TWI776957B - Positive type radiation sensitive resin composition - Google Patents

Abstract

The present invention provides a positive-type radiation-sensitive resin composition capable of forming a pattern excellent in development adhesion and capable of forming a resin film excellent in chemical resistance even when heat-treated at a low temperature. The positive-type radiation-sensitive resin composition of the present invention contains: an alkali-soluble resin, a first acid generator that generates carboxylic acid upon irradiation with radiation, a second acid generator that generates sulfonic acid upon irradiation with radiation, and a fluorine-containing phenol sexual compounds.

Description

Positive type radiation sensitive resin composition

The present invention relates to a positive-type radiation-sensitive resin composition, in particular, to a positive-type radiation-sensitive resin composition that can be suitably used for the formation of planarizing films, protective films, insulating films, and the like used in electronic parts.

Various resin films are provided on electronic components such as liquid crystal display devices, organic EL display devices, integrated circuit elements, and solid-state image sensing elements as planarizing films, protective films, insulating films, and the like.

Specifically, for example, in an organic EL display device, a liquid crystal display device, or the like, a redistribution layer is formed using a patterned interlayer insulating film (passivation film). Also, the patterned interlayer insulating film is patterned by, for example, prebaking the radiation-sensitive resin composition that has been applied on the substrate, and exposing and developing the obtained coating film to pattern the patterned interlayer insulating film. It is formed by exposing and post-baking a coating film to cure it (for example, refer to Patent Document 1).

In addition, as a resin composition used in the formation of a resin film such as an interlayer insulating film that has been patterned, for example, it has been proposed to contain an alkali-soluble resin, a quinonediazide compound, and a resin composition having an absorption maximum wavelength shorter than that of quinonediazide. A positive radiation-sensitive resin composition of a photoacid generator having a maximum absorption wavelength of the compound, etc. (refer to, for example, Patent Document 2).

"Patent Document" "Patent Document 1": International Patent Publication No. 2014/030441 "Patent Document 2": Japanese Patent Publication No. 2016-042127

However, the above-mentioned conventional positive-type radiation-sensitive resin composition still has an improvement in the point of improving the adhesiveness (development adhesiveness) between the pattern and the substrate when the pattern is formed on the substrate using the positive-type radiation-sensitive resin composition. room.

In addition, in recent years, from the viewpoint of using a substrate with low heat resistance as a substrate for forming a resin film, there has been a demand for a positive type that can form a resin film (cured film) well even if heat treatment such as post-baking is performed at a low temperature. Radiation-sensitive resin composition.

However, in the above-mentioned conventional positive-type radiation-sensitive resin composition, if the heat treatment is performed at a low temperature (eg, 150°C or lower, preferably 130°C or lower), the chemical resistance of the obtained resin film may decrease.

Therefore, an object of the present invention is to provide a positive-type radiation-sensitive resin composition capable of forming a pattern excellent in development adhesion and capable of forming a resin film excellent in chemical resistance even when heat-treated at a low temperature.

The inventors of the present invention have devoted themselves to research with the aim of solving the above-mentioned problems. Then, the present inventors found that, according to a positive-type radiation-sensitive resin composition containing an alkali-soluble resin, a specified acid generator, and a fluorine-containing phenolic compound, it is possible to form a pattern with excellent development adhesion and to form a chemical resistance under low temperature conditions. A resin film having excellent properties has been obtained, and the present invention has been completed.

That is, the present invention aims to solve the above-mentioned problems smoothly, and the positive-type radiation-sensitive resin composition of the present invention is characterized by comprising an alkali-soluble resin, a first acid generator capable of generating carboxylic acid upon irradiation with radiation, A second acid generator that generates sulfonic acid upon irradiation with radiation, and a fluorine-containing phenolic compound. When the first acid generator and the fluorine-containing phenolic compound are contained in this manner, a pattern excellent in development adhesiveness can be formed. In addition, if the first acid generator and the second acid generator are contained, a resin film excellent in 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 the aforementioned alkali-soluble resin, which is a cycloolefin-based resin having a protonic polar group. This is because if a cycloolefin-based 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 at the same time, a resin with high transparency and low water absorption can be formed. Because of the membrane.

Furthermore, the positive-type radiation-sensitive resin composition of the present invention preferably further contains a polyfunctional epoxy compound. This is because the chemical resistance of the resin film can be further improved if the polyfunctional epoxy compound is contained.

Furthermore, the positive-type 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.

Moreover, it is preferable that the said sensitizer is a compound which has an anthracene structure. This is because if a compound having an anthracene structure is used as a sensitizer, the chemical resistance of the resin film can be further improved.

According to the positive-type radiation-sensitive resin composition of the present invention, a pattern excellent in development adhesion can be formed, and at the same time, a resin film excellent in chemical resistance can be formed even under low temperature conditions.

Embodiments of the present invention will be described in detail below.

(Positive radiation sensitive resin composition)

Here, the positive radiation-sensitive resin composition of the present invention is not particularly limited. For example, it can be used to form electronic components such as liquid crystal display devices, organic EL display devices, integrated circuit elements, and solid-state image sensing elements. In the case of having a resin film (for example, a planarization film, a protective film, an insulating film, etc.). Among them, the positive-type radiation-sensitive resin composition of the present invention can be suitably used when forming an insulating film, and can be particularly suitable for forming a redistribution insulation used in the redistribution layer (Re-Distribution Layer; RDL) formation. membrane.

Furthermore, the positive-type radiation-sensitive resin composition of the present invention contains an alkali-soluble resin, a first acid generator that generates carboxylic acid upon irradiation with radiation, a second acid generator that generates sulfonic acid upon irradiation with radiation, and a fluorine-containing The phenolic compound may further optionally contain at least one selected from the group consisting of a polyfunctional epoxy compound, a sensitizer, an additive, and a solvent.

In addition, since the positive-working radiation-sensitive resin composition of the present invention contains the first acid generator and the fluorine-containing phenolic compound, a pattern excellent in developing adhesion can be formed by using the positive-working radiation-sensitive resin composition of the present invention. Furthermore, since the positive-type radiation-sensitive resin composition of the present invention contains the first acid generator and the second acid generator, even when heat-treated at low temperature, a resin film excellent in chemical resistance 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. The alkali-soluble resin is not particularly limited, and examples include: novolak resin, polyvinyl alcohol resin, acrylic resin, polyimide resin, polybenzoxazole resin, vinyl phenol resin, and resins containing cyclic olefins. Cycloolefin-based resins, etc., of resins of monomer units. These can be used individually by 1 type or in mixture of 2 or more types. In addition, in this specification, a resin or a polymer "comprising a monomer unit" means "in a resin or polymer obtained by using the monomer, a structural unit derived from a monomer is contained".

Among them, from the viewpoint of sufficiently improving the developing adhesion of the pattern and the chemical resistance of the resin film, and at the same time forming a resin film with high transparency and low water absorption, as the alkali-soluble resin, a cycloolefin-based resin is used. As the resin, it is preferable to use a cycloolefin-based resin having a protonic polar group.

Here, the cycloolefin-based resin having a protonic polar group that is suitable as an alkali-soluble resin is a ring having a cyclic structure (alicyclic or aromatic ring) derived from a cycloolefin monomer and a protonic polar group in the main chain Homopolymers or copolymers of olefin monomers.

In addition, 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 the first period or the second period of Group 15 or Group 16 of the periodic table, preferably an oxygen atom, a nitrogen atom or a sulfur atom, especially an oxygen atom good.

Examples of the monomer for constituting the cycloolefin-based resin having a protonic polar group include a cycloolefin monomer (a) having a protonic polar group, and a cycloolefin monomer (a) having a polar group other than a protonic polar group ( b), cycloolefin monomers (c) without polar groups, and monomers (d) other than cycloolefin monomers (hereinafter, these monomers are referred to as "monomers (a) to (d)"). Here, the monomers (b), (c), and (d) can be used within a range that does not affect the properties.

In addition, in all structural units of the cycloolefin resin having a protonic polar group, the ratio of the cycloolefin monomer unit having a protonic polar group is usually 30% by mass or more and 100% by mass or less, and 50% by mass or more and 100% by mass. The mass % or less is preferred. Furthermore, the cycloolefin-based resin having a protonic polar group is preferably composed of the monomer (a), the monomer (b) and/or the monomer (c), and the monomer (a) and the monomer ( b) The composition is better.

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-methyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, -Carboxymethyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-dihydroxycarbonylbicyclo[2.2.1]hept-2-ene, 4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ] Dodec-9-ene, 9-methyl-9-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodec-4-ene, 9,10 ^{-Dihydroxycarbonyltetracyclo} [ ^{6.2.1.13,6.02,7} ]dodec-4-ene and other carboxyl-containing cycloalkenes; 5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2- alkene, 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} ]dodec-4-ene and other hydroxyl-containing cyclic olefins; etc., among them, as the monomer (a), the carboxyl group-containing cycloolefin is preferable. These cycloolefin monomers (a) having a protonic polar group may be used alone or in combination of two or more.

Specific examples of the polar group other than the protonic polar group contained in the cycloolefin monomer (b) having a polar group other than the protonic polar group include an ester group (meaning an alkoxycarbonyl group and an aryloxycarbonyl group). ), N-substituted imino group, epoxy group, halogen atom, nitrile group, carbonyloxycarbonyl group (anhydride residue of dicarboxylic acid), alkoxy group, carbonyl group, tertiary amino group, sulfonic acid group base and acryloyl group, etc. Among them, as polar groups other than protonic polar groups, ester groups, N-substituted imide groups and nitrile groups are preferred, ester groups and N-substituted imide groups are preferred, and N-substituted imide groups are preferred. Amine groups are particularly preferred.

Moreover, as a specific example of a monomer (b), the following types of cycloolefins are mentioned.

Examples of cycloolefins having an ester group include 5-acetoxybicyclo[2.2.1]hept-2-ene, 5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-acetoxybicyclo[2.2.1]hept-2-ene, Methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 9-acetoxytetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodec-4-ene, 9 -Methoxycarbonyltetracyclo[ ^{6.2.1.13,6.02,7} ] ^dodec -4-ene, 9-ethoxycarbonyltetracyclo[ ^{6.2.1.13,6.02,7} ] ^dodecane -4-ene, 9-n-propoxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodec-4-ene, 9-isopropoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] Dodec-4-ene, 9-n-butoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] Dodec-4-ene, 9-methyl-9-methyl ^{Oxycarbonyltetracyclo} [ ^{6.2.1.13,6.02,7} ] ^dodec -4-ene, 9-methyl-9-ethoxycarbonyltetracyclo[ ^{6.2.1.13,6.02,7} ]dodec-4-ene, 9-methyl-9-n-propoxycarbonyltetracyclo[ ^{6.2.1.13,6.02,7} ] ^dodec -4-ene, 9-methyl-9-iso ^{Propoxycarbonyltetracyclo} [ ^{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, etc.

Examples of cycloolefins having an N-substituted imide group include N-phenylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimide, N-(2-ethyl Hexyl)-1-isopropyl-4-methylbicyclo[2.2.2]oct-5-ene-2,3-dimethylimide, N-(2-ethylhexyl)bicyclo[2.2.1] Hept-5-ene-2,3-dimethylimide, N-[(2-ethylbutoxy)ethoxypropyl]bicyclo[2.2.1]hept-5-ene-2,3- Dicarbimide, N-(endobicyclo[2.2.1]hept-5-ene-2,3-diyldicarbonyl)aspartate dimethyl ester, etc.

Examples of the cycloolefin having a nitrile group include 9- ^{cyanotetracyclo} [ ^{6.2.1.13,6.02,7} ]dodec-4-ene, 9-methyl-9-cyanotetracyclo[ 6.2.1.1 ^3,6 .0 ^2,7 ] Dodec-4-ene, 5-cyanobicyclo[2.2.1]hept-2-ene, etc.

Examples of the cycloolefin having a halogen atom include 9-chlorotetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodec-4-ene, 9-methyl-9-chlorotetracyclo[6.2. 1.1 ^{3,6.0 2,7} ] Dodec-4-ene, etc.

These cycloolefin monomers (b) which have polar groups other than protonic polar groups may be used alone or in combination of two or more.

Specific examples of the cycloolefin monomer (c) having no polar group include bicyclo[2.2.1]hept-2-ene (also referred to as "noralkene"), 5-ethylbicyclo[2.2. 1]hept-2-ene, 5-butylbicyclo[2.2.1]hept-2-ene, 5-ethylenebicyclo[2.2.1]hept-2-ene, 5-methinebicyclo[2.2. 1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, tricyclo[5.2.1.0 ^2,6 ]dec-3,8-diene (common name: dicyclopentadiene) , tetracyclo[10.2.1.0 ^2,11 0 ^4,9 ]pentadec-4,6,8,13-tetraene, tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodec-4-ene (Also known as "tetracyclododecene".), 9-methyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodec-4-ene, 9-ethyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] Dodec-4-ene, 9-Methylenetetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] Dodec-4-ene, 9-Ethylenetetracyclo [6.2.1.1 ^3,6 .0 ^2,7 ] Dodec-4-ene, 9-vinyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] Dodec-4-ene, 9-propenyl Tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodec-4-ene, pentacyclo[9.2.1.1 ^{3,9.0 2,10.0 4,8 ]} pentadec-5,12-di alkene, cyclopentene, cyclopentadiene, 9-phenyltetracyclo[ ^{6.2.1.13,6.02,7} ] ^dodec -4-ene, tetracyclo[ ^{9.2.1.02,10.03 , 8} ] Tetradec- ^3,5,7,12 -tetraene, ^pentacyclo [ ^{9.2.1.13,9.02,10.04,8} ]pentadeca-12-ene, etc.

These cycloolefin monomers (c) having no polar group may be used alone or in combination of two or more.

As a specific example of the monomer (d) other than a cycloolefin, a linear olefin is mentioned. 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, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene Alpha-olefins with 2 to 20 carbon atoms, such as ene, 1-octadecene, and 1-eicosene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl- 1,4-hexadiene, 1,7-octadiene and other non-conjugated dienes; etc.

The monomers (d) other than these cycloolefins can be used alone or in combination of two or more.

The cycloolefin-based resin having a protonic polar group used in the present invention can be obtained by polymerizing the monomer (a) together with one or more monomers selected from the group consisting of monomers (b) to (d) as desired. and obtained. The polymers obtained by polymerization can also be further hydrogenated. In the present invention, the hydrogenated polymer is also included in the cycloolefin-based resin having a protonic polar group.

Further, the cycloolefin-based resin having a protonic polar group used in the present invention is hydrogenated as desired by introducing a protonic polar group into the cycloolefin-based resin having no protonic polar group using a well-known modifier. method can also be obtained. Here, the hydrogenation may be performed on the polymer before the introduction of the protonic polar group.

In addition, the cycloolefin-based resin having a protonic polar group used in the present invention can also be obtained by a method of further introducing a protonic polar group into the cycloolefin-based resin having a protonic polar group.

<First acid generator>

The first acid generator is a compound that decomposes to generate a carboxylic acid upon irradiation with radiation. Furthermore, when the 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, for example: visible light; ultraviolet light; X-ray; light of single wavelength such as g-line, h-line, i-line; KrF excimer laser light, ArF excimer laser light and other lasers Light rays; particle beams such as electron beams; etc.

Moreover, as a 1st acid generator, it does not specifically limit, For example, azide compounds, such as a quinonediazide compound, can be used.

In addition, as the quinonediazide compound, for example, an ester compound of a quinonediazide sulfonium halide and a compound having a phenolic hydroxyl group can be used. Here, specific examples of the quinonediazidesulfonium halide include 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonic acid Acyl chloride, 1,2-benzoquinonediazide-5-sulfonyl chloride, etc. In addition, specific examples of the compound having a phenolic hydroxyl group include 1,1,3-sam(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-( 1-{4-[1-(4-Hydroxyphenyl)-1-methylethyl]phenyl}ethylene)bisphenol, 2,3,4-trihydroxydiphenyl ketone, 2,3, 4,4'-Tetrahydroxydiphenylketone, 2-bis(4-hydroxyphenyl)propane, ginseng(4-hydroxyphenyl)methane, 1,1,1-paras(4-hydroxy-3-methyl) Phenyl)ethane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, oligomers of novolak resins, and compounds with "one or more phenolic hydroxyl groups" and dicyclopentane oligomers obtained by copolymerizing olefins, etc.

Among them, as the first acid generator, 1,2-naphthoquinonediazide-5-sulfonyl chloride and 4,4'-(1-{4-[1-(4-hydroxyphenyl)-1 -Methylethyl]phenyl}ethylene) bisphenol ester compounds are preferred.

Moreover, the 1st acid generator can be used individually by 1 type, or in mixture of 2 or more types.

Here, the amount of the first acid generator in the positive-type radiation-sensitive resin composition is preferably 10 parts by mass or more, preferably 20 parts by mass or more, and less than 60 parts by mass per 100 parts by mass of the alkali-soluble resin Preferably, it is preferably 50 parts by mass or less. When the quantity of a 1st acid generator is more than the said lower limit, when developing the coating film formed using the positive type radiation-sensitive resin composition, the residual film rate can be fully ensured. Moreover, when the quantity of a 1st acid generator is below the said upper limit, when patterning the coating film formed using the positive type radiation-sensitive resin composition, the generation|occurence|production of a reduction in resolution and generation|occurrence|production of a residue can be suppressed.

<Second acid generator>

The second acid generator is a compound that decomposes to generate sulfonic acid upon irradiation with radiation. Furthermore, the positive-type radiation-sensitive resin composition of the present invention contains a second acid generator in addition to the above-mentioned first acid generator. When the coating film of "chemical" is subjected to radiation irradiation and heat treatment to prepare a resin film, even if the heat treatment is performed at a low temperature (for example, below 150°C, preferably below 130°C), a resin with excellent chemical resistance can still be formed. membrane.

Here, the radiation is not particularly limited, for example: visible light; ultraviolet light; X-ray; light of single wavelength such as g-line, h-line, i-line; KrF excimer laser light, ArF excimer laser light and other lasers Light rays; particle beams such as electron beams; etc.

Furthermore, the second acid generator is not particularly limited, and for example, diphenyl-4-methylphenyl perylene trifluoromethanesulfonate, and diphenyl-2,4,6-trifluorotoluenesulfonate can be used. Tolyl perionium, diphenyl (4-methoxyphenyl) perium trifluoromethanesulfonate, nonafluorobutanesulfonic acid ginseng (4-methylphenyl) perium, bis(cyclohexylsulfonyl) diazomethane, 2-Methyl-2-[(4-methylphenyl)sulfonyl]-1-[4-(methylthio)phenyl]-1-propanone, bis(4-methylphenylsulfonyl) ) diazomethane, N-(trifluoromethanesulfonyloxy) butanediimide, N-(trifluoromethanesulfonyloxy)phthalimide, N-(trifluoromethanesulfonyloxy)diimide Phenylmaleimide, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(trifluoromethanesulfonyl Ethyloxy)-7-oxobicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]heptane- 5,6-Oxy-2,3-dicarboxyimide, N-(trifluoromethanesulfonyloxy)naphthyldicarboxyimide, N-(camphorsulfonyloxy)butanediimide , 1,8-naphthalimide trifluoromethanesulfonate (manufactured by Midori Kagaku, product name "NAI-105"), 4-methylbenzenesulfonyloxyimino-α-(4- Methoxyphenyl)acetonitrile (manufactured by Midori Kagaku, product name "PAI-101"), trifluoromethanesulfonyloxyimino-α-(4-methoxyphenyl)acetonitrile (manufactured by Midori Kagaku, product name " PAI-105"), 9-camphorsulfonyloxyimino-α-4-methoxyphenylacetonitrile (manufactured by Midori Kagaku, product name "PAI-106"), butanesulfonic acid-1,8-naphthalenedi Carboxylimide (manufactured by Midori Kagaku, product name "NAI-1004"), 1,8-naphthalimide toluenesulfonate (manufactured by Midori Kagaku, product name "NAI-101"), nonafluoro Butanesulfonic acid-1,8-naphthalimide (manufactured by Midori Kagaku, product name "NAI-109"), 9-camphorsulfonate-1,8-naphthalimide (manufactured by Midori Kagaku) , product name "NAI-106"), N-sulfonyloxyimide derivatives (manufactured by San-Apro, product name "NT-1TF"), etc.

Among them, from the viewpoints of solubility in solvents, storage stability, chemical resistance, etc., as the second acid generator, 1,8-naphthalimide trifluoromethanesulfonate and N-sulfonic acid An oxyimide derivative is preferred.

In addition, the second acid generator may be used alone or in combination of two or more.

Here, the amount of the second acid generator in the positive radiation-sensitive resin composition is preferably 0.1 parts by mass or more, preferably 0.3 parts by mass or more, and less than 10 parts by mass per 100 parts by mass of the alkali-soluble resin Preferably, it is preferably 5 parts by mass or less. If the amount of the second acid generator is at least the above lower limit value, the chemical resistance of the resin film formed using the positive-type radiation-sensitive resin composition can be sufficiently improved. Moreover, when the quantity of a 2nd acid generator is below the said upper limit, the increase of the water absorption of a resin film can be suppressed, and insulation reliability can be ensured.

In addition, the amount of the second acid generator in the positive-type radiation-sensitive resin composition is usually less than the amount of the first acid generator, preferably 0.01 times or more and 0.03 times or less the amount of the first acid generator. If the amount of the second acid generator is at least the above lower limit value, the chemical resistance of the resin film formed using the positive-type radiation-sensitive resin composition can be sufficiently improved. Moreover, when the quantity of a 2nd acid generator is below the said upper limit, the increase of the water absorption of a resin film can be suppressed, and insulation reliability can be ensured.

<Fluorine-containing phenolic compounds>

The fluorine-containing phenolic compound is a compound having one or more fluorine atoms in one molecule and a structure in which a hydroxyl group is directly bonded to a benzene ring. In addition, the fluorine atom may be directly bonded to the benzene ring, or may be indirectly bonded to the benzene ring. Furthermore, since the positive-type radiation-sensitive resin composition of the present invention contains a fluorine-containing phenolic compound in addition to the above-mentioned first acid generator, a pattern excellent in developing adhesion can be formed.

Here, the fluorine-containing phenolic compound is not particularly limited, and for example, fluorine atoms such as 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 3,4,5-trifluorophenol can be used to directly bond to Fluorine-containing phenolic compounds of benzene rings; and 2-trifluorocresol, 3-trifluorocresol, 2-trifluoromethoxyphenol, 3-trifluoromethoxyphenol, 5,5'-[2,2, Fluorine atoms such as 2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol] (manufactured by Honshu Chemical Industry Co., Ltd., product name "TML-BPAF-MF") Fluorine-containing phenolic compounds indirectly bonded to the benzene ring; etc.

Among them, from the viewpoint of further improving the development adhesiveness, as the fluorine-containing phenolic compound, a fluorine-containing phenolic compound having two or more fluorine atoms in one molecule is preferable, and two or more fluorine atoms are indirectly bonded to each other. The fluorine-containing phenolic compound to the benzene ring is preferably, 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis(2-hydroxy-1,3 -benzenedimethanol) is more preferred.

In addition, the fluorine-containing phenolic compound may be used alone or in combination of two or more.

Furthermore, 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 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 value, the development adhesiveness can be sufficiently improved for a pattern formed using a positive-type radiation-sensitive resin composition. Further, when the amount of the fluorine-containing phenolic compound is equal to or less than the above-mentioned upper limit value, the residual film ratio can be sufficiently ensured when developing the coating film formed using the positive-type radiation-sensitive resin composition.

<Polyfunctional epoxy compound>

The positive-type radiation-sensitive resin composition of the present invention may optionally contain a polyfunctional epoxy compound, and is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Moreover, if the positive-type radiation-sensitive resin composition of the present invention contains a polyfunctional epoxy compound, the flexibility of the coating film can be improved, and at the same time, the resin film can be further improved by the cross-linking reaction of the polyfunctional epoxy compound. chemical resistance.

Here, as a compound having two or more epoxy groups which can be used as a polyfunctional epoxy compound, for example, ginseng trimeric isocyanate (2,3-epoxypropyl), 1,4-butane may be mentioned. Glycol Diglycidyl Ether, 1,2-Epoxy-4-(Epoxyethyl)cyclohexane, Glycerol Triglycidyl Ether, Diethylene Glycol Diglycidyl Ether, 2 ,6-Diglycidylphenylglycidyl ether, 1,1,3-para[p-(2,3-glycidoxy)phenyl]propane, 1,2-cyclohexanedi Diglycidyl carboxylate, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexyl Methyl ester, trimethylol ethane triglycidyl ether, bisphenol A diglycidyl ether and neopentylerythritol polyglycidyl ether, etc. Moreover, as a commercial item of a polyfunctional epoxy compound, for example, EPOLEAD GT401, EPOLEAD GT403, EPOLEAD GT301, EPOLEAD GT302, EPOLEAD PB3600, EPOLEAD PB4700, Celloxide 2021, Celloxide 3000 (the above are manufactured by DAICEL Corporation); jER1001, jER1002, jER1003, jER1004, jER1007, jER1009, jER1010, jER828, jER871, jER872, jER180S75, jER807, jER152, jER154 (the above are manufactured by Mitsubishi Chemical Corporation); EPPN201, EPPN202, EOCN-102, EOCN-103S, EOCN-104 EOCN-1020, EOCN-1025, EOCN-1027 (the above are manufactured by Nippon Kayaku Co., Ltd.); EPICLON 200, EPICLON 400 (the above are 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 (the above are manufactured by Nagase ChemteX Corporation); etc.

Among them, from the viewpoint of favorably improving the chemical resistance of the resin film, the polyfunctional epoxy compound is selected from the group consisting of EPOLEAD GT401 (substance name: epoxidized butane tetracarboxylate) (3-cyclohexenyl methyl ester) modified Preferably, at least one of the group consisting of polyfunctional epoxy compounds with alicyclic structure such as ε-caprolactone) and epoxidized polybutadiene with terminal H such as EPOLEAD PB4700 is selected from the group consisting of EPOLEAD Preferably, at least one of the group consisting of multifunctional epoxy compounds with alicyclic structure such as GT401 and epoxidized polybutadiene with terminal H of glycidyl ether structure in the main chain such as EPOLEAD PB4700 is preferred , it is more preferable to modify ε-caprolactone with at least epoxidized butane tetracarboxylic acid tetra(3-cyclohexene methyl ester).

Moreover, a polyfunctional epoxy compound may be used individually by 1 type, or may be used in mixture of 2 or more types.

Moreover, 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 preferably 70 parts by mass or more and 90 parts by mass or less per 100 parts by mass of the alkali-soluble resin. better. If the amount of the polyfunctional epoxy compound is at least the above lower limit value, the chemical resistance of the resin film formed using the positive-type radiation-sensitive resin composition can be sufficiently improved. And when the quantity of a polyfunctional epoxy compound is below the said upper limit, when developing the coating film formed using the positive type radiation-sensitive resin composition, the residual film rate can fully be ensured.

<Sensitizer>

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 p-methanone, 9-oxygen Arbitrary sensitizers, such as sulfur star, 1-phenyl - 1,2-propanedione, compounds with anthracene structure, etc.

Moreover, a sensitizer can be used individually by 1 type, or can be used in mixture of 2 or more types.

Among them, the sensitizer is preferably a compound having an anthracene structure, and more preferably a compound represented by the following general formula (I), from the viewpoint of high radiation decomposition rate and sensitization effect.

〔式（I）中，R表示亦可具有取代基之碳數10以下的烷基。〕"Change 1"

[In formula (I), R represents an alkyl group having 10 or less carbon atoms which may have a substituent. ]

Here, R in the above formula (I) is preferably an alkyl group having 2 or more and 8 or less carbon atoms which may have a substituent, and is preferably an alkyl group having 3 or more and 8 or less carbon atoms which may also have a substituent. . Furthermore, the alkyl group of R is preferably a straight-chain alkyl group.

In addition, the substituent which the alkyl group of R may have is not particularly limited, and examples thereof include carbonyl group and alkoxy group, and among them, carbonyl group is preferable.

Moreover, as a compound represented by the said general formula (I), 9,10-dibutoxyanthracene (made by Kawasaki Chemical Co., Ltd., product name "UVS-1331"), 9,10-diethoxy anthracene, for example, can be mentioned. Keanthracene (manufactured by Kawasaki Chemical Co., Ltd., product name "UVS-1101"), 9,10-bis(octyloxy)anthracene (manufactured by Kawasaki Chemical Co., Ltd., product name "UVS-581"), etc.

In addition, the amount of the sensitizer in the positive-type 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 value, the chemical resistance of the resin film formed using the positive-type radiation-sensitive resin composition can be sufficiently improved. Moreover, when the quantity of a polyfunctional epoxy compound is below the said upper limit, the fall of the transparency of a resin film and the increase of water absorption can be suppressed.

<additive>

Examples of additives which the positive-type radiation-sensitive resin composition of the present invention may optionally contain include silane coupling agents, antioxidants, surfactants, and the like.

Here, the silane coupling agent functions to improve the adhesion between the coating film or resin film obtained by using the positive radiation-sensitive resin composition of the present invention, and the substrate on which the coating film or resin film is formed. In addition, there is no restriction|limiting in particular as a silane coupling agent, A well-known thing can be used (refer, for example, Japanese Patent Laid-Open No. 2015-94910).

Furthermore, the antioxidant can improve the light resistance and heat resistance of the coating film or resin film obtained by using the positive-type radiation-sensitive resin composition of the present invention. The antioxidant is not particularly limited, and well-known phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, lactone-based antioxidants, etc. can be used (for example, refer to International Patent Publication No. 2015/033901). No).

Furthermore, 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 well-known polysiloxane-based surfactants, fluorine-based surfactants, polyoxyalkane-based surfactants, methacrylic acid copolymer-based surfactants, and acrylic copolymer-based surfactants can be used Surfactant, etc. (refer to, for example, International Patent Publication No. 2015/033901).

In addition, these additives can be used individually by 1 type or in mixture of 2 or more types. Also, the amount of additives blended into the positive-type radiation-sensitive resin composition can be adjusted arbitrarily.

<Solvent>

The solvent optionally contained in the positive-type radiation-sensitive resin composition of the present invention is not particularly limited, and a well-known solvent can be used as the solvent for the resin composition. As such a solvent, for example, linear ketones, alcohols, alcohol ethers, esters, xeloxetines, propylene glycols, diethylene glycols such as diethylene glycol ethyl methyl ether, saturated γ -lactones, halogenated hydrocarbons, aromatic hydrocarbons, and polar solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide, etc. (refer to, for example, International Patent Publication No. 2015/033901 ).

Moreover, these solvents can be used individually by 1 type or in mixture of 2 or more types.

Moreover, the amount of the solvent in the positive-type radiation-sensitive resin composition is not particularly limited, and relative to 100 parts by mass of the alkali-soluble resin, preferably 10 parts by mass or more, preferably 50 parts by mass or more, and 10,000 parts by mass parts are preferably not more than 5000 parts by mass, more preferably not more than 1000 parts by mass.

<Method for producing positive radiation-sensitive resin composition>

The positive-type radiation-sensitive resin composition of the present invention can be prepared by mixing the above-mentioned components according to a known method and optionally filtering. Here, in terms of mixing, a stirrer, a ball mill, a sand mill, a bead mill, a pigment disperser, a beater, an ultrasonic disperser, a homogenizer, a planetary mixer, a film gyratory mixer (FILMIX), etc. can be used known mixers. In addition, in the filtration of the mixture, a general filtration method using a filter medium such as a filter can be adopted.

<Formation of coating film and resin film>

The resin film using the positive-type radiation-sensitive resin composition of the present invention is not particularly limited. For example, a coating film can be formed by using the positive-type radiation-sensitive resin composition of the present invention on the substrate on which the resin film is formed. After that, the coating film is irradiated with radiation, and the coating film irradiated with the radiation is further heated to form. In addition, the coating film provided on the board|substrate may be patterned.

In addition, the disposition of the coating film on the substrate on which the resin film is to be formed is not particularly limited, and can be performed by arbitrarily patterning the coating film after forming the coating film on the substrate by a method such as a coating method or a thin film stacking method.

[Formation of coating film]

Here, the formation of the coating film according to the coating method can be performed by applying the positive radiation-sensitive resin composition on the substrate, followed by heating and drying (pre-baking). In addition, as a method of coating the positive-type radiation-sensitive resin composition, for example, a spray coating method, a spin coating method, a roll coating method, a die coating method, a blade coating method, a bar coating method, a screen printing method, an ink jet method, etc. can be used Various methods. The heating and drying conditions vary depending on the type or blending ratio of the components contained in the positive radiation-sensitive resin composition, but the heating temperature is usually 30 to 150°C, preferably 60 to 120°C; the heating time is usually 0.5 to 90 minutes , preferably 1 to 60 minutes, preferably 1 to 30 minutes.

In addition, the formation of the coating film according to the thin film stacking method can be performed by applying the positive radiation-sensitive resin composition to the substrate for B-stage film formation such as a resin film or a metal film, and then heating and drying (pre-baking). After the B-stage film is obtained, the B-stage film is then stacked on the substrate. In addition, the coating of the positive-type radiation-sensitive resin composition on the substrate for forming a B-stage film, and the heating and drying of the positive-type radiation-sensitive resin composition can be compared with the coating and heating of the positive-type radiation-sensitive resin composition in the above-mentioned coating method. dry to proceed. In addition, stacking can be performed using a pressing machine such as a pressure bonding machine, a press, a vacuum bonding machine, a vacuum press, and a roll bonding machine.

For patterning of the coating film provided on the substrate, for example, after the coating film before patterning is irradiated with radiation to form a latent image pattern, a method of making the developing solution contact the coating film having the latent image pattern to visualize the pattern, etc. Well known patterning methods.

Here, the radiation is not particularly limited as long as the solubility of the radiation-irradiated portion to the developer can be improved by decomposing the first acid generator to generate a carboxylic acid, and any radiation can be used. Specifically, for example, visible light; ultraviolet light; X-ray; light of single wavelength such as g-line, h-line, i-line; laser light such as KrF excimer laser light, ArF excimer laser light; particle beam such as electron beam can be used ;Wait. In addition, these radiations may be used alone or in a mixture of two or more.

In addition, as a method of irradiating radiation to a pattern shape to form a latent image pattern, well-known methods such as a method of irradiating radiation through a desired mask pattern using a reduction projection exposure apparatus can be used.

Also, the irradiation conditions of the radiation are appropriately selected depending on the radiation used, but for example, the wavelength of the radiation can be set within a range of 365 nm or more and 436 nm or less, and the irradiation amount can be set to 500 mJ/cm ² or less.

In addition, as a developing solution, a known alkaline developing solution such as an aqueous solution of an alkaline compound described in International Patent Publication No. 2015/141719 can be used.

Furthermore, 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 Patent Publication No. 2015/141719 can be employed.

In addition, the patterned coating film may be rinsed with a rinse agent as required in order to remove the development residue. After the rinsing treatment, the residual rinsing liquid can also be further removed by compressed air or compressed nitrogen.

[Formation of resin film]

The resin film can be formed by curing the coating film by heating (post-baking) after irradiating the coating film with radiation.

Here, the radiation irradiation to the coating film at the time of forming the resin film is usually performed on the entire surface of the coating film.

In addition, as radiation, there is no particular limitation as long as the chemical resistance of the resin film can be improved even when the coating film is heated at a low temperature by decomposing the second acid generator to generate sulfonic acid. Arbitrary radiation. Specifically, for example, visible light; ultraviolet light; X-ray; light of single wavelength such as g-line, h-line, i-line; laser light such as KrF excimer laser light, ArF excimer laser light; particle beam such as electron beam can be used ;Wait. In addition, these radiations may be used alone or in a mixture of two or more.

Furthermore, the irradiation conditions of the radiation are appropriately selected depending on the radiation used, but for example, the wavelength of the radiation can be set in the range of 365 nm or more and 436 nm or less, and the irradiation amount can be set at 750 mJ/cm ² or more.

The heating of the coating film is not particularly limited, and can be performed using a hot plate, an oven, or the like. In addition, heating can also be performed in an inert gas environment as required. As an inert gas, nitrogen, argon, helium, neon, xenon, krypton, etc. are mentioned, for example. Of these, nitrogen and argon are preferred, and nitrogen is particularly preferred.

Here, the temperature at the time of heating the coating film can be, for example, 150° C. or lower, preferably 100° C. or higher and 130° C. or lower. As long as the positive radiation-sensitive resin composition of the present invention is used, a resin film excellent in chemical resistance can be obtained even if the temperature at the time of heating the coating film is equal to or lower than the above-mentioned upper limit value. Furthermore, when the temperature at the time of heating the coating film is set to be equal to or higher than the above lower limit value, the chemical resistance of the resin film can be sufficiently improved.

In addition, 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 set to, for example, 10 to 60 minutes.

"Example"

The present invention is specifically described below based on examples, but the present invention is not limited to these examples. In addition, in the following description, "%" and "part" which show the quantity are based on mass unless otherwise noted.

In Examples and Comparative Examples, the developing adhesion of the coating film and the chemical resistance of the resin film were evaluated by the following methods, respectively.

<Development Adhesion>

The prepared positive-type radiation-sensitive resin composition was coated on a silicon wafer substrate by spin coating, and heated and dried (pre-baking) at 110°C for 2 minutes using a hot plate to form a coating film with a thickness of 2.7 μm . Subsequently, in order to pattern the coating film, the coating film was irradiated with radiation (g, h, i lines, wavelength: 365 m) under the condition of an irradiation dose of 180 mJ/cm ² using a mask capable of forming a 10 μm line width and space pattern. ~436 nm), forming a latent image pattern.

Subsequently, for the coating film on which the latent image pattern has been formed, a tetramethylammonium hydroxide aqueous solution with a concentration of 2.38 mass % is used as a developing solution, and a development treatment is performed at 25° C. for 30 seconds, and rinsed with ultrapure water for 20 seconds. This results in a stack of coating films (patterned coating films) with 10 μm line width and spacing and silicon wafers.

Then, the portions where the line width and the space were formed in the obtained stack were observed with an optical microscope, and the case where the pattern was not peeled was marked as "○ (good)", and the case of peeling was marked as "╳ (poor)", and the evaluation was carried out. Development of adhesion.

<Chemical Resistance>

The prepared positive-type radiation-sensitive resin composition was coated on a silicon wafer substrate by spin coating, and was heated and dried (pre-baked) at 110° C. for 2 minutes using a hot plate to form a coating film with a thickness of 2.7 μm. .

Subsequently, with respect to the formed coating film, a development treatment was performed at 25° C. for 30 seconds using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38 mass % as a developer, and rinsed with ultrapure water for 20 seconds.

After that, the rinsed coating film was irradiated with radiation (g, h, i lines, wavelength: 365-436 nm) under the condition of an irradiation dose of 1000 mJ/cm ² , and then an oven was used, under the atmospheric environment, 130 ℃ Heating (post-baking) under the same conditions for 20 minutes, thereby obtaining a stack of resin films and silicon wafer substrates.

Next, in order to evaluate the chemical resistance of the resin film, the obtained stack was immersed in a photoresist stripping solution (product name "ST106"; Subsoil (DMSO) = 7/3 (mass ratio) mixture) in 200 mL for 5 minutes. Then, the film thickness of the resin film before and after immersion was measured with a light interference type film thickness measuring device (Lambda Ace), and the film thickness change rate of the resin film was calculated (=(film thickness of the resin film after immersion/resin before immersion) film thickness) × 100%). For each immersion temperature (25°C, 60°C), the case where the film thickness change rate of the resin film was 5% or less in absolute value was marked as "○ (good)", and the case where it exceeded 5% and 10% or less was marked as It is "△ (fair)", and the cases exceeding 10% are marked as "╳ (defective)".

(Synthesis Example 1)

<Preparation of alkali-soluble resin>

Combining "N-phenylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimide (NBPI) 40 mol% as a cycloalkene having an N-substituted imino group" with " Monomer mixture 100 consisting of 4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodec-9-ene (TCDC) 60 mol% as a cycloolefin having a protonic polar group parts, 2.8 parts of 1,5-hexadiene, dichloro[1,3-bis(1,3,5-trimethylphenyl)imidazolin-2-ylidene](tricyclohexylphosphine)benzylidene Ruthenium (synthesized by the method described in Org. Lett., Vol. 1, p. 953, 1999) and 200 parts of diethylene glycol ethyl methyl ether were charged into a pressure-resistant glass reactor substituted with nitrogen, and It was made to react at 80 degreeC for 4 hours, stirring, and the polymerization reaction liquid was obtained.

The obtained polymerization reaction liquid was put into an autoclave, and stirred at 150° C. and a hydrogen pressure of 4 MPa for 5 hours to carry out a hydrogenation reaction to obtain a hydrogenated polymer containing a cycloolefin-based resin having a protonic polar group. polymer solution. The polymerization conversion rate of the obtained hydrogenated polymer was 99.9%, the weight average molecular weight in terms of polystyrene was 5550, the number average molecular weight was 3630, the molecular weight distribution was 1.53, and the hydrogenation rate was 99.9%. In addition, the solid content concentration of the obtained polymer solution was 32.4%.

(Example 1)

100 parts of the cycloolefin-based resin having a protonic polar group obtained in Synthesis Example 1 and 4,4'-(1-{4-[1-(4-hydroxyphenyl) as the first acid generator -1-Methylethyl]phenyl}ethylene) bisphenol with 6-diazo-5,6-dihydro-5-oxy-1-naphthalenesulfonyl chloride (1,2-naphthoquinone 36.3 parts of an ester compound of diazido-5-sulfonyl chloride (manufactured by Miyuan Corporation, product name "TPA-525", 2.5 moles), trifluoromethanesulfonic acid- 1,8-Naphthalimide (manufactured by Midori Kagaku, product name "NAI-105") 0.5 part, 9,10-bis(octanoyloxy)anthracene (manufactured by Kawasaki Chemical Co., Ltd.) as a sensitizer Product name "UVS-581") 1 part, epoxidized butanetetracarboxylic acid (3-cyclohexenyl methyl ester) modified ε-caprolactone (manufactured by DAICEL, product name " 60 parts of EPOLEAD GT401") and 20 parts of epoxidized polybutadiene with terminal H (manufactured by DAICEL, product name "EPOLEAD PB4700"), 5,5'-[2,2,2- as a fluorine-containing phenolic compound 3 parts of trifluoro-1-(trifluoromethyl)ethylene]bis(2-hydroxy-1,3-benzenedimethanol) (manufactured by Honshu Chemical Industry Co., Ltd., product name "TML-BPAF-MF") as a silane Two parts of glycidoxypropyltrimethoxysilane (manufactured by XIAMETER, product name "OFS6040") and 3-(aniline)propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-573") as coupling agent 3 parts, tetra{3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionic acid} neopentaerythritol ester (manufactured by BASF, product name "Irganox1010") as antioxidant 2 300 ppm of organosiloxane polymer (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KP341") as surfactant, and diethylene glycol ethyl methyl ether (manufactured by Toho Chemical Co., Ltd., product name "EDM") as solvent ) 100 parts were mixed and dissolved, and then filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare a positive-type radiation-sensitive resin composition.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

(Example 2)

In addition to using 1 part of 9,10-dibutoxyanthracene (manufactured by Kawasaki Chemical Co., Ltd., product name "UVS-1331") instead of UVS-581 as a sensitizer, and changing the amount of EPOLEAD GT401, which is a polyfunctional epoxy compound, In addition to 50 parts, a positive radiation-sensitive resin composition was prepared according to Example 1.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

(Example 3)

A positive-type radiation-sensitive resin composition was prepared according to Example 1, except that only 80 parts of EPOLEAD GT401 were used instead of EPOLEAD GT401 and EPOLEAD PB4700 as the multifunctional epoxy compound.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

(Example 4)

In addition to using 4,4'-(1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylene)bisphenol with 6-diazo-5,6 -Esterate (2.0 moles) of dihydro-5-oxy-1-naphthalenesulfonyl chloride (1,2-naphthoquinonediazide-5-sulfonyl chloride) (manufactured by Miyuan Trading Co., Ltd., Except that 36.3 parts of product name "TPA-520") was used as the first acid generator instead of TPA-525, a positive-type radiation-sensitive resin composition was prepared according to Example 1.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

(Example 5)

A positive-type radiation-sensitive resin composition was prepared as in Example 1, except that the amount of NAI-105 as the second acid generator was changed to 2 parts.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

(Example 6)

Except that no sensitizer was blended, and only 50 parts of EPOLEAD GT401 was used instead of EPOLEAD GT401 and EPOLEAD PB4700 as the multifunctional epoxy compound, and only 1.5 parts of OFS6040 was used instead of OFS6040 and KBM-573 as the silane coupling agent, and will be used as the second acid The amount of NAI-105 as a generator was changed to 1 part, and the amount of Irganox 1010 as an antioxidant was changed to 1.5 parts, and a positive-type radiation-sensitive resin composition was prepared as in Example 1.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

(Examples 7 to 9)

Except that 1 part of p-methanone (Example 7), 1 part of 9 - oxothiocyanate (Example 8) and 1 part of 1-phenyl-1,2-propanedione (Example 9) were used instead of UVS Except -581 as a sensitizer, a positive type radiation-sensitive resin composition was prepared according to Example 1.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

(Example 10)

Positive radiation was prepared as in Example 9, except that 0.5 part of N-sulfonyloxyimide derivative (manufactured by San-Apro, product name "NT-1TF") was used instead of NAI-105 as the second acid generator Sensitive resin composition.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

(Comparative Example 1)

A positive-type radiation-sensitive resin composition was prepared according to Example 6, except that the second acid generator was not blended.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

(Comparative Example 2)

A positive type radiation-sensitive resin composition was prepared 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 part.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

(Comparative Example 3)

A positive type radiation-sensitive resin composition was prepared according to Example 1 except that the fluorine-containing phenolic compound was not blended.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

(Comparative Example 4)

Except for using 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol (Honshu Chemical Industry Co., Ltd.) A positive-type radiation-sensitive resin composition was prepared in accordance with Example 1, except that 3 parts of TML-BPAF-MF, which is a fluorine-containing phenolic compound, was replaced by 3 parts of TML-BPAF-MF, which is a fluorine-containing phenolic compound.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

(Comparative Example 5)

Except for the use of 2,2'-(2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorooctane-1,8 which is a fluorine-containing acyclic compound A positive type radiation-sensitive resin composition was prepared in accordance with Example 1, except that 3 parts of -diyl)bis(ethylene oxide) was used instead of TML-BPAF-MF as the fluorine-containing phenolic compound.

Then, using the obtained positive-type radiation-sensitive resin composition, the development adhesion of the coating film and the chemical resistance of the resin film were evaluated. The results are disclosed in Table 1.

"Table 1"

As can be seen from Table 1, according to the positive-type radiation-sensitive resin composition containing the alkali-soluble resin, the first acid generator, the second acid generator, and the fluorine-containing phenolic compound, a pattern with excellent development adhesion can be formed, and even in Resin films with excellent chemical resistance can be formed even at low temperatures.

In addition, as can be seen from Table 1, in the positive-type radiation-sensitive resin composition of Comparative Example 1 that does not contain the second acid generator, the chemical resistance of the resin film formed under low temperature conditions is reduced; In the positive-type radiation-sensitive resin composition of Comparative Example 2 of the generating agent, the development adhesion of the pattern was reduced, and the chemical resistance of the resin film formed under low temperature conditions was also reduced; compared with no fluorine-containing phenolic compound In the positive-type radiation-sensitive resin compositions of Examples 3 to 5, the development adhesiveness of the pattern decreased.

According to the positive-type radiation-sensitive resin composition of the present invention, a pattern excellent in development adhesion can be formed, and at the same time, a resin film excellent in chemical resistance can be formed even under low temperature conditions.

none.

none.

none.

Claims (4)

A positive type radiation-sensitive resin composition comprising: an alkali-soluble resin, a first acid generator capable of generating carboxylic acid upon irradiation with radiation, a second acid generator capable of generating sulfonic acid upon irradiation with radiation, and a fluorine-containing phenol The alkali-soluble resin is a cycloolefin-based resin having a protonic polar group, the amount of the first acid generator is 10 parts by mass or more and 60 parts by mass or less per 100 parts by mass of the alkali-soluble resin, and the second acid The amount of the generator is 0.1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the alkali-soluble resin. The positive-type radiation-sensitive resin composition according to claim 1, further comprising a polyfunctional epoxy compound. The positive-type radiation-sensitive resin composition according to claim 1 or 2, further comprising a sensitizer. The positive-type radiation-sensitive resin composition according to claim 3, wherein the sensitizer is a compound having an anthracene structure.