the reaction, the size and shape of the reaction vessel, and the like. For example, it is preferable that: the reaction is carried out by adding an acid catalyst and water to an organic silane compound in a solvent at 1 to 180 minutes and then reacting the mixture at room temperature to 110 ℃ for 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably from 30 ℃ to 105 ℃.

The hydrolysis reaction is preferably carried out in the presence of an acid catalyst. The acid catalyst is preferably an acidic aqueous solution containing formic acid, acetic acid, phosphoric acid, and nitric acid. The amount of the acid catalyst to be added is preferably 0.05 to 5 parts by weight based on 100 parts by weight of the total organosilane compound used in the hydrolysis reaction. By setting the amount of the acid catalyst within the above range, the hydrolysis reaction can be more efficiently performed.

Preferably, the condensation reaction is carried out by heating the reaction solution at 50 ℃ or higher and the boiling point of the solvent or lower for 1 to 100 hours after obtaining the silanol compound by generating a silanol group by hydrolysis of the organosilane compound. Further, reheating or addition of an alkali catalyst may be performed in order to increase the polymerization degree of polysiloxane.

Examples of the organic solvent used for the hydrolysis reaction of the organosilane compound and the condensation reaction of the silanol compound include: alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, 1-tert-butoxy-2-propanol, and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptanone; amides such as dimethylformamide and dimethylacetamide; acetic acid esters such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane, γ -butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may also be used. In terms of the transmittance, crack resistance, and the like of the cured film, diacetone alcohol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, γ -butyrolactone, and the like can be preferably used.

When a solvent is generated by the hydrolysis reaction, the hydrolysis may be carried out in the absence of a solvent. It is also preferable to adjust the concentration to an appropriate concentration for the resin composition by further adding a solvent after the reaction is completed. After the hydrolysis, an appropriate amount of the produced alcohol may be distilled off under heating and/or reduced pressure to remove it, and then a preferred solvent may be added.

The amount of the solvent used in the hydrolysis reaction is preferably 80 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the entire organosilane compound. By setting the amount of the solvent within the above range, the hydrolysis reaction can be more efficiently performed.

The water used in the hydrolysis reaction is preferably ion-exchanged water. The amount of water is preferably 1.0 to 4.0 mol based on 1 mol of silicon atom.

The content of the silicone resin having a radical polymerizable group (a) in the negative photosensitive resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more in solid content, from the viewpoint of increasing the crosslinking density of the cured film by the silanol condensation reaction to further increase the pencil hardness of the cured film and further suppress the generation of outgas during the processing of an electrode or a wiring. On the other hand, the content of the (a) silicone resin in the solid content is preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoint of further improving the chemical resistance of the cured film.

The negative photosensitive resin composition of the present invention contains (B) a monomer having a radical polymerizable group. The radical polymerizable group is preferably a group exemplified as the radical polymerizable group of the silicone resin (a), and more preferably a (meth) acryloyl group. From the viewpoint of further improving chemical resistance by further improving the crosslinking density and hydrophobicity of the cured film, it is preferable that: (B) the monomer having a radical polymerizable group includes (B1) a polyfunctional monomer and (B2) a monomer having an aromatic ring and/or an alicyclic carbon ring.

(B1) The polyfunctional monomer is a compound having two or more radical polymerizable groups, and preferably has two or more (meth) acryloyl groups. Examples of the compound having two (meth) acryloyl groups include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, tripropylene glycol di (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) acrylate, and the like. Examples of the compound having three or more (meth) acryloyl groups include: glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, pentapentaerythritol undec (meth) acrylate, pentapentaerythritol dodeca (meth) acrylate, and the like. Two or more of these may be contained. In addition, a compound having two or more radical polymerizable groups is classified as a (B1) polyfunctional monomer even when it contains an aromatic ring or an alicyclic carbon ring.

Examples of the monomer having an aromatic ring and/or an alicyclic carbon ring (B2) include: and acrylates such as 2,2- [ 9H-fluorene-9, 9-diylbis (1, 4-phenylene) dioxy ] diethanol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, and ethoxylated bisphenol A di (meth) acrylate. Two or more of these may be contained.

From the viewpoint of increasing the hydrophobicity of the cured film to further improve the chemical resistance, the content of the monomer having an aromatic ring and/or an alicyclic carbon ring (B2) in the negative photosensitive resin composition of the present invention is preferably 10 mass% or more, and more preferably 15 mass% or more in the solid content. On the other hand, the content of the monomer having an aromatic ring and/or an alicyclic carbon ring (B2) is preferably 35 mass% or less, more preferably 25 mass% or less in the solid content, from the viewpoint of improving solubility in a developer during pattern formation to further improve resolution.

From the viewpoint of increasing the crosslinking density and hydrophobicity of the cured film to further improve chemical resistance, the total content of the monomers having a radical polymerizable group (B) is preferably 20 mass% or more, and more preferably 30 mass% or more in the solid content.

The negative photosensitive resin composition contains (C) a photo radical polymerization initiator having an absorption peak in a region having a wavelength of 350nm to 370nm, and having an absorbance at a wavelength of 400nm of 10% or less of an absorbance at a wavelength of 365 nm. Examples of the photo-radical polymerization initiator (C) include TR-PBG-326, TR-PBG-331, TR-PBG-345 (trade name, manufactured by TRONLY), "イルガキュア (Irgacure)" (registered trademark) OXE03 (trade name, manufactured by BASF), and NCI-738 (trade name, manufactured by ADEKA). Two or more of these may be contained. Among these photopolymerization initiators, those containing two or more ketoxime ester groups in one molecule represented by the following general formula (1) as in TR-PBG-345 are particularly preferable. When two or more oxime ester groups are contained in one molecule, cleavage occurs by light irradiation, and the number of sites where radicals are generated is two or more, whereby the radical concentration can be further increased. This promotes the reaction of the radical polymerizable group, and therefore, the crosslinking density of the film by photocuring can be increased, and pencil hardness or chemical resistance can be further improved. Further, since the unreacted radical polymerizable group can be suppressed from remaining in the cured film, the weather resistance can be further improved, and the out-gassing during the processing of the electrode or the wiring can be reduced. Further, since the oxime ester group is a ketoxime ester group, high transparency can be maintained even after light irradiation.

In the general formula (1), m is 0 or 1. n is an integer of 2 or more. n is preferably 6 or less, and more preferably 4 or less or 3 or less. R¹A hydrogen atom, an alkyl group or a phenyl group, and from the viewpoint of reactivity, a methyl group which generates a methyl radical having a small steric hindrance and high reactivity is most preferable. R²Represents an alkyl group, a cycloalkyl group or a cycloalkylalkyl group, and preferably has 1 to 7 carbon atoms from the viewpoint of solubility in a solvent. In the general formula (1), R¹And R²There are a plurality of each. R¹May be the same or different. R²And may be the same or different. Ar represents an aromatic group. Ar may contain nitrogen, oxygen, sulfur, and a carbonyl group as disclosed in patent documents 3 and 4. Ar also includes the following structures, bonds between these structures, and groups in which other functional groups are bonded to these structures.

9H-fluorene, 9H-carbazole, dibenzo [ b, d ]]Furan, dibenzo [ b, d ]]Thiophene, 9H-fluoren-9-one, 9, 10-dihydroanthracene, 9H-thiaanthracene (thioxanthe), 9, 10-dihydroacridine, 9H-xantheneanthracene-9, 10H-one, 9H-thiaanthracene-9-one, 9H-xanthene-9-one, acridine-9, 10H-one, 10H-thiophene

Oxazines and thiophenes

Thia (phenoxathiin), 10H-phenothiazine, dibenzo-p-dioxazine

Dioxins (oxanthrenes), 5, 10-dihydrophenazines, thianthrenes (thianthrenes), anthracene-9, 10-diones.

1H-indene, 1H-indole, 1-benzofuran, 1-benzothiophene and 1H-indene-1-ketone.

The absorption peak wavelength and absorbance of the photo radical polymerization initiator can be determined by the following methods. First, the photo radical polymerization initiator was diluted to a concentration of 0.001% by weight using propylene glycol methyl ether acetate. The obtained diluted solution was measured for absorbance at a wavelength of 300 to 400nm using an ultraviolet-visible spectrophotometer UV-2600 (manufactured by Shimadzu corporation). From the absorbance spectrum thus obtained, the absorbance at the wavelength of the absorption peak, the absorbance at the wavelength of 365nm and the absorbance at the wavelength of 400nm were determined, respectively.

The content of the photo radical polymerization initiator (C) in the negative photosensitive resin composition of the present invention is preferably 0.1% by weight or more, more preferably 1% by weight or more, and even more preferably 4% by weight or more in the solid content, from the viewpoints of sufficiently performing radical curing, further improving chemical resistance, further improving pencil hardness, and further suppressing the generation of outgas during the processing of an electrode or a wiring. On the other hand, the content of the (C) photo radical polymerization initiator in the solid content is preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 6% by weight or less, from the viewpoints of suppressing the residue of the (C) photo radical polymerization initiator to further improve chemical resistance and suppressing the generation of excessive radicals to further improve resolution.

The negative photosensitive resin composition of the present invention may further contain a radical photopolymerization initiator other than the radical photopolymerization initiator represented by the general formula (1), and examples thereof include: an alkylbenzene-based photoradical polymerization initiator, an acylphosphine oxide-based photoradical polymerization initiator, an oxime ester-based photoradical polymerization initiator of one molecule, a benzophenone-based photoradical polymerization initiator, a thioxanthone-based photoradical polymerization initiator, an imidazole-based photoradical polymerization initiator, a benzothiazole-based photoradical polymerization initiator, a benzo

And inorganic photo radical polymerization initiators such as azole-based photo radical polymerization initiators, carbazole-based photo radical polymerization initiators, triazine-based photo radical polymerization initiators, benzoate-based photo radical polymerization initiators, phosphorus-based photo radical polymerization initiators, and titanates. Two or more of these may be contained.

The negative photosensitive resin composition of the present invention may contain an adhesion improving agent such as a silane coupling agent. Examples of the silane coupling agent include silane coupling agents having a functional group such as a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, and an amino group.

Specifically, it is preferable that: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, glycidyloxypropyltrimethoxysilane, glycidyloxy-ethylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, glycidyloxy-3-aminopropyltrimethoxysilane, glycidyloxy-dimethoxysilane, 3-glycidyloxy-dimethoxysilane, glycidyloxy-dimethoxysilane, and a mixture thereof, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, p-styryltrimethoxysilane, and the like.

The negative photosensitive resin composition of the present invention may contain various curing agents, and the curing of the negative photosensitive resin composition can be accelerated or facilitated. Examples of the curing agent include nitrogen-containing organic compounds, silicone resin curing agents, metal alkoxides, metal chelates, isocyanate compounds and polymers thereof, epoxy compounds and polymers thereof, methylolated melamine derivatives, and methylolated urea derivatives. Two or more of these may be contained. Among them, metal chelate compounds, methylolated melamine derivatives, methylolated urea derivatives and the like can be preferably used in terms of stability of the curing agent, processability of the obtained coating film and the like.

(A) Since the silicone resin is cured by acid acceleration, the negative photosensitive resin composition of the present invention may contain a curing catalyst such as a thermal acid generator. Examples of the thermal acid generator include aromatic diazonium salts, sulfonium salts, and diaryliodonium salts

Salts, triarylsulfonium salts, triarylselenium salts, and the like

Salt compounds, sulfonic acid esters, halogen compounds, and the like.

The negative photosensitive resin composition of the present invention may also contain a polymerization inhibitor. By containing the polymerization inhibitor, the storage stability and the resolution of the negative photosensitive resin composition can be further improved. Examples of the polymerization inhibitor include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2, 6-di (t-butyl) -p-cresol, phenothiazine, and 4-methoxyphenol.

The content of the polymerization inhibitor in the negative photosensitive resin composition of the present invention is preferably 0.01 mass% or more, and more preferably 0.05 mass% or more in the solid content. On the other hand, the content of the polymerization inhibitor in the solid content is preferably 5% by mass or less, more preferably 1% by mass or less, from the viewpoint of further improving the pencil hardness of the cured film.

The negative photosensitive resin composition of the present invention may contain an ultraviolet absorber as long as the effect of the present invention is not impaired. By containing the ultraviolet absorber, the resolution of the negative photosensitive resin composition and the weather resistance of the cured film can be further improved. As the ultraviolet absorber, a benzotriazole-based compound, a benzophenone-based compound, and a triazine-based compound can be preferably used in terms of transparency and non-coloring property.

Examples of the benzotriazole-based compound include 2- (2H-benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4, 6-tert-amylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3, 3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2- (2 '-hydroxy-5' -methacryloyloxyethylphenyl) -2H-benzotriazole, and RUVA-93 (product name, manufactured by tsukamur chemical corporation).

Examples of the benzophenone-based compound include 2-hydroxy-4-methoxybenzophenone.

Examples of the triazine compound include 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5- [ (hexyl) oxy ] -phenol, Tinuvin 477 (product name, manufactured by BASF), and the like.

The content of the ultraviolet absorber in the negative photosensitive resin composition of the present invention is preferably 10% by weight or less, and more preferably 5% by weight or less in the solid content, from the viewpoint of improving the adhesion to a base material such as glass which is a base of a cured film.

The negative photosensitive resin composition of the present invention may contain a solvent. By containing the solvent, each component can be uniformly dissolved. Examples of the solvent include aliphatic hydrocarbons, carboxylic acid esters, ketones, ethers, and alcohols. Two or more of these may be contained. From the viewpoint of uniformly dissolving each component and improving the transparency of the obtained coating film, a compound having an alcoholic hydroxyl group or a cyclic compound having a carbonyl group is preferable.

Examples of the compound having an alcoholic hydroxyl group include: acetol (acetol), 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-tert-butyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, and the like.

Specific examples of the cyclic compound having a carbonyl group include γ -butyrolactone, γ -valerolactone, δ -valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cycloheptanone, and the like. Among these, gamma-butyrolactone can be particularly preferably used.

Examples of the aliphatic hydrocarbon include xylene, ethylbenzene, and mineral spirits (solvent naphtha).

Examples of the carboxylic acid ester include: benzyl acetate, ethyl benzoate, γ -butyrolactone, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, 3-methoxy-3-methyl-butyl acetate, diethyl oxalate, ethyl acetoacetate, cyclohexyl acetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentyl propionate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, ethyl acetate, butyl acetate, isoamyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate, and the like.

Examples of the ketone include cyclopentanone and cyclohexanone.

Examples of ethers include: and aliphatic ethers such as propylene glycol derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol t-butyl ether, and dipropylene glycol monomethyl ether.

The negative photosensitive resin composition of the present invention may also contain a surfactant. By containing the surfactant, fluidity at the time of coating can be improved. Examples of the surfactant include: a fluorine-based surfactant; a silicone surfactant; a fluorine-containing thermally decomposable surfactant; a polyether-modified silicone surfactant; a polyalkylene oxide surfactant; poly (meth) acrylate-based surfactants; anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearylamine acetate and lauryl trimethyl ammonium chloride; lauryl dimethyl amine oxide, lauryl carboxy methyl hydroxy ethyl imidazole

Amphoteric surfactants such as betaine; nonionic such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearateSurfactants, and the like. Two or more of these may be contained.

Examples of commercially available fluorine-based surfactants include "メガファック (Megafac)" (registered trademark) F142D, "Megafac" (registered trademark) F172, "Megafac" (registered trademark) F173, "Megafac" (registered trademark) F183, "Megafac" (registered trademark) F445, "Megafac" (registered trademark) F470, "Megafac" (registered trademark) F475, "Megafac" (registered trademark) F477 (manufactured by DIC (stock Co., Ltd.), NBX-15, and FTX-218(ネオス (Neos) (Strand Co.)). Commercially available silicone surfactants include, for example, "BYK" (registered trademark) -333, BYK-301, BYK-331, BYK-345, BYK-307 (manufactured by ビックケミー & ジャパン (BYK-Chemie Japan)). Examples of commercially available fluorine-containing thermally decomposable surfactants include "メガファック (Megafac)" (registered trademark) DS-21 (manufactured by DIC (manufactured by Kagaku Co., Ltd.). Examples of commercially available products of the polyether-modified silicone surfactant include "BYK" (registered trademark) -345, BYK-346, BYK-347, BYK-348, BYK-349 (manufactured by ビックケミー · ジャパン, supra), "シルフェイス (SILFACE)" (registered trademark) SAG002, "シルフェイス (SILFACE)" (registered trademark) SAG005, "シルフェイス (registered trademark) SAG503A," シルフェイス (SILFACE) "(registered trademark) SAG008 (manufactured by rikk chemical industry (infra).

The negative photosensitive resin composition of the present invention may also contain a dispersant. Examples of the dispersant include polyacrylic dispersants, polycarboxylic dispersants, phosphoric acid dispersants, and silicone dispersants.

The negative photosensitive resin composition of the present invention may contain (a) a resin other than the silicone resin, and may contain, for example, a silicone resin having no radical polymerizable group.

Next, a method for producing the negative photosensitive resin composition of the present invention will be described. The method for producing the negative photosensitive resin composition of the present invention is generally a method in which (a) a silicone resin, (B) a monomer having a radical polymerizable group, (C) a photo radical polymerization initiator, and optionally other components are stirred and mixed.

By curing the negative photosensitive resin composition of the present invention, a cured film can be obtained. The method for producing a cured film preferably includes a step of applying the negative photosensitive resin composition of the present invention to a substrate, a step of exposing the substrate, and a step of curing the substrate at a temperature of 180 ℃.

Next, a method for producing a cured film from the negative photosensitive resin composition of the present invention will be described by way of example.

The negative photosensitive resin composition is coated on a substrate to obtain a coating film. Examples of the substrate include a glass substrate and a resin film. These substrates may have electrodes or wirings formed on the surfaces thereof, such as ITO or a metal containing copper or a copper alloy. Examples of the coating method include: spin coating using a spinner, spray coating, inkjet coating, die coating, roll coating, and the like. The film thickness of the coating film can be selected as appropriate depending on the coating method and the like. The thickness of the film after drying is generally set to 0.1 to 10 μm.

The obtained coating film was dried to obtain a dried film. Examples of the drying method include heat drying, air drying, drying under reduced pressure, and infrared irradiation. Examples of the heating and drying device include an oven and a hot plate. The drying temperature is preferably 50 ℃ to 150 ℃ and the drying time is preferably 1 minute to several hours.

The obtained dried film was irradiated (exposed) with actinic rays through a mask having a desired pattern to obtain an exposed film. Examples of the actinic ray to be irradiated include: ultraviolet rays, visible rays, electron beams, X-rays, and the like. The negative photosensitive resin composition of the present invention is preferably irradiated with i-rays (365nm) from a mercury lamp or light including i-rays.

The obtained exposed film is developed with an alkaline developer or the like to remove the unexposed portion, thereby obtaining a pattern. Examples of the alkaline compound used in the alkaline developer include: inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and ammonia water; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), and quaternary ammonium salts such as choline; alkanolamines such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and the like; and cyclic amines such as pyrrole, piperidine, 1, 8-diazabicyclo [5,4,0] -7-undecene, 1, 5-diazabicyclo [4,3,0] -5-nonane, and morpholine.

The concentration of the alkali compound in the alkali developer is generally 0.01 to 50% by weight, preferably 0.02 to 1% by weight. In addition, in order to improve the pattern shape after development, a surfactant such as a nonionic surfactant may be added in an amount of 0.1 to 5 wt%. Further, when the developer is an aqueous alkali solution, a water-soluble organic solvent such as ethanol, γ -butyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be added to the developer.

Examples of the developing method include: immersion, spraying, liquid coating, and the like. The obtained pattern may be washed and cleaned with pure water or the like.

The obtained pattern is subjected to heat treatment (post-baking) to cure the pattern, whereby a patterned cured film can be obtained. The heat treatment may be performed in any of air, a nitrogen atmosphere, and a vacuum state. The heating temperature is preferably 80 ℃ to 180 ℃, and the heating time is preferably 0.25 hour to 5 hours. The heating temperature may be changed continuously or in stages.

When it is not necessary to pattern the cured film, it is also preferable to expose the entire surface of the dried film to light and then perform heat treatment after photocuring the cured film. By performing photocuring before the heat treatment, rapid film shrinkage during the heat treatment can be suppressed, and the adhesion between the cured film and the substrate can be further improved.

Next, a touch panel of the present invention will be explained. The touch panel of the present invention includes a substrate, an electrode and/or a wiring containing copper, and a cured film obtained by curing the negative photosensitive resin composition of the present invention. For example, it is preferable that the substrate has X-axis electrode via wiring and Y-axis electrode via wiring, and a transparent insulating film including the cured film is provided at a crossing portion of the wirings.

Examples of the substrate include a glass substrate and a resin film.

Examples of the electrode and the wiring include a thin film or a laminated film of a metal such as copper, a copper alloy, gold, silver, aluminum, molybdenum, or a molybdenum-niobium alloy. The negative photosensitive resin composition of the present invention can be cured at a low temperature of 150 ℃. Therefore, it can be preferably used in combination with an electrode and/or a wiring containing copper. The electrodes and the wiring preferably have a pattern called a metal mesh in which conductor lines are arranged in a mesh shape.

Next, a method for manufacturing a touch panel according to the present invention will be described by taking a touch panel having the above-described structure as an example. First, an electrode thin film containing copper is formed on a substrate. Examples of the method for forming the electrode thin film include: physical methods such as vacuum evaporation, sputtering, ion plating, ion beam evaporation and the like; chemical vapor deposition, and the like. Next, a resist material is applied to the electrode thin film, patterning is performed by a photolithography technique, and then the electrode thin film is etched with a chemical using an etching solution, and the resist is peeled off using a peeling solution, thereby forming an X-axis electrode conductive wiring. Then, a cured film is formed at the intersection of the X-axis electrode via wiring and the Y-axis electrode via wiring to be formed later by the above method, thereby forming a transparent insulating film. Then, wirings connected to the IC driver and Y-axis electrode conductive wirings are formed in the same manner as the X-axis electrode conductive wirings. Finally, a transparent protective film is formed by forming a cured film by the above method on a portion other than a portion connected to the IC driver at the end of the substrate, thereby obtaining a touch panel.

The negative photosensitive resin composition of the present invention can be preferably used as various protective films such as a protective film for a touch panel and a protective film for a metal wiring, an insulating film for a touch panel, a glass-reinforced resin layer, an insulating film for a Thin Film Transistor (TFT), various insulating films such as an interlayer insulating film, various hard coat materials, a planarizing film for a TFT, an overcoat film for a color filter, a passivation film, an antireflection film, an optical filter, an optical spacer for a color filter, and a microlens, for example. Since it has negative photosensitivity, it is preferably used for a planarization film for TFT, an insulating film, an antireflection film, an overcoat for color filter, a column material, and the like of a liquid crystal or organic Electroluminescence (EL) display. Among these, even when cured at a low temperature of 180 ℃ or lower, the composition has high chemical resistance and can suppress the generation of outgas during the processing of electrodes and wirings, and therefore, the composition can be preferably used as an insulating film for touch panels, a protective film, and a glass-reinforced resin layer having electrodes and/or wirings containing copper.

Examples

The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

< evaluation method >

"Absorbance"

The photo radical polymerization initiator used in each of examples and comparative examples was diluted to a concentration of 0.001 mass% using propylene glycol methyl ether acetate (hereinafter referred to as "PGMEA"). The obtained diluted solution was measured for absorbance at a wavelength of 300 to 400nm using an ultraviolet-visible spectrophotometer UV-2600 (manufactured by Shimadzu corporation). From the absorbance spectra thus obtained, the absorption peak wavelength, the absorbance at a wavelength of 365nm and the absorbance at a wavelength of 400nm were determined, respectively.

Double bond equivalent "

The siloxane resins obtained in Synthesis examples 1 to 2 were subjected to an automatic titration apparatus using a potential difference (AT-510; manufactured by Kyoto electronics industries, Ltd.) and an ICl solution (ICl)₃＝7.9g、I₂Mixed solution of 8.9g and AcOH (acetic acid) ═ 1,000 mL) as an iodine supply source, an aqueous KI solution of 100g/L as an aqueous solution for trapping unreacted iodine, and Na of 0.1mol/L₂S2O₃The aqueous solution was used as a titration reagent in accordance with Japanese Industrial Standards (JIS) K0070: 1992 method for measuring iodine value by the Wells method (Wijs method) described in "test methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical" section 6 iodine value The value is obtained. From the measured iodine value (in gI/100g), the double bond equivalent (in g/mol) was calculated.

"acid value"

The acrylic resin obtained in synthesis example 4 and the cardol resin obtained in synthesis example 5 were measured for acid value (unit mgKOH/g) by a potentiometric titration method in accordance with JIS K2501(2003) using a potentiometric automatic titrator (AT-510; manufactured by kyoto electronics industries, inc.), 0.1mol/L NaOH/ethanol solution as a titration reagent, and xylene/N, N-Dimethylformamide (DMF) ═ 1/1 (mass ratio) as a titration solvent.

Chemical resistance "

A substrate was prepared by stacking molybdenum-niobium/copper/molybdenum-niobium in this order on an alkali-free glass substrate (glass thickness: 0.55 mm). Hereinafter, the metal laminated substrate will be referred to as "metal laminated substrate". The respective film thicknesses of the laminated molybdenum-niobium/copper/molybdenum-niobium were 20nm, 300nm, and 20 nm. The negative photosensitive resin compositions obtained in the examples and comparative examples were spin-coated on a metal laminated substrate using a spin coater (MS-a 150 manufactured by ミカサ (Mikasa)). The metal laminated substrate coated with the negative photosensitive resin composition was prebaked at 90 ℃ for 2 minutes using a hot plate (HHP-230 SQ manufactured by アズワン (ASONE) (strand)), and a prebaked film having a film thickness of 2.3 μm was produced. Using a mask aligner (LA-610 manufactured by triple permanent magnet machine Co., Ltd.), an ultra-high pressure mercury lamp as a light source, and an exposure amount of 100mJ/cm ²The obtained prebaked film was exposed (i-ray conversion). Thereafter, shower development was carried out for 60 seconds using an automatic developing apparatus (waterfall swamp made of (strand)) using a 0.5 wt% aqueous solution of potassium hydroxide (made of Mitsubishi ガス chemical (strand)), followed by rinsing with water for 30 seconds. Finally, DHS-42 (manufactured by Others oven (エスペック) (Espec) was cured in air at 130 ℃ for 30 minutes to prepare a cured film having a thickness of 2.0. mu.m. The obtained cured film was immersed in "hydrogen peroxide water (30%) (trade name)" as a metal etching solution (manufactured by fuji フイルム and opto pen) at 30 ℃ for 2 minutes, and then the presence or absence of discoloration of the metal under the cured film was visually observed. In the case where no discoloration was confirmed,further, additional immersion was carried out for 3 minutes (5 minutes in total), and the presence or absence of discoloration of the metal was visually observed. When no discoloration was observed, additional immersion was further performed for 2 minutes (total of 7 minutes), and the presence or absence of discoloration of the metal was visually observed. When no discoloration was observed, additional immersion was further performed for 3 minutes (total of 10 minutes), and the presence or absence of discoloration of the metal was visually observed. Chemical resistance was evaluated by the following criteria based on the relationship between immersion time and discoloration. In addition, when the black color derived from the molybdenum-niobium alloy layer before the test changed to red color derived from the copper layer due to corrosion of the molybdenum-niobium alloy after the test, it was judged to be discolored.

A: after 10 minutes of the test, no discoloration was observed on the metal under the cured film.

B: after 10 minutes of testing, the metal below the cured film discoloured.

C: after 7 minutes of testing, the metal below the cured film discoloured.

D: after 5 minutes of testing, the metal below the cured film discoloured.

E: after 2 minutes of testing, the metal below the cured film discoloured.

Pencil hardness "

On an alkali-free glass substrate (glass thickness 0.55mm), a cured film having a film thickness of 2.0 μm was produced using the negative photosensitive resin compositions obtained in the examples and comparative examples in the same manner as described in the above evaluation of "chemical resistance". The pencil hardness of the obtained cured film was measured in accordance with JIS "K5600-5-4 (formulated year, month, and day: 1999/04/20)".

Resolution "

The negative photosensitive resin compositions obtained in the examples and comparative examples were spin-coated on an alkali-free glass substrate (glass thickness 0.55mm) by using a spin coater (MS-a 150 manufactured by ミカサ (Mikasa) (thigh)). The alkali-free glass substrate coated with the negative photosensitive resin composition was prebaked at 90 ℃ for 2 minutes using a hot plate (HHP-230 SQ manufactured by アズワン (ASONE) (strand)), and a prebaked film having a film thickness of 2.3 μm was produced. The obtained prebaked film was exposed to light with a mask gap (mask gap) of 200 μm using a mask aligner (LA-610 manufactured by triple permanent motor fabrication (strand)) with an ultra-high pressure mercury lamp as a light source and 1-to-1 Line and Space (L & S) pattern masks having widths of 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, and 50 μm. Thereafter, shower development was carried out for 60 seconds using an automatic developing apparatus (waterfall swamp made of (strand)) using a 0.5 wt% aqueous solution of potassium hydroxide (made of Mitsubishi ガス chemical (strand)), followed by rinsing with water for 30 seconds. The minimum pattern size after development was measured and used as the resolution.

Weather resistance "

On an alkali-free glass substrate (glass thickness 0.55mm), a cured film having a film thickness of 2.0 μm was produced using the negative photosensitive resin compositions obtained in the examples and comparative examples in the same manner as described in the above evaluation of "chemical resistance". The obtained cured film was subjected to a weathering test (trade name: Q-Sun, manufactured by Q-Lab) at 0.55W/m²The test pieces were irradiated with simulated sunlight (340nm) at 63 ℃ for 300 hours, and Δ b was calculated from the values of b before and after the test using an ultraviolet-visible spectrophotometer UV-2600 (manufactured by shimadzu corporation), to evaluate weather resistance. The weather resistance was evaluated by the following criteria according to Δ b. A or more is defined as being acceptable.

A: Δ b is less than 1.

B: Δ b is 1 or more and less than 3.

C: Δ b is 3 or more.

External gas discharge "

On a silicon wafer substrate, a cured film having a film thickness of 2.0 μm was produced using the negative photosensitive resin composition obtained in each of examples and comparative examples in the same manner as described in the above evaluation of "chemical resistance". The cured film obtained was heated from room temperature to 400 ℃ at a temperature rise rate of 10 ℃/min in a gas atmosphere of helium of 50mL/min, and the amount of gas generated from the cured film was measured using a Mass Spectrometer (MS) apparatus (GC/MS QP2010(8), manufactured by shimadzu corporation), and based on the amount of gas generated, the gas was measured by (the weight of each gas generated/the weight of the sample) × 10 ⁶The concentration was calculated by the formula (2) and the off-gas was evaluated by the following criteria. B or more is defined as pass.

A: less than 250 wtppm.

B: 250wtppm or more and less than 500 wtppm.

C: 500wtppm or more and less than 750 wtppm.

D: 750wtppm or more and less than 1000 wtppm.

E: more than 1000 wtppm.

[ Synthesis example 1 ]

A500 mL three-necked flask was charged with 40.86g (0.30mol) of methyltrimethoxysilane, 59.49g (0.30mol) of phenyltrimethoxysilane, 20.83g (0.10mol) of tetraethoxysilane, 23.63g (0.10mol) of 3-glycidoxypropyltrimethoxysilane, 49.68g (0.20mol) of 3-methacryloxypropyltrimethoxysilane, and 220.99g of PGMEA. The flask was immersed in an oil bath at 40 ℃ and an aqueous nitric acid solution prepared by dissolving 3.1g (0.1 part by weight based on the charged monomer) of 1mol/L nitric acid in 55.8g water was added via a dropping funnel over 10 minutes while stirring the contents. After stirring at 40 ℃ for 1 hour, the oil bath temperature was set to 70 ℃ and stirred for 1 hour, taking 30 minutes to heat the oil bath to 115 ℃.1 hour after the start of the temperature rise, the internal temperature of the solution reached 100 ℃ and then the solution was heated and stirred at an internal temperature of 100 ℃ to 120 ℃ for 2 hours. 120g of methanol and water were distilled off as by-products in the reaction. To the obtained PGMEA solution of silicone resin, PGMEA was added so that the polymer concentration became 30 wt%, to obtain a silicone resin solution (PS-1). The weight average molecular weight (hereinafter, "Mw") of the obtained silicone resin was measured by GPC and found to be 2,000 (in terms of polystyrene). Furthermore, the double bond equivalent weight determined by the method described is 630 g/mol.

[ Synthesis example 2 ]

A500 mL three-necked flask was charged with 40.86g (0.30mol) of methyltrimethoxysilane, 59.49g (0.30mol) of phenyltrimethoxysilane, 20.83g (0.10mol) of tetraethoxysilane, 23.63g (0.10mol) of 3-glycidoxypropyltrimethoxysilane, 46.86g (0.20mol) of 3-acryloyloxypropyltrimethoxysilane, and 216.98g of PGMEA. The flask was immersed in an oil bath at 40 ℃ and an aqueous nitric acid solution prepared by dissolving 3.0g (0.1 part by weight based on the charged monomer) of 1mol/L nitric acid in 55.8g water was added via a dropping funnel over 10 minutes while stirring the contents. After stirring at 40 ℃ for 1 hour, the oil bath temperature was set to 70 ℃ and stirred for 1 hour, taking 30 minutes to heat the oil bath to 115 ℃.1 hour after the start of the temperature rise, the internal temperature of the solution reached 100 ℃ and then the solution was heated and stirred at an internal temperature of 100 ℃ to 120 ℃ for 2 hours. 120g of methanol and water were distilled off as by-products in the reaction. To the obtained PGMEA solution of silicone resin, PGMEA was added so that the polymer concentration became 30 wt%, to obtain a silicone resin solution (PS-2). The Mw of the obtained silicone resin was measured by GPC to obtain 2,000 (polystyrene equivalent). Furthermore, the double bond equivalent weight determined by the method described is 610 g/mol.

[ Synthesis example 3 ]

A500 mL three-necked flask was charged with 47.67g (0.35mol) of methyltrimethoxysilane, 69.41g (0.35mol) of phenyltrimethoxysilane, 31.25g (0.15mol) of tetraethoxysilane, 35.45g (0.15mol) of 3-glycidoxypropyltrimethoxysilane, and 204.83g of PGMEA. The flask was immersed in an oil bath at 40 ℃ and an aqueous nitric acid solution prepared by dissolving 2.9g (0.1 part by weight based on the charged monomer) of 1mol/L nitric acid in 56.7g water was added thereto via a dropping funnel over 10 minutes while stirring the contents. After stirring at 40 ℃ for 1 hour, the oil bath temperature was set to 70 ℃ and stirred for 1 hour, taking 30 minutes to heat the oil bath to 115 ℃.1 hour after the start of the temperature rise, the internal temperature of the solution reached 100 ℃ and then the solution was heated and stirred at an internal temperature of 100 ℃ to 120 ℃ for 2 hours. 120g of methanol and water were distilled off as by-products in the reaction. To the obtained PGMEA solution of silicone resin, PGMEA was added so that the polymer concentration became 30 wt%, to obtain a silicone resin solution (PS-3). The Mw of the obtained silicone resin was measured by GPC to obtain 2,000 (polystyrene equivalent).

[ Synthesis example 4 ]

A500-ml flask was charged with 3g of 2, 2' -azobis (isobutyronitrile) and 50g of PGMEA. Then, 30g of methacrylic acid, 35g of benzyl methacrylate, and tricyclo [5.2.1.0 ] were charged ^2,6]Decan-8-ylmethacrylate 35g, stirring tablet at room temperatureAfter the flask was purged with nitrogen, the mixture was heated and stirred at an internal temperature of 70 ℃ for 5 hours. Then, 15g of glycidyl methacrylate, 1g of dimethylbenzylamine, 0.2g of p-methoxyphenol, and 100g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90 ℃ for 4 hours. To the obtained PGMEA solution of acrylic resin, PGMEA was added so that the solid content concentration became 30 wt%, to obtain an acrylic resin solution (PA-1). The Mw of the obtained acrylic resin was measured by GPC, and the result was 10,000. Further, the acid value of the obtained acrylic resin was 118 mgKOH/g.

[ Synthesis example 5 ]

A500 ml flask was charged with 92.2g of 9, 9-bis (4-glycidyloxyphenyl) fluorene ("PG-100 (trade name)", manufactured by Osaka ガスケミカル Co., Ltd.), 14.4g of acrylic acid, 0.32g of tetrabutylammonium acetate, 0.26g of 2, 6-di-tert-butylcatechol, and 110g of PGMEA, and stirred at an internal temperature of 120 ℃ for 9 hours. Then, 34.8g of biphenyltetracarboxylic dianhydride and 50g of PGMEA were added thereto, and the mixture was stirred at 120 ℃ for 5 hours. To the obtained PGMEA solution of the cardo (カルド) -based resin, PGMEA was added so that the solid content concentration became 30 wt%, to obtain a cardo-based resin solution (PA-2). The Mw of the cardo-multisystem resin obtained was measured by GPC, and was 5,700. Further, the acid value of the obtained cardol resin was 100 mgKOH/g.

[ example 1 ]

0.71g of "TR-PBG-345 (trade name)" (manufactured by TRONLY) and 0.014g of 4-tert-butylcatechol (hereinafter, referred to as TBC) were dissolved in 62.12g of PGMEA under a yellow lamp, and 0.18g of "Tinuvin" (registered trade name) "manufactured by BASF, 0.30g (corresponding to concentration 300ppm) of a 10 mass% solution of PGMEA (manufactured by BASF)," BYK "(registered trade name) -333 (trade name)" ビックケミージャパン (BYK-Chemie Japan) (manufactured by BYK-Chemie Japan) (Strand Japan) as a silicone surfactant, 2.82g of dipentaerythritol hexaacrylate ("" カヤラッド (Kayarad) "(registered trade name)" DPHA (manufactured by Nippon Chemie Japan) (Strand Japan), and 50 mass% solution of 9, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene "" "OG オグソール (SOL)" (registered trade name) "02EA-50P" (registered trade name) "were added Manufactured by saka ガスケミカル (stock), 5.64g, 28.22g of the silicone resin solution (PS-1) obtained by synthesis example 1, and stirring. Then, the mixture was filtered through a 0.20 μm filter to prepare a negative photosensitive resin composition C-1 having a solid content concentration of 15% by weight. The cured film was produced for the obtained negative photosensitive resin composition C-1 in the same manner as in the evaluation method described in the above "chemical resistance" or "resolution", and each item was evaluated by the method.

[ example 2 ]

A negative photosensitive resin composition C-2 was prepared in the same manner as in example 1 except that pentaerythritol tetraacrylate ("" ライトアクリレート (Light Acrylate) (registered trademark) "PE-4A (trade name)" manufactured by Kyowa Kasei corporation) was added instead of ("" カヤラッド (Kayarad) "DPHA (trade name)", and the obtained negative photosensitive resin composition C-2 was used to evaluate the same as in example 1.

[ example 3 ]

0.71g of "TR-PBG-345 (trade name)" and 0.014g of TBC were dissolved in 64.79g of PGMEA under ｃA yellow lamp, and 0.30g of ｃA 10 wt% PGMEA solution of "BYK" -333 (trade name) "," カヤラッド (Kayarad) "DPHA (trade name)" 2.85g of dimethylol-tricyclodecane diacrylate ("" ライトアクリレート (Light Acrylate) "DCP-A (trade name)" manufactured by Kyoho chemical Co., Ltd.) 2.85g and 28.49g of the silicone resin solution (PS-1) obtained in Synthesis example 1 were added and stirred. Then, the mixture was filtered through a 0.20 μm filter to prepare a negative photosensitive resin composition C-3 having a solid content concentration of 15 mass%. The obtained negative photosensitive resin composition C-3 was evaluated in the same manner as in example 1.

[ example 4 ]

0.43g of "TR-PBG-345 (trade name)" and 0.014g of TBC were dissolved in 61.69g of PGMEA under a yellow lamp, and 0.30g of a 10 wt% PGMEA solution of "" Tinuvin "" 477 (trade name) "and" "BYK" -333 (trade name) "and 0.88 g of a" カヤラッド (Kayarad) "DPHA (trade name)" and "" オグソール (OGSOL) "EA-0250P (trade name)" were added to the solution, and 28.76g of the silicone resin solution (PS-1) obtained in Synthesis example 1 was stirred. Then, the mixture was filtered through a 0.20 μm filter to prepare a negative photosensitive resin composition C-4 having a solid content concentration of 15 mass%. The obtained negative photosensitive resin composition C-4 was evaluated in the same manner as in example 1.

[ example 5 ]

"TR-PBG-345 (trade name)" 1.10g and TBC 0.014g were dissolved in PGMEA 62.74g under a yellow lamp, and 0.30g of a PGMEA 10 mass% solution of "" Tinuvin "" 477 (trade name) "and" "BYK" -333 (trade name) "was added, and 27.44g of a" カヤラッド (Kayarad) "DPHA (trade name)" 2.74g and a "オグソール (OGSOL)" EA-0250P (trade name) "were added, and 27.44g of the silicone resin solution (PS-1) obtained in Synthesis example 1 was stirred. Then, the mixture was filtered through a 0.20 μm filter to prepare a negative photosensitive resin composition C-5 having a solid content of 15% by weight. The obtained negative photosensitive resin composition C-5 was evaluated in the same manner as in example 1.

[ example 6 ]

0.71g of "TR-PBG-345 (trade name)" and 0.014g of TBC were dissolved in 63.39g of PGMEA under a yellow lamp, and 0.30g of a 10 wt% PGMEA solution of "" Tinuvin "477 (trade name)" and "" BYK "-333 (trade name)" and 0.09 g of a "カヤラッド (Kayarad)" DPHA (trade name) "4.09 g and" "オグソール (OGSOL)" EA-0250P (trade name) "3.10 g of the silicone resin solution (PS-1)28.22g obtained in Synthesis example 1 were added and stirred. Then, the mixture was filtered through a 0.20 μm filter to prepare a negative photosensitive resin composition C-6 having a solid content of 15% by weight. The obtained negative photosensitive resin composition C-6 was evaluated in the same manner as in example 1.

[ example 7 ]

0.71g of "TR-PBG-345 (trade name)" and 0.014g of TBC were dissolved in 60.71g of PGMEA under a yellow lamp, and 0.30g of a 10 wt% PGMEA solution of "" Tinuvin "" 477 (trade name) "and" "BYK" -333 (trade name) "," "カヤラッド (Kayarad)" DPHA (trade name) "1.41 g and" "" オグソール (OGSOL) "EA-0250P (trade name)" 8.47g and 28.22g of the silicone resin solution (PS-1) obtained in Synthesis example 1 were added and stirred. Then, the mixture was filtered through a 0.20 μm filter to prepare a negative photosensitive resin composition C-7 having a solid content concentration of 15% by weight. The obtained negative photosensitive resin composition C-7 was evaluated in the same manner as in example 1.

[ example 8 ]

0.71g of "TR-PBG-345 (trade name)" and 0.014g of TBC were dissolved in 64.71g of PGMEA under a yellow lamp, and 0.30g of a 10 wt% PGMEA solution of "" Tinuvin "" 477 (trade name) "and" "BYK" -333 (trade name) "and 0.53 g of a" カヤラッド (Kayarad) "DPHA (trade name)" and "" オグソール (OGSOL) "EA-0250P (trade name)" were added to the solution, and 23.52g of the silicone resin solution (PS-1) obtained in Synthesis example 1 was stirred. Then, the mixture was filtered through a 0.20 μm filter to prepare a negative photosensitive resin composition C-8 having a solid content of 15% by weight. The obtained negative photosensitive resin composition C-8 was evaluated in the same manner as in example 1.

[ example 9 ]

0.71g of "TR-PBG-345 (trade name)" and 0.014g of TBC were dissolved in 59.53g of PGMEA under a yellow lamp, and 0.30g of a 10 wt% PGMEA solution of "" Tinuvin "477 (trade name)" and "" BYK "-333 (trade name)" was added, and 32.92g of a "カヤラッド (Kayarad)" DPHA (trade name) "2.11 g and" "オグソール (OGSOL)" EA-0250P (trade name) "were added, and the silicone resin solution (PS-1) obtained in Synthesis example 1 was stirred. Then, the mixture was filtered through a 0.20 μm filter to prepare a negative photosensitive resin composition C-9 having a solid content of 15% by weight. The obtained negative photosensitive resin composition C-9 was evaluated in the same manner as in example 1.

[ example 10 ]

A negative photosensitive resin composition C-10 having a solid content concentration of 15 wt% was prepared in the same manner as in example 1, except that the siloxane resin solution (PS-2) obtained in synthesis example 2 was added instead of the siloxane resin solution (PS-1) obtained in synthesis example 1. The obtained negative photosensitive resin composition C-10 was evaluated in the same manner as in example 1.

[ example 11 ]

A negative photosensitive resin composition C-11 having a solid content concentration of 15% by weight was prepared in the same manner as in example 3, except that the siloxane resin solution (PS-2) obtained in synthesis example 2 was added instead of the siloxane resin solution (PS-1) obtained in synthesis example 1. The obtained negative photosensitive resin composition C-11 was evaluated in the same manner as in example 1.

[ example 12 ]

A negative photosensitive resin composition C-12 having a solid content of 15% by weight was prepared in the same manner as in example 1, except that "TR-PBG-331 (trade name)" (manufactured by TRONLY) was added in place of "TR-PBG-345 (trade name)". The obtained negative photosensitive resin composition C-12 was evaluated in the same manner as in example 1.

[ example 13 ]

A negative photosensitive resin composition C-12 having a solid content of 15 wt% was prepared in the same manner as in example 1, except that "イルガキュア (Irgacure)" (registered trademark) OXE03 (trade name) "(manufactured by BASF) was added instead of" TR-PBG-345 (trade name) ". The obtained negative photosensitive resin composition C-12 was evaluated in the same manner as in example 1.

[ comparative example 1 ]

A negative photosensitive resin composition C-14 was prepared in the same manner as in example 1, except that "イルガキュア (Irgacure)" (registered trademark) OXE01 (trade name) "(manufactured by BASF) was added in place of" TR-PBG-345 (trade name) ". The obtained negative photosensitive resin composition C-14 was evaluated in the same manner as in example 1.

[ comparative example 2 ]

A negative photosensitive resin composition C-15 was prepared in the same manner as in example 1, except that "イルガキュア (Irgacure)" OXE02 (trade name) "(manufactured by BASF) was added in place of" TR-PBG-345 (trade name) ". The obtained negative photosensitive resin composition C-15 was evaluated in the same manner as in example 1.

[ comparative example 3 ]

A negative photosensitive resin composition C-16 having a solid content of 15 wt% was prepared in the same manner as in example 1, except that "アデカアークルズ (ADEKA ARKLS)" (registered trademark) NCI-730 (trade name) "(manufactured by ADEKA corporation)" was added instead of "TR-PBG-345 (trade name)". The obtained negative photosensitive resin composition C-16 was evaluated in the same manner as in example 1.

[ comparative example 4 ]

A negative photosensitive resin composition C-17 having a solid content of 15 wt% was prepared in the same manner as in example 1, except that "アデカアークルズ (ADEKA ARKLS)" (registered trademark) NCI-930 (trade name) "(manufactured by ADEKA corporation) was added instead of" TR-PBG-345 (trade name) ". The obtained negative photosensitive resin composition C-17 was evaluated in the same manner as in example 1.

[ comparative example 5 ]

A negative photosensitive resin composition C-18 having a solid content of 15 wt% was prepared in the same manner as in example 1, except that "アデカアークルズ (ADEKA ARKLS)" (registered trademark) N-1919 (trade name) "(manufactured by ADEKA corporation)" was added instead of "TR-PBG-345 (trade name)". The obtained negative photosensitive resin composition C-18 was evaluated in the same manner as in example 1.

[ comparative example 6 ]

A negative photosensitive resin composition C-19 was prepared in the same manner as in example 1, except that "アデカアークルズ (ADEKA ARKLS)" (registered trademark) NCI-831 (trade name) "(manufactured by ADEKA corporation)" was added instead of "TR-PBG-345 (trade name)". The obtained negative photosensitive resin composition C-19 was evaluated in the same manner as in example 1.

[ comparative example 7 ]

A negative photosensitive resin composition C-20 was prepared in the same manner as in example 1, except that "Omnirad" (registered trademark) 819 (trade name) "(manufactured by IGM) was added instead of" TR-PBG-345 (trade name) ". The obtained negative photosensitive resin composition C-20 was evaluated in the same manner as in example 1.

[ comparative example 8 ]

A negative photosensitive resin composition C-21 was prepared in the same manner as in example 1, except that the siloxane resin solution (PS-3) obtained in synthesis example 3 was added instead of the siloxane resin solution (PS-1) obtained in synthesis example 1. The obtained negative photosensitive resin composition C-21 was evaluated in the same manner as in example 1.

[ comparative example 9 ]

A negative photosensitive resin composition C-22 was prepared in the same manner as in example 1, except that the acrylic resin solution (PA-1) obtained in Synthesis example 4 was added instead of the silicone resin solution (PS-1) obtained in Synthesis example 1. The obtained negative photosensitive resin composition C-22 was evaluated in the same manner as in example 1.

[ comparative example 10 ]

0.75g of "イルガキュア (Irgacure)" OXE01 (trade name) "(manufactured by BASF) and 1.20g of" TBC "and a polyfunctional epoxy compound" テクモア (TECHMEE) "(registered trade name) VG-3101L (trade name)" (manufactured by プリンテック (printec) were dissolved in 69.03g of PGMEA under a yellow lamp, and 0.30g of a 10 wt% PGMEA solution of "BYK" -333 (trade name) "and" カヤラッド (Kayarad) "DPHA (trade name)" 4.49g and 1.79g of 4-hydroxybutylacrylate glycidyl ether ("4 HBAGE (trade name)" manufactured by Nippon chemical Synthesis (stock)) and 22.43g of the Carlo (カルド) type resin solution (PA-2) obtained by Synthesis example 5 were added and stirred. Then, the mixture was filtered through a 0.20 μm filter to prepare a negative photosensitive resin composition C-23 having a solid content of 15% by weight. The obtained negative photosensitive resin composition C-23 was evaluated in the same manner as in example 1.

The compositions (excluding TBC, surfactant and solvent) of the negative photosensitive resin compositions in the examples and comparative examples are shown in table 1, and the evaluation results are shown in table 2.

[ TABLE 2 ]

Therefore, the following steps are carried out: the negative photosensitive resin composition prepared in the examples had a high resolution, and even when cured at 130 ℃, it was able to form a cured film having high pencil hardness, excellent chemical resistance and weather resistance, and capable of suppressing the generation of outgas during electrode or wiring processing.

Industrial applicability

The negative photosensitive resin composition of the present invention has a high resolution, and can be cured at a low temperature of 150 ℃ or lower to obtain a cured film having high pencil hardness, excellent chemical resistance and weather resistance, and capable of suppressing the generation of an external gas during the processing of an electrode or a wiring.

Claims

1. A negative photosensitive resin composition comprising:

(A) a silicone resin having a radical polymerizable group;

(B) a monomer having a radical polymerizable group; and

(C) a photo radical polymerization initiator having a light absorption peak in a wavelength region of 350 to 370nm, wherein the absorbance at a wavelength of 400nm is 10% or less of the absorbance at a wavelength of 365 nm.

2. The negative-type photosensitive resin composition according to claim 1, wherein the photo radical polymerization initiator (C) is represented by the following general formula (1) and contains two or more ketoxime ester groups in one molecule,

in the general formula (1), m is 0 or 1; n is an integer of 2 or more; r¹Represents a hydrogen atom, an alkyl group or a phenyl group, R²Represents alkyl, cycloalkyl or cycloalkylalkyl; ar is an aromatic group.

3. The negative photosensitive resin composition according to claim 1 or 2, wherein the monomer (B) having a radical polymerizable group contains (B1) a polyfunctional monomer and (B2) a monomer having an aromatic ring and/or an alicyclic carbon ring.

4. The negative photosensitive resin composition according to claim 3, wherein the monomer (B2) having an aromatic ring and/or an alicyclic carbon ring is contained in an amount of 10 wt% or more in a solid content.

5. A method for producing a cured film, comprising: a step of applying the negative photosensitive resin composition according to any one of claims 1 to 4 to a substrate, a step of exposing the composition, and a step of curing the exposed composition at a temperature of 150 ℃ or lower.

6. A touch panel comprising a substrate, an electrode and/or wiring containing copper, and a cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 4.