JP7192775B2 - Positive radiation-sensitive resin composition - Google Patents

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 suitably used for forming flattening films, protective films, insulating films and the like used in electronic parts. is.

Electronic parts such as liquid crystal display devices, organic EL display devices, integrated circuit devices, and solid-state imaging devices are provided with various resin films as flattening films, protective films, insulating films, and the like.

Specifically, for example, in an organic EL display device or a liquid crystal display device, a patterned interlayer insulating film (passivation film) is used to form a rewiring layer. Then, the patterned interlayer insulating film is formed by, for example, pre-baking the radiation-sensitive resin composition applied on the substrate, exposing and developing the obtained coating film to form a pattern, and then forming the patterned coating. It is formed by exposing and post-baking the film to cure it (see, for example, Patent Document 1).

The resin composition used for forming a resin film such as a patterned interlayer insulating film includes, for example, an alkali-soluble resin, a quinonediazide compound, and a photoacid having a shorter maximum absorption wavelength than the quinonediazide compound. A positive radiation-sensitive resin composition containing a generating agent has been proposed (see, for example, Patent Document 2).

WO2014/030441 JP 2016-042127 A

However, the above conventional positive radiation-sensitive resin composition does not improve the adhesion (development adhesion) between the pattern and the substrate when the pattern is formed on the substrate using the positive radiation-sensitive resin composition. There was room for improvement in terms of

In recent years, from the viewpoint of enabling the use of a substrate having low heat resistance as a substrate for forming a resin film, a resin film (cured film) can be satisfactorily formed even if heat treatment such as post-baking is performed at a low temperature. There is a need for a positive radiation-sensitive resin composition.
However, with the conventional positive radiation-sensitive resin composition described above, when heat treated at a low temperature (for example, 150° C. or lower, preferably 130° C. or lower), the resulting resin film may have reduced chemical resistance.

Accordingly, the present invention provides a positive radiation-sensitive resin composition capable of forming a pattern with excellent development adhesion and capable of forming a resin film having excellent chemical resistance even when heat-treated at a low temperature. intended to

The inventor of the present invention has made intensive studies with the aim of solving the above problems. The present inventors have found that a positive radiation-sensitive resin composition containing an alkali-soluble resin, a given acid generator, and a fluorine-containing phenolic compound can form a pattern with excellent development adhesion and resist formation. The inventors have found that it is possible to form a resin film having excellent chemical resistance under low-temperature conditions, and have completed the present invention.

That is, an object of the present invention is to advantageously solve the above-mentioned problems, and the positive radiation-sensitive resin composition of the present invention comprises an alkali-soluble resin and a carboxylic acid which is produced when irradiated with radiation. and a second acid generator that generates sulfonic acid when exposed to radiation, and a fluorine-containing phenolic compound. Thus, the inclusion of the first acid generator and the fluorine-containing phenolic compound enables the formation of a pattern with excellent development adhesion. Moreover, if the first acid generator and the second acid generator are included, a resin film having excellent chemical resistance can be formed even when heat-treated at a low temperature.

Here, in the positive radiation-sensitive resin composition of the present invention, the alkali-soluble resin is preferably a cyclic olefin resin having a protonic polar group. If a cyclic olefin resin having a protonic polar group is used as the alkali-soluble resin, the development adhesion of the pattern and the chemical resistance of the resin film can be further improved, and the transparency and water absorption are high. This is because a low resin film can be formed.

Moreover, it is preferable that the positive radiation-sensitive resin composition of the present invention further contains a polyfunctional epoxy compound. This is because the chemical resistance of the resin film can be further improved by containing the polyfunctional epoxy compound.

Furthermore, the positive radiation-sensitive resin composition of the present invention preferably further contains a sensitizer. This is because the chemical resistance of the resin film can be further improved by containing a sensitizer.

The sensitizer is preferably a compound having an anthracene structure. This is because the use of a compound having an anthracene structure as a sensitizer can further improve the chemical resistance of the resin film.

According to the positive 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.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.

(Positive radiation-sensitive resin composition)
Here, the positive radiation-sensitive resin composition of the present invention is not particularly limited, for example, a resin film ( For example, it can be used when forming a planarizing film, a protective film, an insulating film, and the like. Among them, the positive radiation-sensitive resin composition of the present invention can be suitably used when forming an insulating film, and can be used for rewiring used when disposing a redistribution layer (RDL). It can be particularly suitably used when forming an insulating film for industrial use.

The positive radiation-sensitive resin composition of the present invention comprises an alkali-soluble resin, a first acid generator that generates carboxylic acid when irradiated with radiation, and a second acid generator that generates sulfonic acid when irradiated with radiation. It contains a diacid generator and a fluorine-containing phenolic compound, and optionally at least one selected from the group consisting of polyfunctional epoxy compounds, sensitizers, additives and solvents.

Since the positive radiation-sensitive resin composition of the present invention contains a first acid generator and a fluorine-containing phenolic compound, the positive radiation-sensitive resin composition of the present invention can be used for development. A pattern with excellent adhesion can be formed. In addition, 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 even when heat-treated at a low temperature can be formed. can be formed.

<Alkali-soluble resin>
The alkali-soluble resin is not particularly limited as long as it is a resin capable of alkali development. Examples of alkali-soluble resins include, but are not limited to, novolac resins, polyvinyl alcohol resins, acrylic resins, polyimide resins, polybenzoxazole resins, vinylphenol resins, and resins containing cyclic olefin monomer units. A cyclic olefin-based resin and the like can be mentioned. These can be used singly or in combination of two or more.
In this specification, the resin or polymer "containing a monomer unit" means "the resin or polymer obtained using the monomer contains a structural unit derived from the monomer. means that there is

Among them, from the viewpoint of forming a resin film having high transparency and low water absorption while sufficiently improving the development adhesion of the pattern and the chemical resistance of the resin film, as the alkali-soluble resin, cyclic An olefinic resin is preferably used, and a cyclic olefinic resin having a protonic polar group is more preferably used.

Here, a cyclic olefin-based resin having a protic polar group suitable as an alkali-soluble resin has a cyclic structure (alicyclic or aromatic ring) derived from a cyclic olefin monomer and a protic polar group in the main chain. , are homopolymers or copolymers of cyclic olefin monomers.

The term "protonic 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 period 1 or period 2 of group 15 or group 16 of the periodic table, more preferably an oxygen atom, a nitrogen atom or a sulfur atom, particularly An oxygen atom is preferred.

Monomers for constituting the cyclic olefin-based resin having a protonic polar group include a cyclic olefin monomer (a) having a protonic polar group and a cyclic olefin monomer having a polar group other than the protonic polar group. body (b), a cyclic olefin monomer (c) having no polar group, and a monomer (d) other than a cyclic olefin monomer (hereinafter, these monomers are simply referred to as "monomer (a ) ~ (d)”). Here, the monomers (b), (c) and (d) can be used as long as they do not affect the properties.
The ratio of the cyclic olefin monomer unit having a protonic polar group to the total structural units of the cyclic olefin resin having a protonic polar group is usually 30% by mass or more and 100% by mass or less, preferably 50% by mass or more. It is 100% by mass or less. The cyclic olefin resin having a protonic polar group is preferably composed of a monomer (a) and a monomer (b) and/or a monomer (c). More preferably, it consists of a) and a 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-hydroxycarbonyltetra cyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-9-ene, 9-methyl-9-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9,10-dihydroxycarbonyltetracyclo[6.2.1.1 ^3,6 . Carboxy group-containing cyclic olefins such as 0 ^2,7 ]dodeca-4-ene; 5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene, 5-methyl-5-(4-hydroxy phenyl)bicyclo[2.2.1]hept-2-ene, 9-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-methyl-9-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene and other hydroxyl group-containing cyclic olefins, among which carboxy group-containing cyclic olefins are preferred as the monomer (a). These protonic polar group-containing cyclic olefin monomers (a) may be used alone or in combination of two or more.

Specific examples of the polar group other than the protonic polar group, which the cyclic olefin monomer (b) having a polar group other than the protonic polar group, includes an ester group (an alkoxycarbonyl group and an aryloxycarbonyl group are collectively called ), N-substituted imide group, epoxy group, halogen atom, cyano group, carbonyloxycarbonyl group (acid anhydride residue of dicarboxylic acid), alkoxy group, carbonyl group, tertiary amino group, sulfone group, acryloyl group etc. Among them, the polar group other than the protonic polar group is preferably an ester group, an N-substituted imide group or a cyano group, more preferably an ester group or an N-substituted imide group, and particularly preferably an N-substituted imide group.

Specific examples of the monomer (b) include the following cyclic olefins.
Cyclic olefins having an ester group include, for example, 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[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-methoxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-ethoxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-n-propoxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-isopropoxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-n-butoxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-methyl-9-methoxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-methyl-9-ethoxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-methyl-9-n-propoxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-methyl-9-isopropoxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-methyl-9-n-butoxycarbonyltetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-methyl-9-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene and the like.
Cyclic olefins having an N-substituted imide group include, for example, 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)dimethyl aspartate and the like.
Cyclic olefins having a cyano group include, for example, 9-cyanotetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-methyl-9-cyanotetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 5-cyanobicyclo[2.2.1]hept-2-ene and the like.
Halogen-containing cyclic olefins include, for example, 9-chlorotetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-methyl-9-chlorotetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene and the like.
These cyclic olefin monomers (b) having a polar group other than a protonic polar group may be used alone or in combination of two or more.

Specific examples of the cyclic olefin monomer (c) having no polar group include bicyclo[2.2.1]hept-2-ene (also referred to as “norbornene”), 5-ethyl-bicyclo[2.2 .1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-methylidene-bicyclo [2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, tricyclo[5.2.1.0 ^2,6 ]deca-3,8- Diene (common name: dicyclopentadiene), tetracyclo[10.2.1.0 ^{2,1 1} 0 ^4,9 ]pentadeca-4,6,8,13-tetraene, tetracyclo[6.2.1.1 ^{3 , 6} . 0 ^2,7 ]dodeca-4-ene (also referred to as “tetracyclododecene”), 9-methyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-ethyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-methylidene-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-ethylidene-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-vinyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, 9-propenyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, pentacyclo[9.2.1.1 ^3,9 . 0 ^2,10 ]pentadeca-5,12-diene, cyclopentene, cyclopentadiene, 9-phenyl-tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-4-ene, tetracyclo[9.2.1.0 ^2,10 . 0 ^3,8 ]tetradeca-3,5,7,12-tetraene, pentacyclo[9.2.1.1 ^3,9 . 0 ^2,10 ]pentadeca-12-ene and the like.
These polar group-free cyclic olefin monomers (c) may be used alone or in combination of two or more.

Specific examples of monomers (d) other than cyclic olefins include chain olefins. Examples of chain olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, α-olefins having 2 to 20 carbon atoms such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; 1,4-hexadiene, 4-methyl-1 ,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene and other non-conjugated dienes.
These monomers (d) other than cyclic olefins can be used alone or in combination of two or more.

The cyclic olefin resin having a protonic polar group used in the present invention is obtained by polymerizing the monomer (a) together with one or more monomers selected from monomers (b) to (d), if desired. obtained by The polymer obtained by polymerization may be further hydrogenated. In the present invention, hydrogenated polymers are also included in the cyclic olefin resins having protic polar groups.

The cyclic olefin resin having a protonic polar group used in the present invention is obtained by introducing a protonic polar group into a cyclic olefin resin having no protonic polar group using a known modifier, and optionally It can also be obtained by a method involving hydrogenation. Here, the hydrogenation may be performed on the polymer before introduction of the protic polar group.
Moreover, the cyclic olefin resin having a protonic polar group used in the present invention may be obtained by a method of further introducing a protonic polar group into the cyclic olefin resin having a protonic polar group.

<First acid generator>
The first acid generator is a compound that decomposes to produce carboxylic acid when exposed to radiation. When a coating film formed using the positive radiation-sensitive resin composition of the present invention containing a first acid generator is irradiated with radiation, the alkali solubility of the radiation-exposed portion increases.

Here, the radiation is not particularly limited, and examples thereof include visible light; ultraviolet rays; X-rays; single-wavelength light rays such as g-line, h-line, and i-line; laser beams; particle beams such as electron beams;

The first acid generator is not particularly limited, and for example, an azide compound such as a quinonediazide compound can be used.
As the quinonediazide compound, for example, an ester compound of a quinonediazide sulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Here, specific examples of quinonediazide sulfonic acid halides include 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, and 1,2-benzoquinonediazide-5-sulfonic acid. chloride and the like. Further, specific examples of compounds having a phenolic hydroxyl group include 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4′-[1-[4- [1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]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 novolac resins, oligomers obtained by copolymerizing a compound having at least one phenolic hydroxyl group with dicyclopentadiene, and the like can be mentioned.
Among them, as the first acid generator, 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl ]Ethylidene] ester compounds with bisphenol are preferred.
In addition, the first acid generator can be used singly or in combination of two 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, per 100 parts by mass of the alkali-soluble resin. , 60 parts by mass or less, and more preferably 50 parts by mass or less. When the amount of the first acid generator is at least the above 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, when the amount of the first acid generator is not more than the above upper limit, when a coating film formed using a positive radiation-sensitive resin composition is patterned, deterioration of resolution and generation of residue can be prevented. can be suppressed.

<Second acid generator>
The second acid generator is a compound that decomposes to produce sulfonic acid when exposed to radiation. Since the positive radiation-sensitive resin composition of the present invention contains the second acid generator in addition to the first acid generator described above, the positive radiation-sensitive resin composition was used to form the composition. Even if the heat treatment is performed at a low temperature (for example, 150° C. or less, preferably 130° C. or less) when preparing a resin film by subjecting a coating film that may be patterned to radiation and heat treatment, A resin film having excellent chemical resistance can be formed.

Here, the radiation is not particularly limited, and examples thereof include visible light; ultraviolet rays; X-rays; single-wavelength light rays such as g-line, h-line, and i-line; laser beams; particle beams such as electron beams;

The second acid generator is not particularly limited, and examples thereof include diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-p-toluenesulfonate, diphenyl (4 -methoxyphenyl)sulfonium trifluoromethanesulfonate, tris(4-methylphenyl)sulfonium nonafluorobutanesulfonate, 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-(trifluoromethyl sulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)-7-oxa Bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3 -Dicarboximide, N-(trifluoromethylsulfonyloxy) naphthyldicarboximide, N-(camphorsulfonyloxy) succinimide, 1,8-naphthalimidyl triflate (manufactured by Midori Chemical, product name "NAI-105") ), 4-methylphenylsulfonyloxyimino-α-(4-methoxyphenyl)acetonitrile (manufactured by Midori Chemical, product name “PAI-101”), trifluoromethylsulfonyloxyimino-α-(4-methoxyphenyl)acetonitrile ( Midori Chemical, product name “PAI-105”), 9-camphorsulfonyloxyimino-α-4-methoxyphenylacetonitrile (Midori Chemical, product name “PAI-106”), 1,8-naphthalimidylbutanesulfonate (manufactured by Midori Chemical, product name “NAI-1004”), 1,8-naphthalimidyl tosylate (manufactured by Midori Chemical, product name “NAI-101”), 1,8-naphthalimidyl nonafluorobutanesulfonate (Midori Kagaku, product name “NAI-109”), 1,8-naphthalimidyl 9-camphorsulfonate (manufactured by Midori Kagaku, product name “NAI-106”), N-sulfonyloxyimide derivatives (manufactured by San-Apro Co., Ltd., product name “NT-1TF”), and the like can be used.
Among them, 1,8-naphthalimidyl triflate and N-sulfonyloxyimide derivatives are preferred as the second acid generator from the viewpoints of solubility in solvents, storage stability and chemical resistance.
In addition, a 2nd acid generator can be used individually by 1 type or in mixture of 2 or more types.

Here, the amount of the second acid generator in the positive radiation-sensitive resin composition is preferably 0.1 parts by mass or more and 0.3 parts by mass or more per 100 parts by mass of the alkali-soluble resin. is more preferably 10 parts by mass or less, and more preferably 5 parts by mass or less. If the amount of the second acid generator is at least the above lower limit, the chemical resistance of the resin film formed using the positive radiation-sensitive resin composition can be sufficiently enhanced. Moreover, if the amount of the second acid generator is equal to or less than the above upper limit, it is possible to suppress the increase in the water absorbency of the resin film and ensure the insulation reliability.
Moreover, the amount of the second acid generator in the positive radiation-sensitive resin composition is usually less than the amount of the first acid generator, and is 0.01 times or more the amount of the first acid generator to 0.03. It is preferably not more than double. If the amount of the second acid generator is at least the above lower limit, the chemical resistance of the resin film formed using the positive radiation-sensitive resin composition can be sufficiently enhanced. Moreover, if the amount of the second acid generator is equal to or less than the above upper limit, it is possible to suppress the increase in the water absorbency of the resin film and ensure the insulation reliability.

<Fluorine-containing phenolic compound>
A fluorine-containing phenolic compound is a compound having, in one molecule, one or more fluorine atoms and a structure in which a hydroxyl group is directly bonded to a benzene ring. The fluorine atom may be directly or indirectly bonded to the benzene ring. Since the positive radiation-sensitive resin composition of the present invention contains a fluorine-containing phenolic compound in addition to the first acid generator described above, it is possible to form a pattern with excellent development adhesion.

Here, the fluorine-containing phenolic compound is not particularly limited. fluorine-containing phenolic compounds directly attached to the ring; and 2-trifluoromethylphenol, 3-trifluoromethylphenol, 2-trifluoromethoxyphenol, 3-trifluoromethoxyphenol, 5,5′-[2 Fluorine such as 2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol] (manufactured by Honshu Chemical Industry, product name “TML-BPAF-MF”) Fluorine-containing phenolic compounds whose atoms are indirectly bonded to the benzene ring; and the like can be used.
Among them, from the viewpoint of further improving development adhesion, the fluorine-containing phenolic compound is preferably a fluorine-containing phenolic compound having two or more fluorine atoms in one molecule, and the two or more fluorine atoms are indirect to the benzene ring. More preferred are fluorine-containing phenolic compounds that are directly bonded, 5,5′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzene dimethanol] is more preferred.
In addition, the fluorine-containing phenolic compound can be used individually by 1 type, or in mixture of 2 or more types.

The amount of the fluorine-containing phenolic compound in the positive radiation-sensitive resin composition is preferably 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the alkali-soluble resin. When the amount of the fluorine-containing phenolic compound is at least the above lower limit, the development adhesion of the pattern formed using the positive radiation-sensitive resin composition can be sufficiently enhanced. Further, when the amount of the fluorine-containing phenolic compound is equal to or less than the above upper limit, a sufficient residual film rate can be ensured when the coating film formed using the positive radiation-sensitive resin composition is developed. .

<Polyfunctional epoxy compound>
The polyfunctional epoxy compound that may optionally be contained in the positive radiation-sensitive resin composition of the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. By incorporating a polyfunctional epoxy compound into the positive radiation-sensitive resin composition of the present invention, the flexibility of the coating film can be improved, and the resin film can be formed by a cross-linking reaction via the polyfunctional epoxy compound. can further improve the chemical resistance of

Examples of compounds having two or more epoxy groups that can be used as polyfunctional epoxy compounds 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-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl ] Propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4′-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol A diglycidyl ether, pentaerythritol polyglycidyl ether, and the like. Commercially available polyfunctional epoxy compounds include, for example, Epolead GT401, Epolead GT403, Epolead GT301, Epolead GT302, Epolead PB3600, Epolead PB4700, Celoxide 2021, Celoxide 3000 (manufactured by Daicel); jER1001, jER1002, jER1003. , jER1004, jER1007, jER1009, jER1010, jER828, jER871, jER872, jER180S75, jER807, jER152, jER154 (manufactured by Mitsubishi Chemical Corporation); , EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.); Epiclon 200, Epicron 400 (manufactured by DIC Corporation); 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 Corporation);
Among them, polyfunctional epoxy compounds such as Epolead GT401 (substance name: epoxidized butanetetracarboxylic acid tetrakis(3-cyclohexenylmethyl)-modified ε-caprolactone) are preferred from the viewpoint of improving the chemical resistance of the resin film. It preferably contains at least one selected from the group consisting of a polyfunctional epoxy compound having a cyclic structure and an H-terminal epoxidized polybutadiene such as Epolead PB4700, and a polyfunctional compound having an alicyclic structure such as Epolead GT401. More preferably, it contains at least one selected from the group consisting of an epoxy compound and an H-terminated epoxidized polybutadiene having a glycidyl ether structure in the main chain, such as Epolead PB4700, and at least epoxidized butanetetracarboxylic acid tetrakis ( 3-cyclohexenylmethyl)-modified ε-caprolactone is further preferred.
In addition, a polyfunctional epoxy compound can be used individually by 1 type or in mixture of 2 or more types.

The amount of the polyfunctional epoxy compound in the positive radiation-sensitive resin composition is preferably 50 parts by mass or more and 90 parts by mass or less, and 70 parts by mass or more and 90 parts by mass or less per 100 parts by mass of the alkali-soluble resin. is more preferable. If the amount of the polyfunctional epoxy compound is at least the above lower limit, the chemical resistance of the resin film formed using the positive radiation-sensitive resin composition can be sufficiently enhanced. Further, when the amount of the polyfunctional epoxy compound is equal to or less than the above upper limit, a sufficient residual film ratio can be ensured when the coating film formed using the positive radiation-sensitive resin composition is developed.

<Sensitizer>
The sensitizer that may optionally be contained in the positive radiation-sensitive resin composition of the present invention is not particularly limited as long as it is a substance capable of transferring the energy of irradiated radiation to other substances. Any sensitizer such as tolquinone, thioxanthone, 1-phenyl-1,2-propanedione, compounds having an anthracene structure can be used.
In addition, a sensitizer can be used individually by 1 type or in mixture of 2 or more types.

〔式（Ｉ）中、Ｒは置換基を有していてもよい炭素数１０以下のアルキル基を示す。〕Among them, the compound having an anthracene structure is preferable as the sensitizer, and the compound represented by the following general formula (I) is more preferable, from the viewpoint of high radiolytic rate and sensitizing action.

[In Formula (I), R represents an optionally substituted alkyl group having 10 or less carbon atoms. ]

Here, R in the above formula (I) is preferably an optionally substituted alkyl group having 2 to 8 carbon atoms, and an optionally substituted alkyl group having 3 to 8 carbon atoms. The following alkyl groups are more preferred. The alkyl group for R is preferably a linear alkyl group.
Also, 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 preferred.

Examples of the compound represented by the general formula (I) include 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd., product name “UVS-1331”), 9,10-diethoxyanthracene (Kawasaki Kasei company, product name “UVS-1101”), 9,10-bis(octanoyloxy)anthracene (Kawasaki Kasei Co., Ltd., product name “UVS-581”), and the like.

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 per 100 parts by mass of the alkali-soluble resin. If the amount of the sensitizer is at least the above lower limit, the chemical resistance of the resin film formed using the positive radiation-sensitive resin composition can be sufficiently enhanced. Further, if the amount of the polyfunctional epoxy compound is equal to or less than the above upper limit, it is possible to suppress the decrease in transparency and the increase in water absorption of the resin film.

<Additive>
Examples of additives that may optionally be contained in the positive radiation-sensitive resin composition of the present invention include silane coupling agents, antioxidants, surfactants, and the like.
Here, the silane coupling agent improves the adhesion between the coating film or resin film obtained using the positive radiation-sensitive resin composition of the present invention and the substrate on which the coating film or resin film is formed. It works to elevate. The silane coupling agent is not particularly limited, and known ones can be used (see, for example, JP-A-2015-94910).
Moreover, the antioxidant can improve the light resistance and heat resistance of the coating film or 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, and lactone-based antioxidants can be used. (See, for example, International Publication No. 2015/033901).
Furthermore, the surfactant can improve the coatability of the positive radiation-sensitive resin composition of the present invention. The surfactant is not particularly limited, and includes known silicone-based surfactants, fluorine-based surfactants, polyoxyalkylene-based surfactants, methacrylic acid copolymer-based surfactants, and acrylic acid copolymerization. Systematic surfactants and the like can be used (see, for example, WO 2015/033901).
In addition, these additives can be used individually by 1 type or in mixture of 2 or more types. Moreover, the amount of the additive compounded in the positive radiation-sensitive resin composition can be arbitrarily adjusted.

<Solvent>
The solvent that may optionally be contained in the positive radiation-sensitive resin composition of the present invention is not particularly limited, and known solvents for resin compositions can be used. Examples of such solvents include linear ketones, alcohols, alcohol ethers, esters, cellosolve esters, propylene glycols, diethylene glycols such as diethylene glycol ethyl methyl ether, saturated γ-lactones, halogenated Examples include hydrocarbons, aromatic hydrocarbons, and polar solvents such as dimethylacetamide, dimethylformamide and N-methylacetamide (see, for example, International Publication No. 2015/033901).
In addition, these solvents can be used individually by 1 type or in mixture of 2 or more types.
The amount of solvent in the positive radiation-sensitive resin composition is not particularly limited. , preferably 10,000 parts by mass or less, more preferably 5,000 parts by mass or less, and still more preferably 1,000 parts by mass or less.

<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-described components by a known method and optionally filtering. Here, for the mixing, known mixers such as stirrers, ball mills, sand mills, bead mills, pigment dispersers, crushers, ultrasonic dispersers, homogenizers, planetary mixers, and Filmix can be used. In addition, for filtering the mixture, a general filtering method using a filter medium such as a filter can be employed.

<Formation of coating film and resin film>
The resin film using the positive radiation-sensitive resin composition of the present invention is not particularly limited. It can be formed by irradiating the coating film with radiation after providing the coating film and then heating the coating film after the radiation irradiation. The coating film provided on the substrate may be patterned.
In addition, the arrangement of the coating film on the substrate on which the resin film is formed is not particularly limited. It can be done by patterning the film.

[Formation of coating film]
Here, the formation of the coating film by the coating method can be carried out by applying the positive radiation-sensitive resin composition on the substrate and then heat-drying (pre-baking) the composition. Examples of methods for applying the positive radiation-sensitive resin composition include 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, Various methods such as an inkjet method can be employed. The heating and drying conditions vary depending on the types and blending ratios of the components contained in the positive radiation-sensitive resin composition. The heating time is usually 0.5 to 90 minutes, preferably 1 to 60 minutes, more preferably 1 to 30 minutes.

In addition, the formation of a coating film by the film lamination method is performed by applying a positive radiation-sensitive resin composition onto a B-stage film-forming base material such as a resin film or a metal film, followed by heating and drying (pre-baking) to form a B-stage. After obtaining the film, it can then be done by laminating this B-staged film onto a substrate. The application of the positive radiation-sensitive resin composition onto the substrate for forming a B-stage film and the heating and drying of the positive radiation-sensitive resin composition are the same as those of the positive radiation-sensitive resin composition in the coating method described above. It can be carried out in the same manner as coating and heat drying. Also, lamination can be performed using a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator, or the like.

The patterning of the coating film provided on the substrate is performed, for example, by irradiating the coating film before patterning with radiation to form a latent image pattern, and then bringing the coating film having the latent image pattern into contact with a developer to reveal the pattern. It can be performed using a known patterning method such as a method of forming a pattern.

Here, the radiation is not particularly limited as long as it can decompose the first acid generator to generate a carboxylic acid, thereby improving the solubility of the radiation-irradiated portion in the developer. of radiation can be used. Specifically, for example, visible light; ultraviolet rays; X-rays; single-wavelength light beams such as g-line, h-line, and i-line; laser beams such as KrF excimer laser light and ArF excimer laser light; ; and the like can be used. In addition, these radiation can be used individually by 1 type or in mixture of 2 or more types.
As a method of forming a latent image pattern by irradiating radiation in a pattern, known methods such as a method of irradiating radiation through a desired mask pattern using a reduction projection exposure apparatus can be used. .
The radiation irradiation conditions are appropriately selected according to the radiation to be used. For example, the wavelength of the radiation can be in the range of 365 nm or more and 436 nm or less, and the irradiation dose is 500 mJ/cm ² or less. can do.

Moreover, as a developer, a known alkaline developer such as an aqueous solution of an alkaline compound described in WO 2015/141719 can be used.
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 employed.

The coating film patterned as described above can be rinsed with a rinsing liquid to remove development residues, if necessary. After the rinsing process, residual rinse liquid may be further removed with compressed air or compressed nitrogen.

[Formation of resin film]
The resin film can be formed by irradiating the coating film with radiation and then heating (post-baking) the coating film to cure it.

Here, irradiation of radiation to the coating film when forming the resin film is generally carried out on the entire surface of the coating film.
The radiation should decompose the second acid generator to generate sulfonic acid, thereby improving the chemical resistance of the resin film even when the coating film is heated at a low temperature. Any radiation can be used without any particular limitation. Specifically, for example, visible light; ultraviolet rays; X-rays; single-wavelength light beams such as g-line, h-line, and i-line; laser beams such as KrF excimer laser light and ArF excimer laser light; ; and the like can be used. In addition, these radiation can be used individually by 1 type or in mixture of 2 or more types.
The radiation irradiation conditions are appropriately selected according to the radiation to be used. For example, the wavelength of the radiation can be in the range of 365 nm or more and 436 nm or less, and the irradiation dose is 750 mJ/cm ² or more. can do.

Heating of the coating film is not particularly limited, and can be performed using, for example, a hot plate, an oven, or the like. In addition, you may perform a heating in inert gas atmosphere as needed. Examples of inert gases include nitrogen, argon, helium, neon, xenon, krypton, and the like. Among these, nitrogen and argon are preferred, and nitrogen is particularly preferred.

Here, the temperature at which the coating film is heated can be, for example, 150° C. or lower, preferably 100° C. or higher and 130° C. or lower. By using the positive radiation-sensitive resin composition of the present invention, it is possible to obtain a resin film having excellent chemical resistance even when the coating film is heated at a temperature not higher than the above upper limit. Moreover, if the temperature at which the coating film is heated is set to the lower limit value or more, 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, etc., and can be, for example, 10 to 60 minutes.

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" representing amounts are based on mass unless otherwise specified.
In the examples and comparative examples, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated using the following methods.

<Development adhesion>
The prepared positive radiation-sensitive resin composition was applied onto a silicon wafer substrate by spin coating, and dried by heating (pre-baking) at 110° C. for 2 minutes using a hot plate to form a coating film having a thickness of 2.7 μm. formed. Next, in order to pattern the coating film, a mask capable of forming a 10 μm line and space pattern was used to apply radiation (g, h, i lines, wavelength: 365 to 436 nm) to the coating film at a dose of 180 mJ/cm ² . Illuminated to form a latent image pattern.
Next, the coating film on which the latent image pattern was formed was developed using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass as a developer at 25° C. for 30 seconds, followed by rinsing with ultrapure water for 20 seconds. By doing so, a laminate consisting of a coating film (patterned coating film) having 10 μm lines and spaces and a silicon wafer was obtained.
Then, the formed portions of the lines and spaces of the obtained laminate were observed using an optical microscope. Development adhesion was evaluated.
<Chemical resistance>
The prepared positive radiation-sensitive resin composition was applied onto a silicon wafer substrate by spin coating, and dried by heating (pre-baking) at 110° C. for 2 minutes using a hot plate to form a coating film having a thickness of 2.7 μm. formed.
Next, the formed coating film was developed at 25° C. for 30 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass as a developer, and was rinsed with ultrapure water for 20 seconds.
After that, the rinsed coating film was irradiated with radiation (g, h, i lines, wavelength: 365 to 436 nm) at an irradiation dose of 1000 mJ/cm ² , and then using an oven in an air atmosphere at 130 ° C. for 20 minutes. A layered product composed of the resin film and the silicon wafer substrate was obtained by heating (post-baking) for a minute.
Next, in order to evaluate the chemical resistance of the resin film, the obtained laminate was held at 25 ° C. or 60 ° C. in a constant temperature bath. / dimethyl sulfoxide (DMSO) = 7/3 (mass ratio) mixture)) 200 mL for 5 minutes. Then, the film thickness of the resin film before and after the immersion was measured with an optical interference film thickness measuring device (Lambda Ace), and the film thickness change rate of the resin film (=(thickness of the resin film after immersion/before immersion) The film thickness of the resin film)×100%) was calculated. For each immersion temperature (25 ° C., 60 ° C.), if the film thickness change rate of the resin film is 5% or less in absolute value, "○ (good)" )”, and the case of more than 10% was set as “× (defective)”.

(Synthesis example 1)
<Preparation of alkali-soluble resin>
40 mol% of N-phenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (NBPI) as a cyclic olefin having an N-substituted imide group and a cyclic having a protic polar group 4-Hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 . 100 parts of a monomer mixture consisting of 60 mol% of 0 ^2,7 ]dodeca-9-ene (TCDC), 2.8 parts of 1,5-hexadiene, (1,3-dimesitylimidazolin-2-ylidene) (Tricyclohexylphosphine) benzylidene ruthenium dichloride (synthesized by the method described in Org. Lett., Vol. 1, p. 953, 1999) 0.02 parts and glass in which 200 parts of diethylene glycol ethyl methyl ether are substituted with nitrogen A pressure-resistant reactor was filled with the mixture, and the mixture was reacted at 80° C. for 4 hours while stirring to obtain a polymerization reaction liquid.
The resulting polymerization reaction solution was placed in an autoclave and stirred for 5 hours under conditions of 150° C. and a hydrogen pressure of 4 MPa to carry out a hydrogenation reaction, thereby producing a hydrogenated polymer as a cyclic olefin resin having protonic polar groups. A polymer solution containing The resulting hydrogenated polymer had a polymerization conversion rate 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 rate of 99.9%. Moreover, 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, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1- as a first acid generator Ester of methylethyl]phenyl]ethylidene]bisphenol and 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonyl chloride (1,2-naphthoquinonediazide-5-sulfonyl chloride) (Bigen Shoji Co., Ltd., product name "TPA-525", 2.5 mol body) 36.3 parts, 1,8-naphthalimidyl triflate as a second acid generator (Midori Chemical, product name "NAI- 105") 0.5 part, 9,10-bis (octanoyloxy) anthracene (manufactured by Kawasaki Kasei Co., Ltd., product name "UVS-581") as a sensitizer 1 part, epoxidized butane as a polyfunctional epoxy compound 60 parts of tetracarboxylic acid tetrakis(3-cyclohexenylmethyl)-modified ε-caprolactone (manufactured by Daicel, product name “Epolead GT401”) and 20 parts of terminal H-epoxidized polybutadiene (manufactured by Daicel, product name “Epolead PB4700”) , 5,5′-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol] (Honshu Chemical Industry Co., Ltd.) as a fluorine-containing phenolic compound (manufactured by XIAMETER, product name “TML-BPAF-MF”) 3 parts, glycidoxypropyltrimethoxysilane as a silane coupling agent (manufactured by XIAMETER, product name “OFS6040”) 2 parts and 3-(phenylamino)propyltri Methoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-573") 3 parts, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (BASF Corporation) as an antioxidant (manufactured by Toho Chemical Co., Ltd., product name “Irganox 1010”) 2 parts, organosiloxane polymer (manufactured by Shin-Etsu Chemical Co., Ltd., product name “KP341”) 300 ppm as a surfactant, and diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Co., Ltd., product name "EDM") was mixed and dissolved, followed by filtering through a polytetrafluoroethylene filter with a pore size of 0.45 µm to prepare a positive radiation-sensitive resin composition.
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

(Example 2)
Instead of UVS-581 as a sensitizer, 1 part of 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd., product name "UVS-1331") is used, and 50 parts of Epolead GT401 is used as a polyfunctional epoxy compound. A positive radiation-sensitive resin composition was prepared in the same manner as in Example 1, except for changing to .
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

(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 instead of Epolead GT401 and Epolead PB4700 as polyfunctional epoxy compounds.
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

(Example 4)
4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 6-diazo-5 in place of TPA-525 as primary acid generators, Ester (2.0 mol) with 6-dihydro-5-oxo-1-naphthalenesulfonyl chloride (1,2-naphthoquinonediazide-5-sulfonyl chloride) (manufactured by Bigen Shoji Co., Ltd., product name: TPA A positive radiation-sensitive resin composition was prepared in the same manner as in Example 1, except that 36.3 parts of C.-520") was used.
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

(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.
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

(Example 6)
No sensitizer is blended, only 50 parts of Epolead GT401 is used in place of Epolead GT401 and Epolead PB4700 as the polyfunctional epoxy compound, and only 1.5 parts of OFS6040 is used in place of OFS6040 and KBM-573 as the silane coupling agent. was used, the amount of NAI-105 as the second acid generator was changed to 1 part, and the amount of Irganox 1010 as the antioxidant was changed to 1.5 parts. A radiation sensitive resin composition was prepared.
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

(Examples 7-9)
1 part of p-toluquinone (Example 7), 1 part of thioxanthone (Example 8) and 1 part of 1-phenyl-1,2-propanedione (Example 9) were used instead of UVS-581 as sensitizers. A positive radiation-sensitive resin composition was prepared in the same manner as in Example 1, except that
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

(Example 10)
A positive type was prepared in the same manner as in Example 9, except that 0.5 parts of an N-sulfonyloxyimide derivative (manufactured by San-Apro Co., Ltd., product name "NT-1TF") was used instead of NAI-105 as the second acid generator. A radiation sensitive resin composition was prepared.
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

(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 blended.
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

(Comparative example 2)
A positive radiation-sensitive resin composition was prepared in the same manner as in Example 6 except that the first acid generator was not blended and the amount of NAI-105 as the second acid generator was changed to 0.5 parts. did.
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

(Comparative Example 3)
A positive radiation-sensitive resin composition was prepared in the same manner as in Example 1, except that no fluorine-containing phenolic compound was blended.
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

(Comparative Example 4)
3,3′,5,5′-tetrakis(methoxymethyl)-[1,1′-biphenyl]-4, which is a fluorine-free phenolic compound, in place of TML-BPAF-MF as a fluorine-containing phenolic compound, A positive radiation-sensitive resin composition was prepared in the same manner as in Example 1, except that 3 parts of 4'-diol (manufactured by Honshu Kagaku Kogyo, product name "TMOM-BP-MF") was used.
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

(Comparative Example 5)
Fluorine-containing acyclic compound 2,2'-(2,2,3,3,4,4,5,5,6,6,7 A positive radiation-sensitive resin composition was prepared in the same manner as in Example 1, except that 3 parts of ,7-dodecafluorooctane-1,8-diyl)bis(oxirane) was used.
Using the obtained positive radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. Table 1 shows the results.

From Table 1, according to the positive radiation-sensitive resin composition containing an alkali-soluble resin, a first acid generator, a second acid generator, and a fluorine-containing phenolic 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.
In addition, from Table 1, the positive radiation-sensitive resin composition of Comparative Example 1, which does not contain the second acid generator, exhibits reduced chemical resistance of the resin film formed under low-temperature conditions, and contains the first acid generator. In the case of the positive radiation-sensitive resin composition of Comparative Example 2, which does not contain a fluorine-containing phenolic compound, the development adhesion of the pattern is lowered and the chemical resistance of the resin film formed under low temperature conditions is lowered. It can be seen that the positive-type radiation-sensitive resin compositions of Nos.

According to the positive 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.

Claims (4)

an alkali-soluble resin;
a first acid generator that generates a carboxylic acid when irradiated with radiation;
a second acid generator that generates sulfonic acid when exposed to radiation;
a fluorine-containing phenolic compound;
contains
The alkali-soluble resin is a homopolymer or copolymer of a cyclic olefin monomer, which has a cyclic structure derived from a cyclic olefin monomer and a protic polar group in the main chain, and is a positive radiation-sensitive resin. Resin composition. The positive radiation-sensitive resin composition according to claim 1 , further comprising a polyfunctional epoxy compound. 3. The positive radiation-sensitive resin composition according to claim 1, further comprising a sensitizer. 4. The positive radiation-sensitive resin composition according to claim 3 , wherein said sensitizer is a compound having an anthracene structure.