KR101807641B1 - Negative photosensitive resin composition, and protective film and touch panel member using the same - Google Patents

Negative photosensitive resin composition, and protective film and touch panel member using the same Download PDF

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KR101807641B1
KR101807641B1 KR1020127023427A KR20127023427A KR101807641B1 KR 101807641 B1 KR101807641 B1 KR 101807641B1 KR 1020127023427 A KR1020127023427 A KR 1020127023427A KR 20127023427 A KR20127023427 A KR 20127023427A KR 101807641 B1 KR101807641 B1 KR 101807641B1
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resin composition
photosensitive resin
negative
solution
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KR20130070563A (en
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히토시 아라키
미츠히토 스와
토루 오카자와
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도레이 카부시키가이샤
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds

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  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

(A) an alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less, (B) a photopolymerization initiator, (C) a polyfunctional monomer, and (D) a zirconium compound. It is possible to provide an alkali developable negative photosensitive resin composition which is excellent in pattern processability and gives a cured film having high hardness, high transparency and excellent heat and humidity resistance by UV curing and thermal curing.

Description

TECHNICAL FIELD [0001] The present invention relates to a negative photosensitive resin composition, a protective film using the negative photosensitive resin composition, and a touch panel member using the negative photosensitive resin composition.

The present invention relates to a negative photosensitive resin composition, a protective film using the same, and a touch panel member.

Currently, the use of the hard coating material is used to improve the surface hardness of containers, sheets, films, optical disks, thin displays, etc., for example, in automobile parts, cosmetics and the like. Properties required for the hard coating material include heat resistance, weather resistance, adhesion and the like in addition to hardness and scratch resistance.

As a representative example of the hard coating material, there is a UV-curable hard coating of a radical polymerization type (see, for example, Non-Patent Document 1), and its composition is a polymerizable group-containing oligomer, a monomer, a photopolymerization initiator and other additives. The oligomer and the monomer are subjected to radical polymerization by UV irradiation to obtain a film having a high hardness. This hard coating material has an advantage that the time required for curing is short and the productivity is improved, and that a negative photosensitive material by a general radical polymerization mechanism can be used, resulting in a low manufacturing cost.

However, since there are many organic components, there is a problem that a hardness and scratch resistance are low as compared with other hard coating materials, and cracks are generated which cause volume shrinkage due to UV curing.

Capacitive touch panels, which have recently received attention, are one of the uses of hard coating materials. The capacitance type touch panel has a structure having a pattern made of ITO (Indium Tin Oxide) or metal (silver, molybdenum, aluminum, etc.) on glass. In order to protect the ITO and the metal, a film having high hardness, transparency, and moisture resistance is required. However, it is difficult to compatibilize these performances, and a hard coating material which solves this problem has been demanded.

UV curable coating compositions containing polymerizable group-containing oligomers, monomers, photopolymerization initiators and other additives as organic hard coating materials are known. Such a composition has a pattern processability, and a cured film having high hardness and transparency can be obtained. However, there was a problem in humid heat.

As a method for improving the resistance to moist heat, a method of adding a metal chelating agent to a siloxane is known (see Patent Document 1). This is believed to be a mechanism by which titanium or a zirconium chelating agent promotes the crosslinking of the siloxane and improves resistance to humidity.

Further, there has also been reported an example in which a metal chelating agent is used as a polymerization catalyst for siloxane, and a polymerizable functional group is introduced to give negative-type photosensitivity (see, for example, Patent Document 2).

Negative photosensitive materials containing other organometallic compounds have been reported (Patent Document 3).

Japanese Patent Laid-Open No. 07-331173 Japanese Patent Application Laid-Open No. 2008-203605 Japanese Patent Application Laid-Open No. 2007-308688

 OHARA Novoru et al., "Improvement of Material Design and Coating Technology and Hardness in Hard Coating Films Based on Plastic Substrates", Technical Information Association, April 28, 2005, page 301

In the technique of Non-Patent Document 1, since there are many organic components, there is a problem that a hardness and scratch resistance are low as compared with other hard coating materials, and cracks are caused by volume shrinkage due to UV curing.

In the technique of Patent Document 1, the main chain and the side chain of the resin are limited to the hydrophobic siloxane, and the effect on the hydrophilic resin such as the siloxane having the carboxyl group in the side chain and the other carboxyl group-containing resin is not clear.

In the technique of Patent Document 2, in order to suppress the crosslinking of the siloxane at the time of prebaking, the silanol group content is so low that it is difficult to develop with an alkaline aqueous solution.

In the technique of Patent Document 3, the firing is performed in order to form the metal film, and no organic component remains. Therefore, it is not clear what effect the organometallic compound gives to the resin component.

As described above, there is a demand for a negative-working photosensitive material having a high hardness, high transparency, and high humidity resistance and capable of patterning with an alkaline developing solution, but the technique has not been established so far.

Disclosure of the Invention An object of the present invention is to provide a negative-working photosensitive resin composition which is excellent in pattern processability, gives a cured film having high hardness, high transparency and excellent heat and humidity resistance by UV curing and thermal curing, and capable of developing alkali.

That is, an object of the present invention is to provide a photosensitive resin composition containing (A) an alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less, (B) a photopolymerization initiator, (C) a polyfunctional monomer, Type photosensitive resin composition.

Further, the object of the present invention is achieved by a touch panel protective film formed by curing the above negative-working photosensitive resin composition.

An object of the present invention is achieved by a metal wiring protective film formed by curing the above negative photosensitive resin composition.

Further, an object of the present invention is achieved by a touch panel member comprising a cured film of the negative photosensitive resin composition, wherein the molybdenum-containing metal wiring is protected by the cured film.

The negative photosensitive resin composition of the present invention is preferably a composition for forming a cured film.

The negative photosensitive resin composition of the present invention is preferably a composition for forming a protective film.

The negative-working photosensitive resin composition of the present invention is preferably an acrylic resin having an ethylenically unsaturated bond in which the alkali-soluble resin (A) has a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less.

The negative-working photosensitive resin composition of the present invention is preferably an alkali-soluble resin (A) having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less, which is a polysiloxane having an ethylenic unsaturated bond.

In the negative-working photosensitive resin composition of the present invention, the zirconium compound (D) is preferably zirconium oxide particles having an average particle diameter of 100 nm or less.

It is preferable that the negative-working photosensitive resin composition of the present invention is one in which the zirconium compound (D) is at least one compound represented by the general formula (1).

Figure 112012072329808-pct00001

(R 1 is a hydrogen, an alkyl group, an aryl group, an alkenyl group, and the substituents, R 2 and R 3 is hydrogen, an alkyl group, an aryl group, an alkenyl group, a represents an alkoxy group and the substituent A plurality of R 1, R 2 And R 3 may be the same or different and n represents an integer of 0 to 4)

(Effects of the Invention)

INDUSTRIAL APPLICABILITY The negative-working photosensitive resin composition of the present invention is excellent in pattern processability and can obtain a cured film having high hardness, high transparency and excellent heat and humidity resistance by UV curing and thermal curing.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic top view after each step in manufacturing a touch panel member. FIG.
2 is a schematic sectional view showing a touch panel member.

(A) an alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less, (B) a photopolymerization initiator, (C) a polyfunctional monomer, (D) a zirconium compound do.

The negative photosensitive resin composition of the present invention is preferably a composition for forming a cured film. The cured film refers to a film obtained by curing by light and / or heat without a step of removing all the resin components by firing or stripping solution treatment or the like. There is no particular limitation on the method of using the cured film, but various protective films such as a protective film for a touch panel, a hard coating material, a planarizing film for a TFT, an overcoat for a color filter, a passivation film, An insulating film, a TFT insulating film, an interlayer insulating film and the like, an optical filter, a color filter photo spacer, and a microlens. Among these, it is preferable to use it as a protective film in view of high hardness, transparency, and moisture resistance. The protective film means a cured film used for the purpose of protecting various underlying materials. The method of using the protective film is not particularly limited, and specific examples thereof include those described above.

The negative-working photosensitive resin composition of the present invention contains (A) an alkali-soluble resin having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less. The carboxylic acid equivalent represents the weight of the resin necessary for obtaining 1 mol of carboxyl group, and the unit is g / mol. When the carboxylic acid equivalent of the alkali-soluble resin exceeds 1,400 g / mol, the alkali-soluble photosensitive resin composition is inferior in alkali solubility (developability) and can not form a good pattern. Or a large limitation is required for the developer species. On the other hand, if the alkali-soluble resin has unsaturated carboxylic acid equivalent of 200 g / mol, the decrease in film thickness of the exposed portion can not be suppressed. With such a range, it becomes possible to form a good pattern under various developing conditions.

The alkali-soluble resin having a carboxylic acid equivalent (A) of 200 g / mol or more and 1,400 g / mol or less used in the negative-working photosensitive resin composition of the present invention has an ethylenically unsaturated double bond group to improve the crosslinking density, The hardness can be improved. The preferable range of the carboxylic acid equivalent is 300 g / mol or more and 1200 g / mol or less, and more preferably 400 g / mol or more and 800 g / mol or less.

Examples of the alkali-soluble resin having (A) carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less include polysiloxane, acrylic resin, polyimide, polyamic acid and polyamide. In the alkali-soluble resin having an equivalent (A) carboxylic acid of 200 g / mol or more and 1,400 g / mol or less, it is preferable that an ethylenically unsaturated double bond group is introduced at least in part to increase the hardness of the cured film. Among these polymers, a polysiloxane and an acrylic resin are more preferable because of easiness of introduction of an ethylenically unsaturated double bond group. Two or more of these polymers may be contained.

Preferred examples of the alkali-soluble resin having (A) carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less are listed below, but the present invention is not limited thereto.

The polysiloxane is preferably obtained, for example, by hydrolyzing an organosilane compound having a carboxyl group and / or a dicarboxylic acid anhydride group and condensing the hydrolyzate. Further, in order to adjust the carboxylic acid equivalent, it is preferable to use other organosilane compounds at the same time. Among them, it is preferable to use an organosilane compound having an ethylenically unsaturated bond in that the hardness of the resulting cured film becomes high.

The conditions for the hydrolysis reaction can be appropriately set, but it is preferable that the acid catalyst and water are added to the organosilane compound in a solvent over a period of 1 to 180 minutes, and then the reaction is carried out at room temperature or more and 110 ° C or less for 1 to 180 minutes. Under such conditions, a rapid reaction can be suppressed by carrying out a hydrolysis reaction. The reaction temperature is more preferably 30 ° C or more and 105 ° C or less.

The hydrolysis reaction is preferably carried out in the presence of an acid catalyst. As the acid catalyst, an acidic aqueous solution containing formic acid, acetic acid or phosphoric acid is preferable. The preferable content of these acid catalysts is preferably 0.1 part by weight 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, a hydrolysis reaction is required, and the reaction can be easily controlled so as to proceed sufficiently.

The condensation reaction can be carried out, for example, by obtaining the silanol compound by the hydrolysis reaction of the organosilane compound as described above, heating the reaction solution at 50 ° C or higher and at the boiling point or lower of the solvent for 1 to 100 hours, . Re-heating or a base catalyst may be added to increase the degree of polymerization of the polysiloxane. Depending on the intended purpose, the resulting alcohol may be heated and / or depressurized to remove an appropriate amount after hydrolysis, and then the desired solvent may be added.

As the polysiloxane having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less and having an ethylenically unsaturated bond, for example, an organosilane compound having a carboxyl group and / or a dicarboxylic acid anhydride group and an organosilane compound having an ethylenic unsaturated bond It is preferable that the silane compound is obtained by hydrolyzing the silane compound and condensing the hydrolyzate.

Examples of the organosilane compound having a carboxyl group include 3-trimethoxysilylpropionic acid, 3-triethoxysilylpropionic acid, 3-dimethylmethoxysilylpropionic acid, 3-dimethylethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid , 4-triethoxysilylbutyric acid, 4-dimethylmethoxysilylbutyric acid, 4-dimethylethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 5-dimethylmethoxysilylvaler Acid, 5-dimethylethoxysilyl valeric acid, and the like.

Examples of the organosilane compound having a dicarboxylic acid anhydride group include 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3-dimethylethoxy 3-trimethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-triethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-dimethylmethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-dimethylethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, 3-dimethylmethoxysilylpropylphthalic anhydride, 3-dimethylethoxy Silylpropyl phthalic anhydride and the like.

Examples of the other organosilane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltri Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- chloropropyltrimethoxysilane, 3- ) Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane, N -? - (aminoethyl) -? - aminopropyl Trimethoxysilane,? -Cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane,? -Glycidoxyethyltrimethoxysilane,? -Glycidoxyethyl Triethoxysilane,? -Glycidoxyethyltrimethoxysilane,? -Glycidoxyethyltriethoxy Include? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Glycidyl Isopropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltriethoxysilane,? -Glycidoxybutyltrimethoxysilane ,? -glycidoxybutyltriethoxysilane,? -glycidoxybutyltrimethoxysilane,? -glycidoxybutyltriethoxysilane,? -glycidoxybutyltrimethoxysilane,? -glycidoxime (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) (3,4-epoxycyclohexyl) ethyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3,4 -Epoxycyclohexyl) propyltriethoxysilane, 4- (3,4-epoxycyclohexyl) butyltrimethoxysilane, 4- (3,4-epoxycyclohexyl) butyltriethoxysilane, dimethyldimethoxysilane, Dimethyldiethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Aminopropylmethyldimethoxysilane,? -Aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane,? -Glycidoxyethylmethyldimethoxysilane,? -Glycidoxyethylmethyldiethoxysilane,? -Glycidoxyethylmethyldimethoxy Silane,? -Glycidoxyethylmethyldiethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropyl ? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropylethyldimethoxysilane,? -Glycidoxypropylethyldiethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, Tetramethoxysilane, tetraethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, and the like can be used. . Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, Styryltrimethoxysilane, styryltrimethoxysilane, styryltrimethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane,? -Acryloylpropyltrimethoxysilane,? -Acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ- Acryloylpropylmethyldimethoxysilane,? -Acryloylpropylmethyldiethoxysilane, and the like, the ethylenically unsaturated double bond group can be easily introduced.

The carboxylic acid equivalent of the polysiloxane can be calculated by calculating the ratio of the silanol group / carboxyl group in the polysiloxane by 1 H-NMR and measuring the acid value.

When the polysiloxane has an ethylenically unsaturated double bond group, the content thereof is not particularly limited, but the double bond equivalent is preferably 150 g / mol or more and 10,000 g / mol or less. The hardness and crack resistance can be made compatible at a high level in the above range. The double bond equivalent can be calculated by measuring the iodine value.

The weight average molecular weight (Mw) of the polysiloxane is not particularly limited, but is preferably 1,000 to 100,000 in terms of polystyrene measured by gel permeation chromatography (GPC). By setting the Mw within the above range, good coating properties can be obtained and the solubility in a developer at the time of pattern formation becomes good.

As the acrylic resin, a (meth) acrylic acid and a (meth) acrylic acid ester are preferably subjected to radical polymerization. The catalyst for the radical polymerization is not particularly limited, and azo compounds such as azobisisobutyronitrile and organic peroxides such as benzoyl peroxide and the like are generally used.

(Meth) acrylic acid, (meth) acrylic acid ester and a radical polymerization catalyst are added to the reaction vessel and the inside of the reaction vessel is thoroughly purged with nitrogen by bubbling or vacuum degassing, It is preferable to carry out the reaction at 110 DEG C or lower for 30 to 300 minutes. If necessary, a chain transfer agent such as a thiol compound may be used.

Examples of the (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (Meth) acrylate, 2-cyclopentyloxycarbonylethyl (meth) acrylate, 2-cyclohexyloxycarbonyl (meth) acrylate, 2-cyclohexyloxycarbonyl Cyclohexyloxycarbonylethyl (meth) acrylate, 2- (4-methoxycyclohexyl) oxycarbonyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyladamantyl (meth) acrylate, 1-methyladamantyl Is used. Aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene and? -Methylstyrene may be copolymerized.

Examples of the acrylic resin having an ethylenically unsaturated bond include a copolymer having an ethylenically unsaturated double bond group after radical polymerization of a (meth) acrylic acid and a (meth) acrylic acid ester, wherein the equivalent of the carboxylic acid is 200 g / mol or more and 1,400 g / mol or less. It is preferable that an epoxy compound is obtained by an addition reaction. The catalyst to be used for the addition reaction of the epoxy compound having an ethylenically unsaturated double bond group is not particularly limited and a known catalyst can be used. Examples thereof include dimethyl aniline, 2,4,6-tris (dimethylaminomethyl) phenol, dimethyl Amino-based catalysts such as benzylamine, tin-based catalysts such as tin 2-ethylhexanoate (II) and dibutyltin laurate, titanium-based catalysts such as titanium 2-ethylhexanoate (IV) And chromium-based catalysts such as chromium acetylacetonate and chromium chloride. Examples of the epoxy compound having an ethylenically unsaturated double bond group include glycidyl (meth) acrylate,? -Ethylglycidyl (meth) acrylate,? - n-propylglycidyl (meth) (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, , Vinyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,? -Methyl-o-vinyl benzyl glycidyl ether, -m-vinylbenzyl glycidyl ether,? -methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5 - diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3 , 6-triglycidyl When a-methyl styrene, such as 3,4,5-triglycidyl-oxy-methyl-styrene, 2,4,6-triglycidyl-oxy-methyl styrene is used.

When the acrylic resin has an ethylenically unsaturated double bond group, the content thereof is not particularly limited, but the double bond equivalent is preferably 150 g / mol or more and 10,000 g / mol or less. The hardness and crack resistance can be made compatible at a high level in the above range. The double bond equivalent can be calculated by measuring the iodine value.

The weight average molecular weight (Mw) of the acrylic resin is not particularly limited, but is preferably 2,000 or more and 200,000 or less in terms of polystyrene measured by gel permeation chromatography (GPC). By setting the Mw within the above range, good coating properties can be obtained and the solubility in a developer at the time of pattern formation becomes good.

The content of the alkali-soluble resin having a carboxylic acid equivalent (A) of 200 g / mol or more and 1,400 g / mol or less in the negative-type photosensitive resin composition of the present invention is not particularly limited and may be arbitrarily selected depending on the desired film thickness or application It is generally 10 wt% or more and 60 wt% or less based on the solid content of the negative-type photosensitive resin composition.

The negative-working photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. (B) The photopolymerization initiator preferably decomposes and / or reacts with light (including ultraviolet rays and electron beams) to generate radicals.

Specific examples include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- 2-dimethylamino-1- (4-morpholinophenyl) -butanone-l, 2,4,6-trimethylbenzoylphenylphosphine oxide, Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) - (2,4,4-trimethylpentyl) -phosphine oxide, -Propanedione-2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- -Butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrityl-2- (o-ethoxycarbonyl) oxime, ethanone, 1- [ (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (0-acetyloxime), 4,4-bis (dimethylamino) benzophenone, Phenone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, p-diethylaminobenzo 2-methyl-1-phenylpropane-1-one, benzyldimethylketal, 1- (4-isopropylphenyl) -2-hydroxy- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether , Benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl- Benzoyl-N, N-dimethyl-N- [2- (1-oxo < / RTI > (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, Propeneammonium chloride 1 hydrate, 2-isopropylthioxanthone, 2,4-dimethylthio Dihydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy ) -N, N, N-trimethyl-1-propanaminium chloride, 2,2'-bis (o- chlorophenyl) -4,5,4 ', 5'-tetraphenyl- , 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester, eta 5-cyclopentadienyl-η6-cumene- 1 -) - hexafluorophosphate (1-), diphenylsulfide derivative, bis (η5-2,4-cyclopentadien-1-yl) Pyrrol-1-yl) -phenyl) titanium, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl- Diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, benzylmethoxyethyl acetal, Benzoquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-anthraquinone, (P-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, naphthalene sulfonyl chloride, quinoline sulfonyl chloride, A combination of a photo-reducible dye such as benzothiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide, eosin and methylene blue, and a reducing agent such as ascorbic acid and triethanolamine . Two or more of these may be contained.

Among these, an? -Aminoalkylphenone compound, an acylphosphine oxide compound, an oxime ester compound, a benzophenone compound having an amino group, or a benzoate compound having an amino group are preferable for increasing the hardness of the cured film.

Specific examples of the? -aminoalkylphenone compound include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1. Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) - 2,4,4-trimethylpentyl) -phosphine oxide, and the like. Specific examples of the oxime ester compound include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- -Benzoyloxime)], 1-phenyl-1,2-butadione-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrionic- 2- (o-ethoxycarbonyl) oxime , Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (0-acetyloxime) and the like. Specific examples of the benzophenone compound having an amino group include 4,4-bis (dimethylamino) benzophenone and 4,4-bis (diethylamino) benzophenone. Specific examples of the benzoic acid ester compound having an amino group include ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

In the negative photosensitive resin composition of the present invention, the content of the photopolymerization initiator (B) is not particularly limited, but it is preferably 0.1 wt% or more and 20 wt% or less based on the solids content of the negative photosensitive resin composition. When the amount is in the above range, the curing can be sufficiently promoted, and the residual polymerization initiator can be prevented from leaching and the solvent resistance can be ensured.

The negative photosensitive resin composition of the present invention contains (C) a polyfunctional monomer. The polymerization of the polyfunctional monomer (C) proceeds by the photopolymerization initiator (B) by the light irradiation, and the exposed portion of the negative photosensitive resin composition of the present invention is insoluble in the aqueous alkali solution to form a negative pattern have. The multifunctional monomer refers to a compound having at least two ethylenically unsaturated double bonds in the molecule and is not particularly limited, but a multifunctional monomer having a (meth) acrylic group which is easy to radical polymerization is preferable. The double bond equivalent of the polyfunctional monomer (C) is preferably from 80 g / mol to 400 g / mol in view of sensitivity and hardness.

Examples of the polyfunctional monomer (C) include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol Dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol di Methacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate , 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetra Acrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacryl Acrylate, pentapentaerythritol decaacrylate, pentapentaerythritol decaacrylate, tripentaerythritol hepta methacrylate, tripentaerythritol octa methacrylate, tetrapentaerythritol nona methacrylate, tetra Pentaerythritol decamethacrylate, pentapentaerythritol undeca methacrylate, pentapentaerythritol decamethacrylate, dimethylol-tricyclodecane diacrylate, ethoxylated bisphenol A diacryl 9,9-bis [4- (2-methacryloyloxyethoxy) phenyl] fluorene, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, , 9-bis [4- (2-methacryloyloxyethoxy) -3-methylphenyl] fluorene, (2-acryloyloxypropoxy) Dimethylphenyl] fluorene, 9,9-bis [4- (2-methacryloyloxyethoxy) -3,5-dimethylphenyl] Fluorene and the like. Among them, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate and the like are preferable from the viewpoint of sensitivity improvement. From the viewpoint of improvement in hydrophobicity, it is also possible to use dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis [4- Oxy] ethoxy) phenyl] fluorene and the like are preferable.

In the negative-working photosensitive resin composition of the present invention, the content of the polyfunctional monomer (C) is not particularly limited and may be arbitrarily selected depending on the desired film thickness and application, but is preferably 10 wt% or more and 60 wt% .

The negative-working photosensitive resin composition of the present invention contains (D) a zirconium compound. The heat resistance of the cured film obtained by containing the (Z) zirconium compound is improved. Since the alkali-soluble resin having a carboxyl group is hydrophilic originating from a carboxyl group, it has insufficient resistance to moisture and humidity, but (D) contains a zirconium compound, thereby improving the moisture resistance of the cured film. It is known that some zirconium compounds have an effect of improving wet heat resistance of polysiloxanes (see Patent Document 1). In the known examples, the side chains of the polysiloxane are limited to hydrophobic groups, and the resulting cured film also becomes hydrophobic. Of the present invention is not clear. In the present invention, it has been found for the first time that the wettability of the cured film is improved by not containing the polysiloxane but by containing the (D) zirconium compound in the carboxyl group-containing alkali-soluble resin as the hydrophilic resin. (D) the zirconium compound reacts with a plurality of carboxyl groups of an alkali-soluble resin having (A) a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less to form a crosslinked structure, and the film density And at the same time the hydrophilic property derived from the carboxyl group is reduced, it is considered that the heat and humidity resistance of the cured film obtained is improved. The (D) zirconium compound is not particularly limited as long as it is a compound containing a zirconium atom, and for example, zirconium oxide particles having an average particle diameter of 100 nm or less and a compound represented by the general formula (1) are preferable. The average particle diameter of the zirconium oxide particles is more preferably 40 nm or less. It is possible to prevent the cloudiness of the cured film obtained by setting the average particle diameter of the zirconium oxide particles to 100 nm or less.

Figure 112012072329808-pct00002

(R 1 is a hydrogen, an alkyl group, an aryl group, an alkenyl group, and the substituents, R 2 and R 3 is hydrogen, an alkyl group, an aryl group, an alkenyl group, a represents an alkoxy group and the substituent A plurality of R 1, R 2 And R 3 may be the same or different and n represents an integer of 0 to 4)

Here, the average particle diameter means the median diameter obtained from the particle size distribution measured by the Coulter method.

Specific examples of zirconium oxide particles having an average particle diameter of 100 nm or less include commercially available products such as "Bial Zr-C20 (trade name)" (average particle diameter 20 nm, manufactured by Taki Chemical Co., Ltd.) ZSL-10A (trade name) "(average particle diameter: 7 nm) (trade name, manufactured by Nissan Chemical Industries, Ltd.) Nm (manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.).

In the general formula (1), R 1 represents a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a phenyl group or a vinyl group. Of these, the n-propyl group, the n-butyl group and the phenyl group are preferable in that the compound is stable. R 2 and R 3 are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, Propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, benzyloxy group and the like. Of these, a methyl group, a t-butyl group, a phenyl group, a methoxy group and an ethoxy group are preferable in that synthesis is easy and the compound is stable.

Examples of the compound represented by the general formula (1) include zirconium tetra n-propoxide, zirconium tetra n-butoxide, zirconium tetra sec-butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetra , 2,6,6-tetramethyl-3,5-heptanedionate), zirconium tetramethylacetoacetate, zirconium tetraethylacetoacetate, zirconium tetramethylmalonate, zirconium tetraethylmalonate, zirconium tetrabenzoyl acetonate, zirconium Butoxyacetylacetonate bis (ethylacetoacetate), zirconium mono-n-butoxyethylacetoacetate bis (acetylacetonate), zirconium mono-n-butoxy triacetyl acetonate, zirconium Mono n-butoxy triacetyl acetonate, zirconium di-n-butoxybis (ethyl Tosyl acetate), zirconium di-n-butoxybis (acetylacetonate), zirconium di-n-butoxybis (ethylmalonate), zirconium di-n-butoxybis (benzoyl acetonate), zirconium di- (Dibenzoylmethanate), and the like. Among them, zirconium tetra n-propoxide, zirconium tetra n-butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetra (2,2,6 , 6-tetramethyl-3,5-heptanedionate), zirconium tetramethylmalonate, zirconium tetraethyl malonate, zirconium tetraethylacetoacetate, zirconium di n-butoxybis (ethylacetoacetate) Butoxyacetylacetonate bis (ethylacetoacetate) is preferable.

In the negative-working photosensitive resin composition of the present invention, the content of the zirconium compound (D) is not particularly limited, but in the case of zirconium oxide particles having an average particle size of 100 nm or less, 1 wt% or more and 60 wt% or less of the solid content of the negative- And in the case of the other (D) zirconium compound, 0.1 wt% or more and 10 wt% or less of the solid content of the negative-type photosensitive resin composition is preferable. According to the above-mentioned range, both of transparency and wet heat resistance can be compatible with each other.

The negative photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing the polymerization inhibitor, the storage stability of the resin composition is improved and the resolution after development is improved. The content of the polymerization inhibitor is preferably 0.01 wt% or more and 1 wt% or less based on the solid content of the negative-type photosensitive resin composition.

Specific examples of the polymerization inhibitor include phenol, catechol, resorcinol, hydroquinone, 4-t-butyl catechol, 2,6-di (t-butyl) -p- cresol, phenothiazine, 4-methoxyphenol And the like.

The negative-working photosensitive resin composition of the present invention may contain an ultraviolet absorber. The light resistance of the cured film obtained by containing the ultraviolet absorber is improved and the resolution after development is improved in applications requiring pattern processing. The ultraviolet absorber is not particularly limited and a known one can be used. From the viewpoint of transparency and non-colorability, a benzotriazole-based compound, a benzophenone-based compound, and a triazine-based compound are preferably used.

Examples of the ultraviolet absorber of the benzotriazole-based compound include 2- (2H-benzotriazol-2-yl) phenol, 2- (2H-benzotriazol- 2-yl) -6-dodecyl-4-methylphenol, 2- (2H-benzotriazol- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole. Examples of the ultraviolet absorber of the benzophenone compound include 2-hydroxy-4-methoxybenzophenone and the like. Examples of the ultraviolet absorber of the triazine compound include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5 - [(hexyl) oxy] -phenol and the like.

The negative photosensitive resin composition of the present invention may contain a solvent. A compound having an alcoholic hydroxyl group or a cyclic compound having a carbonyl group is preferably used because the components can be uniformly dissolved and the transparency of the resulting coating film can be improved. Two or more of these may be used. Further, a compound having a boiling point at atmospheric pressure of 110 DEG C or more and 250 DEG C or less is more preferable. When the boiling point is 110 占 폚 or higher, drying progresses moderately at the time of the coating film, and a good coating film without coating spreading is obtained. On the other hand, when the boiling point is 250 占 폚 or less, the amount of the residual solvent in the film can be suppressed to a small extent, and film shrinkage during thermal curing can be further reduced.

Specific examples of the compound having an alcoholic hydroxyl group and having a boiling point at atmospheric pressure of 110 캜 to 250 캜 include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy- Methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, 3-methoxy-1-butanol and 3-methyl-3-methoxy-1-butanol. Among them, diacetone alcohol is preferable from the viewpoint of storage stability, and propylene glycol mono-t-butyl ether is particularly preferably used from the viewpoint of step coverage.

Specific examples of the cyclic compound having a carbonyl group and having a boiling point at atmospheric pressure of 110 占 폚 to 250 占 폚 include? -Butyrolactone,? -Valerolactone,? -Valerolactone, propyleneglycol carbonate, , Cycloheptanone, and the like. Of these,? -Butyrolactone is particularly preferably used.

The negative photosensitive resin composition of the present invention may contain a solvent other than the above. Examples thereof include ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether and diethyl ether; Ketones such as methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, and 2-heptanone; Amides such as dimethylformamide and dimethylacetamide; Acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and 3-methyl- .

The content of the solvent is not particularly limited, and any amount can be used depending on the application method and the like. For example, when the film formation is carried out by spin coating, it is generally made 50 wt% or more and 95 wt% or less of the entire negative photosensitive resin composition.

The negative photosensitive resin composition of the present invention may contain various curing agents that promote curing or facilitate curing of the resin composition. The curing agent is not particularly limited and known ones can be used. Specific examples thereof include nitrogen-containing organic compounds, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, . Two or more of these may be contained. Among them, a metal chelate compound, a methylolated melamine derivative and a methylolated urea derivative are preferably used from the viewpoints of the stability of the curing agent and the processability of the obtained coating film.

When the polysiloxane is used in the negative photosensitive resin composition of the present invention, a curing catalyst such as a thermal acid generator may be contained. Examples of the thermal acid generator include, but are not limited to, various known onium salt compounds such as aromatic diazonium salts, sulfonium salts, diaryliodonium salts, triarylsulfonium salts and triarylselenium salts, sulfonic acid esters, .

The negative photosensitive resin composition of the present invention may contain various surfactants such as various fluorine surfactants and silicone surfactants in order to improve the flow property at the time of coating. There is no particular limitation on the kind of the surfactant, and examples thereof include "Megapack (registered trademark)" "F142D (trade name)", "F172 (trade name)", "F173 (trade name)", "F183 (Trade name), "F470 (trade name)", "F475 (trade name)", "F475 BYK-331 (trade name), BYK-301 (trade name), BYK-331 (trade name), BYK-345 A silicone surfactant such as "BYK-307 (trade name)" and "BYK-352 (trade name)" (manufactured by BYK Japan KK), a polyalkylene oxide surfactant and a poly have. Two or more of these may be used.

The negative-working photosensitive resin composition of the present invention may contain additives such as a solubility-controlling agent, a stabilizer, and a defoaming agent, if necessary.

There is no particular limitation on the solid content concentration of the negative photosensitive resin composition of the present invention, and an arbitrary amount of solvent or solute may be used depending on the coating method and the like. For example, when a film is formed by spin coating as described later, it is general to set the solid concentration to 5 wt% or more and 50 wt% or less.

A typical method of producing the negative-working photosensitive resin composition of the present invention will be described below.

For example, a photopolymerization initiator (B), a zirconium compound (D) and other additives are added to an arbitrary solvent, and after stirring and dissolution, (A) an alkali having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less Soluble resin and (C) polyfunctional monomer are added, and the mixture is stirred for further 20 minutes to 3 hours. The resulting solution is filtered to obtain a negative-working photosensitive resin composition.

A method of forming a cured film using the negative photosensitive resin composition of the present invention will be described by way of example.

The negative photosensitive resin composition of the present invention is coated on a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating and slit coating, Pre-baked with a heating apparatus of The prebaking is preferably performed at a temperature of 50 ° C or more and 150 ° C or less for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably 0.1 μm or more and 15 μm or less.

After pre-baking, light of about 10 to 4,000 J / m 2 (corresponding to a wavelength of 365 nm in terms of exposure dose) is irradiated with light from a mask (not shown) using a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner With or without intervening. There is no limitation on the exposure light source, and ultraviolet rays such as i-line, g-ray, and h-line, KrF (wavelength 248 nm) laser and ArF (wavelength 193 nm) laser can be used. Thereafter, this film may be subjected to post-exposure baking in which the film is heated by a heating device such as a hot plate or an oven at a temperature of 150 ° C or higher and 450 ° C or lower for about 1 hour.

The negative photosensitive resin composition of the present invention preferably has a sensitivity of not less than 100 J / m 2 and not more than 4,000 J / m 2 upon exposure to PLA. The sensitivity in the patterning exposure by the PLA is determined, for example, by the following method. The composition is spin-coated on a silicon wafer at an arbitrary number of revolutions using a spin coater and prebaked at 120 DEG C for 2 minutes using a hot plate to prepare a film having a thickness of 2 mu m. The resulting film was exposed using a PLA ("PLA-501F (trade name)" manufactured by Canon Inc.) through a gray scale mask for sensitivity measurement, and then developed using an automatic developing apparatus ("AD" manufactured by TAKIZAWA CO. -2000 (trade name) ") in a 0.4 wt% tetramethylammonium hydroxide aqueous solution for an arbitrary time, and then rinsed with water for 30 seconds. The exposure amount for resolving a line-and-space pattern of 30 占 퐉 in the formed pattern to a width of 1: 1 is determined as sensitivity.

After the patterning exposure, the exposed portion is dissolved by development, and a negative pattern can be obtained. As a developing method, it is preferable to immerse the developing solution for 5 seconds to 10 minutes by a method such as shower, immersion, paddle, or the like. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as hydroxides, carbonates, phosphates, silicates and borates of alkali metals, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and choline Or an aqueous solution containing one or more of these. After development, it is preferable to rinse with water, followed by drying baking in a range of 50 DEG C or more and 150 DEG C or less. Thereafter, this film is thermally cured by a heating device such as a hot plate or an oven at 120 ° C or higher and 280 ° C or lower for about 1 hour to obtain a cured film.

The cured film obtained from the negative photosensitive resin composition of the present invention preferably has a zirconium atom content of 0.02 wt% or more and 7.5 wt% or less, a carbon atom content of 25 wt% or more and 80 wt% or less, and a silicon atom content of 0.5 wt% or more and 20 wt% . Within the above range, the transmittance, the hardness, and the heat and humidity resistance can be maintained in good balance. The resolution is preferably 20 탆 or less. The thickness of the cured film is not particularly limited, but is preferably 0.1 탆 or more and 15 탆 or less. It is preferable that the film has a hardness of 4H or more and a transmittance of 90% or more at a film thickness of 1.5 占 퐉. The transmittance refers to the transmittance at a wavelength of 400 nm. The hardness and the transmittance can be adjusted by selecting the exposure amount and the heat curing temperature.

The cured film obtained by curing the negative photosensitive resin composition of the present invention can be applied to various protective films and optical filters such as a protective film for a touch panel, various hard coating materials, a planarizing film for a TFT, an overcoating for a color filter, A TFT insulating film, a color filter photo spacer, and the like. Among these, it can be preferably used as a protective film for a touch panel since it has high hardness and transparency. Examples of the touch panel method include a resistive film type, an optical type, an electromagnetic induction type, and a capacitive type. The capacitive touch panel can preferably use the cured film of the present invention because a particularly high hardness is required.

In addition, the cured film obtained by curing the negative photosensitive resin composition of the present invention can be preferably used as a metal wiring protective film because of its high moisture resistance. It is possible to prevent deterioration (deterioration of conductivity, etc.) caused by corrosion of the metal or the like by forming it on the metal wiring. Examples of the metal to be protected include, but are not limited to, copper, silver, aluminum, chromium, molybdenum, titanium, ITO, IZO (indium zinc oxide), AZO (aluminum oxide added zinc oxide) and ZnO 2 . Particularly, it can be preferably used in a touch panel member containing molybdenum. The touch panel member referred to herein is a glass or film substrate having an electrode and an insulating film and / or a protective film, and is a member usable as a sensor substrate for a touch panel.

The method of manufacturing the touch panel member is not particularly limited, and for example, the following methods can be used. A transparent electrode thin film is formed on a glass substrate to have an arbitrary film thickness. The resist material is patterned by a photolithography technique, chemical solution etching using an etchant for the transparent electrode, and resist stripping process using a stripping liquid. A glass substrate on which a transparent electrode forming part of the Y-axis electrode is patterned is fabricated (Fig. 1 (a)). Examples of the transparent electrode include metal oxides such as ITO, IZO, AZO, ZnO 2 , and tin antimonic acid, and thin films of metals such as gold, silver, copper, and aluminum. These transparent electrodes can be formed by a conventional method such as a physical method such as vacuum deposition, sputtering, ion plating, ion beam deposition, or chemical vapor deposition. Subsequently, a cured film obtained from the negative-working photosensitive resin composition of the present invention is formed as a transparent insulating film at a portion intersecting the electrode formed from the back (Fig. 1 (b)). Thereafter, the connection wiring with the IC driver and the Y-axis electrode conductive wiring are formed through a process of resist patterning, etching, and resist stripping after the electrode thin film is formed to an arbitrary film thickness (Fig. 1 (c)). As the electrode here, molybdenum, a molybdenum / aluminum / molybdenum laminated film (MAM), a molybdenum-niobium alloy, chromium, titanium, a titanium / aluminum / titanium laminated film (TAT) . A transparent protective film is finally formed as a cured film obtained from the negative photosensitive resin composition of the present invention at a portion other than the connection portion with the IC driver of the substrate end portion (the upper left side portion and the lower right side portion of Fig. 1 (c) Is obtained. 2 is a cross-sectional view of the touch panel member production example.

Example

Hereinafter, the present invention will be described using its embodiments, but the form of the present invention is not limited to these examples.

Synthesis Example 1: Synthesis of polysiloxane solution (i)

In a 500 ml three-necked flask, 47.67 g (0.35 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropylsuccinic acid, (0.35 mol) of diacetone alcohol (hereinafter referred to as DAA) and 185.08 g of diacetone alcohol (hereinafter referred to as DAA) were poured into an oil bath at 40 ° C and stirred. To 55.8 g of water, 0.391 g of phosphoric acid 0.2 wt%) was dissolved in 100 mL of water was added over 10 minutes with a dropping funnel. After stirring at 40 DEG C for 1 hour, the oil bath temperature was set to 70 DEG C, and the mixture was stirred for 1 hour, and the oil bath was heated to 115 DEG C over 30 minutes. After 1 hour from the start of the temperature rise, the inner temperature of the solution reached 100 DEG C, and the mixture was heated and stirred for 2 hours at this point (the inner temperature was 100 to 110 DEG C). During the reaction, a total of 120 g of methanol and water as byproducts were spilled out. DAA was added to the DAA solution of the polysiloxane so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (i). The weight average molecular weight (Mw) of the obtained polymer was measured by GPC to be 8,000 (in terms of polystyrene). The carboxylic acid equivalent was 620 g / mol.

Synthesis Example 2: Synthesis of polysiloxane solution (ii)

In a 500 ml three-necked flask, 54.48 g (0.40 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 13.12 g (0.05 mol) of 3- 82.04 g (0.35 mol) of roylpropyltrimethoxysilane and 174.74 g of DAA were charged. While immersing in an oil bath at 40 DEG C and stirring, 0.379 g of phosphoric acid (0.2 wt% based on the injected monomer) was dissolved Was added over 10 minutes with a dropping funnel. Subsequently, heating and stirring were carried out under the same conditions as in Synthesis Example 1, and 110 g of methanol and water, which are by-products, were spilled out. DAA was added to the DAA solution of the obtained polysiloxane so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (ii). The weight average molecular weight (Mw) of the obtained polymer was measured by GPC to be 6,000 (in terms of polystyrene). The carboxylic acid equivalent was 1,190 g / mol.

(Synthesis Example 3: Synthesis of polysiloxane solution (iii)) [

In a 500 ml three-necked flask, 27.24 g (0.20 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 65.58 g (0.25 mol) of 3- 82.04 g (0.35 mol) of roylpropyltrimethoxysilane and 198.02 g of DAA were charged, and 0.416 g of phosphoric acid (0.2 wt% based on the injected monomer) was dissolved in 58.5 g of water while being immersed in an oil bath at 40 DEG C Was added over 10 minutes with a dropping funnel. Subsequently, heating and stirring were carried out under the same conditions as in Synthesis Example 1. As a result, 130 g of methanol and water as a by-product were spilled out in total. DAA was added to the DAA solution of the obtained polysiloxane so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (iii). The weight average molecular weight (Mw) of the obtained polymer was measured by GPC to be 7,000 (in terms of polystyrene). The carboxylic acid equivalent was 280 g / mol.

(Synthesis Example 4: Synthesis of polysiloxane solution (iv)) [

(0.20 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 41.66 g (0.20 mol) of 3-trimethoxysilylbutyric acid, 0.44 mol 82.04 g (0.35 mol) of monopropyl trimethoxysilane and 182.22 g of DAA were charged, and 0.395 g of phosphoric acid (0.2 wt% with respect to the injected monomer) was dissolved in 54.0 g of water while immersing in an oil bath at 40 DEG C The aqueous phosphoric acid solution was added over 10 minutes with a dropping funnel. Subsequently, heating and stirring were carried out under the same conditions as in Synthesis Example 1, and a total of 120 g of methanol and water as by-products were spilled out. DAA was added to the DAA solution of the polysiloxane so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (iv). The weight average molecular weight (Mw) of the obtained polymer was measured by GPC to be 8,000 (in terms of polystyrene). The carboxylic acid equivalent was 640 g / mol.

(Synthesis Example 5: Synthesis of polysiloxane solution (v)) [

A 500 ml three-necked flask was charged with 68.10 g (0.50 mol) of methyltrimethoxysilane, 99.15 g (0.50 mol) of phenyltrimethoxysilane, 143.37 g of 3-methyl-3-methoxybutanol , And an aqueous phosphoric acid solution in which 0.167 g of phosphoric acid (0.1 wt% based on the injected monomer) was dissolved in 54.0 g of water while immersed in an oil bath at 40 ° C and stirred was added over 10 minutes with a dropping funnel. Subsequently, heating and stirring were carried out under the same conditions as in Synthesis Example 1, and a total of 120 g of methanol and water as by-products were spilled out. MMB was added to the obtained polysiloxane MMB solution so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (v). The weight average molecular weight (Mw) of the obtained polymer was measured by GPC to be 8,000 (in terms of polystyrene). The carboxylic acid equivalent was 0 g / mol. This Synthesis Example 5 is a form described in Patent Document 1.

Synthesis Example 6: Synthesis of acrylic resin solution (a)

3 g of 2,2'-azobis (isobutyronitrile) and 50 g of propylene glycol methyl ether acetate (hereinafter referred to as PGMEA) were introduced into a 500 ml flask. Thereafter, 23.0 g of methacrylic acid, 31.5 g of benzylmethacrylate, and 32.8 g of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate were poured therein, stirred for a while at room temperature, After thoroughly purging with nitrogen by bubbling, the mixture was heated and stirred at 70 캜 for 5 hours. Then, 12.7 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 DEG C for 4 hours to obtain an acrylic resin solution (a) ≪ / RTI > PGMEA was added to the obtained acrylic resin solution (a) so that the solid content concentration became 40 wt%. The weight average molecular weight of the acrylic resin was 18,000 and the carboxylic acid equivalent was 560 g / mol.

(Synthesis Example 7: Synthesis of acrylic resin solution (b)) [

3 g of 2,2'-azobis (isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate) were introduced into a 500 ml flask. Thereafter, 16.8 g of methacrylic acid, 34.4 g of benzylmethacrylate, and 36.9 g of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate were charged, stirred at room temperature for a while, After thoroughly purging with nitrogen by bubbling, the mixture was heated and stirred at 70 캜 for 5 hours. Then, 11.9 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol and 100 g of PGMEA were added and the mixture was heated and stirred at 90 DEG C for 4 hours to obtain an acrylic resin solution (b) ≪ / RTI > PGMEA was added to the obtained acrylic resin solution (b) so that the solid content concentration became 40 wt%. The weight average molecular weight of the acrylic resin was 13,000 and the carboxylic acid equivalent was 890 g / mol.

(Synthesis Example 8: Synthesis of acrylic resin solution (c)) [

3 g of 2,2'-azobis (isobutyronitrile) and 50 g of PGMEA were introduced into a 500 ml flask. Thereafter, 33.9 g of methacrylic acid, 34.4 g of benzylmethacrylate, and 36.9 g of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate were charged, stirred at room temperature for a while, After thoroughly purging with nitrogen by bubbling, the mixture was heated and stirred at 70 캜 for 5 hours. Then, 14.0 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 DEG C for 4 hours to obtain an acrylic resin solution (c) ≪ / RTI > PGMEA was added to the obtained acrylic resin solution (c) so that the solid content concentration became 40 wt%. The weight average molecular weight of the acrylic resin was 24,000 and the carboxylic acid equivalent was 340 g / mol.

(Synthesis Example 9: Synthesis of acrylic resin solution (d)) [

3 g of 2,2'-azobis (isobutyronitrile) and 50 g of PGMEA were introduced into a 500 ml flask. Thereafter, 8.24 g of methacrylic acid, 35.5 g of benzylmethacrylate, and 45.5 g of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate were charged, stirred at room temperature for a while, After thoroughly purging with nitrogen by bubbling, the mixture was heated and stirred at 70 캜 for 5 hours. Then, 10.7 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 DEG C for 4 hours to obtain an acrylic resin solution (d) ≪ / RTI > PGMEA was added to the obtained acrylic resin solution (d) so that the solid concentration became 40 wt%. The weight average molecular weight of the acrylic resin was 9,000, and the carboxylic acid equivalent was 4,600 g / mol.

(Synthesis Example 10: Synthesis of acrylic resin solution (e)) [

3 g of 2,2'-azobis (isobutyronitrile) and 50 g of PGMEA were introduced into a 500 ml flask. Thereafter, 69.5 g of methacrylic acid, 7.9 g of benzylmethacrylate, and 9.9 g of tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate were charged, stirred for a while at room temperature, After thoroughly purging with nitrogen by bubbling, the mixture was heated and stirred at 70 캜 for 5 hours. Then, 12.8 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 DEG C for 4 hours to obtain an acrylic resin solution (e) ≪ / RTI > PGMEA was added to the obtained acrylic resin solution (e) so that the solid concentration became 40 wt%. The weight average molecular weight of the acrylic resin was 40,000, and the carboxylic acid equivalent was 140 g / mol.

Compositions of Synthesis Examples 1 to 9 are summarized in Table 1.

Figure 112012072329808-pct00003

The evaluation method in each example and comparative example is shown below.

(1) Measurement of transmittance

The negative photosensitive resin composition thus prepared was applied onto a 5 cm x 5 cm TEMPAX glass substrate (manufactured by AGC TECNO GLASS CO., LTD.) Using a spin coater ("1H-360S (trade name)" available from Mikasa corporation) And spin-coated at 1,000 rpm for 4 seconds and then pre-baked at 90 DEG C for 2 minutes using a hot plate ("SCW-636 (trade name)" manufactured by DAINIPPON SCREEN MFG. CO. A film having a thickness of 2 mu m was produced. The resulting film was exposed using an ultra-high pressure mercury lamp as a light source by using a parallel optical mask aligner PLA-501F (trade name, manufactured by Canon Inc.) (manufactured by ESPEC Corp., IHPS-222 Quot;) at 230 deg. C in the air for one hour to prepare a cured film having a thickness of 1.5 mu m.

The resulting cured film was measured for transmittance at 400 nm using an ultraviolet-visible spectrophotometer "UV-260 (trade name)" (manufactured by Shimadzu Corporation). In addition, the film thickness was measured by DAINIPPON SCREEN MFG. Quot; Lambda Ace STM-602 (trade name) " manufactured by CO., LTD. The film thicknesses described below are also the same.

(2) Measurement of hardness

The pencil hardness of a cured film having a thickness of 1.5 탆 obtained by the method described in the above (1) was measured according to JIS K 5600-5-4 (1999).

(3) Humidity resistance

A cured film was prepared on the glass having a molybdenum sputter film by the method described in the above (1), and then left in an oven (ESPEC Corp., "EX-111 (trade name)") at a temperature of 85 ° C and a humidity of 85% for 300 hours And the degree of discoloration of molybdenum was evaluated. Further, the glass substrate of only the molybdenum sputter film was tested at the same time, and it was determined as an index of the degree of discoloration before and after the test as follows.

5: No discoloration is seen in molybdenum under the cured film before and after the test.

4: Before and after the test, the molybdenum under the cured film was discolored by about 1% as compared with the case where the cured film was not covered with the molybdenum.

3: Before and after the test, the molybdenum under the cured film was discolored by about 2% compared with the case where it was not covered with the cured film.

2: The molybdenum under the cured film was discolored by about 4% before and after the test, compared with the case where the cured film was not covered with molybdenum.

1: Before and after the test, the molybdenum under the cured film was discolored by about 60% or more as compared with the case where it was not covered with the cured film.

(4) Pattern processability

(4-1) Sensitivity

The negative-type photosensitive resin composition A was spin-coated on a silicon wafer using a spin coater ("1H-360S (trade name)" available from Mikasa corporation) at 500 rpm for 10 seconds and then rotated at 1,000 rpm for 4 seconds to spin- (SCW-636 (trade name) manufactured by SCREEN MFG. CO., LTD.) At 90 DEG C for 2 minutes to prepare a prebaked film having a thickness of 2 mu m. A high-pressure mercury lamp was used as a light source by using PLA in the obtained pre-baking film, and exposed with a gap of 100 mu m through a gray scale mask for sensitivity measurement. Thereafter, a 0.4 wt% (or 2.38 wt%) aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) was sprayed for 90 seconds using an automatic developing apparatus ("AD-2000 (trade name)", manufactured by TAKIZAWA CO. , Followed by rinsing with water for 30 seconds.

The amount of exposure (hereinafter referred to as optimum exposure amount) for forming a line-and-space pattern of 30 mu m after exposure and development with a width of 1: 1 was taken as sensitivity. The amount of exposure was measured with an I-line illuminometer.

(4-2) Resolution

And the minimum pattern size after development in the optimum exposure amount was measured.

(4-3) residue after development

After patterning on a silicon wafer by the method described in the above (4-1), it was judged as follows according to the degree of dissolution residue in the unexposed portion.

5: There is no residue when viewed from the naked eye, and no microscopic pattern of 50 μm or less is observed in microscopic observation.

4: There is no residue when viewed from the naked eye, and there is no residue in the pattern of 50 mu m or more in the microscopic observation, but the residue is in the pattern of 50 mu m or less.

3: There is no residue when viewed from the naked eye, but there is a residue in a pattern of 50 μm or more in microscopic observation.

2: There is a residue on the end of the substrate (thick film portion) when viewed from the naked eye.

1: There is dissolved residue in the entire unexposed portion when viewed with the naked eye.

(Example 1)

0.277 g of 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] ("Irgacure OXE-01 (trade name)" available from Ciba Specialty Chemicals) 2.846 g and PGMEA were dissolved in 2.317 g. To the solution was added zirconium di-n-butoxybis (ethylacetoacetate) (70 wt% 1-butanol solution) ("ORGATIX ZC-580 (trade name)" manufactured by Matsumoto Fine Chemical Co., 0.2000 g of a 1 wt% solution of PGMEA (corresponding to a concentration of 100 ppm) of a silicone surfactant "BYK-333 (trade name)" (BYK Japan KK) and 1.661 g of a 1 wt.% Solution of PGMEA in 4-t- And the mixture was stirred. 5.538 g of a 50% by weight solution of PGMEA in dipentaerythritol hexaacrylate ("Kayarad (registered trademark)" DPHA (trade name) "available from Nippon Kayaku Co., Ltd.) and 6.923 g of the polysiloxane solution (i) And the mixture was stirred. Subsequently, the negative type photosensitive resin composition (S-1) was obtained by filtration with a 0.45 mu m filter. The negative photosensitive resin composition (S-1) obtained was evaluated for transmittance, hardness, wet heat resistance and pattern processability by the above method.

(Example 2)

A negative-working photosensitive resin composition (S-2) was obtained in the same manner as in Example 1 except that the polysiloxane solution (ii) was used instead of the polysiloxane solution (i). Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-2). However, a 2.38 wt% TMAH aqueous solution was used for the developing solution.

(Example 3)

A negative-working photosensitive resin composition (S-3) was obtained in the same manner as in Example 1 except that the polysiloxane solution (iii) was used instead of the polysiloxane solution (i). Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-3).

(Example 4)

A negative-working photosensitive resin composition (S-4) was obtained in the same manner as in Example 1 except that the polysiloxane solution (iv) was used instead of the polysiloxane solution (i). Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-4).

(Example 5)

0.503 g of 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (Irgacure 907 (trade name), available from Ciba Specialty Chemicals) (Manufactured by Hodogaya Chemical Co., Ltd.), 0.030 g of DAA, 2.515 g of PGMEA, 0.227 g of "ZC-580 (trade name)", 0.5 g of a silicone surfactant , And 1.588 g of 4-t-butyl catechol (1 wt% PGMEA solution) were added to the solution and stirred. 5.294 g of "DPHA" (50 wt% PGMEA solution) and 6.617 g of the polysiloxane solution (i) were added thereto and stirred. Subsequently, the negative type photosensitive resin composition (S-5) was obtained by filtration with a 0.45 탆 filter. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-5).

(Example 6)

(9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (0-acetyloxime) Cure OXE-02 (trade name) " manufactured by Ciba Specialty Chemicals) was used in place of celite OXE-02 (trade name, manufactured by Ciba Specialty Chemicals) to obtain a negative photosensitive resin composition (S-6). Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-6).

(Example 7)

Except that tripentaerythritol octaacrylate ("V # 802 (trade name)", manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) Was used in place of "DPHA (trade name)" to prepare a negative photosensitive resin composition (S- 7). Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-7).

(Example 8)

3.323 g of "V # 802 (trade name)" (50% PGMEA solution) and 9.32 g of 9,9-bis [4- (2- acryloyloxyethoxy) phenyl] fluorene (S-8) was obtained in the same manner as in Example 1, except that 2.215 g of a 50 wt% PGMEA solution (manufactured by Osaka Gas Chemicals Co., Ltd.) was used. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-8).

(Example 9)

0.278 g of DAA, 2.016 g of PGMEA, 0.538 g of "Nano-use OZ-30M (trade name)" (methanol solution, solid content = 30.9 wt%), BYK (Corresponding to a concentration of 100 ppm) and 1.661 g of 4-t-butylcatechol (1 wt% PGMEA solution) were added and stirred. 5.538 g of "DPHA (trade name)" (50% PGMEA solution) and 6.923 g of the polysiloxane solution (i) were added and stirred. Subsequently, the negative type photosensitive resin composition (S-9) was obtained by filtration with a filter of 0.45 mu m. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-9).

(Example 10)

(Product name) (methanol solution, solid content = 30.9 wt%) 3.098 g, and silicone surfactant BYK (trade name, manufactured by Nippon Kayaku Co., And 1.436 g of 4-t-butyl catechol (1 wt% PGMEA solution) were added to the solution, and the mixture was stirred. , 4.787 g of "DPHA (trade name)" (50% PGMEA solution) and 5.984 g of the polysiloxane solution (i) were added and stirred. Subsequently, the negative type photosensitive resin composition (S-10) was obtained by filtration with a 0.45 mu m filter. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-10).

(Example 11)

Except that 0.831 g of "BALAL Zr-C20 (trade name)" (methanol solution, solid content = 20 wt%) was used instead of 0.538 g of "Nano-use OZ-30M (trade name)" to obtain a negative photosensitive resin composition (S-11). Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-11).

(Example 12)

(Manufactured by NIHON KAGAKU SANGYO CO., LTD.), 0.277 g of DAA, 2.388 g of PGMEA, zirconium tetraacetylacetonate ("Nacem zirconium (trade name) (Corresponding to a concentration of 100 ppm) and 1.661 g of 4-t-butylcatechol (1 wt% PGMEA solution) were added to the solution and stirred. 5.538 g of "DPHA (trade name)" (50 wt% PGMEA solution) and 6.923 g of the polysiloxane solution (i) were added and stirred. Subsequently, filtration was performed with a filter of 0.45 mu m to obtain a negative-type photosensitive resin composition (S-12). Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-12).

(Example 13)

A negative-type photosensitive resin composition (S-13) was obtained in the same manner as in Example 12 except that the addition amount of nematic zirconium was changed to 0.017 g. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-13).

(Example 14)

The negative-type photosensitive resin composition (S-14) was obtained in the same manner as in Example 12 except that the addition amount of nematic zirconium was changed to 0.323 g. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-14).

(Example 15)

A negative-type photosensitive resin composition (S-13) was obtained in the same manner as in Example 12 except that zirconium tetrapropoxide was used in place of nematic zirconium. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-13).

(Example 16)

A negative-type photosensitive resin composition (S-14) was obtained in the same manner as in Example 12 except that zirconium tetraphenoxide was used in place of zirconium zirconium. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-14).

(Example 17)

(S-15) was obtained in the same manner as in Example 12 except that zirconium tetra (2,2,6,6-tetramethyl-3,5-heptanedionate) was used instead of nematic zirconium. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-15).

(Example 18)

A negative-type photosensitive resin composition (S-16) was obtained in the same manner as in Example 12 except that zirconium tetramethylmalonate was used instead of nematic zirconium. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-16).

(Example 19)

A negative photosensitive resin composition (S-17) was obtained in the same manner as in Example 12 except that zirconium tetrabenzoyl acetonate was used instead of nematic zirconium. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-17).

(Example 20)

(S-18) was obtained in the same manner as in Example 12 except that zirconium mono n-butoxyacetylacetonate bis (ethyl acetoacetate) was used instead of nematic zirconium. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-18).

(Example 21)

A negative-working photosensitive resin composition (S-19) was obtained in the same manner as in Example 12 except that dichlorobis (? 5-cyclopentadienyl) zirconium was used instead of nematic zirconium. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-19).

(Example 22)

Except that bis (? 5-cyclopentadienyl) zirconium chloride hydride was used in place of nasum zirconium, to obtain a negative-type photosensitive resin composition (S-20). Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-20).

(Example 23)

A negative-type photosensitive resin composition (S-21) was obtained in the same manner as in Example 12 except that zirconocene bis (trifluoromethane sulfonate) tetrahydrofuran adduct was used in place of nematic zirconium. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (S-21).

(Reference Example 1)

A negative photosensitive resin composition (A-1) was obtained in the same manner as in Example 1, except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-1).

(Reference Example 2)

A negative photosensitive resin composition (A-2) was obtained in the same manner as in Example 2 except that the acrylic resin solution (b) was used instead of the polysiloxane solution (ii) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-2). However, a 2.38 wt% TMAH aqueous solution was used for the developing solution.

(Reference Example 3)

A negative photosensitive resin composition (A-3) was obtained in the same manner as in Example 3 except that the acrylic resin solution (c) was used instead of the polysiloxane solution (iii) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-3).

(Reference Example 4)

A negative photosensitive resin composition (A-4) was obtained in the same manner as in Example 5, except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-4).

(Reference Example 5)

A negative photosensitive resin composition (A-5) was obtained in the same manner as in Example 6 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-5).

(Reference Example 6)

A negative photosensitive resin composition (A-6) was obtained in the same manner as in Example 7 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-6).

(Reference Example 7)

A negative-type photosensitive resin composition (A-7) was obtained in the same manner as in Example 8 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added in place of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-7).

(Reference Example 8)

A negative photosensitive resin composition (A-8) was obtained in the same manner as in Example 9 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-8).

(Reference Example 9)

A negative photosensitive resin composition (A-9) was obtained in the same manner as in Example 10, except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-9).

(Reference Example 10)

A negative-type photosensitive resin composition (A-10) was obtained in the same manner as in Example 11 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-10).

(Reference Example 11)

A negative-type photosensitive resin composition (A-11) was obtained in the same manner as in Example 12 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-11).

(Reference Example 12)

A negative-type photosensitive resin composition (A-12) was obtained in the same manner as in Example 13 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was used instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-12).

(Reference Example 13)

A negative photosensitive resin composition (A-13) was obtained in the same manner as in Example 14 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-13).

(Reference Example 14)

A negative photosensitive resin composition (A-14) was obtained in the same manner as in Example 15 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-14).

(Reference Example 15)

A negative-type photosensitive resin composition (A-15) was obtained in the same manner as in Example 16 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-15).

(Reference Example 16)

A negative-type photosensitive resin composition (A-16) was obtained in the same manner as in Example 17 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-16).

(Reference Example 17)

A negative-type photosensitive resin composition (A-17) was obtained in the same manner as in Example 18 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was used instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-17).

(Reference Example 18)

A negative-type photosensitive resin composition (A-18) was obtained in the same manner as in Example 19 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was used instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-18).

(Reference Example 19)

A negative-type photosensitive resin composition (A-19) was obtained in the same manner as in Example 20 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was used instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-19).

(Reference Example 20)

A negative-type photosensitive resin composition (A-20) was obtained in the same manner as in Example 21 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was added instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-20).

(Reference Example 21)

A negative-type photosensitive resin composition (A-21) was obtained in the same manner as in Example 22 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was used instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-20).

(Reference Example 22)

A negative-type photosensitive resin composition (A-22) was obtained in the same manner as in Example 23 except that the acrylic resin solution (a) was used instead of the polysiloxane solution (i) and the same amount of PGMEA was used instead of DAA. Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (A-20).

(Example 46)

A touch panel member was produced in the following procedure.

(1) Production of ITO

A glass substrate having a thickness of about 1 mm was sputtered using a sputtering apparatus HSR-521A (manufactured by Shimadzu Corporation) at an RF power of 1.4 kW and a vacuum degree of 6.65 x 10 -1 Pa for 12.5 minutes to obtain a film having a thickness of 150 nm and a surface resistance of 15? A positive photoresist ("OFPR-800" manufactured by TOKYO OHKA KOGYO Co., Ltd.) was applied and pre-baked at 80 ° C for 20 minutes to obtain a resist film having a film thickness of 1.1 μm. The film obtained by using PLA was subjected to pattern exposure through a mask using an ultra-high pressure mercury lamp, followed by shower development for 90 seconds with an aqueous 2.38 wt% TMAH solution using an automatic developing apparatus, followed by rinsing with water for 30 seconds. Subsequently, the ITO was etched by immersing in a mixed solution of HCl / HNO 3 / H 2 O = 18 / 4.5 / 77.5 (weight ratio) at 40 ° C for 80 seconds to remove the peeling solution ("N-300" manufactured by Nagase ChemteX Corporation) For 120 seconds to remove the photoresist, and a glass substrate having a patterned transparent electrode with a thickness of 200 angstroms was produced.

(2) Fabrication of transparent insulating film

The negative-type photosensitive resin composition (A-1) was used to form a transparent insulating film on the obtained glass substrate according to the above-described evaluation method.

(3) Fabrication of a molybdenum / aluminum / molybdenum multilayer film (MAM) wiring

Except that molybdenum and aluminum were used as targets and a mixed solution of H 3 PO 4 / HNO 3 / CH 3 COOH / H 2 O = 65/3/5/27 (weight ratio) was used as an etchant on the obtained glass substrate. ), The MAM wiring was fabricated.

(4) Fabrication of transparent protective film

A transparent protective film was prepared in the order of the evaluation method described above using the negative-type photosensitive resin composition (A-1) on the obtained glass substrate.

As a result of conducting a conduction test of the connection portion using a tester, conduction of current was confirmed.

(Comparative Example 1)

A resin composition (H-1) was obtained in the same manner as in Example 1 except that an acrylic resin solution (d) was used instead of the polysiloxane solution (i) and an equal amount of PGMEA was added in place of DAA. Here, the carboxylic acid equivalent of the acrylic resin solution (d) was 4,600 g / mol. Evaluation was carried out in the same manner as in Example 1 using the obtained resin composition (H-1). Further, since the unexposed portion was not dissolved in the aqueous solution of 2.38 wt% TMAH and pattern processing could not be performed, the evaluation was carried out without performing the development.

(Comparative Example 2)

A resin composition (H-2) was obtained in the same manner as in Example 1 except that an acrylic resin solution (e) was used instead of the polysiloxane solution (i) and an equal amount of PGMEA was added in place of DAA. The carboxylic acid equivalent of the acrylic resin solution (e) was 140 g / mol. Evaluation was carried out in the same manner as in Example 1 using the obtained resin composition (H-2).

(Comparative Example 3)

(Corresponding to a concentration of 100 ppm), 4-t-butylcatechol (1 wt%), and the like were added to the solution, PGMEA solution) were added and stirred. 5.806 g of "DPHA (trade name)" (50 wt% PGMEA solution) and 7.258 g of the acrylic resin solution (a) were added and stirred. Subsequently, filtration was performed with a 0.45 占 퐉 filter to obtain a resin composition (H-3). The resin composition (H-3) does not contain a photopolymerization initiator. Evaluation was carried out in the same manner as in Example 1 using the obtained resin composition (H-3). In addition, since the pattern was not formed because the pattern was dissolved in the 0.4 wt% TMAH aqueous solution together with the exposed portion and the unexposed portion, the other evaluations were carried out without developing.

(Comparative Example 4)

0.277 g of PGMEA, 0.237 g of "ZC-580 (trade name)" and 0.2000 g of a silicone surfactant BYK-333 (1 wt% PGMEA solution) (corresponding to a concentration of 100 ppm) , And 1.661 g of 4-t-butylcatechol (1 wt% PGMEA solution) were added and stirred. 13.846 g of the acrylic resin solution (a) was added and stirred. Subsequently, the resin composition (H-4) was obtained by filtration with a 0.45 mu m filter. The resin composition (H-4) does not contain a polyfunctional monomer. Evaluation was carried out in the same manner as in Example 1 using the obtained resin composition (H-4).

(Comparative Example 5)

(Corresponding to a concentration of 100 ppm), 4-t-butyl catechol (1 wt% PGMEA (trade name)), 0.285 g of "OXE-01 (trade name)", yellow PGMEA, 4.990 g of BYK- 1.709 g) was added and stirred. 5.696 g of "DPHA (trade name)" (50 wt% PGMEA solution) and 7.120 g of the acrylic resin solution (a) were added and stirred. Subsequently, the resin composition (H-5) was obtained by filtration with a 0.45 占 퐉 filter. The resin composition (H-5) does not contain a zirconium compound. Evaluation was carried out in the same manner as in Example 1 using the obtained resin composition (H-5).

(Comparative Example 6)

(Corresponding to a concentration of 100 ppm), 4-t-butyl catheter (corresponding to a concentration of 100 ppm), 0.285 g of "OXE-01 (trade name)", 2.262 g of PGMEA, 2.846 g of DAA and BYK- 1.709 g of Cole (1 wt% PGMEA solution) was added and stirred. 5.696 g of "DPHA (trade name)" (50 wt% PGMEA solution) and 7.120 g of the polysiloxane solution (i) were added and stirred. Subsequently, filtration was performed with a 0.45 占 퐉 filter to obtain a resin composition (H-6). The resin composition (H-6) does not contain a zirconium compound. Evaluation was carried out in the same manner as in Example 1 using the obtained resin composition (H-6).

(Comparative Example 7)

A negative-working photosensitive resin composition (H-7) was obtained in the same manner as in Example 1 except that the polysiloxane solution (v) was used instead of the polysiloxane solution (i). Evaluation was carried out in the same manner as in Example 1 using the obtained negative-type photosensitive resin composition (H-7). In addition, the unexposed portion was not dissolved in the 0.4 wt% TMAH aqueous solution.

Figure 112012072329808-pct00004

Figure 112017098843206-pct00010

Figure 112017098843206-pct00011

The cured film obtained by curing the negative photosensitive resin composition of the present invention can be used for various kinds of hard coating films such as protective films for touch panels and the like, as well as insulating films for touch panels, planarizing films for TFTs for TFTs, metal wiring protective films, Antireflection films, optical filters, overcoats for color filters, and column materials.

1: glass substrate 2: transparent electrode
3: transparent insulating film 4: wiring electrode
5: Transparent protective film

Claims (10)

(A) a polysiloxane having a carboxylic acid equivalent of 200 g / mol or more and 1,400 g / mol or less, (B) a photopolymerization initiator, (C) a polyfunctional monomer, and (D) a zirconium compound,
Wherein the zirconium compound (D) is a zirconium oxide particle having an average particle diameter of 100 nm or less. delete delete delete The method according to claim 1,
Wherein the polysiloxane having a carboxylic acid equivalent (A) of 200 g / mol or more and 1,400 g / mol or less is a polysiloxane having an ethylenic unsaturated bond. delete delete A touch panel protective film formed by curing the negative photosensitive resin composition according to any one of claims 1 to 5. A protective film for metal wiring, which comprises curing the negative photosensitive resin composition according to any one of claims 1 to 5. A touch panel member comprising a cured film of the negative photosensitive resin composition according to any one of claims 1 to 5, wherein the molybdenum-containing metal wiring is protected by the cured film.
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