TW202035471A - Negative photosensitive resin composition, production method of cured film using this, and touch panel - Google Patents

Abstract

A negative photosensitive resin composition is provided which has high resolution, has high pencil hardness even when cured at a low temperature of less than or equal to 150 DEG C, has excellent chemical resistance and weatherability, and can form a cured film that enables suppressing outgassing during electrode/wiring processing. This negative photosensitive resin composition contains (A) a siloxane resin which has a radical polymerizable group, (B) a monomer which has a radical polymerizable group, and (C) a photo radical polymerization initiator which has an absorption peak in the wavelength range 350-370 nm and in which the light absorption at wavelength 400 nm is 10% or less than the light absorption at wavelength 365 nm.

Description

Negative photosensitive resin composition, manufacturing method of cured film using the same, and touch panel

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 its curing Film manufacturing method and touch panel.

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, and a touch panel sensor that detects information input to a specific location. The touch panel method is roughly classified into a resistive film method, an electrostatic capacitance method, an optical method, an electromagnetic induction method, an ultrasonic method, etc. according to a method of detecting an input position. Among them, for reasons such as optical brightness, excellent design, simple structure, and excellent functions, electrostatic capacitive touch panels are widely used. The display portion of the touch panel uses a transparent electrode substrate with a transparent electrode formed on the substrate. As the transparent electrode, tin-doped indium oxide (Indium Tin Oxide (ITO)) has been used previously. In order to enable larger screens of touch panels or pen touch detection, further resistance reduction is required, but the high resistivity of ITO is a problem. Therefore, in recent years, there has been proposed a touch panel having electrodes called a so-called metal mesh in which conductor wires containing conductive metals such as copper or copper alloys are arranged in a mesh shape. However, copper is easily oxidized under high temperature conditions to form an oxide film, and the resistance value increases. Therefore, as a material for the insulating layer or protective layer of the touch panel, a material that can be cured at a low temperature below 150°C is required .

Therefore, as a photosensitive resin composition that has excellent pattern processability and provides sufficient chemical resistance and substrate adhesion even when cured at a low temperature of 150°C or less, for example, a photosensitive resin composition containing ethylenically unsaturated groups and carboxyl groups has been proposed. A photosensitive resin composition of a reactive resin, a specific epoxy compound, a specific polyfunctional epoxy compound, and a photopolymerization initiator (for example, refer to Patent Document 1).

Furthermore, as a raw material composition of an insulating film excellent in adhesion and chemical resistance, a silicone oligomer containing a crosslinkable functional group, a photopolymerization initiator, and aluminum and/or A composition for insulating materials (for example, refer to Patent Document 2) and the like of an adhesion promoter of a zirconium complex compound.

On the other hand, as photo radical polymerization initiators, benzoin-based, benzophenone-based, thioxanthone-based, acetophenone-based, and phosphine-based are known. Recently, oxime ester-based photoradical polymerization initiators have also been introduced (see Patent Document 3 and Patent Document 4). [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2017/110689 [Patent Document 2] International Publication No. 2014/185435 [Patent Document 3] Japanese Patent Special Form 2009-519991 Publication [Patent Document 4] Japanese Patent Special Form 2014-522394 Publication

[The problem to be solved by the invention] According to the technique described in Patent Document 1, even when cured at low temperature, a cured film with excellent chemical resistance and substrate adhesion can be obtained, but the pencil hardness and weather resistance of the cured film are insufficient. , The remaining unreacted radical polymerizable group causes the problem of gas emission during wiring processing. Furthermore, according to the technique described in Patent Document 2, a cured film excellent in pencil hardness can be obtained, but there is a problem of insufficient resolution. Furthermore, since the crosslinking density of the cured film is insufficient, there is a problem of insufficient chemical resistance, such as the penetration of the etching solution into the insulating film when the electrode is formed on the insulating film.

The present invention was created in view of the aforementioned problems of the prior art, and its object is to provide a negative photosensitive resin composition that has high resolution and can be cured even at a low temperature of 150°C or less It forms a cured film with high pencil hardness, excellent chemical resistance, and weather resistance, and can suppress the generation of outgassing during electrode or wiring processing. [Means to solve the problem]

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

First, it is the following negative photosensitive resin composition. A negative photosensitive resin composition containing: (A) a silicone resin having a radical polymerizable group; (B) a monomer having a radical polymerizable group; and (C) a photo-radical polymerization initiator , There is a light absorption peak in the wavelength range of 350 nm to 370 nm, and the absorbance at a wavelength of 400 nm is less than 10% of the absorbance at a wavelength of 365 nm.

Furthermore, based on the characteristics of the negative photosensitive resin composition disclosed in the present invention, the following inventions are also included. A method for producing a cured film, comprising: a step of coating the negative photosensitive resin composition of the present invention on a substrate, a step of exposing the composition, and the exposure of the composition at 150°C or less The step of hardening at a temperature. A touch panel has a substrate, electrodes 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 high resolution. According to the negative photosensitive resin composition of the present invention, even when cured at a low temperature of 150°C or less, high pencil hardness, chemical resistance, and weather resistance can be obtained Excellent cured film that can suppress the generation of outgassing during electrode or wiring processing.

Hereinafter, the present invention will be explained in more detail.

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 sometimes simply referred to as "(A) silicone resin"); B) A monomer having a radical polymerizable group; and (C) a photo-radical polymerization initiator (hereinafter sometimes simply referred to as "(C) a photo-radical polymerization initiator") at a wavelength of 350 nm to 370 There is an absorption peak in the nm region, and the absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a wavelength of 365 nm. By containing (A) silicone resin and (C) photoradical polymerization initiator, (A) silicone resin radical polymerizable group and (B) radical polymerizable group are carried out in the light irradiation part The radical polymerization of the monomers can make it possible to process negative patterns that do not dissolve the light-irradiated part. (A) Silicone resin includes a silicone skeleton with high heat resistance and weather resistance in the main chain, and has a radical polymerizable group. It also undergoes silanol condensation reaction even at 150°C or less, so it can improve The crosslink density of the hardened film can improve chemical resistance and weather resistance, and increase pencil hardness.

On the other hand, in the case of a conventionally known negative photosensitive resin composition, at a curing temperature of 150°C or lower, crosslinking cannot be sufficiently performed, and the chemical resistance of the film is reduced. In contrast, the present invention uses a general ultra-high pressure mercury lamp or light-emitting diode (Light Emitting Diode, LED) with a strong bright-line emission spectrum in the i-ray (wavelength 365 nm) as the light source. In the present invention, a photo-radical polymerization initiator having an absorption peak in the wavelength range of 350 nm to 370 nm is used, and the concentration of radicals generated in the light-irradiated part is increased to promote the reaction of radical polymerizable groups. Therefore, the crosslinking density of the photocurable film can be increased, so that the pencil hardness or chemical resistance can be improved. Furthermore, since the remaining of unreacted radical polymerizable groups can be suppressed, the weather resistance can be improved, and the outgassing during electrode or wiring processing can be reduced.

In addition, the photoradical polymerization initiator of the present invention whose absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a wavelength of 365 nm can suppress the absorption of long-wavelength light that is the main cause of the decrease in resolution, thereby improving the resolution. .

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

The negative photosensitive resin composition of the present invention contains (A) silicone resin. The silicone resin refers to a polymer containing a repeating unit having a silicone skeleton. The (A) silicone resin in the present invention has a radical polymerizable group, and is preferably a hydrolysis condensate of an organosilane compound having a radical polymerizable group. For the hydrolysis and condensation reaction, it is preferable that a hydrolyzable group is directly bonded to the silicon atom of the organosilane compound. As a hydrolyzable group, an alkoxy group, a carboxyl group, etc. can be illustrated.

From the viewpoint of further improving chemical resistance, the weight average molecular weight (Mw) of the (A) silicone resin is preferably 500 or more, and more preferably 1,000 or more. On the other hand, from the viewpoint of improving the solubility in the developer when forming a pattern, the Mw of the (A) silicone resin is preferably 10,000 or less, more preferably 5,000 or less. Here, the Mw of (A) silicone resin means a polystyrene conversion value measured by gel permeation chromatography (GPC).

Examples of radical polymerizable groups include vinyl groups, α-methylvinyl groups, allyl groups, styryl groups, and (meth)acryloyl groups. From the viewpoint of further enhancing the pencil hardness of the cured film and the sensitivity during pattern processing, a (meth)acrylic group is preferred.

From the viewpoint of improving the adhesion with the substrate as the base, the double bond equivalent of the (A) silicone resin is preferably 150 g/mol or more, and more preferably 200 g/mol or more. On the other hand, from the viewpoint of further increasing the cross-linking density of the cured film, further improving chemical resistance, and further improving pencil hardness, the double bond equivalent of (A) silicone resin is preferably 2,000 g/mol or less. More preferably, it is 1,500 g/mol or less. As described above, the (meth)acrylic group is preferred, so although two functional groups are not necessary, the total double bond equivalent of the acrylic group and the methacrylic group will further increase the crosslinking of the cured film Density, from the viewpoint of further improving chemical resistance and further improving pencil hardness, is preferably 2,000 g/mol or less, and more preferably 1,500 g/mol or less. Here, the double bond equivalent of the silicone resin can be calculated by measuring the iodine value.

Examples of the organosilane compound having a radical polymerizable group include: vinyl trimethoxysilane, vinyl triethoxy silane, vinyl tri(methoxyethoxy) silane, vinyl methyl dimethyl dimethyl Oxysilane, vinyl methyl diethoxy silane, vinyl methyl bis(methoxyethoxy) silane, allyl trimethoxy silane, allyl triethoxy silane, allyl tri (Methoxyethoxy)silane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethylbis(methoxyethoxy)silane, styrene Trimethoxysilane, styryltriethoxysilane, styryltris(methoxyethoxy)silane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane , Styrylmethylbis(methoxyethoxy)silane, 3-propenyloxypropyltrimethoxysilane, 3-propenyloxypropyltriethoxysilane, 3-propenyloxy Propyl tris (methoxyethoxy) silane, 3-methacryloxy propyl trimethoxy silane, 3-methacryloxy propyl triethoxy silane, 3-methacrylic acid Tris(methoxyethoxy) silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane , 3-propenyloxypropylmethyldimethoxysilane, 3-propenyloxypropylmethyldiethoxysilane, 3-methacryloxypropyl(methoxyethoxy) ) Silane, etc. Two or more of these can also be used. Among these, from the viewpoint of further improving the pencil hardness of the cured film or the sensitivity during pattern processing, 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxy are preferred. Methoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane.

(A) The silicone resin may be a hydrolysis condensate of the organosilane compound having a radical polymerizable group and other organosilane compounds. It is also preferable that the latter organosilane compound has a hydrolyzable group directly bonded to the silicon atom. As a hydrolyzable group, an alkoxy group, a carboxyl group, etc. can be illustrated.

As other organosilane compounds, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltris(methoxyethoxy)silane, methyltripropoxysilane, methyltriiso Propoxysilane, 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-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 2-cyanoethyltriethoxysilane , Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 1-glycidoxyethyltrimethoxysilane, 1-glycidoxyethyltriethoxysilane , 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 1-glycidoxypropyltrimethoxysilane, 1-glycidoxypropyltri Ethoxysilane, 2-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxysilane 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltriisopropoxysilane, 3-glycidoxypropyltributoxy Silane, 3-glycidoxypropyltris(methoxyethoxy)silane, 1-glycidoxybutyltrimethoxysilane, 1-glycidoxybutyltriethoxysilane, 2- Glycidoxybutyltrimethoxysilane, 2-glycidoxybutyltriethoxysilane, 3-glycidoxybutyltrimethoxysilane, 3-glycidoxybutyltriethoxy Silane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3, 4-Epoxycyclohexyl)methyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltripropoxysilane, 2-(3,4-epoxycyclohexyl) Ethyl tributoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl triethoxy silane, 2 -(3,4-Epoxycyclohexyl)ethyl triphenoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxy Cyclohexyl) propyltriethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxy Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-aminopropyl Methyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, glycidol Oxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, 1-glycidoxyethylmethyldimethoxysilane, 1-glycidoxyethylmethyl Diethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 2-glycidoxyethylmethyldiethoxysilane, 1-glycidoxypropylmethyldimethyldimethyl Oxysilane, 1-glycidoxypropylmethyldiethoxysilane, 2-glycidoxypropylmethyldimethoxysilane, 2-glycidoxypropylmethyldiethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropoxysilane, 2-glycidoxypropylmethyldibutoxysilane, 3-glycidoxypropylmethylbis(methoxyethoxy)silane, 3-glycidoxypropylethyldimethoxy Silane, 3-glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldi Methoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropane Trimethoxysilane, trifluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, perfluoropropyltriethoxysilane, perfluoropentyltrimethoxysilane, perfluoropentyltriethyl Tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, 17 Fluorodecyltrimethoxysilane, heptafluorodecyltriethoxysilane, bis(trifluoromethyl)dimethoxysilane, bis(trifluoropropyl)dimethoxysilane, bis(trifluoropropane) Base) diethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyl Diethoxysilane, heptafluorodecylmethyldimethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 3-triphenoxy Silylpropyl succinic anhydride, 3-trimethoxysilylpropyl cyclohexyl dicarboxylic acid anhydride, 3-trimethoxysilylpropyl phthalic anhydride, etc. Two or more of these can also be used. Among these, methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. are preferred.

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

Regarding the negative photosensitive resin composition of the present invention, since it is desired to further harden it after patterning, it is preferable that the (A) silicone resin is not completely condensed, and hydrolyzable groups or silanol groups remain. If these functional groups disappear, the high molecular weight and further crosslinking will make it difficult to dissolve or disperse in a solvent or to mix with other additives.

Various conditions of the hydrolysis reaction can 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 to add an acid catalyst and water to the organosilane compound in a solvent for 1 minute to 180 minutes, and then react at room temperature to 110°C for 1 minute to 180 minutes. By carrying out the hydrolysis reaction under such conditions, the rapid reaction can be suppressed. The reaction temperature is more preferably 30°C to 105°C.

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 addition amount of the acid catalyst is preferably 0.05 parts by weight to 5 parts by weight relative to 100 parts by weight of the total organosilane compounds used in the hydrolysis reaction. By making the amount of the acid catalyst within the above-mentioned range, the hydrolysis reaction can proceed more efficiently.

Preferably, the silanol group is generated by the hydrolysis reaction of the organosilane compound to obtain the silanol compound, and the reaction liquid is directly heated at 50° C. or higher and the boiling point of the solvent for 1 hour to 100 hours to perform the condensation reaction. Furthermore, in order to increase the degree of polymerization of polysiloxane, reheating or addition of an alkali catalyst may be carried out.

Examples of the organic solvent used in the hydrolysis reaction of the organosilane compound and the condensation reaction of the silanol compound include: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tertiary butanol, and pentanol , 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, 1-tert-butoxy-2-propanol, Alcohols such as diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethyl Glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethyl ether and other ethers; methyl ethyl ketone, acetone, methyl propyl ketone, methyl butyl ketone, methyl Ketones such as isobutyl ketone, diisobutyl ketone, cyclopentanone and 2-heptanone; amides such as dimethylformamide and dimethylacetamide; ethyl acetate, propyl acetate, acetic acid Butyl ester, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Ester, methyl lactate, ethyl lactate, butyl lactate and other acetates; toluene, xylene, hexane, cyclohexane and other aromatic or aliphatic hydrocarbons, γ-butyrolactone, N-methyl-2- Pyrolidone, dimethyl sulfoxide, etc. Two or more of these can also be used. In terms of the permeability and crack resistance of the cured film, diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol mono-tertiary butyl ether, Propylene glycol monopropyl ether, propylene glycol monobutyl ether, γ-butyrolactone, etc.

When a solvent is generated by the hydrolysis reaction, the hydrolysis may be performed without a solvent. It is also preferable to further add a solvent after the completion of the reaction to adjust the concentration to an appropriate concentration as the resin composition. Furthermore, according to the purpose, after hydrolysis, it is heated and/or reduced pressure to distill off and remove an appropriate amount of produced alcohol, etc., and then a preferable solvent is 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 all organosilane compounds. By setting the amount of the solvent within the above range, the hydrolysis reaction can be performed more efficiently.

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

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 to further suppress the generation of outgassing during electrode or wiring processing, the negative photosensitive resin of the present invention The content of the (A) silicone resin having a radical polymerizable group in the composition is preferably 30% by mass or more in the solid content, more preferably 40% by mass or more, and still more preferably 50% by mass or more. On the other hand, from the viewpoint of further improving the chemical resistance of the cured film, the content of the (A) silicone resin in the solid content is preferably 70% by mass or less, and more preferably 60% by mass or less.

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

(B1) The polyfunctional monomer refers to a compound having two or more radically polymerizable groups, and preferably has two or more (meth)acrylic groups. As the compound having two (meth)acrylic groups, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(methyl) ) 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-decane Diol di(meth)acrylate and the like. As the compound having three or more (meth)acrylic groups, for example, glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, Base) acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa (Meth)acrylate, pentaerythritol nona(meth)acrylate, pentaerythritol deca(meth)acrylate, pentaerythritol undeca(meth)acrylate, pentaerythritol dodeca(meth)acrylate, etc. Two or more of these may be contained. Moreover, if it is a compound which has two or more radically polymerizable groups, even when it contains an aromatic ring or an alicyclic hydrocarbon ring, it is classified as a (B1) polyfunctional monomer.

(B2) The monomer having an aromatic ring and/or an alicyclic hydrocarbon ring includes, for example, 2,2-[9H-fluorene-9,9-diylbis(1,4-phenylene)bis Acrylates such as oxy]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 improving the hydrophobicity of the cured film to further improve the chemical resistance, the negative photosensitive resin composition of the present invention (B2) is a monomer having an aromatic ring and/or an alicyclic hydrocarbon ring The content is preferably 10% by mass or more in the solid content, and more preferably 15% by mass or more. On the other hand, from the viewpoint of improving the solubility in the developer during pattern formation to further improve the resolution, (B2) the content of the monomer having an aromatic ring and/or alicyclic hydrocarbon ring in the solid content It is preferably 35% by mass or less, and more preferably 25% by mass or less.

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

The negative photosensitive resin composition of the present invention contains (C) a photo-radical polymerization product that has an absorption peak in the wavelength range of 350 nm to 370 nm, and the absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a wavelength of 365 nm. Beginner. Examples of such (C) photoradical polymerization initiators include TR-PBG-326, TR-PBG-331, TR-PBG-345 (trade names, all manufactured by TRONLY), "Yanjia "Irgacure" (registered trademark) OXE03 (trade name, manufactured by BASF), NCI-738 (trade name, manufactured by ADEKA (stock)), etc. Two or more of these may be contained. Among these photopolymerization initiators, those having two or more ketoxime ester groups in one molecule represented by the following general formula (1) like TR-PBG-345 are particularly preferred. By containing two or more oxime ester groups in one molecule, it is cleaved by light irradiation, and there are two or more sites where free radicals are generated. Therefore, the concentration of free radicals can be further increased. This promotes the reaction of the radical polymerizable group, so the crosslink density of the photocurable film can be increased, and the pencil hardness or chemical resistance can be further improved. In addition, since it is possible to prevent unreacted radical polymerizable groups from remaining in the cured film, it is possible to further improve weather resistance and reduce outgassing during electrode or wiring processing. Furthermore, since the oxime ester group is a ketoxime ester group, high transparency can be maintained even after light irradiation.

[化1]

In the general formula (1), m is 0 or 1. n is an integer of 2 or more. n is preferably 6 or less, more preferably 4 or less or 3 or less. R ¹ represents a hydrogen atom, an alkyl group, or a phenyl group, and from the viewpoint of reactivity, a methyl group that generates a methyl radical with little steric hindrance and high reactivity is most preferable. R ² represents an alkyl group, a cycloalkyl group, or a cycloalkylalkyl group, and the carbon number is preferably 1-7 from the viewpoint of solubility in a solvent. In the general formula (1), there are a plurality of R ¹ and R ² respectively. R ¹ may be the same or different. R ² may be the same or different. Ar represents an aromatic group. As disclosed in Patent Document 3 and Patent Document 4, Ar may contain nitrogen, oxygen, sulfur, and carbonyl groups. In addition, Ar also includes the following structures and bonding products of these structures, and those obtained by bonding other functional groups to these structures. 9H-fluorene, 9H-carbazole, dibenzo[b,d]furan, dibenzo[b,d]thiophene, 9H-fluorene-9-one, 9,10-dihydroanthracene, 9H-thioxanthene (Thioxanthene), 9,10-dihydroacridine, 9H-xanthene-9,10H-one, 9H-thioxanthene-9-one, 9H-xanthene-9-one, acridine-9,10H -Ketones, 10H-phenoxazine, phenoxathiin, 10H-phenoxathiin, dibenzo-p-dioxin (oxanthrene), 5,10-dihydrophenazine, thianthrene, anthracene- 9,10-dione. 1H-indene, 1H-indole, 1-benzofuran, 1-benzothiophene, 1H-indene-1-one.

The absorption peak wavelength and absorbance of the photoradical polymerization initiator can be obtained by the following method. First, the photoradical polymerization initiator was diluted to a concentration of 0.001% by weight using propylene glycol methyl ether acetate. With respect to the obtained dilution, the absorbance at a wavelength of 300 nm to 400 nm was measured using an ultraviolet-visible spectrophotometer UV-2600 (manufactured by Shimadzu Corporation). From the obtained absorbance spectrum, the absorption peak wavelength, the absorbance at a wavelength of 365 nm, and the absorbance at a wavelength of 400 nm can be obtained respectively.

From the viewpoint of sufficient free radical curing, further improvement of chemical resistance, further improvement of pencil hardness, and further suppression of the generation of outgassing during electrode or wiring processing, the negative photosensitive resin composition of the present invention (C) The content of the photoradical polymerization initiator is preferably 0.1% by weight or more in the solid content, more preferably 1% by weight or more, and still more preferably 4% by weight or more. On the other hand, from the viewpoint of suppressing the residue of (C) photo-radical polymerization initiator to further improve chemical resistance, and suppressing the generation of excess free radicals to further improve the resolution, (C) photo-radical polymerization The content of the starting agent is preferably 20% by weight or less in the solid content, more preferably 10% by weight or less, and still more preferably 6% by weight or less.

The negative photosensitive resin composition of the present invention may further contain a photoradical polymerization initiator other than the photoradical polymerization initiator represented by the general formula (1), for example, alkyl phenone-based optical free radicals -Based polymerization initiator, phosphine oxide-based photo-radical polymerization initiator, one molecule of oxime ester-based photo-radical polymerization initiator, benzophenone-based photo-radical polymerization initiator, thioxanthene Ketone-based photo-radical polymerization initiator, imidazole-based photo-radical polymerization initiator, benzothiazole-based photo-radical polymerization initiator, benzoxazole-based photo-radical polymerization initiator, carbazole-based photo-free Base polymerization initiator, triazine-based photo-radical polymerization initiator, benzoate-based photo-radical polymerization initiator, phosphor-based photo-radical polymerization initiator, titanate and other inorganic photo-radical polymerization Starter etc. Two or more of these may be contained.

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

Specifically, preferred are: 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-propenyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1 ,3-Dimethyl-butylene) propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, p-benzene Vinyl trimethoxysilane, etc.

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

(A) The silicone resin is cured by acid. Therefore, 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 various onium salt-based compounds such as aromatic diazonium salts, sulfonium salts, diaryl iodonium salts, triaryl sulfonium salts, and triaryl selenium salts, sulfonate esters, and halogen compounds.

The negative photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, the storage stability and resolution of the negative photosensitive resin composition can be further improved. As the polymerization inhibitor, for example, phenol, catechol, resorcinol, hydroquinone, 4-tertiary butyl catechol, 2,6-bis(tertiary butyl)-p-methyl Phenol, phenothiazine, 4-methoxyphenol, etc.

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

As long as the effect of the present invention is not impaired, the negative photosensitive resin composition of the present invention may contain an ultraviolet absorber. 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, in terms of transparency and non-coloring properties, benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds can be preferably used.

Examples of benzotriazole-based compounds include 2-(2H benzotriazol-2-yl)phenol and 2-(2H-benzotriazol-2-yl)-4,6-tert-pentylphenol , 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'-methacryloxyethylphenyl)-2H-benzotriazole, RUVA-93 (trade name, Otsuka Chemical ( Stock) manufacturing) etc.

As a benzophenone compound, 2-hydroxy-4-methoxybenzophenone etc. are mentioned, for example.

Examples of triazine-based compounds include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, Dinubin ( Tinuvin) 477 (trade name, manufactured by BASF), etc.

From the viewpoint of improving the adhesiveness with substrates such as glass serving as the base of the cured film, the content of the ultraviolet absorber in the negative photosensitive resin composition of the present invention is preferably 10% by weight or less in the solid content , More preferably 5% by weight or less.

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

Examples of compounds having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, and 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-tertiary butyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol, etc.

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

Examples of aliphatic hydrocarbons include xylene, ethylbenzene, solvent naphtha and the like.

Examples of carboxylic acid esters include benzyl acetate, ethyl benzoate, γ-butyrolactone, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxy Ethyl acetate, 3-methoxy-3-methyl-butyl acetate, diethyl oxalate, ethyl acetate, cyclohexyl acetate, 3-methoxy-butyl acetic acid Ester, methyl acetylacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isoamyl propionate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetic acid Ester, ethyl acetate, butyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, etc.

Examples of ketones include cyclopentanone and cyclohexanone.

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

The negative photosensitive resin composition of the present invention may contain a surfactant. By containing a surfactant, the fluidity during coating can be improved. Examples of surfactants include: fluorine-based surfactants; silicone-based surfactants; fluorine-containing thermally decomposable surfactants; polyether-modified silicone-based surfactants; polyalkylene oxide-based surfactants Agent; Poly(meth)acrylate-based surfactants; Anionic surfactants such as ammonium lauryl sulfate, polyoxyethylene alkyl ether sulfate triethanolamine, etc.; Stearyl amine acetate, lauryl trimethyl ammonium chloride Cationic surfactants such as lauryl dimethyl amine oxide, lauryl carboxymethyl hydroxyethyl imidazolium betaine and other amphoteric surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan Nonionic surfactants such as alcohol monostearate, etc. Two or more of these may be contained.

Commercial products of fluorine-based surfactants include, for example, "Megafac" (registered trademark) F142D, "Megafac" (registered trademark) F172, "Megafac" (registered trademark) F173, and "Megafac" (registered trademark). Trademarks) F183, "Megafac" (registered trademark) F445, "Megafac" (registered trademark) F470, "Megafac" (registered trademark) F475, "Megafac" (registered trademark) F477 (above, manufactured by DIC (stock)), NBX -15, FTX-218 (manufactured by Neos (stock)), etc. Examples of commercially available silicone-based surfactants include "BYK" (registered trademark)-333, BYK-301, BYK-331, BYK-345, BYK-307 (BYK-Chemie Japan ) (Stock) Manufacturing) and so on. Examples of commercially available products of the fluorine-containing thermally decomposable surfactant include "Megafac" (registered trademark) DS-21 (manufactured by DIC Corporation). As commercial products of polyether-modified silicone surfactants, for example, "BYK" (registered trademark)-345, BYK-346, BYK-347, BYK-348, BYK-349 (above, Japan completed Made by Gram Chemical (Stock), "SILFACE" (registered trademark) SAG002, "SILFACE" (registered trademark) SAG005, "SILFACE" (registered trademark) ) SAG503A, "SILFACE" (registered trademark) SAG008 (above, manufactured by Nissin Chemical Industry Co., Ltd.), etc.

The negative photosensitive resin composition of the present invention may contain a dispersant. As the dispersant, for example, a polyacrylic dispersant, a polycarboxylic acid dispersant, a phosphoric acid dispersant, a silicone dispersant, etc. can be cited.

The negative photosensitive resin composition of the present invention may contain (A) resins other than the silicone resin, for example, it may contain a silicone resin that does not have a radical polymerizable group.

Next, the manufacturing method of the negative photosensitive resin composition of this invention is demonstrated. As a method for producing the negative photosensitive resin composition of the present invention, (A) a silicone resin, (B) a monomer having a radical polymerizable group, (C) a photo-radical polymerization initiator, and The method of stirring and mixing other ingredients as needed.

By curing the negative photosensitive resin composition of the present invention, a cured film can be obtained. As a method for producing a cured film, a method having a step of applying the negative photosensitive resin composition of the present invention on a substrate, a step of exposing, and a step of curing at a temperature of 180° C. or less is preferable.

Next, a method of manufacturing a cured film from the negative photosensitive resin composition of the present invention will be described with an example.

The negative photosensitive resin composition is applied on the substrate to obtain a coating film. As a substrate, a glass base material, a resin film, etc. are mentioned. These base materials may form electrodes or wirings containing ITO or metals such as copper and copper alloys on the surface. As a coating method, spin coating using a spinner, spray coating, inkjet coating, die coating, roll coating, etc. are mentioned, for example. The thickness of the coating film can be appropriately selected according to the coating method and the like. Generally, the film thickness after drying is set to 0.1 μm to 10 μm.

The obtained coating film is dried to obtain a dry 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°C to 150°C, and the drying time is preferably 1 minute to several hours.

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

The obtained exposed film is developed by using an alkaline developer or the like to remove the unexposed part to obtain 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; ethylamine , N-propylamine and other primary amines; diethylamine, di-n-propylamine and other secondary amines; triethylamine, methyldiethylamine and other tertiary amines; tetramethylammonium hydroxide ( TMAH) and other tetraalkylammonium hydroxides, choline and other quaternary ammonium salts; triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and other alcohol amines; pyrrole, piperidine , 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane, morpholine and other cyclic amines Organic bases such as class.

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

Examples of the development method include a dipping method, a spray method, and a liquid coating method. The obtained pattern can also be rinsed and cleaned with pure water or the like.

By performing heat treatment (post-baking) on the obtained pattern to harden the pattern, a patterned cured film can be obtained. The heat treatment can be performed in any of air, nitrogen atmosphere, and vacuum state. The heating temperature is preferably 80°C to 180°C, and the heating time is preferably 0.25 hours to 5 hours. The heating temperature can be changed continuously or in stages.

When it is not necessary to pattern the cured film, it is also preferable to perform heat treatment after exposing the entire surface of the dried film to light-harden 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, the touch panel of the present invention will be described. The touch panel of this invention has a base material, the electrode and/or wiring containing copper, and the cured film which hardened the negative photosensitive resin composition of this invention. For example, it is preferable to have X-axis electrode conduction wiring and Y-axis electrode conduction wiring on the base material, and to have a transparent insulating film including the cured film at the intersection of these wirings.

As a substrate, a glass substrate, a resin film, etc. are mentioned.

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

Next, the manufacturing method of the touch panel of the present invention will be described by taking the touch panel having the above-mentioned configuration as an example. First, an electrode film containing copper is formed on the substrate. Examples of the method for forming the electrode thin film include physical methods such as vacuum vapor deposition, sputtering, ion plating, and ion beam vapor deposition; chemical vapor deposition methods. Secondly, the resist material is coated on the electrode film, after patterning by photolithography technology, the electrode film is chemically etched with the etching solution, and the resist is peeled off with the stripping solution to form the X-axis electrode conduction Wiring. Then, a cured film is formed by the above-mentioned method at the intersection of the X-axis electrode conduction wiring and the Y-axis electrode conduction wiring formed later, thereby forming a transparent insulating film. Thereafter, the connection wiring to the IC driver and the Y-axis electrode conduction wiring are formed in the same manner as the X-axis electrode conduction wiring. Finally, a cured film is formed by the above method at the part other than the connection part of the IC driver at the end of the base material, thereby forming a transparent protective film, thereby obtaining a touch panel.

The negative photosensitive resin composition of the present invention can be suitably used as various protective films such as protective films for touch panels or protective films for metal wiring, insulating films for touch panels, glass reinforced resin layers, thin film transistors ( Thin Film Transistor, TFT) insulating film, interlayer insulating film and other insulating films, various hard coating materials, flattening film for TFT, overcoat for color filter, passivation film, anti-reflection film, optical filter , Optical spacers and micro lenses for color filters. Due to its negative photosensitivity, it can be preferably used for liquid crystal or organic electroluminescence (Electroluminescence, EL) TFT flattening film, insulating film, anti-reflection film, color filter overcoat, pillar材 etc. Among these, even if hardened at a low temperature of 180°C or less, the chemical resistance is high, and the generation of outgassing during electrode or wiring processing can be suppressed. Therefore, it can be preferably used as a copper-containing electrode and / Or wiring touch panel insulating film, protective film, glass reinforced resin layer. Example

Hereinafter, the present invention will be explained in more detail using examples and comparative examples, but the present invention is not limited to the following examples.

＜Evaluation method＞ "Absorbance" The photoradical polymerization initiator used in each Example and Comparative Example was diluted to a concentration of 0.001% by mass using propylene glycol methyl ether acetate (hereinafter, "PGMEA"). With respect to the obtained dilution, the absorbance at a wavelength of 300 nm to 400 nm was measured using an ultraviolet-visible spectrophotometer UV-2600 (manufactured by Shimadzu Corporation). From the obtained absorbance spectrum, the absorption peak wavelength, the absorbance at a wavelength of 365 nm, and the absorbance at a wavelength of 400 nm were obtained.

"Double bond equivalent" For the silicone resin obtained in Synthesis Example 1 to Synthesis Example 2, a potentiometric automatic titration device (AT-510; manufactured by Kyoto Electronics Co., Ltd.) was used, and ICl solution (ICl ₃ =7.9) g, I ₂ =8.9 g, AcOH (acetic acid) = 1,000 mL mixed solution) as the iodine supply source, use 100 g/L KI aqueous solution as the unreacted iodine capture aqueous solution, use 0.1 mol/L Na ₂ S2O ₃ The aqueous solution is used as a titration reagent in accordance with the Japanese Industrial Standards (JIS) K0070: 1992 "Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value, and unsaponifiable matter of chemical products." The method described in "Iodine Value" measures the iodine value by the Wijs method. From the measured iodine value (unit: gI/100 g), calculate the double bond equivalent (unit: g/mol).

"Acid value" For the acrylic resin obtained by Synthesis Example 4 and the Cardo-based resin obtained by Synthesis Example 5, a potential difference automatic titration device (AT-510; manufactured by Kyoto Electronics Co., Ltd.) was used, and 0.1 mol/L NaOH/ethanol solution is used as titration reagent, xylene/N,N-dimethylformamide (DMF)=1/1 (mass ratio) is used as titration solvent, based on "JIS K2501 (2003)" by potentiometric titration method The acid value (unit: mgKOH/g) is measured and determined.

"Chemical resistance" Molybdenum-niobium/copper/molybdenum-niobium was laminated on an alkali-free glass substrate (glass thickness 0.55 mm) to prepare the substrate. Hereinafter, it is referred to as "metal laminated substrate". The respective film thicknesses of the laminated molybdenum-niobium/copper/molybdenum-niobium are 20 nm, 300 nm, and 20 nm. On the metal laminated substrate, the negative photosensitive resin composition obtained in each of the Examples and Comparative Examples was spin-coated using a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.). Using a hot plate (HHP-230SQ manufactured by ASONE Co., Ltd.), the metal laminate substrate coated with the negative photosensitive resin composition was pre-baked at 90°C for 2 minutes to produce a film thickness of 2.3 μm Of pre-baked film. Use a mask aligner (LA-610 manufactured by Sanyong Electric Co., Ltd.), use an ultra-high pressure mercury lamp as a light source, and use an exposure amount of 100 mJ/cm ² (i-ray conversion) to compare the obtained The pre-baked film is exposed. After that, using an automatic developing device (AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), a 0.5% by weight aqueous potassium hydroxide solution (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used for spray development for 60 seconds, followed by water. Rinse for 30 seconds. Finally, using an oven (DHS-42 manufactured by Espec Co., Ltd.), it was cured in air at 130°C for 30 minutes to produce a cured film with a thickness of 2.0 μm. The cured film obtained was immersed in "hydrogen peroxide water (30%) (trade name)" (manufactured by Fujifilm Wako Pure Chemical (Stock)) as a metal etching solution at 30°C After 2 minutes, the metal under the cured film was visually observed for discoloration. If discoloration is not confirmed, additional immersion is performed for 3 minutes (5 minutes in total), and the metal is visually observed for discoloration. When discoloration is not confirmed, additional immersion is performed for 2 minutes (7 minutes in total), and the metal is visually observed for discoloration. When discoloration is not confirmed, additional immersion is performed for 3 minutes (10 minutes in total), and the metal is visually observed for discoloration. Based on the relationship between immersion time and discoloration, chemical resistance was evaluated based on the following criteria. In addition, when the black color derived from the molybdenum-niobium alloy layer before the test changes to the red color derived from the copper layer due to corrosion of the molybdenum-niobium alloy after the test, it is judged as discoloration. A: After 10 minutes of the test, no discoloration was observed on the metal under the cured film. B: After 10 minutes of the test, the metal under the cured film was discolored. C: 7 minutes after the test, the metal under the cured film was discolored. D: After 5 minutes of the test, the metal under the cured film was discolored. E: Two minutes after the test, the metal under the cured film was discolored.

"Pencil hardness" On an alkali-free glass substrate (glass thickness 0.55 mm), the negative photosensitive resin composition obtained in each of the Examples and Comparative Examples was used in the same manner as the method described in the evaluation of the "chemical resistance" A hardened film with a thickness of 2.0 μm is produced by the method. With respect to the obtained cured film, the pencil hardness was measured in accordance with JIS "K5600-5-4 (established date = 1999/04/20)".

"Resolution" On an alkali-free glass substrate (glass thickness 0.55 mm), a spin coater (MS-A150 manufactured by Mikasa Co., Ltd.) was used to spin coat the negative photosensitive resin obtained in the respective examples and comparative examples. Things. The alkali-free glass substrate coated with the negative photosensitive resin composition was prebaked at 90°C for 2 minutes using a hot plate (HHP-230SQ manufactured by ASONE Co., Ltd.) to produce a film thickness of 2.3 μm pre-baked film. Use a mask alignment machine (LA-610 manufactured by Sanyo Electric Co., Ltd.), use ultra-high pressure mercury lamps as the light source, and use widths of 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, and 50 μm 1 to 1 line and space (L&S) pattern mask, with a mask gap of 200 μm, expose the obtained prebaked film. After that, using an automatic developing device (AD-1200 manufactured by Takizawa Sangyo Co., Ltd.), a 0.5% by weight aqueous potassium hydroxide solution (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used for spray development for 60 seconds, followed by water. Rinse 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 0.55 mm), the negative photosensitive resin composition obtained in each of the Examples and Comparative Examples was used to compare with the evaluation of the "chemical resistance" A cured film with a thickness of 2.0 μm was produced in the same manner as described in the method. The cured film obtained was irradiated with simulated sunlight for 300 hours under the conditions of 0.55 W/m ² (340 nm) and 63°C using a weather resistance tester (trade name "Q-Sun", manufactured by Q-Lab). Δb* was calculated from the value of b* before and after the test using an ultraviolet-visible spectrophotometer UV-2600 (manufactured by Shimadzu Corporation), and the weather resistance was evaluated. Based on Δb*, the weather resistance was evaluated based on the following criteria. Set A or higher to pass. A: Δb* is less than 1. B: Δb* is 1 or more and less than 3. C: Δb* is 3 or more.

"External gas" On the silicon wafer substrate, the negative photosensitive resin composition obtained in each of the Examples and Comparative Examples was used in the same way as the method described in the "Chemical Resistance" evaluation. Method to produce a hardened film with a thickness of 2.0 μm. The obtained cured film was heated from room temperature to 400°C at a heating rate of 10°C/min under a helium gas environment of 50 mL/min, while using mass spectrometry (MS) equipment (GC/MS QP2010 (8) ), manufactured by Shimadzu Corporation) Measure the amount of gas generated from the cured film. Based on the amount of gas generated, calculate the concentration according to the formula of (generation weight of each gas/sample weight)×10 ⁶ and evaluate it based on the following criteria Exhaust gas. Set B or higher to pass. A: Less than 250 wtppm. B: 250 wtppm or more and less than 500 wtppm. C: 500 wtppm or more and less than 750 wtppm. D: 750 wtppm or more and less than 1000 wtppm. E: 1000 wtppm or more.

[Synthesis Example 1] A 500 mL three-necked flask was filled with 40.86 g (0.30 mol) of methyltrimethoxysilane, 59.49 g (0.30 mol) of phenyltrimethoxysilane, 20.83 g (0.10 mol) of tetraethoxysilane, and 3-shrinkage. Glyceroxypropyl trimethoxysilane 23.63 g (0.10 mol), 3-methacryloxypropyl trimethoxysilane 49.68 g (0.20 mol), PGMEA 220.99 g. The flask was immersed in an oil bath at 40°C, and while stirring the contents, it was added using a dropping funnel for 10 minutes. 3.1 g of 1 mol/L nitric acid (0.1 parts by weight relative to the charged monomer) was dissolved in 55.8 g of water The resulting aqueous nitric acid solution. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C and stirred for 1 hour, and then the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and then the solution was heated and stirred at an internal temperature of 100°C to 120°C for 2 hours. A total of 120 g of methanol and water as by-products in the reaction were distilled out. To the obtained PGMEA solution of the silicone resin, PGMEA was added so that the polymer concentration became 30% by weight to obtain a silicone resin solution (PS-1). In addition, the weight average molecular weight (hereinafter, "Mw") of the obtained silicone resin was measured by GPC, and the result was 2,000 (in terms of polystyrene). Moreover, the double bond equivalent measured by the method was 630 g/mol.

[Synthesis example 2] A 500 mL three-necked flask was filled with 40.86 g (0.30 mol) of methyltrimethoxysilane, 59.49 g (0.30 mol) of phenyltrimethoxysilane, 20.83 g (0.10 mol) of tetraethoxysilane, and 3-shrinkage. Glyceroxypropyl trimethoxysilane 23.63 g (0.10 mol), 3-propenoxypropyl trimethoxysilane 46.86 g (0.20 mol), PGMEA 216.98 g. The flask was immersed in an oil bath at 40°C, and while stirring the contents, it was added using a dropping funnel for 10 minutes. 1 mol/L of nitric acid 3.0 g (0.1 parts by weight relative to the charged monomer) was dissolved in 55.8 g of water The resulting aqueous nitric acid solution. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C and stirred for 1 hour, and then the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and then the solution was heated and stirred at an internal temperature of 100°C to 120°C for 2 hours. A total of 120 g of methanol and water as by-products in the reaction were distilled out. To the obtained PGMEA solution of silicone resin, PGMEA was added so that the polymer concentration became 30% by weight to obtain a silicone resin solution (PS-2). In addition, the Mw of the obtained silicone resin was measured by GPC, and the result was 2,000 (in terms of polystyrene). Moreover, the double bond equivalent measured by the method was 610 g/mol.

[Synthesis Example 3] A 500 mL three-necked flask was filled with 47.67 g (0.35 mol) of methyltrimethoxysilane, 69.41 g (0.35 mol) of phenyltrimethoxysilane, 31.25 g (0.15 mol) of tetraethoxysilane, 3-shrinkage Glyceryloxypropyl trimethoxysilane 35.45 g (0.15 mol), PGMEA 204.83 g. The flask was immersed in an oil bath at 40°C, and while stirring the contents, the dropping funnel was used to add 2.9 g of 1 mol/L nitric acid (0.1 parts by weight relative to the charged monomer) in 56.7 g of water. The resulting aqueous nitric acid solution. After stirring at 40°C for 1 hour, the oil bath temperature was set to 70°C and stirred for 1 hour, and then the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and then heating and stirring were performed at an internal temperature of 100°C to 120°C for 2 hours. A total of 120 g of methanol and water as by-products in the reaction were distilled out. To the obtained PGMEA solution of the silicone resin, PGMEA was added so that the polymer concentration became 30% by weight to obtain a silicone resin solution (PS-3). In addition, the Mw of the obtained silicone resin was measured by GPC, and the result was 2,000 (in terms of polystyrene).

[Synthesis Example 4] A 500 ml flask was charged with 3 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA. Then, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate were charged, and stirred at room temperature for a while, After the inside of the flask was replaced with nitrogen, it was heated and stirred at an internal temperature of 70°C for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90°C for 4 hours. In the PGMEA solution of the obtained acrylic resin, PGMEA was added so that the solid content concentration might become 30 weight%, and the acrylic resin solution (PA-1) was obtained. The Mw of the obtained acrylic resin was measured by GPC and the result was 10,000. Also, the acid value of the obtained acrylic resin was 118 mgKOH/g.

[Synthesis Example 5] A 500 ml flask was charged with 9,9-bis(4-glycidyloxyphenyl)fluorene ("PG-100 (trade name)" manufactured by Osaka Gas Chemical Co., Ltd.) 92.2 g, acrylic acid 14.4 g, and acetic acid 0.32 g of tetrabutylammonium, 0.26 g of 2,6-di-tert-butylcatechol, and 110 g of PGMEA were stirred at an internal temperature of 120°C for 9 hours. Next, 34.8 g of biphenyltetracarboxylic dianhydride and 50 g of PGMEA were added, and the mixture was further stirred at 120°C for 5 hours. To the obtained PGMEA solution of cardo-based resin, PGMEA was added so that the solid content concentration became 30% by weight to obtain a cardo-based resin solution (PA-2). The Mw of the obtained cardo-based resin was measured by GPC and the result was 5,700. Furthermore, the acid value of the obtained cardo-based resin was 100 mgKOH/g.

[Example 1] Under a yellow light, dissolve 0.71 g of "TR-PBG-345 (trade name)" (manufactured by TRONLY) and 0.014 g of 4-tert-butylcatechol (hereinafter referred to as TBC) in 62.12 g of PGMEA Add "Tinuvin" (registered trademark) 477 (trade name)" (made by BASF) 0.18 g, "BYK" (registered trademark) -333 as a silicone-based surfactant (Trade name)" (manufactured by BYK-Chemie Japan (Stock)) PGMEA 10% by mass solution 0.30 g (equivalent to a concentration of 300 ppm), dipentaerythritol hexaacrylate (""Kayarade ( Kayarad) "(registered trademark) DPHA (trade name)" manufactured by Nippon Kayaku Co., Ltd.) 2.82 g, PGMEA of 9,9-bis[4-(2-propenyloxyethoxy)phenyl]fluorene 50% by mass solution ""OGSOL" (registered trademark) EA-0250P (trade name)" (manufactured by Osaka Gas Chemical Co., Ltd.) 5.64 g, silicone resin obtained by Synthesis Example 1 The solution (PS-1) was 28.22 g and stirred. Then, it filtered with a 0.20 μm filter to prepare a negative photosensitive resin composition C-1 with a solid content concentration of 15% by weight. With respect to the obtained negative photosensitive resin composition C-1, a cured film was produced in the same manner as the evaluation method described in the "chemical resistance" or "resolution", and each item was evaluated by the method.

[Example 2] Except for adding pentaerythritol tetraacrylate ("Light Acrylate (registered trademark)" PE-4A (trade name)" manufactured by Kyoeisha Chemical Co., Ltd.) instead of ("Kayarad" Except for "DPHA (trade name)", the negative photosensitive resin composition C-2 was prepared in the same manner as in Example 1. The obtained negative photosensitive resin composition C-2 was used to evaluate in the same manner as in Example 1.

[Example 3] Dissolve 0.71 g of "TR-PBG-345 (trade name)" and 0.014 g of TBC in 64.79 g of PGMEA under a yellow light, add 0.30 g of PGMEA 10% by weight solution of "BYK"-333 (trade name), "Kayarad" DPHA (trade name)" 2.85 g, dimethylol-tricyclodecane diacrylate ("Light Acrylate (Light Acrylate)" DCP-A (trade name)" Kyoeisha Chemical Co., Ltd.) 2.85 g, and 28.49 g of the silicone resin solution (PS-1) obtained in Synthesis Example 1 were stirred. Then, it filtered with a 0.20 μm filter to prepare a negative photosensitive resin composition C-3 with a solid content concentration of 15% by mass. Using the obtained negative photosensitive resin composition C-3, evaluation was performed in the same manner as in Example 1.

[Example 4] Dissolve 0.43 g of "TR-PBG-345 (trade name)" and 0.014 g of TBC in PGMEA 61.69 g under a yellow light, and add 0.18 g of "Tinuvin" 477 (trade name)" and "" BYK "-333 (trade name)" PGMEA 10% by weight solution 0.30 g, "Kayarad" DPHA (trade name)" 2.88 g, "OGSOL (OGSOL)" EA-0250P (Trade name)" 5.75 g, 28.76 g of the silicone resin solution (PS-1) obtained in Synthesis Example 1, and stirred. Then, it filtered with a 0.20 μm filter to prepare a negative photosensitive resin composition C-4 with a solid content concentration of 15% by mass. Using the obtained negative photosensitive resin composition C-4, evaluation was performed in the same manner as in Example 1.

[Example 5] Dissolve "TR-PBG-345 (trade name)" 1.10 g and TBC 0.014 g in PGMEA 62.74 g under a yellow light, and add "" Dinubin (Tinuvin)" 477 (trade name)" 0.17 g, "" BYK "-333 (trade name)" PGMEA 10 mass% solution 0.30 g, "Kayarad (Kayarad)" DPHA (trade name)" 2.74 g, ""OGSOL (OGSOL)" EA-0250P (Trade name)" 5.49 g, 27.44 g of the silicone resin solution (PS-1) obtained in Synthesis Example 1, and stirred. Then, it filtered with a 0.20 μm filter to prepare a negative photosensitive resin composition C-5 having a solid content concentration of 15% by weight. Using the obtained negative photosensitive resin composition C-5, evaluation was performed in the same manner as in Example 1.

[Example 6] Under a yellow light, dissolve 0.71 g of "TR-PBG-345 (trade name)" and 0.014 g of TBC in PGMEA 63.39 g, and add 0.18 g of "Tinuvin" 477 (trade name) and "" BYK "-333 (trade name)" PGMEA 10 wt% solution 0.30 g, "Kayarad (Kayarad)" DPHA (trade name)" 4.09 g, ""OGSOL (OGSOL)" EA-0250P (Trade name)" 3.10 g, 28.22 g of the silicone resin solution (PS-1) obtained in Synthesis Example 1, and stirred. Then, it filtered with a 0.20 μm filter to prepare a negative photosensitive resin composition C-6 with a solid content concentration of 15% by weight. Using the obtained negative photosensitive resin composition C-6, evaluation was performed in the same manner as in Example 1.

[Example 7] Dissolve 0.71 g of "TR-PBG-345 (trade name)" and 0.014 g of TBC in PGMEA 60.71 g under a yellow light, and add 0.18 g of "Tinuvin" 477 (trade name), "" BYK "-333 (trade name)" PGMEA 10% by weight solution 0.30 g, "Kayarad (Kayarad)" DPHA (trade name)" 1.41 g, ""OGSOL (OGSOL)" EA-0250P (Trade name)" 8.47 g, 28.22 g of the silicone resin solution (PS-1) obtained in Synthesis Example 1, and stirred. Then, it filtered with a 0.20 μm filter to prepare a negative photosensitive resin composition C-7 with a solid content concentration of 15% by weight. Using the obtained negative photosensitive resin composition C-7, evaluation was performed in the same manner as in Example 1.

[Example 8] Dissolve 0.71 g of "TR-PBG-345 (trade name)" and 0.014 g of TBC in 64.71 g of PGMEA under a yellow light, and add 0.18 g of "Tinuvin" 477 (trade name)" and "" BYK "-333 (trade name)" PGMEA 10% by weight solution 0.30 g, "Kayarad (Kayarad)" DPHA (trade name)" 3.53 g, ""OGSOL (OGSOL)" EA-0250P (Trade name)" 7.05 g, 23.52 g of the silicone resin solution (PS-1) obtained in Synthesis Example 1, and stirred. Then, it filtered with a 0.20 μm filter to prepare a negative photosensitive resin composition C-8 with a solid content concentration of 15% by weight. Using the obtained negative photosensitive resin composition C-8, evaluation was performed in the same manner as in Example 1.

[Example 9] Dissolve 0.71 g of "TR-PBG-345 (trade name)" and 0.014 g of TBC in PGMEA 59.53 g under a yellow light, and add 0.18 g of "Tinuvin" 477 (trade name) and "" BYK "-333 (trade name)" PGMEA 10% by weight solution 0.30 g, "Kayarad (Kayarad)" DPHA (trade name)" 2.11 g, ""OGSOL (OGSOL)" EA-0250P (Trade name)" 4.23 g, 32.92 g of the silicone resin solution (PS-1) obtained in Synthesis Example 1, and stirred. Then, filtration was performed with a 0.20 μm filter, and a negative photosensitive resin composition C-9 having a solid content concentration of 15% by weight was prepared. Using the obtained negative photosensitive resin composition C-9, evaluation was performed in the same manner as in Example 1.

[Example 10] The solid content was prepared in the same manner as in Example 1, except that the silicone resin solution (PS-2) obtained in Synthesis Example 2 was added instead of the silicone resin solution (PS-1) obtained in Synthesis Example 1 Negative photosensitive resin composition C-10 with a concentration of 15% by weight. Using the obtained negative photosensitive resin composition C-10, evaluation was performed in the same manner as in Example 1.

[Example 11] The solid content was prepared in the same manner as in Example 3 except that the silicone resin solution (PS-2) obtained in Synthesis Example 2 was added instead of the silicone resin solution (PS-1) obtained in Synthesis Example 1 Negative photosensitive resin composition C-11 with a concentration of 15% by weight. Using the obtained negative photosensitive resin composition C-11, evaluation was performed in the same manner as in Example 1.

[Example 12] Except that "TR-PBG-331 (trade name)" (manufactured by TRONLY) was added instead of "TR-PBG-345 (trade name)", a negative type with a solid content concentration of 15% by weight was prepared in the same manner as in Example 1. Photosensitive resin composition C-12. Using the obtained negative photosensitive resin composition C-12, evaluation was performed in the same manner as in Example 1.

[Example 13] Except for adding "Irgacure" (registered trademark) OXE03 (trade name)" (made by BASF) instead of "TR-PBG-345 (trade name)", the solid was prepared in the same manner as in Example 1. Negative photosensitive resin composition C-12 with a component concentration of 15% by weight. Using the obtained negative photosensitive resin composition C-12, evaluation was performed in the same manner as in Example 1.

[Comparative Example 1] Except that "Irgacure" (registered trademark) OXE01 (trade name)" (manufactured by BASF) was added instead of "TR-PBG-345 (trade name)", the negative was prepared in the same manner as in Example 1. Type photosensitive resin composition C-14. Using the obtained negative photosensitive resin composition C-14, evaluation was performed in the same manner as in Example 1.

[Comparative Example 2] Except for adding "Irgacure" OXE02 (trade name)" (manufactured by BASF) instead of "TR-PBG-345 (trade name)", a negative photosensitive resin was prepared in the same manner as in Example 1 Composition C-15. Using the obtained negative photosensitive resin composition C-15, evaluation was performed in the same manner as in Example 1.

[Comparative Example 3] In addition to adding ""ADEKA ARKLS" (registered trademark) NCI-730 (trade name)" (made by ADEKA (stock)) instead of "TR-PBG-345 (trade name) Except for ", in the same manner as in Example 1, a negative photosensitive resin composition C-16 with a solid content concentration of 15% by weight was prepared. Using the obtained negative photosensitive resin composition C-16, evaluation was performed in the same manner as in Example 1.

[Comparative Example 4] In addition to adding ""ADEKA ARKLS" (registered trademark) NCI-930 (trade name)" (made by ADEKA (stock)) instead of "TR-PBG-345 (trade name) Except for ", in the same manner as in Example 1, a negative photosensitive resin composition C-17 with a solid content concentration of 15% by weight was prepared. Using the obtained negative photosensitive resin composition C-17, evaluation was performed in the same manner as in Example 1.

[Comparative Example 5] In addition to adding ""ADEKA ARKLS" (registered trademark) N-1919 (trade name)" (made by ADEKA (stock)) instead of "TR-PBG-345 (trade name) Except for ", in the same manner as in Example 1, a negative photosensitive resin composition C-18 having a solid content concentration of 15% by weight was prepared. Using the obtained negative photosensitive resin composition C-18, evaluation was performed in the same manner as in Example 1.

[Comparative Example 6] In addition to adding ""ADEKA ARKLS" (registered trademark) NCI-831 (trade name)" (made by ADEKA (stock)) instead of "TR-PBG-345 (trade name) Except for ", the negative photosensitive resin composition C-19 was prepared in the same manner as in Example 1. Using the obtained negative photosensitive resin composition C-19, evaluation was performed in the same manner as in Example 1.

[Comparative Example 7] Except for adding ""Omnirad" (registered trademark) 819 (trade name)" (manufactured by IGM) instead of "TR-PBG-345 (trade name)", the negative sensitivity was prepared in the same manner as in Example 1. Resin composition C-20. Using the obtained negative photosensitive resin composition C-20, evaluation was performed in the same manner as in Example 1.

[Comparative Example 8] Except that the silicone resin solution (PS-3) obtained in Synthesis Example 3 was added instead of the silicone resin solution (PS-1) obtained in Synthesis Example 1, a negative type was prepared in the same manner as in Example 1. Photosensitive resin composition C-21. Using the obtained negative photosensitive resin composition C-21, evaluation was performed in the same manner as in Example 1.

[Comparative Example 9] 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, negative sensitivity was prepared in the same manner as in Example 1. Resin composition C-22. Using the obtained negative photosensitive resin composition C-22, evaluation was performed in the same manner as in Example 1.

[Comparative Example 10] Under a yellow light, make "Irgacure" OXE01 (trade name)" (made by BASF) 0.75 g, TBC 0.015 g, and multifunctional epoxy compound "TECHMORE" (registered Trademark) VG-3101L (trade name)" (produced by Printec (Stock)) 1.20 g dissolved in PGMEA 69.03 g, added with "BYK"-333 (trade name)" PGMEA 10% by weight solution 0.30 g, "Kayarad" DPHA (trade name)" 4.49 g, 4-hydroxybutyl acrylate glycidyl ether ("4HBAGE (trade name)" manufactured by Nippon Kasei Co., Ltd.) 1.79 g, 22.43 g of the cardo-based resin solution (PA-2) obtained in Synthesis Example 5 was stirred. Then, it filtered with a 0.20 μm filter to prepare a negative photosensitive resin composition C-23 with a solid content concentration of 15% by weight. Using the obtained negative photosensitive resin composition C-23, evaluation was performed in the same manner as in Example 1.

The composition (excluding TBC, surfactant, and solvent) of the negative photosensitive resin composition in each Example and Comparative Example is shown in Table 1, and the evaluation results are shown in Table 2.

[Table 1A] [Table 1A] Negative photosensitive resin composition (A) Silicone resin (mass%) (B) Monomers with radical polymerizable groups (mass%) (C) Light radical polymerization initiator (mass%) UV absorber (mass%) Other (mass%) The absorption peak of the photopolymerization initiator in the wavelength range of 300 nm to 400 nm Photopolymerization initiator absorbance at 400 nm / absorbance at 365 nm (B1) Multifunctional monomer (B2) Monomers with aromatic ring and/or alicyclic hydrocarbon ring Example 1 C-1 Silicone resin PS-1 (56) DPHA (19) EA-0250P (19) TR-PBG-345 (5) Tinuvin 477 (1) ― 363 nm 4.0% Example 2 C-2 Silicone resin PS-1 (56) PE-4A (19) EA-0250P (19) TR-PBG-345 (5) Tinuvin 477 (1) ― 363 nm 4.0% Example 3 C-3 Silicone resin PS-1 (57) DPHA (19) DCP-A (19) TR-PBG-345 (5) ― ― 363 nm 4.0% Example 4 C-4 Silicone resin PS-1 (58) DPHA (19) EA-0250P (19) TR-PBG-345 (3) Tinuvin 477 (1) ― 363 nm 4.0% Example 5 C-5 Silicone resin PS-1 (56) DPHA (18) EA-0250P (18) TR-PBG-345 (7) Tinuvin 477 (1) ― 363 nm 4.0% Example 6 C-6 Silicone resin PS-1 (57) DPHA (27) EA-0250P (10) TR-PBG-345 (5) Tinuvin 477 (1) ― 363 nm 4.0% Example 7 C-7 Silicone resin PS-1 (57) DPHA (9) EA-0250P (28) TR-PBG-345 (5) Tinuvin 477 (1) ― 363 nm 4.0% Example 8 C-8 Silicone resin PS-1 (47) DPHA (24) EA-0250P (24) TR-PBG-345 (5) Tinuvin 477 (1) ― 363 nm 4.0% Example 9 C-9 Silicone resin PS-1 (66) DPHA (14) EA-0250P (14) TR-PBG-345 (5) Tinuvin 477 (1) ― 363 nm 4.0% Example 10 C-10 Silicone resin PS-2 (56) DPHA (19) EA-0250P (19) TR-PBG-345 (5) Tinuvin 477 (1) ― 363 nm 4.0% Example 11 C-11 Silicone resin PS-2 (57) DPHA (19) DCP-A (19) TR-PBG-345 (5) ― ― 363 nm 4.0% Example 12 C-12 Silicone resin PS-1 (56) DPHA (19) EA-0250P (19) TR-PBG-331 (5) Tinuvin 477 (1) ― 357 nm 2.4% Example 13 C-13 Silicone resin PS-1 (56) DPHA (19) EA-0250P (19) OXE-03 (5) Tinuvin 477 (1) ― 355 nm 2.4%

[Table 1B] [Table 1B] Negative photosensitive resin composition (A) Silicone resin (mass%) (B) Monomers with radical polymerizable groups (mass%) (C) Light radical polymerization initiator (mass%) UV absorber (mass%) Other (mass%) The absorption peak of the photopolymerization initiator in the wavelength range of 300 nm to 400 nm The absorbance at 400 nm of the photopolymerization initiator / the absorbance at 365 nm (B1) Multifunctional monomer (B2) Monomers with aromatic ring and/or alicyclic hydrocarbon ring Comparative example 1 C-14 Silicone resin PS-1 (56) DPHA (19) EA-0250P (19) ― Tinuvin 477 (1) OXE-01 (5) 330 nm >0.1% Comparative example 2 C-15 Silicone resin PS-1 (56) DPHA (19) EA-0250P (19) ― Tinuvin 477 (1) OXE-02 (5) 336 nm >0.1% Comparative example 3 C-16 Silicone resin PS-1 (56) DPHA (19) EA-0250P (19) ― Tinuvin 477 (1) NCI-730 (5) 337 nm >0.1% Comparative example 4 C-17 Silicone resin PS-1 (56) DPHA (19) EA-0250P (19) ― Tinuvin 477 (1) N-930 (5) 328 nm 8.6% Comparative example 5 C-18 Silicone resin PS-1 (56) DPHA (19) EA-0250P (19) ― Tinuvin 477 (1) N-1919 (5) 333 nm 19.9% Comparative example 6 C-19 Silicone resin PS-1 (56) DPHA (19) EA-0250P (19) ― Tinuvin 477 (1) NCI-831 (5) 369 nm 33.6% Comparative example 7 C-20 Silicone resin PS-1 (56) DPHA (19) EA-0250P (19) ― Tinuvin 477 (1) Omnirad819 (5) 371 nm 74.1% Comparative example 8 C-21 ― DPHA (19) EA-0250P (19) TR-PBG-345 (5) Tinuvin 477 (1) Silicone resin PS-3 (56) 363 nm 4.0% Comparative example 9 C-22 ― DPHA (19) EA-0250P (19) TR-PBG-345 (5) Tinuvin 477 (1) Acrylic resin PA-1 (56) 363 nm 4.0% Comparative example 10 C-23 ― DPHA (30) ― ― ― Carduo series resin PA-2 (56) 4HBAGE (12) OXE-01 (5) VG-3101L (8) 330 nm >0.1%

[Table 2] [Table 2] Negative photosensitive resin composition Chemical resistance Pencil hardness Resolution (μm) Weather resistance Vent gas Example 1 C-1 A 4H 30 A A Example 2 C-2 A 4H 30 A A Example 3 C-3 A 4H 30 A A Example 4 C-4 B 3H 20 A B Example 5 C-5 A 4H 50 A A Example 6 C-6 B 4H 20 A A Example 7 C-7 A 4H 50 A A Example 8 C-8 A 3H 30 A B Example 9 C-9 B 4H 30 A A Example 10 C-10 A 4H 30 A A Example 11 C-11 A 4H 30 A A Example 12 C-12 B 3H 30 B B Example 13 C-13 B 2H 50 B B Comparative example 1 C-14 D H 20 B C Comparative example 2 C-15 D H 30 B C Comparative example 3 C-16 D H 20 B C Comparative example 4 C-17 D H 30 B C Comparative example 5 C-18 D H 30 B C Comparative example 6 C-19 C H 150 B B Comparative example 7 C-20 D HB 100 B C Comparative example 8 C-21 E 4B 30 B D Comparative example 9 C-22 C 4B 30 C E Comparative example 10 C-23 B 4B 50 C D

It can be seen that the negative photosensitive resin composition produced in the examples has high resolution, even if it is cured at 130°C, it can be formed with high pencil hardness, chemical resistance, and excellent weather resistance, and can prevent external exposure during electrode or wiring processing. Hardened film produced by gas. [Industrial availability]

The negative photosensitive resin composition of the present invention has high resolution, and even when cured at a low temperature of 150°C or less, it is possible to obtain high pencil hardness, chemical resistance, and weather resistance, and can suppress gas emission during electrode or wiring processing The resulting cured film of, can be preferably used as an insulating film, a protective film, and a glass-reinforced resin layer for touch panels having copper-containing electrodes and/or wiring.

Claims (6)

A negative photosensitive resin composition containing: (A) Silicone resin with radical polymerizable groups; (B) Monomers with radical polymerizable groups; and (C) The photoradical polymerization initiator has a light absorption peak in the wavelength region of 350 nm to 370 nm, and the absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a wavelength of 365 nm. The negative photosensitive resin composition according to claim 1, wherein the (C) photoradical polymerization initiator is a molecule containing two or more ketoxime esters represented by the following general formula (1) base;

(In the general formula (1), m is 0 or 1; n is an integer of 2 or more; R ¹ represents a hydrogen atom, an alkyl group or a phenyl group, and R ² represents an alkyl group, a cycloalkyl group or a cycloalkyl alkyl group ; Ar is an aromatic group). The negative photosensitive resin composition according to claim 1 or 2, wherein the (B) monomer having a radical polymerizable group contains (B1) a polyfunctional monomer and (B2) has an aromatic ring and/ Or alicyclic hydrocarbon ring monomer. The negative photosensitive resin composition according to claim 3, which contains 10% by weight or more of the monomer having an aromatic ring and/or an alicyclic hydrocarbon ring in the solid content of (B2). A method of manufacturing a cured film, comprising: a step of coating the negative photosensitive resin composition according to any one of claims 1 to 4 on a substrate, a step of exposing the composition, and The step of curing the exposed composition at a temperature of 150°C or lower. A touch panel has a substrate, electrodes and/or wires containing copper, and a cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 4.