CN110998442A - Positive radiation-sensitive resin composition - Google Patents
Positive radiation-sensitive resin composition Download PDFInfo
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- CN110998442A CN110998442A CN201880054622.9A CN201880054622A CN110998442A CN 110998442 A CN110998442 A CN 110998442A CN 201880054622 A CN201880054622 A CN 201880054622A CN 110998442 A CN110998442 A CN 110998442A
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- resin composition
- radiation
- sensitive resin
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- film
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- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- 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
-
- 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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
Abstract
The invention provides a positive type radiation sensitive resin composition which can form a pattern with excellent developing adhesion and can form a resin film with excellent chemical resistance even if heat treatment is carried out at low temperature. The positive-type radiation-sensitive resin composition of the present invention contains a resin soluble in alkali, a first acid generator that generates a carboxylic acid when irradiated with radiation, a second acid generator that generates a sulfonic acid when irradiated with radiation, and a fluorine-containing phenolic compound.
Description
Technical Field
The present invention relates to a positive radiation-sensitive resin composition, and more particularly to a positive radiation-sensitive resin composition that can be preferably used for forming a planarizing film, a protective film, an insulating film, and the like used for electronic components.
Background
In electronic components such as liquid crystal display devices, organic EL display devices, integrated circuit devices, and solid-state imaging devices, various resin films are provided as a planarizing film, a protective film, an insulating film, and the like.
Specifically, for example, in an organic EL display device, a liquid crystal display device, or the like, a rewiring layer is formed using a patterned interlayer insulating film (passivation film). The patterned interlayer insulating film is formed by, for example, pre-baking a radiation-sensitive resin composition applied on a substrate, exposing and developing the resulting coating film to form a pattern, and then exposing and post-baking the patterned coating film to cure the pattern (see, for example, patent document 1).
As a resin composition used for forming a resin film such as a patterned interlayer insulating film, for example, a positive-type radiation-sensitive resin composition containing a resin soluble in an alkali, a quinone diazide compound, and a photoacid generator having a maximum absorption wavelength shorter than that of the quinone diazide compound has been proposed (for example, see patent document 2).
Documents of the prior art
Patent document
Patent document 1: international publication No. 2014/030441;
patent document 2: japanese patent laid-open publication No. 2016-042127.
Disclosure of Invention
Problems to be solved by the invention
However, the conventional positive-type radiation-sensitive resin composition described above has room for improvement in terms of improving the adhesion (development adhesion) between a pattern and a substrate when the pattern is formed on the substrate using the positive-type radiation-sensitive resin composition.
In recent years, a positive-type radiation-sensitive resin composition capable of favorably forming a resin film (cured film) even when subjected to a heat treatment such as post-baking at a low temperature has been demanded from the viewpoint that a substrate having low heat resistance can also be used as a substrate for forming a resin film.
However, the conventional positive-type radiation-sensitive resin composition may have a reduced chemical resistance of the resin film obtained by heat treatment at a low temperature (for example, 150 ℃ or lower, preferably 130 ℃ or lower).
Accordingly, an object of the present invention is to provide a positive-type radiation-sensitive resin composition which can form a pattern having excellent development adhesion and can form a resin film having excellent chemical resistance even when heat-treated at a low temperature.
Means for solving the problems
The present inventors have conducted intensive studies with a view to solving the above problems. Then, the present inventors have found that a positive-type radiation-sensitive resin composition containing a resin soluble in an alkali, a predetermined acid generator and a fluorine-containing phenolic compound enables formation of a pattern having excellent development adhesion and formation of a resin film having excellent chemical resistance under low temperature conditions, and have completed the present invention.
That is, the present invention is directed to advantageously solve the above problems, and a positive-type radiation-sensitive resin composition of the present invention is characterized by containing a resin soluble in an alkali, a first acid generator that generates a carboxylic acid when irradiated with radiation, a second acid generator that generates a sulfonic acid when irradiated with radiation, and a fluorine-containing phenolic compound. When the positive radiation-sensitive resin composition contains the first acid generator and the fluorine-containing phenolic compound, a pattern having excellent development adhesion can be formed. Further, if the positive radiation-sensitive resin composition contains the first acid generator and the second acid generator, a resin film having excellent chemical resistance can be formed even when heat treatment is performed at a low temperature.
Here, the positive radiation-sensitive resin composition of the present invention is preferably such that the alkali-soluble resin is a cycloolefin resin having a protic polar group. This is because if a cycloolefin resin having a protic polar group is used as the resin soluble in an alkali, the development adhesion of the pattern and the chemical resistance of the resin film can be further improved, and the resin film having high transparency and low water absorption can be formed.
The positive radiation-sensitive resin composition of the present invention preferably further contains a polyfunctional epoxy compound. This is because, if a polyfunctional epoxy compound is contained, the chemical resistance of the resin film can be further improved.
Further, the positive radiation-sensitive resin composition of the present invention preferably further contains a sensitizer. This is because if a sensitizer is contained, the chemical resistance of the resin film can be further improved.
In addition, the sensitizer is preferably a compound having an anthracene structure. This is because if a compound having an anthracene structure is used as a sensitizer, the chemical resistance of a resin film can be further improved.
Effects of the invention
According to the positive-type radiation-sensitive resin composition of the present invention, a pattern having excellent development adhesion can be formed, and a resin film having excellent chemical resistance can be formed even under low temperature conditions.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
(Positive type radiation-sensitive resin composition)
The positive radiation-sensitive resin composition of the present invention is not particularly limited, and can be used for forming a resin film (for example, a planarizing film, a protective film, an insulating film, or the like) of an electronic component such as a liquid crystal display device, an organic EL display device, an integrated circuit element, or a solid-state imaging element. In particular, the positive-type radiation-sensitive resin composition of the present invention can be preferably used for forming an insulating film, and can be particularly preferably used for forming an insulating film for rewiring used for arranging a redistribution Layer (RDL).
The positive-type radiation-sensitive resin composition of the present invention contains a resin soluble in alkali, a first acid generator that generates a carboxylic acid when irradiated with radiation, a second acid generator that generates a sulfonic acid when irradiated with radiation, and a fluorine-containing phenolic compound, and can optionally further contain at least 1 selected from a polyfunctional epoxy compound, a sensitizer, an additive, and a solvent.
Further, since the positive-type radiation-sensitive resin composition of the present invention contains the first acid generator and the fluorine-containing phenolic compound, a pattern having excellent development adhesion can be formed if the positive-type radiation-sensitive resin composition of the present invention is used. Further, since the positive radiation-sensitive resin composition of the present invention contains the first acid generator and the second acid generator, a resin film having excellent chemical resistance can be formed even when heat treatment is performed at a low temperature.
< resin soluble in alkali >
The resin soluble in alkali is not particularly limited as long as it is a resin capable of alkali development. The resin soluble in alkali is not particularly limited, and examples thereof include novolak resins, polyvinyl alcohol resins, acrylic resins, polyimide resins, and polybenzo resins
An azole resin, a vinyl phenol resin, a cyclic olefin resin which is a resin containing a cyclic olefin monomer unit, and the like. These can be used singly or in combination of 2 or more.
In the present invention, the phrase "the resin or the polymer" contains a monomer unit "means" the resin or the polymer obtained using the monomer contains a structural unit derived from the monomer.
In particular, from the viewpoint of sufficiently improving the development adhesion of the pattern and the chemical resistance of the resin film and enabling the formation of a resin film having high transparency and low water absorption, the resin soluble in the base is preferably a cycloolefin-based resin, and more preferably a cycloolefin-based resin having a protic polar group.
The cycloolefin resin having a protic polar group, which is preferable as the resin soluble in an alkali, is a homopolymer or a copolymer of a cycloolefin monomer having a cyclic structure (alicyclic or aromatic ring) derived from a cycloolefin monomer and a protic polar group in a main chain.
The "protic polar group" refers to an atomic group in which hydrogen is directly bonded to an atom belonging to group 15 or group 16 of the periodic table. The atom to which hydrogen is directly bonded is preferably an atom belonging to group 15 or group 16 of the periodic table of elements, either cycle 1 or cycle 2, more preferably an oxygen atom, a nitrogen atom or a sulfur atom, and particularly preferably an oxygen atom.
Examples of the monomers for constituting the cycloolefin resin having a protic polar group include a cycloolefin monomer (a) having a protic polar group, a cycloolefin monomer (b) having a polar group other than the protic polar group, a cycloolefin monomer (c) having no polar group, and a monomer (d) other than the cycloolefin monomer (hereinafter, these monomers are simply referred to as "monomers (a) to (d)"). The monomers (b), (c) and (d) can be used in a range that does not affect the properties.
In addition, the proportion of the cyclic olefin monomer unit having a protic polar group in the entire structural units of the protic polar group-containing cyclic olefin resin is usually 30% by mass or more and 100% by mass or less, and preferably 50% by mass or more and 100% by mass or less. The cycloolefin-based resin having a protic polar group is preferably composed of the monomer (a) and the monomer (b), composed of the monomer (a) and the monomer (c), composed of the monomer (a), the monomer (b), and the monomer (c), and more preferably composed of the monomer (a) and the monomer (b).
Specific examples of the monomer (a) include: 5-Hydroxycarbonylbicyclo [2.2.1]Hept-2-ene, 5-methyl-5-hydroxycarbonylbicyclo [2.2.1]Hept-2-ene, 5-carboxymethyl-5-hydroxycarbonylbicyclo [2.2.1]Hept-2-ene, 5, 6-dihydroxycarbonylbicyclo [2.2.1]]Hept-2-ene, 4-hydroxycarbonyltetracyclo [6.2.1.13,6.02,7]Dodec-9-ene, 9-methyl-9-hydroxycarbonyltetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9, 10-dihydroxycarbonyltetracyclo [6.2.1.13,6.02,7]Carboxyl group-containing cyclic olefins such as dodec-4-ene; 5- (4-hydroxyphenyl) bicyclo [2.2.1]Hept-2-ene,5-methyl-5- (4-hydroxyphenyl) bicyclo [2.2.1]Hept-2-ene, 9- (4-hydroxyphenyl) tetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-methyl-9- (4-hydroxyphenyl) tetracyclo [6.2.1.13,6.02,7]A hydroxyl group-containing cyclic olefin such as dodec-4-ene, and particularly, a carboxyl group-containing cyclic olefin is preferable as the monomer (a). These cyclic olefin monomers (a) having a protic polar group may be used alone or in combination of 2 or more.
Specific examples of the polar group other than the protic polar group, which the cyclic olefin monomer (b) having a polar group other than the protic polar group has, include an ester group (an alkoxycarbonyl group and an aryloxycarbonyl group are collectively referred to), an N-substituted imide group, an epoxy group, a halogen atom, a cyano group, a carbonyloxycarbonyl group (an acid anhydride residue of a dicarboxylic acid), an alkoxy group, a carbonyl group, a tertiary amino group, a sulfo group, an acryloyl group, and the like. In particular, as the polar group other than the protic polar group, an ester group, an N-substituted imide group and a cyano group are preferable, an ester group and an N-substituted imide group are more preferable, and an N-substituted imide group is particularly preferable.
Specific examples of the monomer (b) include the following cyclic olefins.
Examples of the cyclic olefin having an ester group include 5-acetoxybicyclo [2.2.1]Hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1]]Hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1]Hept-2-ene, 9-acetoxytetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-methoxycarbonyltetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-ethoxycarbonyltetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-n-propoxycarbonyltetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-isopropoxycarbonyltetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-n-butyloxycarbonyl-tetracyclo [6.2.1.13 ,6.02,7]Dodec-4-ene, 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-methyl-9-ethoxycarbonyltetracyclo [6.2.1.13,6.02,7]Dodeca-4-ene, 9-methyl-9-n-propoxycarbonyltetracyclic rings[6.2.1.13, 6.02,7]Dodec-4-ene, 9-methyl-9-isopropoxycarbonyltetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-methyl-9-n-butoxycarbonyltetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9- (2,2, 2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-methyl-9- (2,2, 2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, and the like.
Examples of the cyclic olefin having an N-substituted imide group include N-phenylbicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (2-ethylhexyl) -1-isopropyl-4-methylbicyclo [2.2.2] oct-5-ene-2, 3-dicarboximide, N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, n- [ (2-ethylbutoxy) ethoxypropyl ] -bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (endo-bicyclo [2.2.1] hept-5-ene-2, 3-diyldicarbonyl) aspartic acid dimethyl ester, and the like.
Examples of the cyclic olefin having a cyano group include 9-cyanotetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-methyl-9-cyanotetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 5-cyanobicyclo [2.2.1]Hept-2-ene, and the like.
Examples of the cyclic olefin having a halogen atom include 9-chlorotetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-methyl-9-chlorotetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, and the like.
These cyclic olefin monomers (b) having a polar group other than the protic polar group may be used alone or in combination of 2 or more.
Specific examples of the cyclic olefin monomer (c) having no polar group include bicyclo [2.2.1]Hept-2-ene (also known as "norbornene"), 5-ethyl-bicyclo [2.2.1]Hept-2-ene, 5-butyl-bicyclo [2.2.1]Hept-2-ene, 5-ethylene-bicyclo [2.2.1]Hept-2-ene, 5-methylene-bicyclo [2.2.1]Hept-2-ene, 5-vinyl-bicyclo [2.2.1]Hept-2-ene, tricyclo [5.2.1.02,6]Deca-3, 8-diene (common name: dicyclopentadiene), tetracyclo [10.2.1.0 ]2,1104,9]Pentadecane-4, 6,8, 13-tetraene and tetracyclo [6.2.1.13,6.02,7]Dodec-4-enes (also known as "tetracyclododecenes"), 9-methyl-tetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-ethyl-tetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-methylene-tetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-ethylene-tetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-vinyl-tetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, 9-propenyl-tetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, pentacyclo [9.2.1.13,9.02,10]Pentadecane-5, 12-diene, cyclopentene, cyclopentadiene, 9-phenyl-tetracyclo [6.2.1.13,6.02,7]Dodec-4-ene, tetracyclo [9.2.1.0 ]2,10.03,8]Tetradec-3, 5,7, 12-tetraene and pentacyclic [9.2.1.1 ]3,9.02,10]Pentadec-12-ene, and the like.
These cyclic olefin monomers (c) having no polar group may be used alone or in combination of 2 or more.
Examples of the chain olefin include, for example, α -olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-hexene, 4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and nonconjugated dienes such as 1, 4-hexadiene, 4-methyl-1, 4-hexadiene, 5-methyl-1, 4-hexadiene, and 1, 7-octadiene.
These monomers (d) other than the cyclic olefin can be used singly or in combination of 2 or more.
The cycloolefin resin having a protic polar group used in the present invention can be obtained by polymerizing the monomer (a) together with 1 or more monomers selected from the monomers (b) to (d) as desired. The polymer obtained by polymerization may be further subjected to hydrogenation. In the present invention, the hydrogenated polymer is also included in the cycloolefin resin having a protic polar group.
The cycloolefin resin having a protic polar group used in the present invention can also be obtained by introducing a protic polar group into a cycloolefin resin having no protic polar group by a known modifier and hydrogenating the introduced protic polar group as desired. Here, the hydrogenation may be performed on the polymer before the introduction of the protic polar group.
The cycloolefin resin having a protic polar group used in the present invention can also be obtained by introducing a protic polar group into the cycloolefin resin having a protic polar group.
< first acid Generator >
The first acid generator is a compound that decomposes upon irradiation with radiation to generate a carboxylic acid. Further, when a coating film formed using the positive type radiation-sensitive resin composition of the present invention containing the first acid generator is irradiated with radiation, the alkali solubility of the radiation-irradiated portion increases.
Here, the radiation is not particularly limited, and examples thereof include: visible light rays; ultraviolet rays; x-rays; g line, h line, i line and other single wavelength light; laser beams such as KrF excimer laser and ArF excimer laser; a particle beam such as an electron beam, and the like.
The first acid generator is not particularly limited, and an azide compound such as a quinone diazide compound can be used.
Further, as the quinonediazide compound, for example, an ester compound of a quinonediazide sulfonyl halide and a compound having a phenolic hydroxyl group can be used. Specific examples of the quinonediazide sulfonyl halide include 1, 2-naphthoquinonediazide-5-sulfonyl chloride, 1, 2-naphthoquinonediazide-4-sulfonyl chloride, and 1, 2-benzoquinonediazide-5-sulfonyl chloride. Further, as a specific example of the compound having a phenolic hydroxyl group, examples thereof include 1,1, 3-tris (2, 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '- [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol, 2,3, 4-trihydroxybenzophenone, 2,3,4, 4' -tetrahydroxybenzophenone, 2-bis (4-hydroxyphenyl) propane, tris (4-hydroxyphenyl) methane, 1,1, 1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2, 2-tetrakis (4-hydroxyphenyl) ethane, oligomers of a novolak resin, and oligomers obtained by copolymerizing dicyclopentadiene with a compound having 1 or more phenolic hydroxyl groups.
In particular, as the first acid generator, an ester compound of 1, 2-naphthoquinonediazide-5-sulfonyl chloride and 4, 4' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol is preferable.
The first acid generator may be used singly or in combination of 2 or more.
Here, the amount of the first acid generator in the positive radiation-sensitive resin composition is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, preferably 60 parts by mass or less, and more preferably 50 parts by mass or less, relative to 100 parts by mass of the alkali-soluble resin. If the amount of the first acid generator is not less than the lower limit, a sufficient residual film ratio can be ensured when a coating film formed using the positive radiation-sensitive resin composition is developed. Further, if the amount of the first acid generator is not more than the upper limit, it is possible to suppress the reduction in resolution and the generation of residue when a coating film formed using the positive radiation-sensitive resin composition is patterned.
< second acid Generator >
The second acid generator is a compound that decomposes upon irradiation with radiation to generate a sulfonic acid. Further, since the positive-type radiation-sensitive resin composition of the present invention contains the second acid generator in addition to the first acid generator, when a resin film is prepared by irradiating a coating film that can be patterned and is formed using the positive-type radiation-sensitive resin composition with radiation and heat treatment, a resin film having excellent chemical resistance can be formed even when heat treatment is performed at a low temperature (for example, 150 ℃ or lower, preferably 130 ℃ or lower).
Here, the radiation is not particularly limited, and examples thereof include: visible light rays; ultraviolet rays; x-rays; g line, h line, i line and other single wavelength light; laser beams such as KrF excimer laser and ArF excimer laser; a particle beam such as an electron beam, and the like.
Further, the second acid generator is not particularly limited, and for example, (4-methylphenyl) diphenylsulfonium trifluoromethanesulfonic acid, (2,4, 6-trimethylphenyl) diphenylsulfonium p-tolylsulfonic acid, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonic acid, tris (4-methylphenyl) sulfonium nonafluorobutaneylsulfonic acid, bis (cyclohexylsulfonyl) diazomethane, 2-methyl-2- [ (4-methylphenyl) sulfonyl ] -1- [4- (methylthio) phenyl ] -1-propanone, bis (4-methylphenylsulfonyl) diazomethane, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [ 2.1] naphthalene-6-naphthalene-imide, (1, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyl) bis [ 2.1.1 ] naphthalene-6-4 ] succinimide, N- (3-dimethylimide, N- (3-naphthalene-sulfonyl) imide, N- (3-dimethylimide, N- (3-naphthalene-3-dimethylimide, N- (3-naphthalene-sulfonyloxy) succinimide, N- (3-naphthalene-3-naphthalene-3-dimethylimide, N- (Mi-3-bis (Mi) imide, N- (3-naphthalene-3-naphthalene-bis-naphthalene-3-imide, N- (3-naphthalene-sulfonic acid, N- (3-naphthalene-imide, N- (3-naphthalene-sulfonic acid, N-naphthalene-.
In particular, from the viewpoints of solubility in a solvent, storage stability, chemical resistance, and the like, 1, 8-naphthalimide trifluoromethanesulfonate and N-sulfonyloxyimide derivatives are preferable as the second acid generator.
The second acid generator may be used singly or in combination of 2 or more.
Here, the amount of the second acid generator in the positive radiation-sensitive resin composition is preferably 0.1 part by mass or more, more preferably 0.3 part by mass or more, preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, relative to 100 parts by mass of the alkali-soluble resin. If the amount of the second acid generator is not less than the lower limit, the chemical resistance of the resin film formed using the positive radiation-sensitive resin composition can be sufficiently improved. Further, if the amount of the second acid generator is equal to or less than the upper limit value, the water absorption of the resin film can be suppressed from being improved, and insulation reliability can be ensured.
The amount of the second acid generator in the positive radiation-sensitive resin composition is usually smaller than the amount of the first acid generator, and is preferably 0.01 to 0.03 times the amount of the first acid generator. If the amount of the second acid generator is not less than the lower limit, the chemical resistance of the resin film formed using the positive radiation-sensitive resin composition can be sufficiently improved. Further, if the amount of the second acid generator is equal to or less than the upper limit value, the water absorption of the resin film can be suppressed from being improved, and insulation reliability can be ensured.
< fluorinated phenol-containing Compound >
The fluorine-containing phenolic compound is a compound having a structure in which 1 or more fluorine atoms and hydroxyl groups are directly bonded to a benzene ring in 1 molecule. The fluorine atom may be bonded to the benzene ring directly or indirectly. Further, since the positive-type radiation-sensitive resin composition of the present invention contains not only the first acid generator but also a fluorine-containing phenolic compound, a pattern having excellent development adhesion can be formed.
Here, the fluorinated phenolic compound is not particularly limited, and for example: fluorine-containing phenolic compounds in which fluorine atoms such as 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 3,4, 5-trifluorophenol and the like are directly bonded to a benzene ring; and fluorine-containing phenolic compounds in which a fluorine atom is indirectly bonded to a benzene ring, such as 2-trifluoromethylphenol, 3-trifluoromethylphenol, 2-trifluoromethoxyphenol, 3-trifluoromethoxyphenol, and 5, 5' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] bis [ 2-hydroxy-1, 3-benzenedimethanol ] (product name "TML-BPAF-MF", manufactured by chemical industry of this state).
In particular, from the viewpoint of further improving development adhesion, the fluorine-containing phenolic compound is preferably a fluorine-containing phenolic compound having 2 or more fluorine atoms in 1 molecule, more preferably a fluorine-containing phenolic compound in which 2 or more fluorine atoms are indirectly bonded to a benzene ring, and further preferably 5, 5' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] bis [ 2-hydroxy-1, 3-benzenedimethanol ].
The fluorine-containing phenolic compound may be used singly or in combination of 2 or more.
The amount of the fluorine-containing phenolic compound in the positive-type radiation-sensitive resin composition is preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin soluble in an alkali. When the amount of the fluorine-containing phenolic compound is not less than the lower limit, development adhesion can be sufficiently improved with respect to a pattern formed using the positive type radiation-sensitive resin composition. Further, if the amount of the fluorinated phenolic compound is not more than the above upper limit, a sufficient residual film ratio can be secured when a coating film formed using the positive radiation-sensitive resin composition is developed.
< polyfunctional epoxy Compound >
The polyfunctional epoxy compound that can be optionally contained in the positive radiation-sensitive resin composition of the present invention is not particularly limited as long as it is a compound having 2 or more epoxy groups in 1 molecule. Further, if the positive radiation-sensitive resin composition of the present invention contains a polyfunctional epoxy compound, the flexibility of the coating film can be improved, and the chemical resistance of the resin film can be further improved by a crosslinking reaction via the polyfunctional epoxy compound.
Examples of the compound having 2 or more epoxy groups that can be used as the polyfunctional epoxy compound include tris (2, 3-epoxypropyl) isocyanurate, 1, 4-butanediol diglycidyl ether, 1, 2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2, 6-diglycidyl phenyl glycidyl ether, 1, 3-tris [ p- (2, 3-epoxypropoxy) phenyl ] propane, 1, 2-cyclohexanedicarboxylic acid diglycidyl ester, 4' -methylenebis (N, N-diglycidylaniline), 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylcarboxylate, trimethylolethane triglycidyl ether, and mixtures thereof, Bisphenol a diglycidyl ether, pentaerythritol polyglycidyl ether, and the like. Further, as a commercially available product of the polyfunctional epoxy compound, for example: EPOLEAD GT401, EPOLEAD GT403, EPOLEAD GT301, EPOLEAD GT302, EPOLEAD PB3600, EPOLEAD PB4700, CELLOXIDE 2021, CELLOXIDE 3000 (manufactured by Daicel corporation, supra); jER1001, jER1002, jER1003, jER1004, jER1007, jER1009, jER1010, jER828, jER871, jER872, jER180S75, jER807, jER152, and jER154 (manufactured by Mitsubishi chemical corporation); EPPN201, EPPN202, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon chemical Co., Ltd.); EPICLON 200, EPICLON 400 (available from DIC corporation, supra); DENACOL EX-611, DENACOL EX-612, DENACOL EX-614, DENACOL EX-622, DENACOL EX-411, DENACOL EX-512, DENACOL EX-522, DENACOL EX-421, DENACOL EX-313, DENACOL EX-314, DENACOL EX-321 (manufactured by Nagase ChemteX, Inc., supra), and the like.
In particular, from the viewpoint of improving the chemical resistance of the resin film, the polyfunctional epoxy compound preferably contains at least 1 selected from the group consisting of a polyfunctional epoxy compound having an alicyclic structure such as EPOLEAD GT401 (substance name: epoxidized butanetetracarboxylic acid tetra (3-cyclohexenylmethyl) -modified e-caprolactone) and an epoxidized polybutadiene having an H terminal such as EPOLEAD PB4700, more preferably contains at least 1 selected from the group consisting of a polyfunctional epoxy compound having an alicyclic structure such as EPOLEAD GT401 and an epoxidized polybutadiene having a glycidyl ether structure in the main chain and an H terminal such as EPOLEAD PB4700, and still more preferably contains at least epoxybutanetetracarboxylic acid tetra (3-cyclohexenylmethyl) -modified e-caprolactone.
The polyfunctional epoxy compounds may be used singly or in combination of 2 or more.
The amount of the polyfunctional epoxy compound in the positive-type radiation-sensitive resin composition is preferably 50 parts by mass or more and 90 parts by mass or less, and more preferably 70 parts by mass or more and 90 parts by mass or less, with respect to 100 parts by mass of the resin soluble in an alkali. If the amount of the polyfunctional epoxy compound is not less than the lower limit, the chemical resistance of a resin film formed using the positive radiation-sensitive resin composition can be sufficiently improved. Further, if the amount of the polyfunctional epoxy compound is not more than the above upper limit, a sufficient residual film ratio can be secured when a coating film formed using the positive radiation-sensitive resin composition is developed.
< sensitizing agent >
The sensitizer that can be optionally contained in the positive-type radiation-sensitive resin composition of the present invention is not particularly limited as long as it can transfer the energy of the irradiated radiation to other substances, and any sensitizer such as methyl-p-benzoquinone, thioxanthone, 1-phenyl-1, 2-propanedione, or a compound having an anthracene structure can be used.
Further, the sensitizer may be used singly or in combination of 2 or more.
In particular, from the viewpoint of high radiation decomposition rate and sensitizing effect, a compound having an anthracene structure is preferable as the sensitizer, and a compound represented by the following general formula (I) is more preferable.
[ chemical formula 1]
[ in the formula (I), R represents an alkyl group having 10 or less carbon atoms which may have a substituent. ]
Here, R in the formula (I) is preferably an alkyl group having 2 to 8 carbon atoms which may have a substituent, and more preferably an alkyl group having 3 to 8 carbon atoms which may have a substituent. Furthermore, the alkyl group of R is preferably a straight-chain alkyl group.
The substituent that the alkyl group of R may have is not particularly limited, and examples thereof include a carbonyl group and an alkoxy group, with a carbonyl group being particularly preferred.
Examples of the compound represented by the general formula (I) include 9, 10-dibutoxyanthracene (product name "UVS-1331" manufactured by Kawasaki chemical Co., Ltd.), 9, 10-diethoxyanthracene (product name "UVS-1101" manufactured by Kawasaki chemical Co., Ltd.), 9, 10-bis (octanoyloxy) anthracene (product name "UVS-581" manufactured by Kawasaki chemical Co., Ltd.), and the like.
In addition, the amount of the sensitizer in the positive radiation-sensitive resin composition is preferably 0.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the resin soluble in an alkali. If the amount of the sensitizer is not less than the lower limit, the chemical resistance of the resin film formed using the positive radiation-sensitive resin composition can be sufficiently improved. Further, if the amount of the polyfunctional epoxy compound is not more than the above upper limit value, the decrease in transparency and the increase in water absorption of the resin film can be suppressed.
< additives >
Examples of the additive that can be optionally contained in the positive radiation-sensitive resin composition of the present invention include a silane coupling agent, an antioxidant, and a surfactant.
Here, the silane coupling agent functions to improve the adhesion between the coating film or the resin film obtained using the positive radiation-sensitive resin composition of the present invention and the substrate on which the coating film or the resin film is formed. Further, the silane coupling agent is not particularly limited, and a known silane coupling agent can be used (for example, refer to japanese patent laid-open publication No. 2015-94910).
Further, the antioxidant can improve the light resistance and heat resistance of a coating film or a resin film obtained using the positive radiation-sensitive resin composition of the present invention. The antioxidant is not particularly limited, and known phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, lactone-based antioxidants, and the like can be used (see, for example, international publication No. 2015/033901).
Further, the surfactant can improve the coatability of the positive type radiation-sensitive resin composition of the present invention. The surfactant is not particularly limited, and known silicone surfactants, fluorine surfactants, polyoxyalkylene surfactants, methacrylic copolymer surfactants, acrylic copolymer surfactants, and the like can be used (see, for example, international publication No. 2015/033901).
These additives may be used singly or in combination of 2 or more. In addition, the amount of the additive to be blended in the positive type radiation-sensitive resin composition can be arbitrarily adjusted.
< solvent >
The solvent that can be optionally contained in the positive-type radiation-sensitive resin composition of the present invention is not particularly limited, and a known solvent can be used as the solvent for the resin composition. Examples of such solvents include linear ketones, alcohols, alcohol ethers, esters, cellosolve esters, propylene glycols, diethylene glycols such as diethylene glycol methyl ethyl ether, saturated γ -lactones, halogenated hydrocarbons, aromatic hydrocarbons, and polar solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide (see, for example, international publication No. 2015/033901).
These solvents may be used singly or in combination of 2 or more.
The amount of the solvent in the positive radiation-sensitive resin composition is not particularly limited, but is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, preferably 10000 parts by mass or less, more preferably 5000 parts by mass or less, and further preferably 1000 parts by mass or less, based on 100 parts by mass of the resin soluble in an alkali.
< method for producing Positive-type radiation-sensitive resin composition >
The positive radiation-sensitive resin composition of the present invention can be prepared by mixing the above components by a known method and optionally filtering. Here, the mixing can use a known mixer such as a stirrer, a ball mill, a sand mill, a bead mill, a pigment dispersing machine, an attritor, an ultrasonic dispersing machine, a homogenizer, a planetary mixer, and Filmix. Further, the mixture can be filtered by a common filtration method using a filter device such as a filter.
< formation of coating film and resin film >
The resin film using the positive radiation-sensitive resin composition of the present invention can be formed, without particular limitation, by, for example, providing a coating film on a substrate on which the resin film is formed using the positive radiation-sensitive resin composition of the present invention, irradiating the coating film with radiation, and further heating the coating film after the radiation irradiation. In addition, the coating film provided on the substrate may also be patterned.
The coating film can be provided on the substrate on which the resin film is formed by, without particular limitation, forming the coating film on the substrate by a coating method, a film lamination method, or the like, and then optionally patterning the coating film.
[ formation of coating film ]
Here, the formation of the coating film by the coating method can be performed by applying a positive radiation-sensitive resin composition onto a substrate and then heating and drying (pre-baking). As a method for applying the positive radiation-sensitive resin composition, various methods such as a spray coating method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a spin coating method, a bar coating method, a screen printing method, and an ink jet method can be used. The conditions for the heating and drying vary depending on the kind and the blending ratio of the components contained in the positive radiation-sensitive resin composition, and the heating temperature is usually 30 to 150 ℃, preferably 60 to 120 ℃, and the heating time is usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more preferably 1 to 30 minutes.
The formation of a coating film by the film lamination method can be performed by applying a positive radiation-sensitive resin composition to a substrate for B-stage film formation such as a resin film or a metal film, heating and drying (pre-baking) the composition to obtain a B-stage film, and then laminating the B-stage film on a substrate. The application of the positive radiation-sensitive resin composition onto the B-stage film formation substrate and the heat drying of the positive radiation-sensitive resin composition can be performed in the same manner as the application and the heat drying of the positive radiation-sensitive resin composition in the above-described application method. The lamination can be performed using a press such as a pressure laminator, a press, a vacuum laminator, a vacuum press, or a roll laminator.
The coating film provided on the substrate can be patterned by, for example, a known patterning method in which a coating film before patterning is irradiated with radiation to form a latent image pattern, and then a developing solution is brought into contact with the coating film having the latent image pattern to develop the pattern.
Here, the radiation is not particularly limited as long as it is a radiation that can improve the solubility of the radiation irradiation portion with respect to the developing solution by decomposing the first acid generator to generate a carboxylic acid, and any radiation can be used. Specifically, for example: visible light rays; ultraviolet rays; x-rays; g line, h line, i line and other single wavelength light; laser beams such as KrF excimer laser and ArF excimer laser; a particle beam such as an electron beam, and the like. These radiations can be used singly or in combination of 2 or more.
As a method of forming a latent image pattern by pattern-wise irradiating radiation, a known method of irradiating radiation through a desired mask pattern using a reduction projection exposure apparatus, or the like can be used.
The irradiation conditions of the radiation are appropriately selected depending on the radiation used, and for example, the wavelength of the radiation may be in the range of 365nm to 436nm, and the irradiation dose may be 500mJ/cm2The following.
As the developer, a known alkali developer such as an aqueous solution of a basic compound described in international publication No. 2015/141719 can be used.
Further, the method and conditions for bringing the developer into contact with the coating film are not particularly limited, and for example, the method and conditions described in international publication No. 2015/141719 can be used.
The coating film patterned as described above can be washed with a washing liquid as necessary to remove development residues. After the rinsing treatment, the remaining rinsing liquid can be further removed by compressed air or compressed nitrogen.
[ formation of resin film ]
The resin film can be formed by irradiating the coating film with radiation and then curing the coating film by heating (post-baking).
Here, irradiation of the radiation ray to the coating film in forming the resin film is generally performed on the entire surface of the coating film.
The radiation is not particularly limited as long as it is a radiation that can generate a sulfonic acid by decomposing the second acid generator and improve the chemical resistance of the resin film even when the coating film is heated at a low temperature, and any radiation can be used. Specifically, for example: visible light rays; ultraviolet rays; x-rays; g line, h line, i line and other single wavelength light; laser beams such as KrF excimer laser and ArF excimer laser; a particle beam such as an electron beam, and the like. These radiations can be used singly or in combination of 2 or more.
The irradiation conditions of the radiation are appropriately selected depending on the radiation used, and for example, the wavelength of the radiation may be in the range of 365nm to 436nm, and the irradiation dose may be 750mJ/cm2The above.
The coating film can be heated using, for example, a hot plate, an oven, or the like. The heating may be performed in an inert gas atmosphere, if necessary. Examples of the inert gas include nitrogen, argon, helium, neon, xenon, krypton, and the like. Among these, nitrogen and argon are preferable, and nitrogen is particularly preferable.
Here, the temperature at which the coating film is heated may be, for example, 150 ℃ or lower, preferably 100 ℃ or higher and 130 ℃ or lower. When the positive radiation-sensitive resin composition of the present invention is used, a resin film having excellent chemical resistance can be obtained even when the temperature at which the coating film is heated is not higher than the upper limit. Further, if the temperature at the time of heating the coating film is not lower than the above lower limit, the chemical resistance of the resin film can be sufficiently improved.
The time for heating the coating film can be appropriately selected depending on the area and thickness of the coating film, the equipment used, and the like, and can be, for example, 10 to 60 minutes.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "%" and "part" representing amounts are based on mass.
In the examples and comparative examples, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated by the following methods.
< development adhesion >
The prepared positive radiation-sensitive resin composition was applied to a silicon wafer substrate by a spin coating method, and dried by heating (prebaking) at 110 ℃ for 2 minutes using a hot plate to form a coating film having a thickness of 2.7 μm. Next, in order to pattern the coating film, a mask capable of forming a 10 μm line and space (line and space) pattern was used at an irradiation dose of 180mJ/cm2The coating film is irradiated with radiation (g, h, i rays, wavelength: 365 to 436nm) to form a latent image pattern.
Next, the coating film having the latent image pattern formed thereon was subjected to a developing treatment at 25 ℃ for 30 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38 mass% as a developing solution, and rinsed with ultrapure water for 20 seconds, thereby obtaining a laminate composed of a coating film (patterned coating film) having 10 μm lines and gaps and a silicon wafer.
Then, the formed portions of the lines and gaps of the obtained laminate were observed with an optical microscope, and the development adhesion was evaluated by assuming that the pattern did not fall off as "○ (good)" and that the pattern fallen off as "x (poor)".
< chemical resistance >
The prepared positive radiation-sensitive resin composition was applied to a silicon wafer substrate by a spin coating method, and dried by heating (prebaking) at 110 ℃ for 2 minutes using a hot plate to form a coating film having a thickness of 2.7 μm.
Next, the formed coating film was subjected to a development treatment at 25 ℃ for 30 seconds using a tetramethylammonium hydroxide aqueous solution having a concentration of 2.38 mass% as a developer, and rinsed with ultrapure water for 20 seconds.
Thereafter, the coating film after the rinsing was irradiated at an irradiation dose of 1000mJ/cm2A laminate comprising a resin film and a silicon wafer substrate is obtained by irradiating the laminate with radiation (g, h, i rays, wavelength: 365 to 436nm) and then heating (post-baking) the laminate at 130 ℃ for 20 minutes in an air atmosphere using an oven.
Next, in order to evaluate the chemical resistance of the resin film, the obtained laminate was immersed in 200mL of a resist stripping solution (product name "ST 106"; a mixed solution of Monoethanolamine (MEA)/Dimethylsulfoxide (DMSO) ═ 7:3 (mass ratio)) maintained at 25 ℃ or 60 ℃ in a thermostatic bath for 5 minutes, and then the film thickness of the resin film before and after immersion was measured with an optical diffraction film thickness measuring instrument (Lambda Ace), and the film thickness change rate of the resin film (i.e., (film thickness of the resin film after immersion/film thickness of the resin film before immersion) × 100%) was calculated.
(Synthesis example 1)
< preparation of resin soluble in alkali >
A glass pressure-resistant reactor subjected to nitrogen substitution was charged with 100 parts of 40 mol% of N-phenylbicyclo [2.2.1] as a cyclic olefin having an N-substituted imide group]Hept-5-ene-2, 3-dicarboximide (NBPI) and 60 mol% of 4-hydroxycarbonyltetracyclo [6.2.1.1 ] as cyclic olefin having protic polar group3,6.02,7]A monomer mixture of dodec-9-ene (TCDC), 2.8 parts of 1, 5-hexadiene, 0.02 part of (1, 3-ditrimethylphenylimidazolin-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride (synthesized by the method described in org. Lett., Vol.1, p.953, 1999) and 200 parts of diethylene glycol monoethyl ether, monoethyl etherThe reaction mixture was reacted at 80 ℃ for 4 hours while stirring to obtain a polymerization reaction solution.
The obtained polymerization reaction solution was placed in an autoclave, and the polymerization reaction was carried out by stirring at 150 ℃ and a hydrogen pressure of 4MPa for 5 hours to obtain a polymer solution containing a hydrogenated polymer which is a cycloolefin resin having a protic polar group. The hydrogenated polymer obtained had a polymerization conversion of 99.9%, a polystyrene-equivalent weight average molecular weight of 5550, a number average molecular weight of 3630, a molecular weight distribution of 1.53, and a hydrogen conversion of 99.9%. The solid content concentration of the obtained polymer solution was 32.4%.
(example 1)
100 parts of the cyclic olefin resin having a protic polar group obtained in Synthesis example 1, 36.3 parts of an ester of 4, 4' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol as a first acid generator and 6-diazo-5, 6-dihydro-5-oxo-1-naphthalenesulfonyl chloride (1, 2-naphthoquinone diazide-5-sulfonyl chloride) (product name "TPA-525", 2.5 mols) were mixed, 0.5 part of 1, 8-naphthalimide trifluoromethanesulfonate as a second acid generator (product name "NAI-105" manufactured by Midori Kagaku) and 1 part of 9, 10-bis (octyloxy) anthracene as a sensitizer (manufactured by Kawasaki Kazaki Kaisha) were mixed, a product name "UVS-581"), 60 parts of epoxidized butane tetracarboxylic acid tetra (3-cyclohexenylmethyl) modified epsilon-caprolactone (product name "EPOLEAD GT 401" as a polyfunctional epoxy compound, and 20 parts of epoxidized polybutadiene having terminal H (product name "EPOLEADPB 4700" manufactured by Daicel), 3 parts of 5, 5' - [2,2, 2-trifluoro-1- (trifluoromethyl) ethylene ] bis [ 2-hydroxy-1, 3-benzenedimethanol ] (product name "TML-BPAF-MF" manufactured by Nippon chemical industries, Inc.) as a fluorine-containing phenolic compound, 2 parts of glycidoxypropyltrimethoxysilane (product name "OFS 6040" manufactured by XIAMETER) as a silane coupling agent, and 3 parts of 3- (phenylamino) propyltrimethoxysilane (product name "OFS 6040" manufactured by shin Etsu chemical Co., Ltd., a product name "KBM-573"), 2 parts of pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (product name "Irganox 1010" manufactured by BASF corporation) as an antioxidant, 300ppm of an organosiloxane polymer (product name "KP 341" manufactured by shin-Etsu chemical corporation) as a surfactant, and 100 parts of diethylene glycol methyl ethyl ether (product name "EDM" manufactured by Toho chemical corporation) as a solvent, and after dissolving them, they were filtered with a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a positive type radiation-sensitive resin composition.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
(example 2)
A positive radiation-sensitive resin composition was prepared in the same manner as in example 1, except that 1 part of 9, 10-dibutoxyanthracene (product name "UVS-1331" manufactured by kawasaki chemical company) was used as a sensitizer in place of UVS-581, and the amount of EPOLEAD GT401 as a polyfunctional epoxy compound was changed to 50 parts.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
(example 3)
A positive radiation-sensitive resin composition was prepared in the same manner as in example 1, except that only 80 parts of EPOLEAD GT401 was used as the polyfunctional epoxy compound instead of EPOLEAD GT401 and EPOLEAD PB 4700.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
(example 4)
A positive radiation-sensitive resin composition was prepared in the same manner as in example 1, except that 36.3 parts of an esterified product (2.0 mol) of 4, 4' - [1- [4- [1- [ 4-hydroxyphenyl ] -1-methylethyl ] phenyl ] ethylene ] bisphenol and 6-diazo-5, 6-dihydro-5-oxo-1-naphthalenesulfonyl chloride (1, 2-naphthoquinonediazide-5-sulfonyl chloride) (product name "TPA-520" manufactured by mei yuan business) was used instead of TPA-525 as the first acid generator.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
(example 5)
A positive radiation-sensitive resin composition was prepared in the same manner as in example 1, except that the amount of NAI-105 as the second acid generator was changed to 2 parts.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
(example 6)
A positive type radiation-sensitive resin composition was prepared in the same manner as in example 1 except that only 50 parts of EPOLEAD GT401 was used instead of EPOLEAD GT401 and EPOLEAD pb4700 as the polyfunctional epoxy compound and only 1.5 parts of OFS6040 was used instead of OFS6040 and KBM-573 as the silane coupling agent without adding a sensitizer, the amount of NAI-105 as the second acid generator was changed to 1 part, and the amount of Irganox1010 as the antioxidant was changed to 1.5 parts.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
(examples 7 to 9)
A positive-type radiation-sensitive resin composition was prepared in the same manner as in example 1, except that 1 part of methyl-p-benzoquinone (example 7), 1 part of thioxanthone (example 8), and 1 part of 1-phenyl-1, 2-propanedione (example 9) were used as sensitizers in place of UVS-581.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
(example 10)
A positive radiation-sensitive resin composition was prepared in the same manner as in example 9, except that 0.5 part of an N-sulfonyloxy imide derivative (product name "NT-1 TF" manufactured by San-Apro Co.) was used in place of the NAI-105 as the second acid generator.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
Comparative example 1
A positive radiation-sensitive resin composition was prepared in the same manner as in example 6, except that the second acid generator was not added.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
Comparative example 2
A positive radiation-sensitive resin composition was prepared in the same manner as in example 6, except that the amount of NAI-105 as the second acid generator was changed to 0.5 parts without blending the first acid generator.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
Comparative example 3
A positive-type radiation-sensitive resin composition was prepared in the same manner as in example 1, except that the fluorine-containing phenolic compound was not added.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
Comparative example 4
A positive radiation-sensitive resin composition was prepared in the same manner as in example 1, except that 3 parts of 3,3 ', 5, 5' -tetrakis (methoxymethyl) - [1,1 '-biphenyl ] -4, 4' -diol (product name "TMOM-BP-MF", manufactured by chemical industry of this state) as the non-fluorophenol compound was used instead of the TML-BPAF-MF as the fluorophenol compound.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
Comparative example 5
A positive type radiation-sensitive resin composition was prepared in the same manner as in example 1, except that 3 parts of 2, 2' - (2,2,3,3,4,4,5,5,6,6,7, 7-dodecafluorooctane-1, 8-diyl) bis (ethylene oxide), which is a fluorine-containing acyclic compound, was used instead of TML-BPAF-MF, which is a fluorine-containing phenolic compound.
Then, the obtained positive radiation-sensitive resin composition was used to evaluate development adhesion of the coating film and chemical resistance of the resin film. The results are shown in Table 1.
[ Table 1]
As is clear from table 1, by using a positive-type radiation-sensitive resin composition containing a resin soluble in an alkali, a first acid generator, a second acid generator, and a fluorinated phenol compound, a pattern having excellent development adhesion can be formed, and a resin film having excellent chemical resistance can be formed even under low-temperature conditions.
As is clear from table 1, the positive radiation-sensitive resin composition of comparative example 1 containing no second acid generator exhibited a decrease in the chemical resistance of the resin film formed under low temperature conditions, while the positive radiation-sensitive resin composition of comparative example 2 containing no first acid generator exhibited a decrease in the development adhesion of the pattern, and the positive radiation-sensitive resin compositions of comparative examples 3 to 5 containing no fluorine-containing phenolic compound exhibited a decrease in the development adhesion of the pattern.
Industrial applicability
The positive-type radiation-sensitive resin composition of the present invention can form a pattern having excellent development adhesion and can form a resin film having excellent chemical resistance even under low-temperature conditions.
Claims (5)
1. A positive radiation-sensitive resin composition comprising:
a resin capable of dissolving in alkali,
A first acid generator which generates a carboxylic acid when irradiated with radiation,
A second acid generator which generates a sulfonic acid when irradiated with radiation, and
a fluorophenol-containing compound.
2. The positive radiation-sensitive resin composition according to claim 1, wherein the resin soluble in an alkali is a cycloolefin-based resin having a protic polar group.
3. The positive radiation-sensitive resin composition according to claim 1 or 2, further comprising a polyfunctional epoxy compound.
4. The positive radiation-sensitive resin composition according to any one of claims 1 to 3, further containing a sensitizer.
5. The positive radiation-sensitive resin composition according to claim 4, wherein the sensitizer is a compound having an anthracene structure.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-190288 | 2017-09-29 | ||
| JP2017190288 | 2017-09-29 | ||
| PCT/JP2018/033932 WO2019065262A1 (en) | 2017-09-29 | 2018-09-13 | Positive radiosensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110998442A true CN110998442A (en) | 2020-04-10 |
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| CN201880054622.9A Pending CN110998442A (en) | 2017-09-29 | 2018-09-13 | Positive radiation-sensitive resin composition |
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| JP (1) | JP7192775B2 (en) |
| KR (1) | KR20200060366A (en) |
| CN (1) | CN110998442A (en) |
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| WO2021200241A1 (en) * | 2020-03-30 | 2021-10-07 | 日産化学株式会社 | Composition for forming resist underlayer film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008309885A (en) * | 2007-06-12 | 2008-12-25 | Hitachi Chem Co Ltd | Positive photosensitive resin composition, method for producing resist pattern and electronic device |
| JP2009251538A (en) * | 2008-04-11 | 2009-10-29 | Nippon Zeon Co Ltd | Radiation-sensitive resin composition |
| JP2013167781A (en) * | 2012-02-16 | 2013-08-29 | Fujifilm Corp | Photosensitive resin composition, production method of cured film, cured film, organic el display device and liquid crystal display device |
| TW201431940A (en) * | 2013-02-08 | 2014-08-16 | Fujifilm Corp | Pattern forming method, actinic ray sensitive resin composition, radiation sensitive resin composition, resist film, method for producing electronic device and electronic device |
| CN106432574A (en) * | 2015-08-05 | 2017-02-22 | 信越化学工业株式会社 | Polymer compound, positive resist composition, laminate, and resist patterning process |
Family Cites Families (2)
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| WO2014030441A1 (en) | 2012-08-23 | 2014-02-27 | 富士フイルム株式会社 | Positive photosensitive resin composition, method for manufacturing curable film, curable film, organic el display device, and liquid-crystal display device |
| JP2016042127A (en) | 2014-08-15 | 2016-03-31 | Jsr株式会社 | Radiation-sensitive resin composition, interlayer insulation film of display element, method of forming the same, and display element |
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- 2018-09-13 JP JP2019544560A patent/JP7192775B2/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008309885A (en) * | 2007-06-12 | 2008-12-25 | Hitachi Chem Co Ltd | Positive photosensitive resin composition, method for producing resist pattern and electronic device |
| JP2009251538A (en) * | 2008-04-11 | 2009-10-29 | Nippon Zeon Co Ltd | Radiation-sensitive resin composition |
| JP2013167781A (en) * | 2012-02-16 | 2013-08-29 | Fujifilm Corp | Photosensitive resin composition, production method of cured film, cured film, organic el display device and liquid crystal display device |
| TW201335714A (en) * | 2012-02-16 | 2013-09-01 | Fujifilm Corp | Photosensitive resin composition, method of producing cured film, cured film, liquid crystal display device, and organic electroluminescent display device |
| TW201431940A (en) * | 2013-02-08 | 2014-08-16 | Fujifilm Corp | Pattern forming method, actinic ray sensitive resin composition, radiation sensitive resin composition, resist film, method for producing electronic device and electronic device |
| CN106432574A (en) * | 2015-08-05 | 2017-02-22 | 信越化学工业株式会社 | Polymer compound, positive resist composition, laminate, and resist patterning process |
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| TWI776957B (en) | 2022-09-11 |
| JPWO2019065262A1 (en) | 2020-09-10 |
| TW201915043A (en) | 2019-04-16 |
| WO2019065262A1 (en) | 2019-04-04 |
| KR20200060366A (en) | 2020-05-29 |
| JP7192775B2 (en) | 2022-12-20 |
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