SG184526A1 - 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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Publication number
SG184526A1
SG184526A1 SG2012075073A SG2012075073A SG184526A1 SG 184526 A1 SG184526 A1 SG 184526A1 SG 2012075073 A SG2012075073 A SG 2012075073A SG 2012075073 A SG2012075073 A SG 2012075073A SG 184526 A1 SG184526 A1 SG 184526A1
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SG
Singapore
Prior art keywords
resin composition
negative
photosensitive resin
tone photosensitive
mol
Prior art date
Application number
SG2012075073A
Inventor
Hitoshi Araki
Mitsuhito Suwa
Toru Okazawa
Original Assignee
Toray Industries
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Publication of SG184526A1 publication Critical patent/SG184526A1/en

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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

Abstract

5 Provided is a negative-tone photosensitive resin composition comprising (A)an alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol, (B) a photopolymerization initiator, (C) a polyfunctional monomer, and (D) azirconium compound. Also provided is an alkali-developable negative-tone photosensitive resin composition that provides a cured film having excellent pattern 10 processability, high hardness and high transparency due to UV curing and heat curing, and excellent humidity and heat resistance.

Description

DESCRIPTION
Negative-Tone Photosensitive Resin Composition, and Protective Film and Touch
Panel Component Using the Same
TECHNICAL FIELD
[0001]
The present invention relates to a negative-tone photosensitive resin composition, and a protective film and a touch panel component using the same.
BACKGROUND ART
[0002]
Currently, hard coating materials find use in various applications and used, for example, to improve surface hardness, for example, of automotive parts, containers for cosmetics and the like, sheets, films, optical disks, and flat displays.
Examples of the properties required for hard coating materials include heat resistance, weatherability, and adhesion as well as hardness and abrasion resistance.
PRIOR ART DOCUMENTS
PATENT DOCUMENTS
[0003]
Representative examples of hard coating materials include radical polymerizable and UV-curable hard coating (see, for example, Non-patent Document 1), and the constituents thereof are a polymerizable group-containing oligomer, a monomer, a photopolymerization initiator, and other additives. An oligomer and a monomer are radically polymerized by UV irradiation and thus cross-linked to obtain a film with high hardness. This hard coating material has advantages in that it improves productivity because it requires little time for curing and besides that it reduces production cost because a negative-tone photosensitive material based on a common radical polymerization mechanism can be used.
[0004]
However, there has been a problem in that the hardness and abrasion resistance are low compared to other hard coating materials because of a large amount of organic components, and cracks generates as a result of volume shrinkage due to UV curing.
[0005]
A capacitive-type touch panel, which has been receiving attention in recent years, is one application of hard coating materials. The capacitive-type touch panel has a structure with a pattern formed from ITO (Indium Tin Oxide) or metal (such as silver, molybdenum, or aluminum) on a glass. To protect this ITO and metal, films having high hardness, transparency, and humidity and heat resistance are demanded.
However, it is difficult to simultaneously achieve these performances, and hard coating materials that overcome this problem have been demanded.
[0006]
As an organic hard coating material, an UV-curable coating composition containing a polymerizable group-containing oligomer, a monomer, a photopolymerization initiator, and other additives is known. Such a composition provides a cured film having pattern processability and having high hardness and transparency. However, the composition has had a problem with humidity and heat resistance.
[0007]
As a method of improving humidity and heat resistance, the method of adding a metal chelating agent to siloxane is known (see Patent Document 1). This is considered to be a mechanism in which titanium or a zirconium chelating agent promotes cross-linking of siloxane to thereby improve humidity and heat resistance.
[0008]
Also reported is the case where a polymerizable functional group is introduced using a metal chelating agent as a polymerization catalyst for siloxane to provide negative-tone photosensitivity (see, for example, Patent Document 2).
[0009]
In addition, a negative-tone photosensitive material containing an organic metal compound is reported (Patent Document 3).
Patent Document 1: JP 07-331173 A
Patent Document 2: JP 2008-203605 A
Patent Document 3: JP 2007-308688 A
NON-PATENT DOCUMENTS
[0010]
Non-patent Document 1: "Material design, coating technique, and hardness improvement in hard coating film on plastic substrate", Ohara Noboru et al.,
TECHNICAL INFORMATION INSTITUTE CO., LTD., Apr. 28, 2005, p 301.
SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION
[0011]
According to the technique of Non-patent Document 1, there has been a problem in that the hardness and abrasion resistance are low compared to other hard coating materials because of a large amount of organic components, and cracks generates as a result of volume shrinkage due to UV curing.
[0012]
According to the technique of Patent Document 1, resins are limited to siloxanes with a main chain and side chains that are hydrophobic, so that the effect, for example, on hydrophilic resins such as siloxanes having carboxyl groups in its side chain and other carboxyl-containing resins is not clear.
[0013]
According to the technique of Patent Document 2, the content of silanol groups is small in order to reduce cross-linking of siloxane during pre-baking, and it was difficult to carry out development with an aqueous alkaline solution.
[0014]
According to the technique of Patent Document 3, baking is carried out to form a metal film, and organic components do not remain. Therefore, it is not clear what effect an organic metal compound has on a resin component.
[0015]
As described above, although there is a need for a negative-tone photosensitive material that has high hardness, high transparency, and high humidity and heat resistance and can be patterned with an alkaline developing solution, the technique therefor has not hitherto been established.
[0016]
An object of the present invention is to provide an alkali-developable negative-tone photosensitive resin composition that provides a cured film having excellent pattern processability, high hardness and high transparency due to UV curing and heat curing, and excellent humidity and heat resistance.
MEANS FOR SOLVING THE PROBLEMS
[0017]
Thus, the object of the present invention is achieved by a negative-tone photosensitive resin composition comprising (A) an alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol, (B) a photopolymerization initiator, (C) a polyfunctional monomer, and (D) a zirconium compound.
[0018]
Further, the object of the present invention is achieved by a touch panel protective film obtained by curing the negative-tone photosensitive resin composition described above.
[0019]
The object of the present invention is achieved by a metal wire protective film obtained by curing the negative-tone photosensitive resin composition described above.
[0020]
Further, the object of the present invention is achieved by a touch panel component comprising a cured film of the negative-tone photosensitive resin composition described above, wherein a molybdenum-containing metal wire is protected by the cured film.
[0021]
The negative-tone photosensitive resin composition of the present invention is preferably a composition for forming a cured film.
[0022]
The negative-tone photosensitive resin composition of the present invention is preferably a composition for forming a protective film.
[0023]
In the negative-tone photosensitive resin composition of the present invention, (A) the alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol is preferably an acrylic resin having an ethylenically unsaturated bond.
[0024]
In the negative-tone photosensitive resin composition of the present invention, (A) the alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol is preferably a polysiloxane having an ethylenically unsaturated bond.
[0025]
In the negative-tone photosensitive resin composition of the present invention, (D) the zirconium compound is preferably zirconium oxide particles having an average particle size of 100 nm or less.
[0026]
In the negative-tone photosensitive resin composition of the present invention,
(D) the zirconium compound is preferably any one or more of compounds represented by Formula (1):
[0027][Chamical Formula 1]
R?2 0= rir 7 1) n 0
R® 4-n
[0028] (R' represents hydrogen, alkyl, aryl, alkenyl, and substitution products thereof, and R? and R’ represent hydrogen, alkyl, aryl, alkenyl, alkoxy, and substitution products thereof. A plurality of R', R%, and R® may be the same or different. n represents an integer of 0 to 4.)
EFFECTS OF THE INVENTION
[0029]
The negative-tone photosensitive resin composition of the present invention provides a cured film having excellent pattern processability, high hardness and high transparency due to UV curing and heat curing, and excellent humidity and heat resistance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030]
Figure 1 1s schematic top views after each process in the production of a touch panel component; and
Figure 2 1s a schematic cross-sectional view illustrating the touch panel component.
BEST MODE FOR CARRYING OUT THE INVENTION
[0031]
The negative-tone photosensitive resin composition of the present invention contains (A) an alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol, (B) a photopolymerization initiator, (C) a polyfunctional monomer, and (D) a zirconium compound.
[0032]
The negative-tone 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 with light and/or heat without the step of removing all the resin components by, for example, baking or stripping solution treatment. Examples of applications of the cured film include, but are not limited to, various protective films such as a protective film for a touch panel, a hard coating material, a planarization film for a TFT, an overcoat for a color filter, a passivation film, an antireflection film, and a metal wire protective film, various insulating films such as an insulating film for a touch panel, an insulating film for a TFT, and an interlayer insulating film, an optical filter, a photo spacer for a color filter, and a microlens, and the like. Among them, the cured film is preferably used as a protective film because it has high hardness, transparency, and humidity and heat resistance. The protective film means a cured film used for the purpose of protecting various base materials.
Specific examples of applications of the protective film include, but are not limited to, those mentioned above.
[0033]
The negative-tone photosensitive resin composition of the present invention contains (A) the alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol. The carboxylic acid equivalent refers to the weight of resin necessary to obtain one molar amount of carboxyl groups, and its unit is g/mol.
When a carboxylic acid equivalent of the alkali-soluble resin is more than 1,400 g/mol, problems arise in that the alkali solubility (developability) of the negative- tone photosensitive resin composition will be poor, and a good pattern cannot be formed, and that, if developed, residue after development cannot be reduced, or a severe restriction on the type of developing solution will be needed. On the other hand, when a carboxylic acid equivalent of the alkali-soluble resin is less than 200 g/mol, film loss at an exposed portion cannot be prevented, and not only humidity and heat resistance but also resolution will be poor. Within such a range, a good pattern can be formed under various developing conditions.
[0034] (A) the alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol used in the negative-tone photosensitive resin composition of the present invention has an ethylenically unsaturated double bond group, and therefore is able to enhance crosslink density and enhance hardness of a cured film. The preferred range of the carboxylic acid equivalent is from 300 g/mol to 1200 g/mol and more preferably from 400 g/mol to 800 g/mol.
[0035]
Examples of (A) the alkali-soluble resin having a carboxylic acid equivalent 0f 200 g/mol to 1,400 g/mol include polysiloxanes, acrylic resins, polyimides, polyamic acids, polyamides, and the like. In (A) the alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol, an ethylenically unsaturated double bond group is preferably introduced at least in a portion thereof in order to increase hardness of a cured film. Among these polymers, polysiloxanes and acrylic resins are more preferred from the standpoint of ease of introduction of an ethylenically unsaturated double bond group. Further, two or more of these polymers may be contained.
[0036]
Without limitation thereto, preferred examples of (A) the alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol will be described below.
[0037]
As a polysiloxane, for example, preferred are those obtained by hydrolyzing an organosilane compound having a carboxyl group and/or a dicarboxylic anhydride group and condensing the hydrolysate. For adjusting a carboxylic acid equivalent, it is preferable to simultaneously use other organosilane compounds. In particular, it is preferable to use an organosilane compound having an ethylenically unsaturated bond because a resulting cured film will have high hardness.
[0038]
Although the hydrolysis reaction conditions can be appropriately set, it is preferable, for example, to add an acid catalyst and water to an organosilane compound in a solvent over 1 to 180 minutes and then allow the resulting mixture to react at room temperature to 110°C for 1 to 180 minutes. By carrying out a hydrolysis reaction under such conditions, a sudden reaction can be prevented. The reaction temperature is more preferably from 30°C to 105°C.
[0039]
The hydrolysis reaction is preferably carried out in the presence of an acid catalyst. As an acid catalyst, an acidic aqueous solution containing formic acid, acetic acid, or phosphoric acid is preferred. The preferred content of such an acid catalyst is preferably from 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the total organosilane compounds used during the hydrolysis reaction. When the amount of an acid catalyst is in the above range, the hydrolysis reaction can be readily controlled to proceed necessarily and sufficiently.
[0040]
Preferred condensation reaction conditions are, for example, as follows: after obtaining a silanol compound by hydrolysis reaction of an organosilane compound as described above, the reaction solution is heated as it is at from 50°C to the boiling point of a solvent for 1 to 100 hours and allowed to react. To increase the degree of polymerization of the polysiloxane, reheating or addition of a base catalyst may be carried out. Further, after the hydrolysis, an appropriate amount of the product alcohol and the like may be distilled and removed under heating and/or reduced pressure, and then a suitable solvent may be added, depending on the purpose.
[0041]
As a polysiloxane having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol and an ethylenically unsaturated bond, for example, those obtained by hydrolyzing an organosilane compound having a carboxyl group and/or a dicarboxylic anhydride group and an organosilane compound having an ethylenically unsaturated bond and condensing the hydrolysate are preferred.
[0042]
Examples of organosilane compounds having a carboxyl group include 3- trimethoxysilyl propionic acid, 3-triethoxysilyl propionic acid, 3- dimethylmethoxysilyl propionic acid, 3-dimethylethoxysilyl propionic acid, 4- trimethoxysilyl butyric acid, 4-triethoxysilyl butyric acid, 4-dimethylmethoxysilyl butyric acid, 4-dimethylethoxysilyl butyric acid, 5-trimethoxysilyl valeric acid, 5- triethoxysilyl valeric acid, 5-dimethylmethoxysilyl valeric acid, 5- dimethylethoxysilyl valeric acid, and the like.
[0043]
Examples of organosilane compounds having a dicarboxylic anhydride group include 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3- dimethylethoxysilylpropylsuccinic anhydride, 3- trimethoxysilylpropyleyclohexyldicarboxylic anhydride, 3- triethoxysilylpropylcyclohexyldicarboxylic anhydride, 3- dimethylmethoxysilylpropylcyclohexyldicarboxylic anhydride, 3- dimethylethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-
trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, 3-dimethylmethoxysilylpropylphthalic anhydride, 3- dimethylethoxysilylpropylphthalic anhydride, and the like.
[0044]
Examples of other organosilane compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3- aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3- chloropropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane, 3- glycidoxypropyltrimethoxysilane, y-aminopropyltrimethoxysilane, v- aminopropyltriethoxysilane, N-f-(aminoethyl)-y-aminopropyltrimethoxysilane, [3- cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, a-glycidoxyethyltrimethoxysilane, o- glycidoxyethyltriethoxysilane, -glycidoxyethyltrimethoxysilane, B- glycidoxyethyltriethoxysilane, a-glycidoxypropyltrimethoxysilane, a- glycidoxypropyltriethoxysilane, -glycidoxypropyltrimethoxysilane, B- glycidoxypropyltriethoxysilane, y-glycidoxypropyltrimethoxysilane, y- glycidoxypropyltriethoxysilane, a-glycidoxybutyltrimethoxysilane, a- glycidoxybutyltriethoxysilane, f-glycidoxybutyltrimethoxysilane, 3- glycidoxybutyltriethoxysilane, y-glycidoxybutyltrimethoxysilane, y- glycidoxybutyltriethoxysilane, §-glycidoxybutyltrimethoxysilane, 8- glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4- epoxycyclohexyl)methyltriethoxysilane, 2-(3.,4- epoxycyclohexyl)ethyltripropoxysilane, 2-(3,4-epoxycyclohexyl)ethyltributoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4- epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, 3-(3.,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-
epoxycyclohexyl)propyltriethoxysilane, 4-(3,4- epoxycyclohexyl)butyltrimethoxysilane, 4-(3,4- epoxycyclohexyl)butyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, y-glycidoxypropylmethyldimethoxysilane, v-
aminopropylmethyldimethoxysilane, y-aminopropylmethyldiethoxysilane, N-(2- aminoethyl)-3-aminopropylmethyldimethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, a- glycidoxyethylmethyldimethoxysilane, a-glycidoxyethylmethyldiethoxysilane, 3- glycidoxyethylmethyldimethoxysilane, f-glycidoxyethylmethyldiethoxysilane, a-
glycidoxypropylmethyldimethoxysilane, a-glycidoxypropylmethyldiethoxysilane, - glycidoxypropylmethyldimethoxysilane, B-glycidoxypropylmethyldiethoxysilane, y- glycidoxypropylmethyldimethoxysilane, y-glycidoxypropylmethyldiethoxysilane, y- glycidoxypropylethyldimethoxysilane, y-glycidoxypropylethyldiethoxysilane, 3- chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane,
cyclohexylmethyldimethoxysilane, octadecylmethyldimethoxysilane, tetramethoxysilane, tetracthoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, and the like.
Further, by using vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane,
allyltrimethoxysilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, y- acryloylpropyltrimethoxysilane, y-acryloylpropyltriethoxysilane, y- methacryloylpropyltrimethoxysilane, y-methacryloylpropyltriethoxysilane, y-
methacryloylpropylmethyldimethoxysilane, y- methacryloylpropylmethyldiethoxysilane, y-acryloylpropylmethyldimethoxysilane, y-acryloylpropylmethyldiethoxysilane, and the like, an ethylenically unsaturated double bond group can be readily introduced.
[0045]
The carboxylic acid equivalent of a polysiloxane can be calculated by calculating the ratio of silanol groups/carboxyl groups in the polysiloxane by 1H-
NMR and then determining the acid number.
[0046]
When a polysiloxane has an ethylenically unsaturated double bond group, although the content thereof is not particularly restricted, the double bond equivalents are preferably from 150 g/mol to 10,000 g/mol. When the content is in the above range, hardness and crack resistance can be simultaneously achieved at a high level. The double bond equivalents can be calculated by determining the iodine value.
[0047]
The weight average molecular weight (Mw) of a polysiloxane is not particularly restricted and preferably from 1,000 to 100,000 in terms of polystyrene according to gel permeation chromatography (GPC). When the Mw is in the above range, good application properties are obtained, and solubility in a developing solution during pattern formation will also be good.
[0048]
As an acrylic resin, those obtained by radical polymerization of (meth)acrylic acid or (meth)acrylic acid ester are preferred. The catalyst for radical polymerization is not particularly restricted, and azo compounds such as azobisisobutyronitrile and organic peroxides such as benzoyl peroxide are commonly used.
[0049]
Although radical polymerization conditions can be appropriately set, it is preferable, for example, to add (meth)acrylic acid, (meth)acrylic acid ester, and a radical polymerization catalyst into a solvent, purge a reaction vessel sufficiently with nitrogen by, for example, bubbling or degassing under reduced pressure, and then allow the resulting mixture to react at 60°C to 110°C for 30 to 300 minutes.
Chain transfer agents such as thiol compounds may be used as required.
[0050]
As a (meth)acrylic acid ester, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexenyl (meth)acrylate, 4-methoxycyclohexyl (meth)acrylate, 2-cyclopropyloxycarbonylethyl (meth)acrylate, 2- cyclopentyloxycarbonylethyl (meth)acrylate, 2-cyclohexyloxycarbonylethyl (meth)acrylate, 2-cyclohexenyloxycarbonylethyl (meth)acrylate, 2-(4- methoxycyclohexyl)oxycarbonylethyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tetracyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyladamantyl (meth)acrylate, 1- methyladamantyl (meth)acrylate, and the like are used. Aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and a- methylstyrene may be copolymerized therewith.
[0051]
As an acrylic resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol and an ethylenically unsaturated bond, for example, those obtained by radical polymerization of (meth)acrylic acid and (meth)acrylic acid ester and the following reaction by adding an epoxy compound having an ethylenically unsaturated double bond group are preferred. Although the catalyst used in the addition reaction of an epoxy compound having an ethylenically unsaturated double bond group is not particularly restricted and a known catalyst can be used, for example, amino catalysts such as dimethylaniline, 2,4,6-tris(dimethylaminomethyl)phenol, and dimethylbenzylamine; tin catalysts such as tin 2-ethylhexanoate (II) and tin dibutyl laurate; titanium catalysts such as titanium 2-ethylhexanoate (IV); phosphorus catalysts such as triphenylphosphine; and chromium catalysts such as acetylacetonate chromium and chromium chloride, and the like are used. As an epoxy compound having an ethylenically unsaturated double bond group, for example, glycidyl (meth)acrylate, a-ethyl glycidyl (meth)acrylate, a-n-propyl glycidyl (meth)acrylate, a-n-butyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxyheptyl (meth)acrylate, a-ethyl-6,7-epoxyheptyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p- vinylbenzyl glycidyl ether, a-methyl-o-vinylbenzyl glycidyl ether, a-methyl-m- vinylbenzyl glycidyl ether, a-methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyl oxymethylstyrene, 2,4-diglycidyl oxymethylstyrene, 2,5-diglycidyl oxymethylstyrene, 2,6-diglycidyl oxymethylstyrene, 2,3,4-triglycidyl oxymethylstyrene, 2,3,5-triglycidyl oxymethylstyrene, 2,3,6-triglycidyl oxymethylstyrene, 3,4,5-triglycidyl oxymethylstyrene, 2,4,6-triglycidyl oxymethylstyrene, or the like is used.
[0052]
When an acrylic resin has an ethylenically unsaturated double bond group, although the content thereof is not particularly restricted, the double bond equivalents are preferably from 150 g/mol to 10,000 g/mol. When the content is in the above range, hardness and crack resistance can be simultaneously achieved at a high level. The double bond equivalents can be calculated by determining the iodine value.
[0053]
The weight average molecular weight (Mw) of an acrylic resin is not particularly restricted and preferably from 2,000 to 200,000 in terms of polystyrene according to gel permeation chromatography (GPC). When the Mw is in the above range, good application properties are obtained, and solubility in a developing solution during pattern formation will also be good.
[0054]
In the negative-tone photosensitive resin composition of the present invention, although the content of (A) the alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol is not particularly restricted and can be arbitrarily selected depending on the desired film thickness and application, it is generally from 10 wt% to 60 wt% based on the solid content of the negative-tone photosensitive resin composition.
[0055]
The negative-tone photosensitive resin composition of the present invention contains (B) the photopolymerization initiator. (B) the photopolymerization initiator is preferably one that is decomposed and/or reacted by light (including ultraviolet light and electron beam) to generate radicals.
[0056]
Specific examples thereof include 2-methyl-[4-(methylthio)phenyl]-2- morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4- yl-phenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)- butanone-1, 2.4,6-trimethylbenzoyl phenylphosphine oxide, bis(2,4,6- trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4- trimethylpentyl)-phosphine oxide, 1-phenyl-1,2-propanedione-2-(o- ethoxycarbonyl)oxime, 1,2-octanedione,1-[4-(phenylthio)-2-(O-benzoyloxime)], 1- phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o- ethoxycarbonyl)oxime, ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-y1]- ,1-(O -acetyloxime), 4,4-bis(dimethylamino)benzophenone, 4,4- bis(diethylamino)benzophenone, ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p- dimethylaminobenzoate, ethyl p-diethylaminobenzoate, diethoxyacetophenone, 2- hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-(4-
isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(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-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4- benzoyl-N,N-dimethyl-N-[2-(1-0x0-2-propenyloxy)ethyl ]benzenemethanaminium bromide, (4-benzoylbenzyl)trimethylammonium chloride, 2-hydroxy-3-(4- benzoylphenoxy)-N,N,N-trimethyl-1-propene aminium chloride monohydrate, 2- isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2.,4- dichlorothioxanthone, 2-hydroxy-3-(3,4-dimethyl-9-o0x0-9H-thioxanthen-2-yloxy)-
N,N,N-trimethyl-1-propanaminium chloride, 2,2'-bis(o-chlorophenyl)-4,5.,4',5'- tetraphenyl-1,2-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methylphenyl glyoxyester, 15- cyclopentadienyl-n6-cumenyl-iron(1+)-hexafluorophosphate(1-), diphenyl sulfide derivatives, bis(n5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)- phenyl)titanium, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4- benzoyl-4-methylphenyl ketone, dibenzyl ketone, fluorenone, 2,3- diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy- 2-methylpropiophenone, p-t-butyldichloroacetophenone, benzyl methoxyethyl acetal, anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, p-chloranthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4- azidobenzalacetophenone, 2,6-bis(p-azidobenzylidene)cyclohexane, 2,6-bis(p- azidobenzylidene)-4-methylcyclohexanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide, combinations of a photoreducible dye such as eosin or methylene blue and a reducing agent such as ascorbic acid or triethanolamine, and the like. Two or more of them may be contained.
[0057]
Among them, a-aminoalkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, benzophenone compounds having an amino group, or benzoic acid ester compounds having an amino group are preferred to further increase the hardness of a cured film.
[0058]
Specific examples of a-aminoalkylphenone compounds include 2-methyl-[4- (methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4- methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-benzyl-2- dimethylamino-1-(4-morpholinophenyl)-butanone-1, and the like. Specific examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6- dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide, and the like. Specific examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-(o- ethoxycarbonyl)oxime, 1,2-octanedione,1-[4-(phenylthio)-2-(O-benzoyloxime)], 1- phenyl-1,2-butadione-2-(o-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(o- ethoxycarbonyl)oxime, ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]- ,1-(O -acetyloxime), and the like. Specific examples of benzophenone compounds having an amino group include 4,4-bis(dimethylamino)benzophenone, 4,4- bis(diethylamino)benzophenone, and the like. Specific examples of benzoic acid ester compounds having an amino group include ethyl p-dimethylaminobenzoate, 2- ethylhexyl-p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, and the like.
[0059]
In the negative-tone photosensitive resin composition of the present invention, the content of (B) the photopolymerization initiator is not particularly restricted and preferably from 0.1 wt% to 20 wt% based on the solid content of the negative-tone photosensitive resin composition. When the content is within the above range, sufficient progress of curing can be made, and the remaining polymerization initiator can be prevented from, for example, dissolving to thereby ensure solvent resistance.
[0060]
The negative-tone photosensitive resin composition of the present invention contains (C) the polyfunctional monomer. Upon light irradiation, (B) the photopolymerization initiator described above promotes polymerization of (C) the polyfunctional monomer, and an exposed portion of the negative-tone photosensitive resin composition of the present invention becomes insoluble in an aqueous alkaline solution, whereby a negative-tone pattern can be formed. The polyfunctional monomer refers to a compound having in its molecule at least two or more ethylenically unsaturated double bonds, and preferred is a polyfunctional monomer having a (meth)acrylic group susceptible to radical polymerization but is not limited thereto. A double bond equivalent of (C) the polyfunctional monomer is preferably from 80 g/mol to 400 g/mol in terms of sensitivity and hardness.
[0061]
Examples of (C) the polyfunctional monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetracthylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3- butanediol diacrylate, 1,3-butanediol dimethacrylate, 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 tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate, pentapentaerythritol dodecaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, tetrapentaerythritol decamethacrylate, pentapentaerythritol undecamethacrylate, pentapentaerythritol dodecamethacrylate, dimethylol-tricyclodecane diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2- methacryloyloxyethoxy)phenyl}fluorene, 9,9-bis[4-(2-methacryloyloxyethoxy)-3- methylphenyl]fluorene, (2-acryloyloxypropoxy)-3-methylphenyl]fluorene, 9,9-bis[4- (2-acryloyloxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis[4-(2- methacryloyloxyethoxy)-3,5-dimethylphenyl}fluorene, and the like.
In particular, from the standpoint of improvement in sensitivity, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, and the like are preferred. Further, from the standpoint of improvement in hydrophobicity, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, and the like are preferred.
[0062]
In the negative-tone photosensitive resin composition of the present invention, although the content of (C) the polyfunctional monomer is not particularly restricted and can be arbitrarily selected depending on the desired film thickness and application, it is generally from 10 wt% to 60 wt% based on the solid content of the negative-tone photosensitive resin composition.
[0063]
The negative-tone photosensitive resin composition of the present invention contains (D) the zirconium compound. By containing (D) the zirconium compound, a resulting cured film will have improved humidity and heat resistance. Although an alkali-soluble resin having a carboxyl group has poor humidity and heat resistance because of its hydrophilicity deriving from the carboxyl group, the humidity and heat resistance of a cured film is improved by containing (D) the zirconium compound.
Some zirconium compounds have ever been known to have the effect of improving humidity and heat resistance on polysiloxanes (see Patent Document 1); however, in the prior art reference, the side chain of polysiloxanes is limited to be hydrophobic groups, and the resulting cured film is hydrophobic, thus the effect has not been clear when having hydrophilic groups such as a carboxyl group. In the present invention, it was discovered for the first time that humidity and heat resistance of a cured film improves when a carboxyl-containing alkali-soluble resin without limitation to polysiloxanes, which is a hydrophilic resin, contains (D) the zirconium compound.
Although not clear, the detailed mechanism is thought to be as follows: (D) the zirconium compound reacts with a plurality of carboxyl groups in (A) the alkali- soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol to form a cross-linked structure, which improves film density and at the same time decreases hydrophilicity deriving from the carboxyl groups, thereby improving humidity and heat resistance of a resulting cured film. Although (D) the zirconium compound is not particularly restricted as long as it is a compound containing a zirconium atom, it is preferably, for example, zirconium oxide particles having an average particle size of 100 nm or less or compounds represented by Formula (1).
The average particle size of the zirconium oxide particles is more preferably 40 nm or less. When the average particle size of the zirconium oxide particles is 100 nm or less, cloudiness of a resulting cured film can be prevented.
[0064] [Chamical Formula 2]
R2
O= rir 7 (1) n O
R® 4-n
[0065] (R' represents hydrogen, alkyl, aryl, alkenyl, and substitution products thereof, and R* and R’ represent hydrogen, alkyl, aryl, alkenyl, alkoxy, and substitution products thereof. A plurality of R', R?, and R* may be the same or different. n represents an integer of 0 to 4.)
The average particle size as used herein means a median diameter determined from a particle size distribution measured using the Coulter method.
[0066]
As zirconium oxide particles having an average particle size of 100 nm or less, commercially available products can be used, and specific examples thereof include "Bairahru Zr-C20 (trade name)" (average particle size: 20 nm, available from TAKI
CHEMICAL CO., LTD.), "NanoUse OZ-30M (trade name)" (average particle size: 7 nm) (available from NISSAN CHEMICAL INDUSTRIES, LTD.), "ZSL-10T (trade name)" (average particle size: 15 nm) and "ZSL-10A (trade name)" (average particle size: 70 nm) (available from DAIICHI KIGENSO KOGYO CO., LTD.), and the like.
[0067]
In Formula (1), R' is methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, phenyl, vinyl, and the like. In particular, n-propyl, n-butyl, and phenyl are preferred in terms of compound stability. R? and R® are hydrogen, methyl, ethyl, n-propyl, i- propyl, n-butyl, s-butyl, t-butyl, phenyl, vinyl, methoxy, ethoxy, n-propoxy, i- propoxy, n-butoxy, s-butoxy, benzyloxy, and the like. In particular, methyl, t-butyl, phenyl, methoxy, and ethoxy are preferred in terms of ease of synthesis and compound stability.
[0068]
Examples of compounds represented by Formula (1) include zirconium tetra- n-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium (IV) 2,2,6,6-tetramethyl- 3,5-heptanedionate, zirconium tetramethylacetoacetate, zirconium tetraethylacetoacetate, zirconium tetramethylmalonate, zirconium tetracthylmalonate, zirconium tetrabenzoylacetonate , zirconium tetradibenzoylmethanate, zirconium mono-n-butoxy acetylacetonate bis(ethylacetoacetate), zirconium mono-n-butoxy ethylacetoacetate bis(acetylacetonate), zirconium mono-n-butoxy triacetylacetonate, zirconium mono-n-butoxy triacetylacetonate, zirconium di-n-butoxy bis(ethylacetoacetate), zirconium di-n-butoxy bis(acetylacetonate), zirconium di-n- butoxy bis(ethylmalonate), zirconium di-n-butoxy bis(benzoylacetonate), zirconium di-n-butoxy bis(dibenzoylmethanate), and the like. In particular, in terms of solubility in various solvents and/or stability of a compound, 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 tetracthylmalonate, zirconium tetracthylacetoacetate, zirconium di-n-butoxy bis(ethylacetoacetate), and zirconium mono-n-butoxy acetylacetonate bis(ethylacetoacetate) are preferred.
[0069]
In the negative-tone photosensitive resin composition of the present invention, the content of (D) the zirconium compound is not particularly restricted; in the case of zirconium oxide particles having an average particle size of 100 nm or less, it is preferably from 1 wt% to 60 wt% based on the solid content of the negative-tone photosensitive resin composition, and in the case of (D) the zirconium compound other than the above, it is preferably from 0.1 wt% to 10 wt% based on the solid content of the negative-tone photosensitive resin composition. When the content is within the above range, transparency and humidity and heat resistance can be simultaneously achieved at a high level.
[0070]
The negative-tone photosensitive resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, storage stability of the resin composition is improved, and resolution after development is improved. The content of the polymerization inhibitor is preferably from 0.01 wt% to 1 wt% based on the solid content of the negative-tone photosensitive resin composition.
[0071]
Specific examples of the polymerization inhibitor include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di(t-butyl)-p-cresol, phenothiazine, 4-methoxyphenol, and the like.
[0072]
The negative-tone photosensitive resin composition of the present invention may contain an UV absorber. By containing an UV absorber, light resistance of a resulting cured film is improved, and resolution after development is improved in applications that require pattern processing. Although the UV absorber is not particularly limited and a known absorber can be used, benzotriazole compounds, benzophenone compounds, and triazine compounds are preferably used in terms of transparency and uncolorability.
[0073]
Examples of the UV absorber of a benzotriazole compound include 2- (2Hbenzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-tert-pentylphenol, 2- (2Hbenzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-2-yl)- 6-dodecyl-4-methylphenol, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H- benzotriazole, and the like. Examples of the UV absorber of a benzophenone compound include 2-hydroxy-4-methoxybenzophenone and the like. Examples of the UV absorber of a triazine compound include 2-(4,6-diphenyl-1,3,5 triazin-2-yl1)- 5-[(hexyl)oxy]-phenol and the like.
[0074]
The negative-tone photosensitive resin composition of the present invention may contain solvents. Compounds having an alcoholic hydroxyl group or cyclic compounds having a carbonyl group are preferably used because they can dissolve each component uniformly and improve the transparency of a resulting coated film.
Two or more of them may be used. Compounds having a boiling point from 110°C to 250°C under atmospheric pressure are more preferred. When the boiling point is 110°C or higher, drying proceeds moderately during coating, and a good coated film without uneven coating is obtained. On the other hand, when the boiling point is 250°C or lower, the amount of residual solvents in a film can be kept small, and film shrinkage upon heat curing can be reduced furthermore; thus better planarization properties can be obtained.
[0075]
Specific examples of compounds having an alcoholic hydroxyl group and a boiling point of 110°C to 250°C under atmospheric pressure include acetol, 3- hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2- pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n- butyl ether, propylene glycol mono t-butyl ether, 3-methoxy-1-butanol, 3-methyl-3- methoxy-1-butanol, and the like. Among them, diacetone alcohol is preferred from the standpoint of storage stability, and propylene glycol mono t-butyl ether is particularly preferably used in terms of step coverage.
[0076]
Specific examples of cyclic compounds having a carbonyl group and a boiling point of 110°C to at 250°C under atmospheric pressure include y- butyrolactone, y-valerolactone, 6-valerolactone, propylene carbonate, N- methylpyrrolidone, cyclohexanone, cycloheptanone, and the like. Among them, v- butyrolactone is particularly preferably used.
[0077]
Further, the negative-tone photosensitive resin composition of the present invention may contain solvents 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-3- methoxybutyl acetate; and the like.
[0078]
The content of solvents is not particularly restricted, and the solvents can be used in any amount depending, for example, on the coating method. For example, in the case where films are formed by spin coating, it is generally from 50 wt% to 95 wt% based on the total negative-tone photosensitive resin composition.
[0079]
The negative-tone photosensitive resin composition of the present invention may contain various curing agents that promote or facilitate curing of the resin composition. The curing agent is not particularly limited and a known curing agent can be used, and specific examples thereof include nitrogen-containing organic matter, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, methylolated urea derivatives, and the like. Two or more of them may be contained. Among them, metal chelate compounds, methylolated melamine derivatives, and methylolated urea derivatives are preferably used in terms, for example, of stability of a curing agent and processability of a resulting coated film.
[0080]
Because the hardening of polysiloxanes is accelerated by acid, curing catalysts such as a thermal acid generator may be contained when polysiloxanes are used in the negative-tone photosensitive resin composition of the present invention.
The thermal acid generator is not particularly limited, and a known thermal acid generator can be used; example thereof include various onium salt compounds such as aromatic diazonium salts, sulfonium salts, diaryliodonium salts, triarylsulfonium salts, and triarylselenium salts, sulfonic acid esters, halogen compounds, and the like.
[0081]
The negative-tone photosensitive resin composition of the present invention may contain various surfactants such as various fluorine-based surfactants and silicone-based surfactants in order to improve flowability during coating. The type of surfactants is not particularly restricted, and, for example, fluorochemical surfactants such as "MEGAFACE (registered trademark)" "F142D (trade name)", "F172 (trade name)", "F173 (trade name)", "F183 (trade name)", "F445 (trade name)", "F470 (trade name)", "F475 (trade name)", "F477 (trade name)" (available from Dainippon Ink and Chemicals, Incorporated), and "NBX-15 (trade name)", "FTX-218 (trade name)" (available from NEOS COMPANY LIMITED); silicone- based surfactants such as "BYK-333 (trade name)", "BYK-301 (trade name)", "BYK-331 (trade name)", "BYK-345 (trade name)", "BYK-307 (trade name)", and "BYK-352 (trade name)" (available from BYK-Chemie Japan); polyalkylene oxide- based surfactants; poly(meth)acrylate-based surfactants; and the like can be used.
Two or more of them may be used.
[0082]
The negative-tone photosensitive resin composition of the present invention can also contain additives such as a dissolution inhibitor, a stabilizer, and an antifoaming agent as required.
[0083]
The solid content concentration of the negative-tone photosensitive resin composition of the present invention is not particularly restricted, and any amount of solvents and solutes can be used depending, for example, on the coating method.
For example, in the case where films are formed by spin coating as described below, the solid content concentration is generally from 5 wt% to 50 wt%.
[0084]
The representative method of preparing the negative-tone photosensitive resin composition of the present invention will now be described.
[0085]
For example, (B) a photopolymerization initiator, (D) a zirconium compound, and other additives are added to any solvent and dissolved by stirring, after which (A) an alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol and (C) a polyfunctional monomer are added, and the resulting mixture is further stirred for 20 minutes to 3 hours. The solution obtained is filtered to obtain a negative-tone photosensitive resin composition.
[0086]
A method of forming a cured film using the negative-tone photosensitive resin composition of the present invention will be described by way of example.
[0087]
The negative-tone photosensitive resin composition of the present invention is applied onto a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, or slit coating, and pre-baked with a heating apparatus such as a hot plate or an oven. The pre- baking is preferably carried out in the range from 50°C to 150°C for 30 seconds to 30 minutes to a film thickness after pre-baking of 0.1 um to 15 pm.
[0088]
After the pre-baking, using an exposure apparatus such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (hereinafter referred to as PLA), the film is irradiated with light of about 10 to 4,000 J/m” (in terms of exposure at a wavelength of 365 nm) through or not through a desired mask. The exposure light source is not limited, and UV rays such as i-ray, g-ray, and h-ray, KrF (wavelength: 248 nm) laser, ArF (wavelength: 193 nm) laser, and the like can be used. Thereafter, a post-exposure bake, in which this film is heated with a heating apparatus such as a hot plate or an oven in the range of 150°C to 450°C for about 1 hour, may be carried out.
[0089]
The negative-tone photosensitive resin composition of the present invention preferably has a sensitivity of 100 J/m? to 4,000 J/m? after exposure with a PLA.
The sensitivity after patterning exposure with a PLA described above is determined, for example, by the following method. A composition is spin-coated on a silicon wafer using a spin coater at any rotation speed and pre-baked at 120°C for 2 minutes using a hot plate to produce a film with a film thickness of 2 um. The film produced is exposed to an ultra-high pressure mercury lamp through a gray-scale mask for sensitivity measurement using a PLA ("PLA-501F (trade name)" manufactured by Canon Inc.). Thereafter, the film is puddle developed with a 0.4 wt% aqueous tetramethylammonium hydroxide solution for an arbitrary period of time using an automatic developing apparatus ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.) and then rinsed with water for 30 seconds. For a pattern formed, the exposure amount at which a 30-um line-and- space pattern is resolved at a width ratio of 1:1 is determined as the sensitivity.
[0090]
After the patterning exposure, the exposed portion is dissolved by development, so that a negative-tone pattern can be obtained. A preferred method for development is immersion in a developing solution for 5 seconds to 10 minutes by means of, for example, showering, dipping, or puddling. As a developing solution, a known alkaline developing solution can be used. Specific examples include, for example, an aqueous solution containing one or two or more of inorganic alkalis such as hydroxides, carbonates, phosphates, silicates, and borates of alkali metals; amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine; and quarternary ammonium salts such as tetramethylammonium hydroxide and choline. After the development, it is preferable to rinse with water, and then dry baking may also be carried out in the range of 50°C to 150°C.
Thereafter, this film is heat-cured with a heating apparatus such as a hot plate or an oven in the range of 120°C to 280°C for about 1 hour to thereby obtain a cured film.
[0091]
A cured film obtained from the negative-tone photosensitive resin composition of the present invention preferably has a zirconium atom content of 0.02 wt% to 7.5 wt%, a carbon atom content of 25 wt% to 80 wt%, and a silicon atom content of 0.5 wt% to 20 wt%. When the contents are within the above range, transmittance, hardness, and humidity and heat resistance can be maintained in a well-balanced manner. The resolution is preferably not more than 20 pum. The film thickness of a cured film is not particularly restricted and preferably from 0.1 pum to 15 pm. Further, the cured film, when having a film thickness of 1.5 pm, preferably has a hardness of 4H or more and a transmittance of 90% or more. The transmittance refers to a transmittance at a wavelength of 400 nm. The hardness and the transmittance can be controlled by selection of exposure amount and heat- curing temperature.
[0092]
The cured film obtained by curing the negative-tone photosensitive resin composition of the present invention can be used as various protective films such as a protective film for a touch panel, various hard coating materials, a planarization film for a TFT, an overcoat for a color filter, and an antireflection film, an optical filter, an insulating film for a touch sensor, an insulating film for a TFT, a photo spacer for a color filter, and the like. Among them, the cured film can be suitably used as a protective film for a touch panel because it has high hardness and transparency. Examples of types of a touch panel include the resistive type, the optical type, the electromagnetic induction type, the capacitive type, and the like.
Because a capacitive-type touch panel requires particularly high hardness, the cured film of the present invention can be suitably used therefor.
[0093]
In addition, a cured film obtained by curing the negative-tone photosensitive resin composition of the present invention can be suitably used as a metal wire protective film because it has high humidity and heat resistance. By forming the cured film on a metal wire, degradation (such as reduced conductivity) due, for example, to metal corrosion can be prevented. Examples of metals to be protected include, but are not limited to, copper, silver, aluminum, chromium, molybdenum, titanium, ITO, IZO (indium zinc oxide), AZO (aluminum-doped zinc oxide), ZnO», and the like. The cured film can be suitably used particularly in a touch panel component containing molybdenum. The touch panel component as used herein refers to a component that can be used as a touch panel sensor substrate comprising an electrode and an insulating film and/or a protective film, which substrate is a glass or film substrate.
[0094]
Examples of the method of preparing the touch panel component include, but are not limited to, the method as described below. A transparent electrode thin film with an arbitrary film thickness is formed on a glass substrate, and after the steps of patterning a resist material with a photolithographic technique, solution etching of the transparent electrode using an etchant, and resist stripping with a stripping solution, a glass substrate on which a transparent electrode forming a part of an X- axis electrode and a Y-axis electrode is patterned is produced (Figure 1-a).
Examples of transparent electrodes include thin films of metal oxides such as ITO, 120, AZO, ZnO,, and tin antimonate and of metals such as gold, silver, copper, and aluminum. Such a transparent conductive electrode can be formed by the conventional methods such as chemical vapor deposition and physical methods such as vacuum deposition, sputtering, ion plating, and ion beam deposition. Next, at sites intersecting the electrodes that will be formed later, cured films obtained from the negative-tone photosensitive resin composition of the present invention are formed as a transparent insulating film (Figure 1-b). Thereafter, an electrode thin film with an arbitrary film thickness is formed, and after the steps of resist patterning, etching, and resist stripping, connecting wires to an IC driver and Y-axis electrode continuity wires are formed (Figure 1-¢c). Examples of the electrode here include, in addition to the transparent electrode material described above, molybdenum, molybdenum/aluminum/molybdenum-laminated film (MAM), molybdenum-niobium alloy, chromium, titanium, titanium/aluminum/titanium-laminated film (TAT), aluminum, and the like. Finally, at parts in substrate ends (left part of the upper side and lower part of the right side in Figure 1-¢) excluding connecting sites to an
IC driver, a transparent protective film is formed as a cured film obtained from the negative-tone photosensitive resin composition of the present invention to obtain a touch panel component. Figure 2 is a cross-sectional view of a preparation example of the touch panel component described above.
Examples
[0095]
The present invention will now be described using Examples thereof, but the embodiments of the present invention are not limited to these Examples. (Synthesis Example 1: Synthesis of Polysiloxane Solution (i))
A 500-mL three-necked flask was charged with 47.67 g (0.35 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 26.23 g (0.10 mol) of 3-trimethoxysilylpropyl succinic acid, 82.04 g (0.35 mol) of y- acryloylpropyltrimethoxysilane, and 185.08 g of diacetone alcohol (hereinafter referred to as DAA). The flask was immersed in an oil bath at 40°C, and, with stirring, an aqueous phosphoric acid solution obtained by dissolving 0.391 g (0.2 wt% based on the monomer charged) of phosphoric acid in 55.8 g of water was added thereto from a dropping funnel over 10 minutes. After stirring at 40°C for 1 hour, the oil bath temperature was set at 70°C, and the flask was stirred for 1 hour.
Further, the temperature of the oil bath was raised to 115°C over 30 minutes. After 1 hour from the start of temperature rise, the inner temperature of the solution reached 100°C, and then the flask was heated under stirring for 2 hours (the inner temperature was 100 to 110°C). During the reaction, by-products, methanol and water, in a total amount of 120 g were distilled out. To the resulting polysiloxane solution in DAA, DAA was added to a polymer concentration of 40 wt% to obtain a polysiloxane solution (i). The weight average molecular weight (Mw) of the resulting 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 (i1))
A 500-mL three-necked flask was charged with 54.48 g (0.40 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 13.12 g (0.05 mol) of 3-trimethoxysilylpropyl succinic acid, 82.04 g (0.35 mol) of y- acryloylpropyltrimethoxysilane, and 174.74 g of DAA. The flask was immersed in an oil bath at 40°C, and, with stirring, an aqueous phosphoric acid solution obtained by dissolving 0.379 g (0.2 wt% based on the monomer charged) of phosphoric acid in 54.9 g of water was added thereto from a dropping funnel over 10 minutes. Then, upon heating under stirring under the same conditions as in Synthesis Example 1, by- products, methanol and water, in a total amount of 110 g were distilled out. To the resulting polysiloxane solution in DAA, DAA was added to a polymer concentration of 40 wt% to obtain a polysiloxane solution (ii). The weight average molecular weight (Mw) of the resulting 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))
A 500-mL three-necked flask was charged with 27.24 g (0.20 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 65.58 g (0.25 mol) of 3-trimethoxysilylpropyl succinic acid, 82.04 g (0.35 mol) of y- acryloylpropyltrimethoxysilane, and 198.02 g of DAA. The flask was immersed in an oil bath at 40°C, and, with stirring, an aqueous phosphoric acid solution obtained by dissolving 0.416 g (0.2 wt% based on the monomer charged) of phosphoric acid in 58.5 g of water was added thereto from a dropping funnel over 10 minutes. Then, upon heating under stirring under the same conditions as in Synthesis Example 1, by- products, methanol and water, in a total amount of 130 g were distilled out. To the resulting polysiloxane solution in DAA, DAA was added to a polymer concentration of 40 wt% to obtain a polysiloxane solution (iii). The weight average molecular weight (Mw) of the resulting 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))
A 500-mL three-necked flask was charged with 34.05 g (0.20 mol) of methyltrimethoxysilane, 39.66 g (0.20 mol) of phenyltrimethoxysilane, 41.66 g (0.20mol) of 3-trimethoxysilyl butyric acid, 82.04 g (0.35 mol) of y- acryloylpropyltrimethoxysilane, and 182.22 g of DAA. The flask was immersed in an oil bath at 40°C, and, with stirring, an aqueous phosphoric acid solution obtained by dissolving 0.395 g (0.2 wt% based on the monomer charged) of phosphoric acid in 54.0 g of water was added thereto from a dropping funnel over 10 minutes. Then, upon heating under stirring under the same conditions as in Synthesis Example 1, by- products, methanol and water, in a total amount of 120 g were distilled out. To the resulting polysiloxane solution in DAA, DAA was added to a polymer concentration of 40 wt% to obtain a polysiloxane solution (iv). The weight average molecular weight (Mw) of the resulting 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, and 143.37 g of 3-methyl-3-methoxybutanol (hereinafter referred to as MMB). The flask was immersed in an oil bath at 40°C, and, with stirring, an aqueous phosphoric acid solution obtained by dissolving 0.167 g (0.1 wt% based on the monomer charged) of phosphoric acid in 54.0 g of water was added thereto from a dropping funnel over 10 minutes. Then, upon heating under stirring under the same conditions as in
Synthesis Example 1, by-products, methanol and water, in a total amount of 120 g were distilled out. To the resulting polysiloxane solution in MMB, MMB was added to a polymer concentration of 40 wt% to obtain a polysiloxane solution (v).
The weight average molecular weight (Mw) of the resulting polymer was measured by GPC to be 8,000 (in terms of polystyrene). The carboxylic acid equivalent was 0 g/mol. The Synthesis Example 5 is the embodiment described in Patent Document
(Synthesis Example 6: Synthesis of Acrylic Resin Solution (a))
A 500-ml flask was charged with 3 g of 2,2'-azobis(isobutyronitrile) and 50 g of propylene glycol methyl ether acetate (hereinafter referred to as PGMEA).
Thereafter, the flask was charged with 23.0 g of methacrylic acid, 31.5 g of benzyl methacrylate, and 32.8 g of tricyclo[5.2.1.02,6]decane-8-yl methacrylate and stirred at room temperature for some time. The flask was sufficiently purged with nitrogen by bubbling and then heated under stirring at 70°C for 5 hours. Next, 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 solution obtained, and the resulting mixture was heated under stirring at 90°C for 4 hours to obtain an acrylic resin solution (a). To the acrylic resin solution (a) obtained, PGMEA was added to a solid content concentration of 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))
A 500-ml flask was charged with 3 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA (propylene glycol methyl ether acetate). Thereafter, the flask was charged with 16.8 g of methacrylic acid, 34.4 g of benzyl methacrylate, and 36.9 g of tricyclo[5.2.1.02,6]decane-8-yl methacrylate and stirred at room temperature for some time. The flask was sufficiently purged with nitrogen by bubbling and then heated under stirring at 70°C for 5 hours. Next, 11.9 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the solution obtained, and the resulting mixture was heated under stirring at 90°C for 4 hours to obtain an acrylic resin solution (b). To the acrylic resin solution (b) obtained, PGMEA was added to a solid content concentration of 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 (¢))
A 500-ml flask was charged with 3 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA. Thereafter, the flask was charged with 33.9 g of methacrylic acid, 34.4 g of benzyl methacrylate, and 36.9 g of tricyclo[5.2.1.02,6]decane-8-yl methacrylate and stirred at room temperature for some time. The flask was sufficiently purged with nitrogen by bubbling and then heated under stirring at 70°C for 5 hours. Next, 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 solution obtained, and the resulting mixture was heated under stirring at 90°C for 4 hours to obtain an acrylic resin solution (¢). To the acrylic resin solution (¢) obtained, PGMEA was added to a solid content concentration of 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))
A 500-ml flask was charged with 3 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA. Thereafter, the flask was charged with 8.24 g of methacrylic acid, 35.5 g of benzyl methacrylate, and 45.5 g of tricyclo[5.2.1.02,6]decane-8-yl methacrylate and stirred at room temperature for some time. The flask was sufficiently purged with nitrogen by bubbling and then heated under stirring at 70°C for 5 hours. Next, 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 solution obtained, and the resulting mixture was heated under stirring at 90°C for 4 hours to obtain an acrylic resin solution (d). To the acrylic resin solution (d) obtained, PGMEA was added to a solid content concentration of 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 (¢))
A 500-ml flask was charged with 3 g of 2,2'-azobis(isobutyronitrile) and 50 g of PGMEA. Thereafter, the flask was charged with 69.5 g of methacrylic acid, 7.9 g of benzyl methacrylate, and 9.9 g of tricyclo[5.2.1.02,6]decane-8-yl methacrylate and stirred at room temperature for some time. The flask was sufficiently purged with nitrogen by bubbling and then heated under stirring at 70°C for 5 hours. Next, 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 solution obtained, and the resulting mixture was heated under stirring at 90°C for 4 hours to obtain an acrylic resin solution (e). To the acrylic resin solution (e) obtained, PGMEA was added to a solid content concentration of 40 wt%. The weight average molecular weight of the acrylic resin was 40,000, and the carboxylic acid equivalent was 140 g/mol.
[0096]
The compositions of Synthesis Examples 1 to 9 are collectively shown in
Table 1.
[0097] [Table 1]
— i — Ly — 7 A RA 7 7 © 00 0 © 0 s|&8| 8&2 |5 |5 |g |§5 |z3 © ~~ ~~ ~~ ~~ © Q Q © 2 Tv Se se 5 = sR = = = = = ~ a & = wy 7 ‘@ ‘7 ‘a 7 oO No oo 0° oo > > > > > - - 1 - 2 . = = > “4 x # oN ow In ER] NN © om a2 o o o o oO cz Oo << mT <u eo» = = = = = . = oe Lo Lo J — r= Se at Fe 3 -— —_— — yt LD o @ o Q L Los .o® 1 .o& a £ E E £ £ Ng lag | ag as | aE = = = = = |MEg|ME|nE| BEDE = = = = = = = > > > > o «= = = © © © © < 2 < = 2 = <= = = = = OS Oo oO Oo o c a. [9 a a. > > > PY > 2 2 2 2 2 ot St ft St fr sh — Ne — —— = = = = = = = = = = 2 2 a a zg 2 7 z @ z = 3 = = = > > 3 = =~ = = = = S SI. 8 o~ 8 = — Fey ry Ron] ws wag rt cles | eg |e 2d | 228230881888 x2)
Evol Eo | Ee | Eo] E203 = = = = = > EN By > > N Rg N N N
S p= = = = = = = co = = = 5 z 5 5 2 2 2 2 2 = jaa] 0 om jaa] om gl = = = = = o g © [5 © o 8 = = = 5 2 2 2 2 2 < < Lo] I= = — = — = — = — _— — Po oo oN Zr Pye o wn n 0 © ov ow 5 on ow 5 © e 2 fo 2 = c= 8 = a & = &
Ss > ad > > =e =~ oN - EN = oS c o © = = = = = = = = = © + DO QQ = D+ © «= < = — — -— Oo [= OQ 13 OD =| 2 5 : 5 zz2|12z2|2z2122|22 = oN oN =o oo
Twn =n Eon Ton 22 22 23 232 23
En ll En En Eo e = gS = og = Q Qf on ~ =~ = Ea NES <= = = © = o- ou Ox Qn Lo 2 Lo Lo Lo 2 2 2 £ ZS] =| E555] 38 £ & £ = ex 22 52 52] 52 2 > > > ooh < oh < 8h < &b © oo
Q < < o o— To = T oo To go e 2 ge e = = = 2 = 2 = 2 = 2 « Qo 153 ] o LQ © LQ w 9 Ww » WD $ F ? 7 Sc | === |=°* > > > > 2 > > > = 2 |g |&_ |¢% ssa] 35] 3 oo OS ~ oc ~~ = on o3 + = oo
PE [ENA =n ££ ~ ~~ ~~ ~ ~~ £&=| 22 | £8 27 | = 27 | =o = = = 2 = 22 | 22 | 22 | 28 2 2 3 8 2 0 3 0 wr Ser : ~ I ® Zo 5 = > 2 L 2 = 2 > pled — -_ — — = .2 = = = .2 = — > = Fa =, — = pre) ~~ = me = = 5 2 Sz | = S = = SS ® Qo 9 oS oS = 0 = 8 = 0 © & & & S < = EQ &= = = = = = = 0 = 2 = 0 = = = = = =
Ez l|l&2|5z| EZ 5 5 5 3 5
Tw V Tw fa = al on on = = = = = <+ © o Lo Oo —~ © = =~ o =~ = so =] i= = > sl 53=]l Z| Fl 3] ae
BN wo © < Ja J © QD LQ a a
Xz 5 = 5 = X = 5 = St = So ja ££
Le Es | BEE] 25 =22c 0 = 0 = © = 0 = 0 =
ZB = ho mE | BE =o = 3 = 8 = 3 = 3 22 | 22 | 23 | 22 | 22 | 2E| BE | EE | BE &¢
S © © © 5 cD cS 2 Qo = o 2 0 2 0 = © = a“ se = = & a a a = < © <5 < 5 < 2 < c wi wy wv ow wx
Lo Low Low Lo Low Low L ow Lu Low Le
Ro et nd ped — wit rT — ——" —— © = © = Oo 2 o Oo = LS Oo & vo & © = © S
EEE EE EemE EE EnE Eo EE E ws EE EZ
Es = © = © = & = © = © = ec a = 8 = 8 ™ > = X > xX =X 5% > 0% = 2% =% 50% wn wy HH wn = wn wn | on Bd wn Hl [ZS wn =H ny KH
[0098]
Evaluation methods in each Example/Comparative Example will be described below. (1) Measurement of Transmittance
The negative-tone photosensitive resin composition prepared was spin-coated on a 5-cm square TEMPAX glass substrate (available from AGC TECNO GLASS
CO., LTD) by rotation at 500 rpm for 10 seconds, followed by rotation at 1,000 rpm for 4 seconds, using a spin coater ("1H-360S (trade name)" manufactured by
MIKASA CO., LTD.), and then pre-baked at 90°C for 2 minutes using a hot plate ("SCW-636 (trade name)" manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a film with a film thickness of 2 um. The film produced was exposed to light using a parallel light mask aligner (hereinafter referred to as PLA) ("PLA-501F (trade name)" manufactured by Canon Inc.) and an ultra-high pressure mercury lamp as a light source, and cured in air at 230°C for 1 hour using an oven ("[HPS-222" manufactured by ESPEC CORP.) to produce a cured film with a film thickness of 1.5 pm.
[0099]
For the cured film obtained, transmittance at 400 nm was measured using an ultraviolet-visible spectrophotometer "UV-260 (trade name)" (manufactured by
Shimadzu Corporation). The film thickness was measured using "Lambda Ace
STM-602 (trade name)" manufactured by Dainippon Screen Mfg. Co., Ltd. at a refractive index of 1.55. This also applies to the film thickness described below. (2) Measurement of Hardness
For the cured film with a film thickness of 1.5 um obtained by the method described in (1) above, pencil hardness was measured in accordance with JIS K 5600-5-4 (1999). (3) Humidity and Heat Resistance
After producing a cured film on a glass comprising a sputtered molybdenum film by the method described in (1) above, a test in which the cured film is left to stand in an oven ("EX-111 (trade name)" ESPEC CORP.) at a temperature of 85°C and a humidity of 85% for 300 hours was performed, and then the degree of color change of molybdenum was evaluated. Further, a glass substrate comprising only a sputtered molybdenum film was tested at the same time to provide an indication of the degree of color change before and after the test, and evaluation was performed as described below.
[0100] 5: No observable color change of molybdenum under a cured film before and after the test.
[0101] 4: Molybdenum under a cured film underwent an about 10% color change before and after the test, compared to one that was not covered with a cured film.
[0102] 3: Molybdenum under a cured film underwent an about 20% color change before and after the test, compared to one that was not covered with a cured film.
[0103] 2: Molybdenum under a cured film underwent an about 40% color change before and after the test, compared to one that was not covered with a cured film.
[0104] 1: Molybdenum under a cured film underwent an about 60% or more color change before and after the test, compared to one that was not covered with a cured film (4) Pattern Processability (4-1) Sensitivity
A negative-tone photosensitive resin composition A was spin-coated on a silicon wafer by rotation at 500 rpm for 10 seconds, followed by rotation at 1,000 rpm for 4 seconds, using a spin coater ("1H-360S (trade name)" manufactured by
MIKASA CO., LTD.), and then pre-baked at 90°C for 2 minutes using a hot plate ("SCW-636 (trade name)" manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a pre-baked film with a film thickness of 2 pm. Using a PLA and an ultra- high pressure mercury lamp as a light source, the pre-baked film obtained was exposed to light through a gray-scale mask for sensitivity measurement with a gap of 100 pm. Thereafter, using an automatic developing apparatus ("AD-2000 (trade name)", manufactured by Takizawa Sangyo Co., Ltd.), the film was developed by showering of a 0.4 wt% (or 2.38 wt%) aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 90 seconds and then rinsed with water for 30 seconds.
[0105]
After the exposure and development, the exposure amount at which a 30-um line-and-space pattern is formed at a width ratio of 1:1 (which is hereinafter referred to as the optimal exposure amount) was taken as the sensitivity. The exposure amount was measured with an [-ray intensity meter. (4-2) Resolution
A minimum pattern size after development at the optimal exposure amount was measured. (4-3) Residue after Development
After patterning on a silicon wafer by the method described in (4-1) above, evaluation was performed as described below according to the level of undissolved residue in the unexposed portion.
[0106] 5: By visual observation, there is no undissolved residue, and also by observation under a microscope, there is no residue even in a fine pattern of 50 um or less.
[0107] 4: By visual observation, there is no undissolved residue, and by microscope observation, there is no residue in a pattern of not less than 50 um but there are residues in a pattern of 50 um or less.
[0108] 3: By visual observation, there is no undissolved residue, but by microscope observation, there are residues in a pattern of not less than 50 um.
[0109] 2: By visual observation, there are undissolved residues at substrate ends (thick film portions).
[0110] 1: By visual observation, there are undissolved residues over the unexposed portion. (Example 1)
Under yellow light, 0.277 g of 1,2-octanedione, 1-[4-(phenylthio)-2-(O- benzoyloxime)] ("Irgacure OXE-01 (trade name)" available from Ciba Specialty
Chemicals K. K.) was dissolved in 2.846 g of DAA and 2.317 g of PGMEA, to which solution 0.227 g of zirconium di-n-butoxy bis(ethylacetoacetate) (70 wt% 1- butanol solution) ("ORGATIX ZC-580 (trade name)", available from Matsumoto
Fine Chemical Co., Ltd.), 0.2000 g of a 1 wt% solution of silicone-based surfactant "BYK-333 (trade name)" (available from BYK-Chemie Japan) in PGMEA (corresponding to a concentration of 100 ppm), and 1.661 g of a 1 wt% solution of 4- t-butylcatechol in PGMEA were added, and the resulting mixture was stirred. To the resultant, 5.538 g of a 50% by weight solution of dipentaerythritol hexaacrylate (""KAYARAD (registered trademark)" DPHA (trade name)", available from Nippon
Kayaku Co., Ltd.) in PGMEA and 6.923 g of the polysiloxane solution (i) were added, and the resulting mixture was stirred. Then, the resultant was filtered through a 0.45-pm filter to obtain a negative-tone photosensitive resin composition (S-1). The negative-tone photosensitive resin composition (S-1) obtained was evaluated for transmittance, hardness, humidity and heat resistance, and pattern processability by the method described above. (Example 2)
A negative-tone photosensitive resin composition (S-2) was obtained in the same manner as in Example 1 except using the polysiloxane solution (ii) in place of the polysiloxane solution (i). Using the negative-tone photosensitive resin composition (S-2) obtained, evaluations were performed in the same manner as in
Example 1. As a developing solution, a 2.38 wt% aqueous TMAH solution was used. (Example 3)
A negative-tone photosensitive resin composition (S-3) was obtained in the same manner as in Example 1 except using the polysiloxane solution (iii) in place of the polysiloxane solution (i). Using the negative-tone photosensitive resin composition (S-3) obtained, evaluations were performed in the same manner as in
Example 1. (Example 4)
A negative-tone photosensitive resin composition (S-4) was obtained in the same manner as in Example 1 except using the polysiloxane solution (iv) in place of the polysiloxane solution (i). Using the negative-tone photosensitive resin composition (S-4) obtained, evaluations were performed in the same manner as in
Example 1. (Example 5)
Under yellow light, 0.503 g of 2-methyl-[4-(methylthio)phenyl]-2- morpholinopropan-1-one ("Irgacure 907 (trade name)" available from Ciba Specialty
Chemicals K. K.), 0.026 g of 4,4-bis(diethylamino)benzophenone ("EAB-F (trade name)" available from HODOGAYA CHEMICAL CO., LTD.), 3.030 g of DAA, 2.515 g of PGMEA, 0.227 g of "ZC-580 (trade name)", 0.2000 g of a silicone-based surfactant BYK-333 (1 wt% PGMEA solution) (corresponding to a concentration of 100 ppm), and 1.588 g of 4-t-butylcatechol (1 wt% PGMEA solution) were added, and the resulting mixture was stirred. To the resultant, 5.294 g of "DPHA" (50 wt%
PGMEA solution) and 6.617 g of the polysiloxane solution (i) were added, and the resulting mixture was stirred. Then, the resultant was filtered through a 0.45-um filter to obtain a negative-tone photosensitive resin composition (S-5). Using the negative-tone photosensitive resin composition (S-5) obtained, evaluations were performed in the same manner as in Example 1. (Example 6)
A negative-tone photosensitive resin composition (S-6) was obtained in the same manner as in Example 1 except using ethanone,1-[9-ethyl-6-(2- methylbenzoyl)-9H-carbazol-3-yl]-,1-(O -acetyloxime) ("Irgacure OXE-02 (trade name)" available from Ciba Specialty Chemicals K. K.) in place of Irgacure OXE-01.
Using the negative-tone photosensitive resin composition (S-6) obtained, evaluations were performed in the same manner as in Example 1. (Example 7)
A negative-tone photosensitive resin composition (S-7) was obtained in the same manner as in Example 1 except using tripentaerythritol octaacrylate ("V#802 (trade name)", available from OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) in place of "DPHA (trade name)". Using the negative-tone photosensitive resin composition (S-7) obtained, evaluations were performed in the same manner as in
Example 1. (Example 8)
A negative-tone photosensitive resin composition (S-8) was obtained in the same manner as in Example 1 except using 3.323 g of "V#802 (trade name)" (50%
PGMEA solution) and 2.215 g of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene ("BPEFA (trade name)", available from Osaka Gas Chemicals Co., Ltd.) (50 wt%
PGMEA solution) in place of "DPHA (trade name)". Using the negative-tone photosensitive resin composition (S-8) obtained, evaluations were performed in the same manner as in Example 1. (Example 9)
Under yellow light, 0.277 g of "OXE-01 (trade name)", 2.846 g of DAA, 2.016 g of PGMEA, 0.538 g of "NanoUse OZ-30M (trade name)" (methanol solution, solid content = 30.9 wt%), 0.2000 g of a silicone-based 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 the resulting mixture was stirred. "DPHA (trade name)" (50% PGMEA solution) in an amount of 5.538 g and 6.923 g of the polysiloxane solution (i) were added, and the resulting mixture was stirred. Then, the resultant was filtered through a 0.45-pm filter to obtain a negative-tone photosensitive resin composition (S-9). Using the negative-tone photosensitive resin composition (S-9) obtained, evaluations were performed in the same manner as in Example 1. (Example 10)
Under yellow light, 0.239 g of "OXE-01 (trade name)", 3.410 g of DAA, 0.846 g of PGMEA, 3.098 g of "NanoUse OZ-30M (trade name)" (methanol solution, solid content = 30.9 wt%), 0.2000 g of a silicone-based surfactant BYK-333 (1 wt%
PGMEA solution) (corresponding to a concentration of 100 ppm), and 1.436 g of 4-t- butylcatechol (1 wt% PGMEA solution) were added, and the resulting mixture was stirred. "DPHA (trade name)" (50% PGMEA solution) in an amount of 4.787 g and 5.984 g of the polysiloxane solution (i) were added, and the resulting mixture was stirred. Then, the resultant was filtered through a 0.45-pm filter to obtain a negative-tone photosensitive resin composition (S-10). Using the negative-tone photosensitive resin composition (S-10) obtained, evaluations were performed in the same manner as in Example 1. (Example 11)
A negative-tone photosensitive resin composition (S-11) was obtained in the same manner as in Example 9 except using 0.831 g of "Bairahru Zr-C20 (trade name)" (methanol solution, solid content = 20 wt%) in place of 0.538 g of "NanoUse
OZ-30M (trade name)". Using the negative-tone photosensitive resin composition (S-11) obtained, evaluations were performed in the same manner as in Example 1. (Example 12)
Under yellow light, 0.277 g of "OXE-01 (trade name)", 2.846 g of DAA, 2.388 g of PGMEA, 0.166 g of zirconium tetraacetylacetonate ("Nacem zirconium (trade name)", available from NIHON KAGAKU SANGYO CO., LTD.), 0.2000 g of a silicone-based 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 the resulting mixture was stirred. "DPHA (trade name)" (50 wt% PGMEA solution) in an amount of 5.538 g and 6.923 g of the polysiloxane solution (i) were added, and the resulting mixture was stirred. Then, the resultant was filtered through a 0.45-um filter to obtain a negative-tone photosensitive resin composition (S-12). Using the negative-tone photosensitive resin composition (S- 12) obtained, evaluations were performed in the same manner as in Example 1. (Example 13)
A negative-tone photosensitive resin composition (S-13) was obtained in the same manner as in Example 12 except that the amount of Nacem zirconium was 0.017 g. Using the negative-tone photosensitive resin composition (S-13) obtained, evaluations were performed in the same manner as in Example 1. (Example 14)
A negative-tone photosensitive resin composition (S-14) was obtained in the same manner as in Example 12 except that the amount of Nacem zirconium was 0.323 g. Using the negative-tone photosensitive resin composition (S-14) obtained, evaluations were performed in the same manner as in Example 1. (Example 15)
A negative-tone photosensitive resin composition (S-13) was obtained in the same manner as in Example 12 except using zirconium tetra propoxide in place of
Nacem zirconium. Using the negative-tone photosensitive resin composition (S-13) obtained, evaluations were performed in the same manner as in Example 1. (Example 16)
A negative-tone photosensitive resin composition (S-14) was obtained in the same manner as in Example 12 except using zirconium tetraphenoxide in place of
Nacem zirconium. Using the negative-tone photosensitive resin composition (S-14) obtained, evaluations were performed in the same manner as in Example 1. (Example 17)
A negative-tone photosensitive resin composition (S-15) was obtained in the same manner as in Example 12 except using zirconium (IV) 2,2,6,6-tetramethyl-3,5- heptanedionate in place of Nacem zirconium. Using the negative-tone photosensitive resin composition (S-15) obtained, evaluations were performed in the same manner as in Example 1. (Example 18)
A negative-tone photosensitive resin composition (S-16) was obtained in the same manner as in Example 12 except using zirconium tetramethylmalonate in place of Nacem zirconium. Using the negative-tone photosensitive resin composition (S- 16) obtained, evaluations were performed in the same manner as in Example 1. (Example 19)
A negative-tone photosensitive resin composition (S-17) was obtained in the same manner as in Example 12 except using zirconium tetrabenzoylacetonate in place of Nacem zirconium. Using the negative-tone photosensitive resin composition (S-17) obtained, evaluations were performed in the same manner as in
Example 1. (Example 20)
A negative-tone photosensitive resin composition (S-18) was obtained in the same manner as in Example 12 except using zirconium mono-n-butoxy acetylacetonate bis(ethylacetoacetate) in place of Nacem zirconium. Using the negative-tone photosensitive resin composition (S-18) obtained, evaluations were performed in the same manner as in Example 1. (Example 21)
A negative-tone photosensitive resin composition (S-19) was obtained in the same manner as in Example 12 except using dichlorobis(n5- cyclopentadienyl)zirconium in place of Nacem zirconium. Using the negative-tone photosensitive resin composition (S-19) obtained, evaluations were performed in the same manner as in Example 1. (Example 22)
A negative-tone photosensitive resin composition (S-20) was obtained in the same manner as in Example 12 except using bis(n5-cyclopentadienyl)zirconium chloride hydride in place of Nacem zirconium. Using the negative-tone photosensitive resin composition (S-20) obtained, evaluations were performed in the same manner as in Example 1. (Example 23)
A negative-tone photosensitive resin composition (S-21) was obtained in the same manner as in Example 12 except using zirconocene bis(trifluoromethanesulfonate) tetrahydrofuran adduct in place of Nacem zirconium.
Using the negative-tone photosensitive resin composition (S-21) obtained,
evaluations were performed in the same manner as in Example 1. (Example 24)
A negative-tone photosensitive resin composition (A-1) was obtained in the same manner as in Example 1 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-1) obtained, evaluations were performed in the same manner as in
Example 1. (Example 25)
A negative-tone photosensitive resin composition (A-2) was obtained in the same manner as in Example 2 except that the acrylic resin solution (b) was used in place of the polysiloxane solution (ii) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-2) obtained, evaluations were performed in the same manner as in
Example 1. As a developing solution, a 2.38 wt% aqueous TMAH solution was used. (Example 26)
A negative-tone photosensitive resin composition (A-3) was obtained in the same manner as in Example 3 except that the acrylic resin solution (c) was used in place of the polysiloxane solution (iii) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-3) obtained, evaluations were performed in the same manner as in
Example 1. (Example 27)
A negative-tone photosensitive resin composition (A-4) was obtained in the same manner as in Example 5 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-4) obtained, evaluations were performed in the same manner as in
Example 1. (Example 28)
A negative-tone photosensitive resin composition (A-5) was obtained in the same manner as in Example 6 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-5) obtained, evaluations were performed in the same manner as in
Example 1. (Example 29)
A negative-tone photosensitive resin composition (A-6) was obtained in the same manner as in Example 7 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-6) obtained, evaluations were performed in the same manner as in
Example 1. (Example 30)
A negative-tone photosensitive resin composition (A-7) was obtained in the same manner as in Example 8 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-7) obtained, evaluations were performed in the same manner as in
Example 1. (Example 31)
A negative-tone photosensitive resin composition (A-8) was obtained in the same manner as in Example 9 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-8) obtained, evaluations were performed in the same manner as in
Example 1. (Example 32)
A negative-tone photosensitive resin composition (A-9) was obtained in the same manner as in Example 10 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-9) obtained, evaluations were performed in the same manner as in
Example 1. (Example 33)
A negative-tone photosensitive resin composition (A-10) was obtained in the same manner as in Example 11 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-10) obtained, evaluations were performed in the same manner as in
Example 1. (Example 34)
A negative-tone photosensitive resin composition (A-11) was obtained in the same manner as in Example 12 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-11) obtained, evaluations were performed in the same manner as in
Example 1. (Example 35)
A negative-tone photosensitive resin composition (A-12) was obtained in the same manner as in Example 13 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-12) obtained, evaluations were performed in the same manner as in
Example 1. (Example 36)
A negative-tone photosensitive resin composition (A-13) was obtained in the same manner as in Example 14 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-13) obtained, evaluations were performed in the same manner as in
Example 1. (Example 37)
A negative-tone photosensitive resin composition (A-14) was obtained in the same manner as in Example 15 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-14) obtained, evaluations were performed in the same manner as in
Example 1. (Example 38)
A negative-tone photosensitive resin composition (A-15) was obtained in the same manner as in Example 16 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-15) obtained, evaluations were performed in the same manner as in
Example 1. (Example 39)
A negative-tone photosensitive resin composition (A-16) was obtained in the same manner as in Example 17 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-16) obtained, evaluations were performed in the same manner as in
Example 1. (Example 40)
A negative-tone photosensitive resin composition (A-17) was obtained in the same manner as in Example 18 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-17) obtained, evaluations were performed in the same manner as in
Example 1. (Example 41)
A negative-tone photosensitive resin composition (A-18) was obtained in the same manner as in Example 19 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-18) obtained, evaluations were performed in the same manner as in
Example 1. (Example 42)
A negative-tone photosensitive resin composition (A-19) was obtained in the same manner as in Example 20 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-19) obtained, evaluations were performed in the same manner as in
Example 1.
(Example 43)
A negative-tone photosensitive resin composition (A-20) was obtained in the same manner as in Example 21 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-20) obtained, evaluations were performed in the same manner as in
Example 1. (Example 44)
A negative-tone photosensitive resin composition (A-21) was obtained in the same manner as in Example 22 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-20) obtained, evaluations were performed in the same manner as in
Example 1. (Example 45)
A negative-tone photosensitive resin composition (A-22) was obtained in the same manner as in Example 23 except that the acrylic resin solution (a) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA. Using the negative-tone photosensitive resin composition (A-20) obtained, evaluations were performed in the same manner as in
Example 1. (Example 46)
A touch panel component was prepared according to the following procedure. (1) Preparation of ITO
On a glass substrate having a thickness of about 1 mm, ITO with a film thickness of 150 nm and a surface resistance of 15Q/0 was deposited by sputtering at an RF power of 1.4 kW and a vacuum degree of 6.65 x 10” Pa for 12.5 minutes using a sputtering system HSR-521A (manufactured by Shimadzu Corporation), and a positive-tone photoresist ("OFPR-800" available from TOKYO OHKA KOGYO
CO., LTD.) was applied thereto. The resultant was pre-baked at 80°C for 20 minutes to obtain a resist film with a film thickness of 1.1 um. Using a PLA, the film obtained was subjected to a pattern exposure to an ultra-high pressure mercury lamp through a mask, after which the film was developed by showering of a 2.38 wt% aqueous TMAH solution for 90 seconds using an automatic developing apparatus and then rinsed with water for 30 seconds. Thereafter, the ITO was etched by immersion into a mixed solution of HCI/HNO;/H,O = 18/4.5/77.5 (weight ratio) at 40°C for 80 seconds, and the photoresist was removed by treating with a stripping solution ("N-300" available from Nagase ChemteX Corporation) at 50°C for 120 seconds to prepare a glass substrate having a patterned transparent electrode with a film thickness of 200 Angstrom. (2) Production of Transparent Insulating Film
On the glass substrate obtained, a transparent insulating film was produced by using the negative-tone photosensitive resin composition (A-1) according to the procedure in the evaluation method mentioned above. (3) Production of Molybdenum/Aluminum/Molybdenum-Laminated Film (MAM)
Wire
On the glass substrate obtained, an MAM wire was produced in the same manner as in (1) except using molybdenum and aluminum as a target and a mixed solution of H3PO,/HNO3/CH3;COOH/H,0 = 65/3/5/27 (weight ratio) as an etchant. (4) Production of Transparent Protective Film
On the glass substrate obtained, a transparent protective film was produced by using the negative-tone photosensitive resin composition (A-1) according to the procedure in the evaluation method mentioned above.
[0111]
A continuity test at a connection was performed using a tester, and continuity of current was confirmed. (Comparative Example 1)
A resin composition (H-1) was obtained in the same manner as in Example 1 except that the acrylic resin solution (d) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA.
The carboxylic acid equivalent of the acrylic resin solution (d) was 4,600 g/mol.
Using the resin composition (H-1) obtained, evaluations were performed in the same manner as in Example 1. The unexposed portion was not dissolved in a 2.38 wt% aqueous TMAH solution so that the patterning could not be achieved, and thus the other evaluations were performed without carrying out development. (Comparative Example 2)
A resin composition (H-2) was obtained in the same manner as in Example 1 except that the acrylic resin solution (e) was used in place of the polysiloxane solution (i) and that the same amount of PGMEA was further added in place of DAA.
The carboxylic acid equivalent of the acrylic resin solution (e) was 140 g/mol.
Using the resin composition (H-2) obtained, evaluations were performed in the same manner as in Example 1. (Comparative Example 3)
Under yellow light, 4.740 g of PGMEA, 0.249 g of "ZC-580 (trade name)", 0.2000 g of a silicone-based surfactant BYK-333 (1 wt% PGMEA solution) (corresponding to a concentration of 100 ppm), and 1.742 g of 4-t-butylcatechol (1 wt% PGMEA solution) were added, and the resulting mixture was stirred. "DPHA (trade name)" (50 wt% PGMEA solution) in an amount of 5.806 g and 7.258 g of the acrylic resin solution (a) were added, and the resulting mixture was stirred. Then, the resultant was filtered through a 0.45-pum filter to obtain a resin composition (H-3).
The resin composition (H-3) does not comprise a photopolymerization initiator.
Using the resin composition (H-3) obtained, evaluations were performed in the same manner as in Example 1. Both the exposed portion and the unexposed portion were dissolved in a 0.4 wt% aqueous TMAH solution so that the patterning could not be achieved, and thus the other evaluations were performed without carrying out development. (Comparative Example 4)
Under yellow light, 0.277 g of "OXE-01 (trade name)", 3.778 g of PGMEA, 0.237 g of "ZC-580 (trade name)", 0.2000 g of a silicone-based 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 the resulting mixture was stirred. The acrylic resin solution (a) in an amount of 13.846 g was added, and the resulting mixture was stirred. Then, the resultant was filtered through a 0.45-pm filter to obtain a resin composition (H-4). The resin composition (H-4) does not comprise a polyfunctional monomer. Using the resin composition (H-4) obtained, evaluations were performed in the same manner as in Example 1. (Comparative Example 5)
Under yellow light, 0.285 g of "OXE-01 (trade name)", 4.990 g of PGMEA 0.2000 g of a silicone-based surfactant BYK-333 (1 wt% PGMEA solution) (corresponding to a concentration of 100 ppm), and 1.709 g of 4-t-butylcatechol (1 wt% PGMEA solution) were added, and the resulting mixture was stirred. "DPHA (trade name)" (50 wt% PGMEA solution) in an amount of 5.696 g and 7.120 g of the acrylic resin solution (a) were added, and the resulting mixture was stirred. Then, the resultant was filtered through a 0.45-um filter to obtain a resin composition (H-5).
The resin composition (H-5) does not comprise a zirconium compound. Using the resin composition (H-5) obtained, evaluations were performed in the same manner as in Example 1. (Comparative Example 6)
Under yellow light, 0.285 g of "OXE-01 (trade name)", 2.262 g of PGMEA, 2.846 g of DAA, 0.2000 g of a silicone-based surfactant BYK-333 (1 wt% PGMEA solution) (corresponding to a concentration of 100 ppm), and 1.709 g of 4-t- butylcatechol (1 wt% PGMEA solution) were added, and the resulting mixture was stirred. "DPHA (trade name)" (50 wt% PGMEA solution) in an amount of 5.696 g and 7.120 g of the polysiloxane solution (i) were added, and the resulting mixture was stirred. Then, the resultant was filtered through a 0.45-um filter to obtain a resin composition (H-6). The resin composition (H-6) does not comprise a zirconium compound. Using the resin composition (H-6) obtained, evaluations were performed in the same manner as in Example 1. (Comparative Example 7)
A negative-tone photosensitive resin composition (H-7) was obtained in the same manner as in Example 1 except using the polysiloxane solution (v) in place of the polysiloxane solution (i). Using the negative-tone photosensitive resin composition (H-7) obtained, evaluations were performed in the same manner as in
Example 1. The unexposed portion was not dissolved in a 0.4 wt% aqueous TMAH solution.
[0112][ Table 2]
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DESCRIPTION OF SYMBOLS
[0115] 1: Glass substrate 2: Transparent electrode 3: Transparent insulating film 4: Wire electrode 5: Transparent protective film
INDUSTRIAL APPLICABILITY
[0116]
The cured film obtained by curing the negative-tone photosensitive resin composition of the present invention is suitably used not only as various hard coating films such as a protective film for a touch panel but also as an insulating film for a touch panel, a planarization film for a TFT in a liquid crystal display or an organic
EL display, a metal wire protective film, an insulating film, an antireflection coating, an antireflection film, an optical filter, an overcoat for a color filter, a column material, and the like.

Claims (10)

1. A negative-tone photosensitive resin composition, comprising (A) an alkali- soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol, (B) a photopolymerization initiator, (C) a polyfunctional monomer, and (D) a zirconium compound.
2. The negative-tone photosensitive resin composition according to claim 1, wherein the negative-tone photosensitive resin composition is a composition for forming a cured film.
3. The negative-tone photosensitive resin composition according to claim 1 or 2, wherein the negative-tone photosensitive resin composition is a composition for forming a protective film.
4. The negative-tone photosensitive resin composition according to any one of claims 1 to 3, wherein (A) the alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol is an acrylic resin having an ethylenically unsaturated bond.
5. The negative-tone photosensitive resin composition according to any one of claims 1 to 3, wherein (A) the alkali-soluble resin having a carboxylic acid equivalent of 200 g/mol to 1,400 g/mol is a polysiloxane having an ethylenically unsaturated bond.
6. The negative-tone photosensitive resin composition according to any one of claims 1 to 5, wherein (D) the zirconium compound is zirconium oxide particles having an average particle size of 100 nm or less.
7. The negative-tone photosensitive resin composition according to any one of claims 1 to 5, wherein (D) the zirconium compound is any one or more of compounds represented by Formula (1): [Chamical Formula 1]
RZ 0= rir 7 1) n 0 R® 4-n (R' represents hydrogen, alkyl, aryl, alkenyl, and substitution products thereof, and R” and R* represent hydrogen, alkyl, aryl, alkenyl, alkoxy, and substitution products thereof. A plurality of R', R?, and R? may be the same or different. n represents an integer of 0 to 4.)
8. A touch panel protective film obtained by curing the negative-tone photosensitive resin composition according to any one of claims 1 to 7.
9. A metal wire protective film obtained by curing the negative-tone photosensitive resin composition according to any one of claims 1 to 7.
10. A touch panel component comprising a cured film of the negative-tone photosensitive resin composition according to any one of claims 1 to 7, wherein a molybdenum-containing metal wire is protected by the cured film.
SG2012075073A 2010-04-14 2011-04-04 Negative photosensitive resin composition, and protective film and touch panel member using the same SG184526A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9977329B2 (en) 2014-01-24 2018-05-22 Toray Industries, Inc. Negative photosensitive resin composition, cured film obtained by curing same, method for producing cured film, optical device provided with cured film, and backside-illuminated CMOS image sensor

Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5708522B2 (en) 2011-02-15 2015-04-30 信越化学工業株式会社 Resist material and pattern forming method using the same
JP2012215833A (en) * 2011-03-31 2012-11-08 Toyo Ink Sc Holdings Co Ltd Photosensitive resin composition and insulating film for touch panel
JP6212970B2 (en) * 2011-12-05 2017-10-18 日立化成株式会社 Protective film for touch panel electrode and touch panel
JP2013200577A (en) * 2011-12-05 2013-10-03 Hitachi Chemical Co Ltd Formation method of cured resin film pattern, photosensitive resin composition, photosensitive element, manufacturing method of touch panel and cured resin film
WO2013084282A1 (en) * 2011-12-05 2013-06-13 日立化成株式会社 Method for forming resin cured film pattern, photosensitive resin composition, and photosensitive element
WO2013084284A1 (en) * 2011-12-05 2013-06-13 日立化成株式会社 Method for forming protective film for touch panel electrodes, photosensitive resin composition, and photosensitive element
JP2015146038A (en) * 2011-12-05 2015-08-13 日立化成株式会社 Formation method of cured resin film pattern, photosensitive resin composition, photosensitive element, manufacturing method of touch panel and cured resin film
KR20170106655A (en) * 2011-12-05 2017-09-21 히타치가세이가부시끼가이샤 Method for forming protective film on electrode for touch panel, photosensitive resin composition and photosensitive element, and method for manufacturing touch panel
WO2013084283A1 (en) * 2011-12-05 2013-06-13 日立化成株式会社 Method for forming protective film for touch panel electrodes, photosensitive resin composition, and photosensitive element
CN110095941B (en) * 2011-12-26 2023-02-17 东丽株式会社 Photosensitive resin composition and method for producing semiconductor element
US9377686B2 (en) * 2012-07-09 2016-06-28 Toray Industries, Inc. Photosensitive resin composition, conductive wire protection film, and touch panel member
JP6022870B2 (en) * 2012-09-25 2016-11-09 旭化成株式会社 Photosensitive resin composition
JP6430098B2 (en) * 2013-01-15 2018-11-28 日立化成株式会社 Photosensitive transparent material for protective film of touch panel electrode
JP6217296B2 (en) * 2013-01-22 2017-10-25 東洋インキＳｃホールディングス株式会社 Photosensitive resin composition and coating film using the same
KR20150118582A (en) * 2013-02-12 2015-10-22 도레이 카부시키가이샤 Photosensitive resin composition, protective film or insulation film obtained by heat curing said composition, touch panel using said film, and production method for said touch panel
JP6417669B2 (en) * 2013-03-05 2018-11-07 東レ株式会社 Photosensitive resin composition, protective film, insulating film, and method of manufacturing touch panel
KR20150135320A (en) * 2013-03-28 2015-12-02 도레이 카부시키가이샤 Photosensitive resin composition, protection film or insulation film, touch panel and method for manufacturing same
JP6236885B2 (en) * 2013-06-04 2017-11-29 日立化成株式会社 Method for producing substrate for touch panel with protective film, photosensitive resin composition, photosensitive element, and touch panel
CN104427742B (en) * 2013-08-28 2017-08-22 鹏鼎控股(深圳)股份有限公司 Cover layer and circuit board
JP6255806B2 (en) * 2013-09-04 2018-01-10 Jsr株式会社 Gate insulating film, radiation sensitive resin composition, cured film, method for forming gate insulating film, semiconductor element, and display device
JP2015108881A (en) * 2013-12-03 2015-06-11 日立化成株式会社 Method for manufacturing touch panel substrate with cured film, photosensitive resin composition, photosensitive element, and touch panel
JP6400289B2 (en) * 2013-12-24 2018-10-03 日立化成株式会社 Base material for touch panel with cured film and method for producing the same, photosensitive element and touch panel
KR102458628B1 (en) * 2014-05-13 2022-10-26 쇼와덴코머티리얼즈가부시끼가이샤 Photosensitive resin composition, photosensitive element, method for forming resist pattern, and process for producing printed wiring board
CN105278239A (en) * 2014-05-30 2016-01-27 青岛科技大学 Stereo-lithography rapid-prototyping polysiloxane photosensitive resin composition and preparation method and application thereof
JP6284913B2 (en) 2014-08-29 2018-02-28 富士フイルム株式会社 Composition for forming touch panel electrode protective film, transfer film, laminate, protective film for touch panel electrode and method for forming the same, capacitive input device, and image display device
JP6764636B2 (en) * 2014-10-08 2020-10-07 東京応化工業株式会社 Radiation-sensitive resin composition, pattern manufacturing method, transparent insulating film, and display device
KR101564872B1 (en) * 2015-02-10 2015-10-30 동우 화인켐 주식회사 Negative-type photosensitive resin composition
CN108027561B (en) * 2015-09-30 2021-10-08 东丽株式会社 Negative photosensitive resin composition, cured film, element and display device provided with cured film, and method for producing same
US10040967B2 (en) 2015-11-06 2018-08-07 Hitachi Chemical Company, Ltd. Photosensitive film, photosensitive element, cured product and touch panel
KR102630893B1 (en) * 2015-11-25 2024-01-31 롬엔드하스전자재료코리아유한회사 Photosensitive resin composition and cured film prepared therefrom
TW201741766A (en) * 2015-12-17 2017-12-01 陶氏全球科技責任有限公司 Photo-imageable thin films with high dielectric constants
JP6551277B2 (en) * 2016-03-24 2019-07-31 日立化成株式会社 Method for producing cured substrate with touch panel, photosensitive resin composition used therefor, photosensitive element and touch panel
WO2018029750A1 (en) * 2016-08-08 2018-02-15 東レ株式会社 Laminated member and touch panel
JP6558419B2 (en) * 2017-09-14 2019-08-14 日立化成株式会社 Photosensitive transparent material for protective film of touch panel electrode
TWI795523B (en) * 2018-02-05 2023-03-11 日商Ｊｓｒ股份有限公司 Wiring components
JP6875325B2 (en) * 2018-05-21 2021-05-19 信越化学工業株式会社 Pattern formation method
CN108793766B (en) * 2018-06-12 2021-05-25 西安理工大学 Electrochromic film capable of effectively modulating mid-infrared transmittance and preparation method thereof
JP2019046499A (en) * 2018-12-05 2019-03-22 日立化成株式会社 Production method of touch panel substrate with cured film, photosensitive resin composition used for the method, photosensitive element, and touch panel
KR102622934B1 (en) * 2021-04-22 2024-01-09 주식회사 아모텍 Method for manufacturing multi-layered ceramic electronic component and multi-layered ceramic electronic component therefrom

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07331173A (en) * 1995-02-21 1995-12-19 Toray Ind Inc Coating composition for formation of optical material and optical material
JPH11202123A (en) * 1997-10-09 1999-07-30 Dainippon Printing Co Ltd Composition for nonconductive light shielding layer, nonconductive light shielding layer and color filter
JP4419635B2 (en) * 2003-03-28 2010-02-24 東レ株式会社 Photosensitive paste, plasma display partition, method for manufacturing transparent dielectric pattern for plasma display, and method for manufacturing plasma display
TWI295303B (en) * 2003-08-21 2008-04-01 Toyo Boseki Optical-use adhesive polyester film and optical-use laminatede film
JP2006137932A (en) * 2004-10-12 2006-06-01 Toray Ind Inc Coating composition and display device using the same
JP2008039872A (en) * 2006-08-02 2008-02-21 Toray Ind Inc Photosensitive composition for baking and display member using the same
WO2008133312A1 (en) * 2007-04-25 2008-11-06 Asahi Glass Company, Limited Photosensitive composition, partition wall, black matrix, and method for producing color filter
JP4392464B2 (en) * 2008-01-15 2010-01-06 積水化学工業株式会社 Resist material and laminate
JP2009186510A (en) * 2008-02-01 2009-08-20 Fujifilm Corp Photosensitive composition, photosensitive film, photosensitive laminate, method for forming permanent pattern, and printed wiring board
JP5507255B2 (en) * 2008-05-28 2014-05-28 東レ株式会社 Laminated polyester film and antireflection film
JP5201066B2 (en) * 2008-06-19 2013-06-05 Ｊｓｒ株式会社 Radiation sensitive resin composition for forming protective film of touch panel and method for forming the same
JP2010039056A (en) * 2008-08-01 2010-02-18 Sekisui Chem Co Ltd Photosensitive composition and method of manufacturing pattern film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9977329B2 (en) 2014-01-24 2018-05-22 Toray Industries, Inc. Negative photosensitive resin composition, cured film obtained by curing same, method for producing cured film, optical device provided with cured film, and backside-illuminated CMOS image sensor

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